The present application is National Stage of International Application No. PCT/JP2015/079007 filed Oct. 14, 2015, the disclosure of which hereby incorporated by reference herein in its entirety.
The present invention relates to a catalyst block for purifying exhaust gas and a method for manufacturing the same.
Exhaust gas generated from various types of stationary combustion devices such as a boiler, a private power generator, and a combustion furnace, and metal etching contains a nitrogen oxide (NOx). The nitrogen oxide (NOx) is a substance causing photochemical smog. For this reason, it is necessary that the nitrogen oxide be purified by a denitration device.
Such a denitration device has a denitration catalyst layer in which many catalyst blocks are spread.
The outer frame 102 is constituted by a C-shaped frame 102a and a top frame 102b. As shown in
As another conventional technique, Patent Literature 1 discloses a denitration catalyst layer in which catalyst blocks each having a frame body and a catalyst contained in the frame body are entirely spread and layered. In the denitration catalyst layer, a plate-shaped catalyst is attached to a circumference of the frame bodies of the catalyst blocks. This is a technique of removing a nitrogen oxide from exhaust gas flowing out from a gap formed between the catalyst blocks using the plate-shaped catalyst, to decrease NOx and the like at an outlet of the catalyst layer.
Patent Literature 1: JPH6-154555
However, the treatment temperature at which the block for a catalyst 100 is baked so as to be integrated with the honeycomb core 101 and the outer frame 102 is very high (about 1,200° C.). Therefore, during baking of the block for a catalyst 100, the outer frame 102 may be thermally deformed to distort the shape of the block for a catalyst 100. When the shape of the block for a catalyst 100 is distorted, a gap is formed between the adjacent blocks for a catalyst 100 during spreading of the blocks for a catalyst 100. From the gap, exhaust gas flows out without denitration. Therefore, the denitration performance of the catalyst layer is deteriorated.
In order to suppress thermal deformation during baking, a method for forming a rib in the outer frame 102 to enhance the rigidity of the outer frame 102 is also considered. However, the cost is increased since it is necessary that the outer frame 102 be molded into a complicated shape. A method for immersing the honeycomb core 101 in a catalyst bath followed by sintering before housing of the honeycomb core 101 in the outer frame 102 is also considered. However, the shape of the honeycomb core may be distorted during operation of immersion in the catalyst bath or transport to the catalyst bath since the honeycomb core 101 made of a metal foil is fragile.
When the block for a catalyst 100 is immersed in the catalyst bath, the catalyst flows into the clearance CL of the C-shaped frame 102a. Thus, a catalyst CAT shown by black may be attached to the C-shaped frame 102a. In order to get the catalyst CAT away, a drain hole 102a1 is formed in the C-shaped frame 102a. However, the catalyst CAT attached to the C-shaped frame 102a cannot be all got away. Since exhaust gas does not flow into the C-shaped frame 102a, the catalyst may be unnecessarily used for a part different from an exhaust gas passage.
In the technique of Patent Literature 1, it is necessary that a plate-shaped catalyst be installed to purify exhaust gas flowing out from the gap formed between the catalyst blocks. Therefore, an operation for installation is complex and the cost is increased.
An object of the invention of the present application is to provide a catalyst block in which the distortion of the outer surface is small. Another object of the invention of the present application is to prevent a catalyst from being carried on a part that does not contribute to purification of exhaust gas. Further, an object of the invention of the present application is to make the maintenance of a catalyst block inexpensive. This is achieved by removing a honeycomb core from a spent catalyst block and easily exchanging a honeycomb core to which a catalyst is applied.
In order to solve the above-described problems, a catalyst block according to the invention of the present application is (1) a catalyst block for purification of exhaust gas including: a rectangular honeycomb core having a large number of exhaust gas passages for allowing exhaust gas to pass, first and second outer surfaces that face to each other in an orthogonal direction that is orthogonal to the exhaust gas passages, and third and fourth outer surfaces that face to each other in the orthogonal direction; a first plate attached to the first outer surface; a second plate attached to the second outer surface; and an outer frame that is disposed along an outer periphery of a rigid honeycomb core formed from the honeycomb core, the first plate, and the second plate, and includes a concave part capable of housing at least the first plate, the second plate, the third outer surface, and the fourth outer surface, wherein a catalyst is carried on the honeycomb core, the first plate, and the second plate carry, and the catalyst is not carried on the outer frame.
