JP2011126756A - Intra-laminate heat exchange type reactor, and method for manufacturing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an intra-laminate heat exchange type reactor which has a high heat exchange function in spite of compactness, and is easily produced. <P>SOLUTION: A silicon carbide laminated body having the shape same as that of a laminated precursor is formed from a laminated precursor obtained by laminating a paper-made flat sheet and paper-made corrugated sheet, where a flow-in side unit having an outward route between the mountain part of the corrugated sheet and the flat sheet, and a flow-out side unit having a homeward route between the valley part of the corrugated sheet and the flat sheet are alternately laminated, the laminated body is sealed into a casing having a flow-in port and a flow-out port. The fluid made to flow into the outward route from the flow-in port enters a communication space formed between the laminated body and the casing, and is made to flow from the communication space through the homeward route. A heat generating means is formed in the communication space or the laminated body, and the fluid is heated by the heat generating means to be made to flow out from the flow-out port. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a laminated internal heat exchange reactor in which a plurality of flow paths through which fluid flows are arranged in the left-right direction and the up-down direction, and a manufacturing method thereof, and more particularly, a laminated internal heat exchange reaction made of silicon carbide ceramics. The present invention relates to a container and a manufacturing method thereof.

  Temporarily heating a fluid is performed in response to various demands in various industrial fields. For example, in the chemical industry field, a raw material is preheated to a temperature suitable for a target chemical reaction, and is performed in many chemical apparatuses.

  In addition, harmful gases such as malodorous gases and volatile organic solvents (VOC) can generally be converted into odorless and harmless gases by combustion or catalysts. However, since the concentration of harmful gases contained in the atmosphere is generally low and the temperature is low, in order to start and continue the combustion of harmful gases, they are preheated and then flowed into the combustion region. .

In addition, when purifying exhaust gas from an internal combustion engine such as an automobile engine using an oxidation catalyst, a three-way catalyst, a NO _x selective reduction catalyst, a NO _x storage reduction catalyst, a filter catalyst, etc., CO is used at low temperatures such as when the engine is started. It becomes difficult to purify HC, NO _x and PM. Further, a lean burn engine such as a diesel engine has a problem that the purification efficiency by the catalyst is low because the combustion temperature is low. Therefore, it is desirable to supply the catalyst after preheating the exhaust gas.

  Therefore, conventionally, for example, a catalyst carrying a large amount of a catalytic metal such as Pt is disposed upstream of a normal catalyst. According to such a catalytic device, since the upstream catalyst exhibits oxidation activity early, the exhaust gas is heated by the oxidation reaction heat of CO and HC, and the exhaust gas temperature flowing into the downstream catalyst can be increased. . However, the heating temperature possible with this method is only the adiabatic rise temperature determined by the concentration of CO, HC, or the like serving as a heating source. That is, for example, the elevated temperature caused by the reaction heat of 0.1% CO or ethylene complete oxidation is only 10K or 48K, respectively. For this reason, when a temperature increase is required, fuel is added to the exhaust gas, but a lot of fuel is required. Thus, there is a problem that fuel efficiency is greatly deteriorated only by preheating by catalytic combustion.

  On the other hand, as is done in chemical equipment, using preheating by recovery of reaction heat makes it possible to increase the rising temperature to 2 to 4 times the adiabatic rising temperature depending on the heat exchange performance. . However, in a device for preheating automobile exhaust gas, the size of the device is required to be compact from the viewpoint of mountability. In order to ensure this compactness, there is a demand for practical use of a counter-current plate type heat exchange structure with high heat exchange performance.

  For example, Japanese Patent Laid-Open No. 2004-069293 proposes a heat exchanger in which a number of stainless steel plates are bent in an accordion shape and bent into an accordion-shaped structure as a whole, and this is housed in a rectangular parallelepiped container. The structure has one end in the longitudinal direction sealed and the other end opened, and the container has a fluid inlet and outlet near the sealed side. The gas flowing in from the inlet flows along one surface of the accordion shape (outward path), exits from the open end, reverses the flow direction, flows along the other surface of the accordion shape (return path), and flows out from the outlet of the container. By supporting the catalyst in the vicinity of the open end of the structure, CO and HC in the exhaust gas can be oxidized, and the reaction heat and the internal heat recovery from the return path to the forward path, The exhaust gas can be remarkably heated.

  This internal heat exchange reactor can increase the heat transfer area and the exhaust gas passage width in a limited volume, so that the heat exchange performance is high, and the folded portion where the exhaust gas temperature is maximum is maximized. Since the volume is small, heat dissipation loss is small, and there are no moving parts, and the structure is simple, so that it is inexpensive.

