JP4014701B2 - Hydrogen separator - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a structure of a hydrogen separator using a hydrogen separation membrane that selectively permeates only hydrogen gas from a hydrogen mixed gas.
[0002]
[Prior art]
Hydrogen gas is used in large quantities as a basic raw material gas for petrochemicals, and high expectations are placed on it as a clean energy source. High-purity hydrogen gas is obtained by converting natural gas, naphtha or the like into a gas containing hydrogen using a catalyst, and further separating the hydrogen gas from the hydrogen-containing gas.
[0003]
Specifically, it can be separated by utilizing the property that palladium or a palladium alloy selectively transmits only hydrogen gas.
Usually, a hydrogen separator in which a thin film of palladium or a palladium alloy is deposited on the surface of a tubular porous substrate such as ceramics is used (Japanese Patent Laid-Open No. 62-273030).
[0004]
Further, in order to improve the processing capacity of such a hydrogen separator, the membrane area of the hydrogen separator per unit volume is improved, and an integrated structure (hereinafter referred to as a monolithic structure) in which a plurality of through holes are formed. A so-called monolithic hydrogen separator is disclosed in which a palladium thin film is deposited on the inner surface of a through-hole (Japanese Patent Laid-Open No. 8-40703).
[0005]
By the way, the hydrogen separation ability of palladium is exhibited only at a high temperature and a high pressure of 5 to 10 atmospheres and 300 to 500 ° C. Therefore, both ends of the hydrogen separator made of ceramics are sealed in a sealed container made of metal containing the hydrogen separator. If fixed, the hydrogen separator may be damaged due to the difference in thermal expansion coefficient between the two.
For this reason, only one end of the hydrogen separator is fixed to the sealed container and supported in a suspended form, and the end on the non-supporting side is set to an unfixed state, whereby the difference in thermal expansion between the hydrogen separator and the sealed container is achieved. Has been disclosed (Japanese Patent Laid-Open No. 6-191802).
[0006]
[Problems to be solved by the invention]
However, when the above-described suspended support is applied to a hydrogen separator using a monolith type hydrogen separator, the following problems occur.
[0007]
In the conventional tube-type hydrogen separator, a palladium membrane is formed on the outer surface of the tubular porous substrate. When the gas to be treated is introduced into the sealed container 64 from the inlet 66 as shown in FIG. Hydrogen gas contained in the processing gas permeates to the inner wall side of the tubular hydrogen separator 65 and is recovered from the outlet 68 through the upper chamber 72, and the processing residual gas is discharged from the recovery port 67. .
[0008]
On the other hand, in the monolith type hydrogen separator 85, in order to improve the membrane area per unit volume of the separator 85, it is essential to form a palladium membrane on the inner surface of the through hole of the porous substrate. As shown in FIG. 5, when the gas to be treated is introduced into the sealed container 84 from the introduction port 86, it flows into the through hole from the support side end of the separator 85 via the upper chamber 92, and the hydrogen gas passes through the palladium membrane. The light is transmitted to the outer peripheral portion of the separator 85.
[0009]
Accordingly, a partition wall is further provided at the end of the non-support side of the separator 85, or the end of the non-support side of the separator 85 is connected to a pipe communicating with the outside of the container 84 by a flange. The separated hydrogen gas and residual processing gas are mixed.
However, in such a structure, both ends of the hydrogen separator are fixed to the sealed container, and it is not possible to avoid problems associated with the difference in thermal expansion between the hydrogen separator and the sealed container.
That is, an object of the present invention is to avoid problems associated with a difference in thermal expansion between a hydrogen separator and a sealed container, such as damage to the hydrogen separator, in a hydrogen separator using a monolith type hydrogen separator.
[0010]
[Means for Solving the Problems]
The present invention provides a plurality of hydrogen separators formed by forming a large number of through holes in parallel in the longitudinal direction of a porous substrate, and depositing a hydrogen separation membrane on the inner surface of the through holes, and a gas to be processed. In a hydrogen separator comprising an inlet, a recovery port for recovering separated separation gas, and an outlet for extracting separated hydrogen gas, the hydrogen separator or the hydrogen separator is individually One end of the built-in bottomed container is fixed to a partition plate provided so as to separate the sealed container into two upper and lower chambers, and is supported in a suspended form, thereby reducing the thermal expansion difference between the hydrogen separator and the sealed container. While allowing, a part of a tubular member connected to the non-supporting end of the plurality of hydrogen separators and communicating with the introduction port or the recovery port is orthogonal to the longitudinal direction of the hydrogen separator. to, Fran both ends of the metal bellows By connecting the flexible hose has a structure, a hydrogen separation apparatus characterized in that a flexible portion that allows the thermal expansion difference between the sealed container and the hydrogen separator.
