JP2005058823A - Selective permeation membrane type reactor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a selective permeation membrane type reactor which is high in permeation speed of a selective permeation membrane not only in the vicinity of the gas inlet of a reaction tube colliding with the upstream side in the supply direction of a raw material gas but also in the vicinity of the gas outlet of the reaction tube colliding with the downstream side in the supply direction of the raw material gas and can effectively extract a produced gas to be separated over the entire selective permeation membrane. <P>SOLUTION: This selective permeation membrane type reactor has the cylindrical reaction tube 1 in which one end part is the gas inlet 9 and the other end part is the gas outlet 10, a separation tube 4 which is inserted into the reaction tube 1 and has the selective permeation membrane 5 on the surface, and a catalyst 6 arranged between the reaction tube 1 and the separation tube 4. In the reactor, the distance between the reaction tube 1 and the selective permeation membrane 5 in the inside of the reaction tube 1 is gradually narrowed from the inlet 9 toward the outlet 10. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

[0001]
The present invention relates to hydrocarbons such as methane, butane and kerosene, and oxygen-containing hydrocarbons such as methanol as the main raw material gas, and water, carbon dioxide and oxygen as the second raw material gases. Selective membrane type reaction used to generate, separate and take out gases of specific components such as hydrogen using the steam, carbon dioxide reforming reaction, partial oxidation reaction, decomposition reaction, etc. Related to the vessel.
[0002]
2. Description of the Related Art Hydrogen gas is used in large quantities as a basic raw material gas for petrochemicals, and there is a great expectation as a clean energy source. The hydrogen gas used for such purposes is mainly composed of hydrocarbons such as methane, butane and kerosene, and oxygen-containing hydrocarbons such as methanol, reforming reaction of steam or carbon dioxide, partial oxidation reaction, decomposition It is produced by using a reaction or the like, and is obtained by separating it with a permselective membrane that can selectively permeate hydrogen, such as a palladium alloy membrane.
In recent years, in the production of hydrogen gas, a selectively permeable membrane reactor (membrane reactor) capable of performing the above-described reaction and separation at the same time is used (for example, see Patent Document 1). . FIG. 4 is a schematic cross-sectional view showing the structure of a selectively permeable membrane reactor generally used conventionally. This selectively permeable membrane type reactor has a tubular reaction tube 21 having one end portion serving as a gas inlet 29 and the other end serving as a gas outlet 30, and a permselective membrane inserted into the reaction tube 21. 25, a separation tube 24 having a bottomed cylindrical shape with a porous base material portion, and a catalyst 26 disposed between the reaction tube 21 and the separation tube 24.
Normally, the catalyst 26 is in the form of pellets, and the gap between the reaction tube and the separation tube is packed in a packed bed shape, and the raw material gas containing water vapor supplied from the inlet 29 is supplied to the catalyst 26. In contact with the catalyst 26, a target gas such as hydrogen gas is generated by a steam reforming reaction or the like. For example, in steam reforming of methane, it is decomposed into hydrogen, carbon monoxide, and carbon dioxide according to the reaction formulas of Chemical Formula 1 and Chemical Formula 2.
[Chemical 1]
CH ₄ + H ₂ O ← → CO + 3H ₂ (reforming reaction)
[Chemical 2]
CO + H ₂ O ← → CO ₂ + H ₂ (shift reaction)
The product gas such as hydrogen gas thus obtained permeates through the permselective membrane 26 and is selectively extracted into the separation tube 24 and separated from other gas components and taken out. Further, other gas components that do not pass through the permselective membrane 25 are discharged from the outlet 30 to the outside of the reactor.
[0006]
[Patent Document 1]
Japanese Patent Laid-Open No. 6-40703
The permselective membrane reactor having such a structure draws out the generated gas in addition to the advantage of downsizing the apparatus by simultaneously performing the reaction and the separation as described above. Thus, the equilibrium of the reaction can be shifted to the production side, and the reaction temperature can be lowered. As a result, effects such as a reduction in operating temperature, suppression of deterioration of metal members, and energy saving can be expected.
By the way, the permeation speed of the permselective membrane that selectively permeates specific components in the gas as described above is not only the permeation capability of the membrane itself, but also the entrance side of the membrane (the side that enters the membrane). ) And the outlet side (the side exiting the membrane), and the product gas concentration at the membrane inlet side is low, resulting in a small concentration difference between the membrane inlet and outlet sides. In such a case, the product gas to be separated becomes difficult to permeate.