(2) In the configuration of (1) described above, the first plate is fixed in the concave part of the outer frame, and the second plate, the third outer surface, and the fourth outer surface may not be fixed in the concave part of the outer frame. According to the configuration of (2), a fixing part is limited to only the first plate. Therefore, deformation of the rigid honeycomb core into an abnormal shape or breakage by expansion and shrinkage due to temperature cycle can be prevented.
(3) In the configuration of (1) or (2) described above, the outer frame includes a bottom frame and a side frame that are integrally formed, and a top frame attached to the side frame, the first plate can be housed in the concave part of the top frame, the second plate can be housed in the concave part of the bottom frame, and the third outer surface and the fourth outer surface can be housed in the concave part of the side frame. According to the configuration of (3), the catalyst block can be maintained (for example, the catalyst is regenerated or reapplied or a novel honeycomb core is exchanged) by pulling out the top frame and the rigid honeycomb core that are integrated, from the outer frame.
(4) In the configuration of any one of (1) to (3) described above, the honeycomb core can be configured by alternately layering a flat foil and a corrugated foil in a direction in which the first outer surface and the second outer surface face to each other.
(5) In the configuration of any one of (1) to (4) described above, the first plate and the second plate can be formed from a ferrite-based stainless. According to the configuration of (5), while the first plate and the second plate are adsorbed by magnetic force, the rigid honeycomb core can be transported to a catalyst bath. Therefore, a load applied to the honeycomb core during transport can be decreased.
A method for manufacturing the catalyst block for purification of exhaust gas according to the invention of the present application is (6) a method for manufacturing a catalyst block for purification of exhaust gas that includes a rectangular honeycomb core having a large number of exhaust gas passages for allowing exhaust gas to pass, first and second outer surfaces that face to each other in an orthogonal direction that is orthogonal to the exhaust gas passages, and third and fourth outer surfaces that face to each other in the orthogonal direction, the method including: a fixation step of fixing the honeycomb core using a first plate and a second plate that are disposed on the first outer surface and the second outer surface, respectively, of the honeycomb core with the honeycomb core being held and pressurized; a first baking step of baking the honeycomb core, the first plate, and the second plate together with a brazing material to manufacture a rigid honeycomb core; a second baking step of applying a catalyst to the rigid honeycomb core and baking the rigid honeycomb core, causing the rigid honeycomb core to carry the catalyst; and a frame attachment step of inserting the first plate, the second plate, the third outer surface, and the fourth outer surface of the rigid honeycomb core carrying the catalyst into the concave part of the outer frame, to cover an outer periphery of the rigid honeycomb core with the outer frame.
(7) In the configuration of (6) described above, the outer frame includes a bottom frame and a side frame that are integrally formed, and a top frame, and the frame attachment step may include a step of fixing the first plate of the rigid honeycomb core in the concave part of the top frame; a step of inserting the rigid honeycomb core having the fixed top frame along the concave part of the side frame; and a step of fixing the top frame to the side frame.
(8) In the configuration of (6) or (7) described above, the first plate and the second plate are formed from a ferrite-based stainless. In the second baking step, the rigid honeycomb core is transported to and immersed in a catalyst bath in which the catalyst is pooled while the first plate and the second plate are adsorbed by a magnet, and then the rigid honeycomb core can be baked. According to the configuration of (8), a load applied to the honeycomb core during transport can be decreased.
According to the present invention, for the outer frame of the catalyst block, a high-temperature baking treatment for integrating the honeycomb core and the outer frame and a baking treatment for carrying the catalyst on the honeycomb core are not performed. Therefore, the present invention can provide the outer frame with little distortion that is hardly influenced by thermal deformation. For this reason, the distortion of the outer surface of the catalyst block is decreased. Therefore, a gap from which exhaust gas flows out is unlikely to be formed between the adjacent catalyst blocks. Since the catalyst is not carried on the outer frame that does not contribute to purification of exhaust gas, the unnecessary amount of the catalyst can be decreased. Further, a honeycomb core part can be removed from a spent catalyst block. Therefore, exchanging of a honeycomb core to which a catalyst is newly applied is facilitated, and the maintenance of the catalyst block can be performed at low cost.