[0011]
In the hydrogen-separation device, the hydrogen separation membrane, has preferably be made of an alloy containing palladium or palladium.
[0013]
Further, the present invention provides a plurality of hydrogen separators formed by forming a large number of through holes in parallel in the longitudinal direction of a porous substrate and depositing a hydrogen separation membrane on the inner surface of the through holes, and an upper chamber In the hydrogen separation apparatus, the hydrogen separator is provided with an inlet for introducing the gas to be treated and a discharge port for taking out the separated hydrogen gas, and a closed vessel provided with a recovery port for recovering the separation residual gas in the lower chamber. One end of a bottomed container with a separate built-in container is fixed to a partition plate provided so as to separate the sealed container into two upper and lower chambers, and is supported in a suspended form, whereby the heat of the hydrogen separator and the sealed container is Allowing differential expansion, each open end of the bottomed container in which the plurality of hydrogen separators are individually housed in the sealed container is supported in a suspended manner with respect to the partition plate so as to communicate with the upper chamber. While fixing, only the lower ends of the plurality of hydrogen separators communicate with the lower chamber A tubular member is connected to the bottom of the bottomed container and the upper ends of the plurality of hydrogen separators communicate with the inlet, and the length of the hydrogen separator is partially connected to the tubular member. By connecting a flexible hose with a flange structure at both ends of a metal bellows so as to be orthogonal to the direction, a flexible portion allowing a thermal expansion difference between the hydrogen separator and the sealed container was provided. It is the hydrogen separator characterized.
[0014]
DETAILED DESCRIPTION OF THE INVENTION
Since the present invention relates to the structure of a hydrogen separator, first, the configuration of a general hydrogen separator will be outlined with reference to the illustrated example.
For example, as shown in FIG. 5, the hydrogen separator is configured by accommodating a plurality of hydrogen separators 105 in a sealed container 104 including a container body 102 and a lid 103.
[0015]
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, and is formed with an introduction port 106 and a recovery port 107 communicating with the outside of the container 104, and the lid 103 is located outside the open end. A dome shape having an outward flange 110 at the periphery, and a lead-out port 108 communicating with the outside of the container 104 is formed at the center of the top of the lid 103.
The container main body 102 and the lid 103 constitute a sealed container 104 in which the partition plate 111 is hermetically sandwiched between the outward flanges 109 and 110 and the inside of the container 104 is partitioned into an upper chamber 112 and a lower chamber 113.
[0016]
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 airtightly fixed to the partition plate 111 with the upper opening end opened to the upper chamber 112. Then, it is supported in a suspended manner in the lower chamber 113.
Note that the lower opening end is hermetically sealed by the crown member.
[0017]
In the hydrogen separator 101 having such a configuration, the gas to be processed is supplied from the inlet 106 into the lower chamber 113 of the sealed container 104, and only the hydrogen gas in the gas to be processed selectively selects the separation membrane on the outer surface of the separator 105. And then 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.
[0018]
The hydrogen separator of the present invention uses a monolith type hydrogen separator in the hydrogen separator as described above, and the open end on the non-support side of the hydrogen separator is communicated with the outside of the sealed container by a tubular member. In addition, the tubular member is provided with a flexible portion that allows thermal expansion of the hydrogen separator.
With such a structure, even with a monolith type hydrogen separator whose end on the non-support side is constrained by a tubular member, problems associated with the difference in thermal expansion between the hydrogen separator and the sealed container can be avoided.
[0019]
The flexible part has thermal expansion in the longitudinal direction of the hydrogen separator of the sealed container by providing flexibility to a part of the tubular member that communicates the outside of the sealed container and the open end of the non-support side of the hydrogen separator. On the other hand, the tubular member may be bent to absorb the difference in thermal expansion between the hydrogen separator and the sealed container.
For example, it is preferable to provide a flexible portion by connecting a flexible hose to a portion of the tubular member perpendicular to the longitudinal direction of the hydrogen separator.
[0020]
As the flexible hose, a commercially available one having a flange structure at both ends of a metal bellows can be used, and it is more preferable to use one with a blade.
This blade is a tubular body made of a metal net, covers the bellows surface, and has both open ends fixed to the flange or bellows.
The bellows-only flexible hose has a slight problem with pressure resistance, and it may be damaged by the internal pressure when a high-pressure gas of 5 to 10 atmospheres flows, but if it is a flexible hose covered with a blade, the hose longitudinal direction Although the expansion to is slightly suppressed, the pressure strength can be ensured.
[0021]
【Example】
Next, the present invention will be described in more detail based on the illustrated embodiments, but the present invention is not limited to these embodiments.