In the permselective membrane reactor having the above-described conventional structure, the amount of reaction on the catalyst is high in the vicinity of the gas inlet 29 of the reaction tube 21 to which the source gas is supplied. As a result, since the product gas is also high in concentration, the permeation rate of the product gas to be separated increases.
However, in the vicinity of the gas outlet 30 of the reaction tube 21, since the raw material gas concentration is lower due to the reaction on the upstream side (gas inlet side), the reaction amount on the catalyst is also small, and as a result, the generated gas is reduced. Since the concentration is low, the permeation rate of the product gas to be separated also becomes low, and the above-described effect of extracting the product gas is not sufficiently exhibited.
The present invention has been made in view of the above-described conventional circumstances, and its object is not only in the vicinity of the gas inlet of the reaction tube corresponding to the upstream side in the supply direction of the raw material gas, but also in the raw material gas. Even in the vicinity of the gas outlet of the reaction tube on the downstream side in the supply direction, the permselective membrane has a high permeation rate, and the product gas to be separated can be effectively withdrawn over the entire permselective membrane. The object is to provide a permeable membrane reactor.
[0012]
According to the present invention, a cylindrical reaction tube having one end serving as a gas inlet and the other end serving as a gas outlet, and a surface inserted into the reaction tube are selected. A selectively permeable membrane reactor comprising a separation tube having a permeable membrane, and a catalyst disposed between the reaction tube and the separation tube, wherein the reaction tube and the selectively permeable membrane therein A selectively permeable membrane reactor (first invention) in which the interval gradually decreases from the inlet toward the outlet is provided.
In addition, according to the present invention, a cylindrical reaction tube having one end serving as a gas inlet and the other end serving as a gas outlet, and a permselective membrane inserted on the surface of the reaction tube. A selectively permeable membrane reactor having a separation tube and a catalyst disposed between the reaction tube and the separation tube, the reactor being located at a position on the outlet side from the center in the reaction tube length direction inside the reaction tube. A selectively permeable membrane reactor (second invention) provided with a structure for disturbing the flow of the gas supplied into the reaction tube and stirring the gas is provided.
[0014]
DESCRIPTION OF THE PREFERRED EMBODIMENTS FIG. 1 is a schematic cross-sectional view showing an example of an embodiment of a selectively permeable membrane reactor according to the first invention. This selectively permeable membrane reactor has a tubular reaction tube 1 with one end being a gas inlet 9 and the other end being a gas outlet 10, and a selectively permeable membrane on the surface inserted into the reaction tube 1. 5 having a bottomed cylindrical shape with a porous base material portion and a catalyst 6 disposed between the reaction tube 1 and the separation tube 4. The distance between the reaction tube 1 and the permselective membrane 5 inside the reaction tube 1 gradually decreases from the inlet 9 toward the outlet 10.
The catalyst 6 can be obtained by forming the catalyst component into a pellet shape or a bead shape, or coating the catalyst component on a pellet-shaped substrate, which is separated from the reaction tube 1 as shown in the figure. It arrange | positions by filling the space | gap between the pipes 4, etc. When the raw material gas supplied from the inlet 9 comes into contact with the catalyst 6, a target gas such as hydrogen gas is generated by a steam reforming reaction or the like, and the obtained generated gas passes through the permselective membrane 5. It is selectively withdrawn into the separation tube 4 and separated from other gas components and taken out. Further, other gas components that do not pass through the permselective membrane 5 are discharged from the outlet 10 to the outside of the reactor.
Here, as described above, the concentration of the raw material gas is high in the vicinity of the gas inlet 9 of the reaction tube 1 corresponding to the upstream side in the supply direction of the raw material gas, and the product gas reacted and generated on the catalyst has a high concentration. As a result, the permeation rate of the product gas to be separated increases.
On the other hand, in the vicinity of the gas outlet 10 of the reaction tube 1 corresponding to the downstream side of the supply direction of the raw material gas, the raw material gas concentration is already low due to the reaction on the upstream side, and the product gas that is reacted and generated on the catalyst. However, in the permselective membrane reactor of the first invention, the distance between the reaction tube 1 and the permselective membrane 5 in the interior thereof is changed from the inlet 9 to the outlet as shown in FIG. Since the structure gradually decreases toward 10, the product gas tends to gather around the permselective membrane 5 as it approaches the outlet 10, and the product gas to be separated comes into contact with the permselective membrane 5. It becomes easy. For this reason, there is no phenomenon (concentration polarization) in which the concentration of the permeable component decreases in the vicinity of the selective permeable membrane 5, and as a result, the concentration of the transmissive component in the vicinity of the selective permeable membrane 5 increases, so that a high transmission rate is obtained.