First Embodiment
One embodiment of the catalyst block of the present invention will be described with reference to the drawings.
Y1-Y2 in
With reference to
With reference to
The honeycomb core 11 is formed in a rectangular shape (rectangular parallelepiped shape). For the sake of convenience of description, outer surfaces of the honeycomb core 11 facing in the layering direction are referred to as a first outer surface 11a and a second outer surface 11b. Outer surfaces of the honeycomb core 11 facing in a direction orthogonal to the layering direction are referred to as a third outer surface 11c and a fourth outer surface 11d. The first outer surface 11a and the second outer surface 11b are approximately parallel to each other, and the third outer surface 11c and the fourth outer surface 11d are approximately parallel to each other. The first outer surface 11a forms an approximately right angle with the third outer surface 11c and the fourth outer surface 11d. The second outer surface 11b forms an approximately right angle with the third outer surface 11c and the fourth outer surface 11d. The layering direction of the corrugated plate 110a and the flat plate 110b corresponds to a direction facing to the first outer surface 11a and the second outer surface 11b.
A lower end part of the first plate 12 is fixed so as to cover the first outer surface 11a of the honeycomb core 11. As means for fixing, a brazing material can be used. The second plate 13 is fixed so as to cover the second outer surface 11b of the honeycomb core 11. As the means for fixing, a brazing material can be used.
For the first plate 12 and the second plate 13, a metal (for example, SUS steel sheet) can be used. The SUS steel sheet is preferably a ferrite-based stainless steel sheet having little thermal expansion and capable of adsorbing by magnetic force.
With reference to
When in the aforementioned configuration, the rigid honeycomb core 10 is slid and shifted in the gas flow direction by external force, the second plate 13 and the part of the honeycomb core 11 collide with the wall part of the bottom frame 21. At that time, an impact during collision can be absorbed by the second plate 13. Therefore, a load applied to the honeycomb core 11 can be decreased. It is preferable that the width of the second plate 13 in the gas flow direction be larger than the width of the honeycomb core 11 in the gas flow direction. Herein, when the second plate 13 is omitted, only the honeycomb core 11 that is fragile is housed in the concave part 21a of the bottom frame 21. Therefore, a load during collision is received by only the honeycomb core 11. According to the rigid honeycomb core 10 of this embodiment, the second plate 13 is housed in the concave part 21a of the bottom frame 21. Therefore, a load applied to the honeycomb core 11 during collision can be largely relaxed.
When the mechanical strength in the gas flow direction is enhanced, the rigid honeycomb core 10 can be layered vertically with the gas flow direction set to a vertical direction, as shown in
The first plate 12 and a part of the honeycomb core 11 are housed in a concave part (not shown) of the top frame 22. This is the same as that in the case of the second plate 13 described above, and therefore, a description thereof is omitted.
The first plate 12 and the second plate 13 are fixed in the upper and lower end parts, respectively, in the layering direction of the honeycomb core 11, as described above, and reinforced. Therefore, the height of wall of the concave part of the outer frame 20 can be decreased. For this reason, the area of the honeycomb core 11 housed in the inside thereof can be relatively increased as compared with a conventional product. Accordingly, in order to increase the area of the honeycomb core 11 to be brought into contact with exhaust gas, the pressure loss (increase in back pressure) of the catalyst block 2 can be suppressed and the purification performance can be enhanced.