  In the pamphlet of International Patent Publication No. 2004/099577, a rectangular parallelepiped structure in which a number of thin box-shaped heat transfer plates are stacked is enclosed in a casing, and the longitudinal direction of the structure is determined from an inflow opening formed at one end of the casing. The exhaust gas is caused to flow into the forward path extending to the outside, the exhaust gas emitted from the structure is reversed in the flow direction in the casing, and then flows into the return path extending in the longitudinal direction of the structure, and flows out from the outlet of the casing formed in the vicinity of the inlet. An exhaust gas purifying apparatus configured as described above and further having a catalyst supported on a structure has been proposed. Also with this apparatus, the exhaust gas can be largely heated by the oxidation reaction heat of CO and HC in the exhaust gas and the internal heat exchange function.

  However, the above-described reactor has a problem that it is difficult to make a structure for evenly distributing the exhaust gas to a plurality of forward paths of the structure and a seal structure between the forward path and the return path.

  In view of this, Japanese Patent Application Laid-Open No. 2008-155752 proposes a heat exchange structure in which thin plates formed of cordierite or the like are laminated with a space therebetween to form a planar channel between the thin plates. In this heat exchange structure, every other forward path and return path arranged across a planar flow path are extended in one direction, and an inflow port for the forward path is formed in one region of one end surface in the extension direction. The outlets are provided every other one of the planar flow paths in another area. In addition, a communication space for connecting the forward path and the return path through a space between the casing and the casing is provided at the end in the extending direction opposite to the side where the inlet and the outlet are provided. Then, by providing a heater or an oxidation catalyst in the vicinity of the communication space to heat the fluid, the fluid temperature in the vicinity of the folded portion can be increased.

JP 2004-069293 JP International Patent Publication No. 2004/099577 Pamphlet JP 2008-155752 A

  However, when the heat exchanging structure described in Patent Document 3 is formed from a ceramic plate such as cordierite or a stainless plate, the number of parts or man-hours is large. There was a problem that it was difficult to make an integrated structure with excellent strength.

  This invention is made | formed in view of the said situation, and makes it the subject which should be solved to provide a lamination | stacking internal heat exchange type | mold reactor which has a high heat exchange function while being compact, and is easy to manufacture.

The feature of the method for producing a laminated internal heat exchange reactor of the present invention that solves the above problems is that a flat plate made of an organic porous material and a corrugated plate made of an organic porous material and having peaks and valleys formed alternately. An inflow side unit having a forward path between at least a crest and a flat plate of a corrugated sheet, and an outflow side unit having a return path between at least a trough of the corrugated sheet and a flat plate. A precursor forming step in which both the forward path and the return path are open on one end surface, and a stacked precursor having a regulating wall in front of the return path is formed on the other end surface opposite to the one end surface; ,
An impregnation step of impregnating a slurry containing a resin and silicon powder, or a slurry in which the resin is dissolved or a slurry containing a silicon carbide powder into a laminate precursor;
A carbonization step in which the impregnated body is heated in a vacuum or in a non-oxidizing atmosphere to carbonize the resin and thermally decompose the laminated precursor to form a carbonaceous laminated precursor having substantially the same shape as the laminated precursor;
By heating the carbonaceous laminate precursor in vacuum or in a non-oxidizing atmosphere, silicon and carbon are reacted to form a silicon carbide laminate in the same shape as the laminate precursor from the carbonaceous laminate precursor. Performing a firing step,
In a casing having an inlet and an outlet, a laminate obtained by enclosing the forward path that opens to the other end surface to the inlet and the fluid flowing in the return path is guided to the outlet by the restriction wall is provided. A communication space that communicates with the forward path and the return path that open to the one end surface is formed between the one end surface and the casing, and heat generation means is formed in at least one of the communication space and the laminated body in the vicinity of the communication space.