In this example, the distance between the reaction tube 1 and the permselective membrane 5 is changed by gradually reducing the diameter of the reaction tube 1 from the inlet 9 to the outlet 10. The interval between the reaction tube 1 and the permselective membrane 5 may be changed by making the diameter of the tube 1 constant and gradually increasing the diameter of the separation tube 4 from the inlet 9 toward the outlet 10. In addition, the diameter of the reaction tube 1 is gradually reduced from the inlet 9 toward the outlet 10 and the diameter of the separation tube 4 is gradually increased from the inlet 9 toward the outlet 10, thereby allowing the reaction tube 1 and the selectively permeable membrane. The interval from 5 may be changed.
FIG. 2 is a schematic sectional view showing an example of the embodiment of the selectively permeable membrane reactor according to the second invention. This selectively permeable membrane reactor has a tubular reaction tube 11 having one end portion serving as a gas inlet 19 and the other end serving as a gas outlet 20, and a selectively permeable membrane inserted into the reaction tube 11 on the surface. 15 having a bottomed cylindrical shape with a porous base material portion, and a catalyst 16 disposed between the reaction tube 11 and the separation tube 14, A structure for stirring the gas by disturbing the flow of the gas supplied into the reaction tube 11 is provided at a position on the outlet 20 side from the center in the length direction of the reaction tube 11 inside the reaction tube 11.
The catalyst 16 can be obtained by forming the catalyst component into a pellet shape or a bead shape, or coating the catalyst component on a pellet-shaped substrate, which is separated from the reaction tube 11 as shown in the figure. It arrange | positions by filling the space | gap between the pipes 14, etc. Further, in this example, as a structure for disturbing the flow of the gas supplied into the reaction tube 11 and stirring the gas, a stirring plate extending from the inner peripheral surface of the reaction tube 11 toward the inside upward as shown in the figure The gas in contact with the stirring plate 17 is disturbed in its flow and stirred around the permselective membrane 15.
In this reactor, when the raw material gas supplied from the inlet 19 comes into contact with the catalyst 16, a target gas such as hydrogen gas is generated by a steam reforming reaction or the like. It permeates through the permeable membrane 15 and is selectively extracted into the separation tube 14 and separated from other gas components and taken out. Further, other gas components that do not pass through the permselective membrane 15 are discharged from the outlet 20 to the outside of the reactor.
Here, as described above, the concentration of the source gas is high in the vicinity of the gas inlet 19 of the reaction tube 11 corresponding to the upstream side in the supply direction of the source gas, and the product gas reacted and generated on the catalyst has a high concentration. As a result, the permeation rate of the product gas to be separated increases.
On the other hand, in the vicinity of the gas outlet 20 of the reaction tube 11 corresponding to the downstream side of the supply direction of the raw material gas, the raw material gas concentration is already low due to the reaction on the upstream side, and the product gas that is reacted and generated on the catalyst. However, in the permselective membrane reactor of the second invention, the outlet 20 side from the center in the length direction of the reaction tube 11 inside the reaction tube 11 as in the stirring plate 17 of FIG. Is provided with a structure for disturbing the flow of the gas supplied into the reaction tube 11 and stirring the gas, so that the generated gas is stirred around the permselective membrane 15 in the vicinity of the outlet 20 and separated. The generated gas to be contacted is easily brought into contact with the selectively permeable membrane 15. For this reason, there is no phenomenon (concentration polarization) in which the concentration of the permeable component decreases in the vicinity of the selectively permeable membrane 15, and as a result, the concentration of the permeable component in the vicinity of the selectively permeable membrane 15 increases.
In the example of FIG. 2, a stirring plate 17 is provided as a structure for stirring the gas by disturbing the flow of the gas supplied into the reaction tube 11. However, the structure is not limited to this. Any structure may be used as long as the gas can be effectively stirred. For example, as shown in FIG. 3, a catalyst 18 having a catalyst component supported on larger beads or pellets than the others is disposed only near the outlet 20 of the reaction tube 11, and the gas flow is caused by the large catalyst 18. You may make it disturb and stir. Alternatively, the gas stirring effect can be obtained by arranging large beads and pellets that do not carry a catalyst component at the same position.
In the selectively permeable membrane reactors of the first and second inventions, the material of the catalyst and the selectively permeable membrane can be selected according to the raw material gas used, the type of the target product gas, etc. When hydrogen gas is generated and separated from hydrocarbons such as methane, noble metal catalysts such as nickel and Pt, Ru and Rh are highly dispersed on alumina, titania and zirconia with a high specific surface area. A selectively permeable membrane made of a supported material and a palladium alloy such as palladium or Pd—Ag alloy can be preferably used.