With reference to
It is preferable that the rigid honeycomb core 10 be fixed through the first plate 12 to the top frame 22 of the outer frame 20 and another part be not fixed. Specifically, the rigid honeycomb core 10 is fixed to only the top frame 22, and not fixed to the bottom frame 21 and the side frame 23. When the rigid honeycomb core 10 is used especially in an environment where the temperature cycle of repeating increase and decrease in temperature is severe, thermal expansion and shrinkage are repeated in the honeycomb core 11 itself. When the first plate 12 and the second plate 13 are fixed to the top frame 22 and the bottom frame 21, respectively, both end surfaces in the layering direction of the honeycomb core 11 are restrained. Therefore, the rigid honeycomb core 10 may be deformed into an abnormal shape or broken by expansion and shrinkage due to the temperature cycle. A method for fixing the top frame 22 and the first plate 12 is preferably a fixation method in which detachment is easy, such as bolting and spot welding.
According to the configuration of this embodiment, the rigid honeycomb core 10 is fixed to only the top frame 22. Therefore, the thermal expansion and shrinkage due to the temperature variation of the rigid honeycomb core 10 can be allowed using the clearance formed between the outer frame 20 and the honeycomb core 10. Thus, the deformation of the rigid honeycomb core 10 into an abnormal shape or breakage can be suppressed.
In a simple fixation method in which a fixing part of the rigid honeycomb core 10 is only on a side of the top frame 22, the rigid honeycomb core 10 may be likely to shift in the gas flow direction. However, even when the rigid honeycomb core 10 shifts, the first plate 12 and the second plate 13 can be strongly fixed with the honeycomb core 11, as described above. Shifting of the first plate 12 can be prevented by a wall of the concave part of the top frame 22, and shifting of the second plate 13 can be prevented by a wall of the concave part of the bottom frame 21. Therefore, the rigid honeycomb core 10 cannot be dropped from the outer frame 20, and defects such as crush of the honeycomb core 11 can be unlikely to occur.
The top frame 22 is detached from the side frame 23, and the top frame 22 and the rigid honeycomb core 10 that are integrated are pulled out from the outer frame 20. Thus, the catalyst block 2 can be maintained (for example, the catalyst is regenerated or reapplied or a novel honeycomb core is exchanged) . Herein, when the outer frame 20 is configured by connection of a plurality of frame members by welding, the rigid honeycomb core 10 cannot be pulled out from the outer frame 20 without cutting of welded parts by a grinder. According to the configuration of this embodiment, an operation of cutting the welded parts by a grinder is unnecessary, and an operation for maintenance is easy.
As shown in
The maintenance is performed by immersing the top frame 22 and the rigid honeycomb core 10 that are detached from the outer frame 20 in a catalyst bath. However, the top frame 22 and the rigid honeycomb core 10 are closely fixed without formation of a large clearance CL similar to the clearance formed between the side frame 23 and the rigid honeycomb core 10. The amount of catalyst to be attached to the top frame 22 during immersion in the catalyst bath can be decreased. It is preferable that simple fixation between the top frame 22 and the rigid honeycomb core 10 be removed, and only the rigid honeycomb core 10 be immersed in the catalyst bath, sintered, and simply fixed to the top frame 22 again. Thus, use of unnecessary catalyst can be completely prevented.
When the maintenance is impossible due to large damage of the honeycomb core 11, it is necessary that one group of the top frame 22 and the rigid honeycomb core 10 be exchanged into a new group, or the simple fixation between the top frame 22 and the rigid honeycomb core 10 be removed, and only the rigid honeycomb core 10 be exchanged. However, the bottom frame 21 and the side frame 23, and in some cases, the top frame 22 can be reused. Therefore, the cost can be largely decreased as compared with a case where the whole catalyst block 2 is exchanged.
According to the configuration of this embodiment, the catalyst is not carried on the outer frame 20. Therefore, it is not necessary that a drain hole of discharging the catalyst during the immersion in the catalyst bath be formed in the outer frame 20, unlike the conventional catalyst block. This is due to a method for manufacturing the catalyst block 2 of this embodiment, and the details will be described below.