(Example 1) A hydrogen separator 1 shown in FIG. 1 is configured by accommodating six monolithic hydrogen separators 5 in a sealed container 4 including a container body 2 and a lid 3. It is set on the floor surface by the legs 22.
The lid 3 is formed with an introduction port 6 that communicates with the outside of the container 4, and the container body 2 is formed with a collection port 7 and a discharge port 8 that communicate with the outside of the container 4, and the container body 2 and the lid 3 have an outward flange A partition plate 11 is hermetically sandwiched between 9 and 10 to partition the inside of the container 4 into an upper chamber 12 and a lower chamber 13.
[0022]
Each separator 5 is fitted with sockets 14 and 15 so as to converge through holes on both end faces.
The socket 14 on the support side penetrates the partition plate 11 and is fixed to the bolt 20 by fitting. However, the contact surface between the outer periphery of the socket and the partition plate is kept close to the airtightness between the upper chamber and the lower chamber. To hold.
The socket 15 on the non-support side is directly connected to a flexible hose 16 with a blade of 8A in the same direction as the separator 5.
The flexible hose 16 has an effect of buffering the thermal expansion in the longitudinal direction of the sealed container 4 and the separator 5 but has an effect of relaxing the generated stress in the lateral direction.
[0023]
The six flexible hoses 16 are converged by joining to the ring-shaped metal tube 17 with a flange, and are connected to a 20A bladed flexible hose 19 via an L-shaped tube 18.
Since this flexible hose 19 is disposed so as to be orthogonal to the longitudinal direction of the separator 5, it can be bent in the vertical direction. That is, it is a flexible part in a present Example, and it bends so that the thermal expansion difference of the container 4 and the isolation | separation body 5 may be absorbed at the time of high temperature.
[0024]
In the present embodiment, the gas to be treated is supplied from the inlet 6 into the upper chamber 12 of the sealed container 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 led out 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 treated pass through the through-holes without passing through the separation membrane, pass through the pipes 16 to 19 connected to the lower end of the separator 5, and pass through the recovery port 7 to the outside of the container 4. To be discharged.
As shown in the figure, it is preferable that the separator 5 is housed in a metal bottomed container 21 for protection, but the bottomed container 21 is not essential in this embodiment.
[0025]
(Embodiment 2) The hydrogen separator 31 shown in FIG. 2 has a configuration similar to that of Embodiment 1, but the separator 35 is not directly fixed to the partition plate 41, but the bottomed container 51 is attached to the partition plate 41. It is characterized in that it is suspended and fixed, and the separator 35 is fixed to the bottom of the bottomed container 51. That is, in this embodiment, the lower end of the separator 35 is the support side and the upper end is the non-support side.
[0026]
In the present embodiment, the gas to be processed flows from the inlet 36 through the pipes 49 to 46 into the through holes of the separator 35 from the upper opening end of each separator 35. 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 35, is guided from the bottomed container 51 to the upper chamber 42, and is discharged from the outlet 38 to the outside of the container 34. Released.
On the other hand, gas components other than hydrogen in the gas to be processed pass through the socket 45 connected to pass through the bottomed container 51 at the lower end of the separator 5 without passing through the separation membrane. It flows into the lower chamber 43 and is discharged from the collection port 37 to the outside of the container 34.
[0027]
The present embodiment is the same as the first embodiment in that the flexible hose 49 becomes a flexible portion, but the bottomed container 51 is not only for protecting the separated body, but also for supporting the separated body, and between the upper chamber and the lower chamber. Since it also plays the role of a partition, it is different in that it becomes an essential component.
The socket 44 is supported while being loosely inserted into the support plate 50 so as to ensure a degree of freedom in the vertical direction, and the support plate 50 guides hydrogen gas flowing out from the separator 35 to the upper chamber. Are formed.
[0028]
【The invention's effect】
As described above, according to the hydrogen separator of the present invention, even when a monolith type hydrogen separator is used, damage to the hydrogen separator due to the difference in thermal expansion between the hydrogen separator and the sealed container is prevented. Can be prevented.
[Brief description of the drawings]
FIG. 1 is a front sectional view showing one embodiment of a hydrogen separator according to the present invention.
FIG. 2 is a front sectional view showing another embodiment of the hydrogen separator according to the present invention.
FIG. 3 is a schematic view showing a tube-type hydrogen separator.
FIG. 4 is a schematic view showing a monolith type hydrogen separator.
FIG. 5 is a front sectional view showing an example of a general hydrogen separator.