The reaction tube is preferably composed mainly of a metal having high heat resistance and good thermal conductivity such as SUS or incoloy, but a ceramic material such as cordierite may be used. It is preferable to use a porous ceramic body such as titania or alumina, or a porous metal body such as stainless steel, as the base material of the porous separation tube that forms a permselective membrane on the surface. In addition, the permselective membrane may be inside the separation tube instead of the outside of the separation tube, or may be coated on both sides of the separation tube.
In the embodiment shown in FIGS. 1 to 3, a bottomed cylindrical separation tube is used. Even if the bottomed shape is not a bottomed shape, one end is hermetically sealed by a flange or the like. It can be used if the structure can be devised. Furthermore, it is preferable to devise a method for reducing the partial pressure on the permeation outlet side of the permselective membrane as the usage form of the permselective membrane reactor of the present invention, because the permeability of the permselective membrane is improved. Specifically, a method of flowing a sweep gas such as water vapor on the permeate outlet side or lowering the partial pressure on the permeate outlet side with a vacuum pump is preferable.
The type of gas to be produced and separated in the selectively permeable membrane reactors of the first and second inventions is not particularly limited, but hydrogen is produced and separated from hydrocarbon gas such as methane. It can be particularly preferably used.
[0029]
The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples.
[0030]
(Example 1)
A permselective membrane reactor having a structure as shown in FIG. 1 was produced. The separation tube 4 is made of a bottomed cylindrical porous alumina body (outer diameter: 10 mm, length: 200 mm) with one end closed, and as a permselective membrane 5 on its surface, Pd-Ag that selectively permeates hydrogen. An alloy film is formed by plating. The alloy film composition was such that Pd was 80 wt% and Ag was 20 wt% in consideration of hydrogen permeation performance. The reaction tube 1 is made of SUS so that it can withstand high temperatures of about 300 to 1000 ° C., the inner diameter of the inlet 9 that is the largest inner diameter portion is 30 mm, the inner diameter of the outlet 10 that is the smallest inner diameter portion is 15 mm, and the inlet 9 The inner diameter gradually decreased from the outlet toward the outlet 10. As the catalyst 6, a nickel-based catalyst formed in a pellet shape having a size of about 3 mm was used.
[0031]
(Example 2)
A selectively permeable membrane reactor having a structure as shown in FIG. 2 was produced. The reaction tube 11 has a constant inner diameter (40 mm), but a stirring plate 17 is provided at a position on the outlet 20 side from the center in the length direction. Other configurations are the same as those of the first embodiment.
[0032]
(Example 3)
A selectively permeable membrane reactor having a structure as shown in FIG. 3 was produced. The reaction tube 11 has a constant inner diameter (40 mm), but is loaded with silica beads (φ7 mm) having a diameter larger than that of the catalyst 16 at a position on the outlet 20 side from the center in the length direction. Other configurations are the same as those of the first embodiment.
[0033]
(Comparative example)
A conventional permselective membrane reactor having a structure as shown in FIG. 4 was produced. The reaction tube 21 has a constant inner diameter (40 mm), but the other configuration is the same as that of the first embodiment.
[0034]
(Evaluation)
Using the apparatus as shown in FIG. 5, the selectively permeable membrane reactors of Examples 1 to 3 and the comparative example were evaluated. This equipment is connected to a line so that hydrocarbons such as methane and butane, oxygen-containing hydrocarbons such as methanol, water, carbon dioxide, and oxygen can be used as source gas sources, and these are selected and mixed as necessary. Thus, it can be supplied to a selectively permeable membrane reactor. In addition, water is vaporized and supplied with a vaporizer. Further, in the case where a nickel-based catalyst is used in the selectively permeable membrane reactor, when the catalyst surface is oxidized, it is necessary to perform the reduction treatment before supplying the raw material gas. Thus, hydrogen for reduction can be supplied to the selectively permeable membrane reactor.
The upstream side of the membrane permeation gas line and the membrane non-permeation gas line are connected to the membrane permeation side (inside the separation tube) and the membrane non-permeation side (reaction tube outlet) of the selective permeation membrane reactor, respectively. Yes. A flow meter for measuring the amount of gas and a gas chromatograph for quantifying gas components are connected to the downstream side of the membrane permeation gas line. Similarly, a flow meter and a gas chromatograph are connected to the downstream side of the non-permeating gas line, but a liquid trap for collecting liquid components such as water at room temperature is further provided on the upstream side of the flow meter. Is provided. A heater for heating is installed around the permselective membrane reactor so that the reactor can be externally heated.