Next, the method for manufacturing the catalyst block 2 will be described in detail with reference to
In Step S101, a brazing material is applied in advance to both or one of the corrugated plate 110a and the flat plate 110b, and a sample of the honeycomb core 11 in which the corrugated plate 110a and the flat plate 110b are alternately layered in the layering direction is produced. The first plate 12 and the second plate 13 are disposed on the first outer surface 11a and the second outer surface 11b, respectively, of the honeycomb core 11, and a first jig 14 and a second jig 15 are pressed on the first plate 12 and the second plate 13, respectively. Thus, the honeycomb core 11 is held between the jigs through the first plate 12 and the second plate 13 in the layering direction, uniformly pressurized, and fixed (corresponding to a fixation step). The number of the first jig 14 may be one or more. When a plurality of first jigs 14 are used, the pressure applied to the honeycomb core 11 can be increased, or the variation can be decreased even under the same pressure. The same can be applied to the second jig 15.
In Step S102, the honeycomb core 11 held and pressurized between the first plate 12 and the second plate 13 is baked (corresponding to a first baking step). For example, the baking temperature can be set to about 1,200° C. The corrugated plate 110a and the flat plate 110b that are adjacent to each other are fixed with the brazing material, and the first plate 12 and the second plate 13 are fixed to the honeycomb core 11 with the brazing material. Thus, the rigid honeycomb core 10 having high rigidity and including the first plate 12, the second plate 13, and the honeycomb core 11 is manufactured.
Herein, a method in which the honeycomb core 11 is directly held between the first jig 14 and the second jig 15 without the first plate 12 and the second plate 13, and baked is also considered. However, in this method, a pressure is transferred to only parts where the jigs exist and a pressure is not applied to other parts. This is because a metal foil forming the honeycomb core 11 has considerably small thickness and no rigidity. Thus, a state where the corrugated plate 110a and the flat plate 110b are fixed by brazing is instable, and the corrugated plate 110a and the flat plate 110b are not partially connected, forming a gap. Even when the number of the first jig 14 and the second jig 15 is increased to decrease the variation in pressure, a difference in pressure between the parts where the jigs exist and the parts where the jigs do not exist is not cancelled. The state where the corrugated plate 110a and the flat plate 110b are fixed by brazing remains instable, and the gap is not cancelled.
On the other hand, when the honeycomb core 11 is held between the first plate 12 and the second plate 13, the honeycomb core 11 can be baked while the variation in surface pressure applied to the honeycomb core 11 is suppressed. As a result, the corrugated plate 110a and the flat plate 110b are not partially connected, and a trouble such as formation of the gap can be prevented.
In Step S103, the first jig 14 and the second jig 15 are detached, and the rigid honeycomb core 10 is transported to a catalyst bath not shown and immersed in the catalyst bath. As a catalyst, a solution containing γ alumina, an additive, and a precious metal catalyst as components can be used. Herein, the structure of the rigid honeycomb core 10 is enhanced by connecting the first plate 12 and the second plate 13. Therefore, a trouble such as distortion of the honeycomb core can be unlikely to occur during operation of immersion in the catalyst bath and transport. Specifically, when the structure of the honeycomb core 11 is enhanced by connecting the first plate 12 and the second plate 13, the immersion workability and the handleability can be enhanced.
When the first plate 12 and the second plate 13 are formed from a ferrite-based stainless, the rigid honeycomb core 10 can be grasped by adsorbing the first plate 12 and the second plate 13 by magnetic force. Thus, the rigid honeycomb core 10 can be adsorbed by a magnet and transported to the catalyst bath.
Therefore, a load applied to the honeycomb core 11 can be further decreased.
In Step S104, the rigid honeycomb core 10 to which the catalyst is attached is baked again (corresponding to a second baking step). For example, the baking temperature can be set to about 600° C. Thus, the catalyst is carried on the rigid honeycomb core 10. In Step S105, the rigid honeycomb core 10 and the top frame 22 are connected. For a connection method, bolting or spot welding can be used. In Step S106, the rigid honeycomb core 10 and the top frame 22 that are integrated is inserted from an opening side of the side frame 23 as shown in
According to the manufacturing method of this embodiment, the rigid honeycomb core 10 is baked before the rigid honeycomb core 10 is housed in the outer frame 20 as described above. Therefore, the outer frame 20 is not thermally deformed by exposure to heat during baking. Accordingly, the outer surface of the outer frame 20 is kept flat. For this reason, when the catalyst blocks 2 are spread as shown in
Second Embodiment
With reference to
The top frame 22 is disposed along the first plate 12, the bottom frame 21 is disposed along the second plate 13, the side frame 23 is disposed along the third outer surface 11c of the honeycomb core 11, and the side frame 23′ is disposed along the fourth outer surface 11d of the honeycomb core 11. On both end parts of the side frame 23, a flange connection part 231 is formed. On both end parts of the side frame 23′, a flange connection part 231′ is formed.