[Explanation of symbols]
DESCRIPTION OF SYMBOLS 1 ... Hydrogen separator, 2 ... Container main body, 3 ... Cover body, 4 ... Sealed container, 5 ... Hydrogen separator, 6 ... Inlet port, 7 ... Recovery port, 8 ... Outlet port, 9, 10 ... Outward flange, 11 ... partition plate, 12 ... upper chamber, 13 ... lower chamber, 14, 15 ... socket, 16 ... flexible hose, 17 ... ring-shaped metal tube, 18 ... L-shaped tube, 19 ... flexible hose, 20 ... bolt, 21 ... yes Bottom container, 22 ... Leg, 23 ... Drain valve, 31 ... Hydrogen separator, 32 ... Container body, 33 ... Lid, 34 ... Sealed container, 35 ... Hydrogen separator, 36 ... Inlet, 37 ... Recovery port, 38 Deriving port 39, 40 Outward flange, 41 Partition wall, 42 Upper chamber, 43 Lower chamber, 44, 45 Socket, 46 Flexible hose, 47 Ring-shaped metal tube, 48 L-shaped tube, 49 ... Flexible hose, 50 ... Support plate, 51 ... Bottomed container 52 ... Leg, 53 ... Drain valve, 64 ... Sealed container, 65 ... Hydrogen separator, 66 ... Inlet port, 67 ... Recovery port, 68 ... Outlet port, 71 ... Partition plate, 72 ... Upper chamber, 84 ... Sealed vessel, 85 ... Hydrogen separator, 86 ... Inlet, 91 ... Partition plate, 92 ... Upper chamber, 101 ... Hydrogen separator, 102 ... Container body, 103 ... Lid, 104 ... Sealed container, 1055 ... Hydrogen separator, 106 ... Inlet 107, recovery port 108, outlet, 109, 110 outward flange, 111 partition plate, 112 upper chamber, 113 lower chamber.

Claims (4)

A plurality of hydrogen separators formed by forming a large number of through holes in parallel in the longitudinal direction of the porous substrate, and depositing a hydrogen separation membrane on the inner surface of the through holes;
A sealed container having an inlet for the gas to be treated, a recovery port for recovering the separation residual gas, and an outlet for extracting the separated hydrogen gas;
A hydrogen separator comprising:
By fixing one end of the hydrogen separator or a bottomed container individually containing the hydrogen separator to a partition plate provided so as to separate the sealed container into two upper and lower chambers, and supporting it in a suspended form While allowing the thermal expansion difference between the hydrogen separator and the sealed container,
It is made of metal so as to be orthogonal to the longitudinal direction of the hydrogen separator in a part of the tubular member connected to the non-support side end of the plurality of hydrogen separators and communicating with the introduction port or the recovery port . A hydrogen separation apparatus comprising a flexible portion that allows a difference in thermal expansion between a hydrogen separator and a sealed container by connecting a flexible hose having flange structures at both ends of the bellows .   The hydrogen separator according to claim 1, wherein the hydrogen separation membrane is made of palladium or an alloy containing palladium. In a sealed container with an inlet in the upper chamber and a recovery port and outlet in the lower chamber, only the upper ends of multiple hydrogen separators are supported in a suspended manner on the partition plate so as to communicate with the upper chamber The hydrogen separator according to claim 1 or 2 , wherein the hydrogen separator is fixed and each lower end of the plurality of hydrogen separators is connected to a tubular member so as to communicate with the recovery port . A plurality of hydrogen separators formed by forming a large number of through holes in parallel in the longitudinal direction of the porous substrate, and depositing a hydrogen separation membrane on the inner surface of the through holes;
An airtight container provided with an inlet for the gas to be treated in the upper chamber and an outlet for extracting the separated hydrogen gas, and a recovery port for recovering the separation residual gas in the lower chamber;
A hydrogen separator comprising:
One end of a bottomed container in which the hydrogen separator is individually incorporated is fixed to a partition plate provided so as to separate the sealed container into two upper and lower chambers, and supported in a suspended form to be sealed from the hydrogen separator. to allow for thermal expansion difference between the container,
In the closed container, each open end of the bottomed container in which the plurality of hydrogen separators are individually incorporated is supported and fixed in a suspended manner with respect to the partition plate so as to communicate with the upper chamber. A tubular member is connected so that only the lower end of the hydrogen separator is fixed to the bottom of the bottomed container so as to communicate with the lower chamber, and the upper ends of the plurality of hydrogen separators are communicated with the inlet. Then, by connecting a flexible hose having a flange structure at both ends of the metal bellows so as to be orthogonal to the longitudinal direction of the hydrogen separator, a part of the tubular member is connected to the hydrogen separator and the sealed container. A hydrogen separation apparatus, characterized in that a flexible portion allowing a difference in thermal expansion is provided.

Images