In such an apparatus, first, hydrogen is supplied to the selectively permeable membrane reactor while being heated to about 400 ° C. to reduce the nickel-based catalyst whose surface is oxidized. Thereafter, source gases mixed at a constant ratio from various source gas sources are supplied from the inlet side of the selectively permeable membrane reactor, and partial oxidation, decomposition, reforming reaction, etc. are advanced by the catalyst. Of hydrogen, carbon monoxide, carbon dioxide, water, etc. produced by this reaction, only hydrogen that is a membrane permeation component permeates the permselective membrane (Pd-Ag alloy membrane), and from the membrane permeation gas line It is supplied to the gas chromatograph through the flow meter, and the components are analyzed. Membrane non-permeating gases other than hydrogen are sent to a membrane non-permeating gas line, and after liquid components such as water are removed by a liquid trap, they are supplied to a gas chromatograph through a flow meter.
With this apparatus, partial oxidation, decomposition and reforming reactions were carried out under various reaction conditions, and hydrogen was separated and recovered. When the selectively permeable membrane reactors of Examples 1 to 3 were used, Compared with the case of using the selectively permeable membrane reactor of the comparative example, the hydrogen recovery efficiency increased by 5 to 20 points. From this result, it can be seen that by using the selectively permeable membrane reactor of the present invention, hydrogen is effectively extracted over the entire selectively permeable membrane, and the hydrogen recovery efficiency is improved. That is, in the selectively permeable membrane reactor of the present invention, when trying to obtain the same amount of hydrogen recovery as that of the conventional selectively permeable membrane reactor, the apparatus can be configured more compactly or the operating temperature can be reduced. Thus, it is possible to suppress deterioration of the metal member and to save energy.
[0038]
As described above, according to the permselective membrane reactor of the present invention, not only the vicinity of the gas inlet of the reaction tube corresponding to the upstream side in the feed gas supply direction but also the downstream in the feed gas feed direction. Even in the vicinity of the gas outlet of the reaction tube that hits the side, the permeation rate of the permselective membrane is high, and the product gas to be separated can be effectively withdrawn across the entire permselective membrane. In this case, the effect of shifting the equilibrium such as reforming reaction on the catalyst to the production side is improved. As a result, the operating temperature of the reactor can be lowered as compared with the conventional case, so that deterioration of the metal member can be suppressed and energy can be saved.
[Brief description of the drawings]
FIG. 1 is a schematic cross-sectional view showing an example of an embodiment of a selectively permeable membrane reactor according to the first invention.
FIG. 2 is a schematic cross-sectional view showing an example of an embodiment of a selectively permeable membrane reactor according to the second invention.
FIG. 3 is a schematic cross-sectional view showing another example of the embodiment of the selectively permeable membrane reactor according to the second invention.
FIG. 4 is a schematic cross-sectional view showing the structure of a selectively permeable membrane reactor generally used conventionally.
FIG. 5 is a schematic diagram showing a configuration of a test apparatus used in Examples.
[Explanation of symbols]
DESCRIPTION OF SYMBOLS 1 ... Reaction tube, 4 ... Separation tube, 5 ... Selective permeable membrane, 6 ... Catalyst, 9 ... Inlet, 10 ... Outlet, 11 ... Reaction tube, 14 ... Separation tube, 15 ... Selective permeable membrane, 16 ... Catalyst, 17 ... Stirring plate, 18 ... catalyst, 19 ... inlet, 20 ... outlet, 21 ... reaction tube, 24 ... separation tube, 25 ... selective permeable membrane, 26 ... catalyst, 29 ... inlet, 30 ... outlet.

Claims (2)

A cylindrical reaction tube whose one end is a gas inlet and the other end is a gas outlet, a separation tube having a permselective membrane on its surface, inserted into the reaction tube, the reaction tube and the separation tube A permselective membrane reactor having a catalyst disposed between
A permselective membrane reactor in which the distance between the reaction tube and the permselective membrane inside thereof gradually decreases from the inlet toward the outlet. A cylindrical reaction tube whose one end is a gas inlet and the other end is a gas outlet, a separation tube having a permselective membrane on its surface, inserted into the reaction tube, the reaction tube and the separation tube A permselective membrane reactor having a catalyst disposed between
A selectively permeable membrane reactor provided with a structure in which the flow of gas supplied into the reaction tube is disturbed to stir the gas at a position on the outlet side from the center in the reaction tube length direction inside the reaction tube.

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