In the aforementioned configuration, the flange connection parts 231 and 231′ are welded to the top frame 22 and the bottom frame 21 while the rigid honeycomb core 10 is held and pressurized between the top frame 22 and the bottom frame 21. Thus, the outer frame 20 is formed. Since a welded part is restricted to the end parts of the side frames 231 and 231′, distortion of the outer frame 20 due to heat during welding can be suppressed.
The rigid honeycomb core 10 and the outer frame 20 are not at all connected. Therefore, expansion and shrinkage due to the temperature cycle of the rigid honeycomb core 10 are not prevented by the connection parts. However, any one of the first plate 12 and the second plate 13 may be connected to the outer frame 20, like the first embodiment.
Modification 1
In the aforementioned embodiment, the honeycomb core 11 is configured by alternately layering the corrugated plate 110a and the flat plate 110b. However, the present invention is not limited to this embodiment. For example, the honeycomb core 11 may be configured by layering only the corrugated plate 110a in a predetermined direction. In this case, the strength of the honeycomb core 11 may be secured by fitting the corrugated plate 110a adjacent in the layering direction to a concave part of another corrugated plate 110a.
Modification 2
In the aforementioned embodiment, the first plate 12 and the second plate 13 are disposed on both end parts in the layering direction of the honeycomb core 11. However, the present invention is not limited to this embodiment. The first plate 12 and the second plate 13 may be disposed on an end surface in a direction orthogonal to the layering direction of the honeycomb core 11.
Filing Document | Filing Date | Country | Kind |
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PCT/JP2015/079007 | 10/14/2015 | WO | 00 |
Publishing Document | Publishing Date | Country | Kind |
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WO2017/064762 | 4/20/2017 | WO | A |
Number | Name | Date | Kind |
---|---|---|---|
4849185 | Wittig | Jul 1989 | A |
4916001 | Whittenberger et al. | Apr 1990 | A |
5278125 | Iida | Jan 1994 | A |
5403558 | Kono | Apr 1995 | A |
5436216 | Toyao et al. | Jul 1995 | A |
6080371 | Tanabe | Jun 2000 | A |
7404254 | Kurth et al. | Jul 2008 | B2 |
7943096 | Kurth et al. | May 2011 | B2 |
Number | Date | Country |
---|---|---|
101486002 | Jul 2009 | CN |
H01-218636 | Aug 1989 | JP |
H06-126191 | May 1994 | JP |
H06-154555 | Jun 1994 | JP |
H07-171410 | Jul 1995 | JP |
H08-229410 | Sep 1996 | JP |
H08-266907 | Oct 1996 | JP |
2001-225130 | Aug 2001 | JP |
03087549 | Oct 2003 | WO |
Entry |
---|
PCT/ISA/210, “International Search Report for International Application No. PCT/JP2015/079007,” dated Jan. 19, 2016. |
Japan Patent Office, “Office Action for Japanese Patent Application No. 2017-545028,” dated Nov. 21, 2017. |
PCT/IB/338, “Notification of Transmittal of Translation of the International Preliminary Report on Patentability for International Application No. PCT/JP2015/079007,” dated Apr. 26, 2018. |
PCT/IB/373, “International Preliminary Report on Patentability for International Application No. PCT/JP2015/079007,” dated Apr. 17, 2018. |
PCT/ISA/237, “Written Opinion of the International Searching Authority for International Application No. PCT/JP2015/079007,” dated Jan. 19, 2016. |
Europe Patent Office, “Search Report for European Patent Application No. 15906226.4,” dated Dec. 7, 2018. |
Number | Date | Country | |
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20180161766 A1 | Jun 2018 | US |