In addition, the manufacturing method of the laminated internal heat exchange reactor according to the second invention is characterized in that a flat plate made of an organic porous material and a corrugated plate made of an organic porous material and having peaks and valleys alternately formed. An inflow side unit having a forward path between at least a crest and a flat plate of a corrugated sheet; an outflow side unit having a return path between at least a trough of the corrugated sheet and a flat plate; And a precursor forming step of forming a laminated precursor having a restriction wall in front of the return path on the other end surface opposite to the one end face, the forward path and the return path being open on one end face,
An impregnation step in which a solution containing a resin in a dissolved state or a slurry containing silicon carbide powder in the solution is further impregnated into a laminated precursor to form an impregnated body;
A carbonization step in which the impregnated body is heated in a vacuum or in a non-oxidizing atmosphere to carbonize the resin and thermally decompose the laminated precursor to form a carbonaceous laminated precursor having substantially the same shape as the laminated precursor;
In a vacuum or non-oxidizing atmosphere, a carbonaceous laminate precursor is impregnated with molten silicon, and silicon and carbon are reacted to form a silicon carbide laminate having substantially the same shape as the laminate precursor from the carbonaceous laminate precursor. A melt impregnation step to form,
In a casing having an inlet and an outlet, a laminate obtained by enclosing the forward path that opens to the other end surface to the inlet and the fluid flowing in the return path is guided to the outlet by the restriction wall is provided. A communication space that communicates with the forward path and the return path that open to the one end surface is formed between the one end surface and the casing, and heat generation means is formed in at least one of the communication space and the laminated body in the vicinity of the communication space.

The feature of the laminated internal heat exchange reactor of the present invention produced by the production method of the present invention is that flat plates made of silicon carbide ceramics and peaks and valleys made of silicon carbide ceramics are alternately formed. A laminated body having a plurality of flow paths partitioned by crests and valleys of the corrugated sheet and a flat plate, and a casing having an inlet and an outlet in which the laminated body is enclosed, A laminated internal heat exchange reactor comprising:
The laminated body includes a flat plate and a corrugated plate and an inflow side unit having a forward path between at least the crest and the flat plate of the corrugated plate, a flat plate and a corrugated plate, and at least a trough and a flat plate of the corrugated plate. Outflow side units with a return path between them are stacked alternately,
A forward path and a return path are opened at one end surface of the laminate, a regulating wall is provided in front of the return path on the other end surface opposite to the one end surface, and the forward path and the return path are communicated between the one end surface of the laminate and the casing. A communication space is formed, and at least one of the stacked body in the communication space and in the vicinity of the communication space has a heating means,
The fluid that flows in from the inflow port flows into the communication space from the forward path that opens to the other end surface, receives heat from the fluid flowing in the return path before flowing into the communication space in the forward path, and rises in temperature and flows into the return path from the communication space In this case, the temperature further rises due to heating by the heat generating means, and the temperature gradually decreases by passing the heat to the forward path in the return path, and is guided to the regulation wall and flows out from the outlet.

  The inventor of the present application has proposed a method for producing a silicon carbide structural material from a sponge-like organic porous structure in Japanese Patent No. 3699992, Japanese Patent No. 4273195, Japanese Patent No. 4110244, and the like. In this manufacturing method, for example, a urethane sponge is impregnated with a slurry containing a phenol resin and silicon powder, and fired in an inert atmosphere so that a silicon carbide structural material is obtained by reactive sintering through a carbonaceous porous structure. Is to be manufactured. According to this manufacturing method, the obtained silicon carbide based porous structural material has the same skeleton as the urethane sponge used.

  Therefore, the present inventor recalled that an internal heat exchange type reactor was produced using the method described in the above patent. By using this manufacturing method, silicon carbide structural materials having various internal structures can be easily formed. Therefore, an internal heat exchange type reactor having excellent heat resistance and corrosion resistance, high strength and high thermal conductivity. Can be manufactured. And by using the skeleton of corrugated paper as the skeleton of the internal heat exchange type reactor, it can be easily clogged, and the linear passage formed by corrugated paper and flat plates is used as the flow path. The present invention has been completed by finding out what can be done.

  That is, according to the production method of the present invention, the lamination precursor is formed using an organic porous material such as corrugated paper, so that the lamination precursor can be formed very easily like a paper work. Also, when the flow path needs to be clogged, it can be very easily carried out by using a slurry having a high viscosity or by crushing a peak portion. Furthermore, since processes such as bending, crushing, and excision are easy, the flow path of the laminated precursor can be freely adjusted. And because it is possible to produce a laminated internal heat exchange type reactor with the shape of the laminated precursor as it is, unlike the extrusion method normally used in the production of ceramic structures, even complex shapes are very easy with a small number of man-hours. Can be manufactured.

  And according to the lamination | stacking internal heat exchange type | mold reactor of this invention manufactured with the manufacturing method of this invention, since it is silicon carbide, it is excellent in thermal conductivity. Further, since the flow path is formed between the corrugated plate and the flat plate, the contact area (heat transfer area) between the fluid and the flow path wall surface can be greatly increased, and a high heat exchange function is provided. Then, the direction in which the fluid flows in the forward path and the direction in which the fluid flows in the reverse path are opposite to each other, so that an ideal counterflow is formed and the speed and temperature of the fluid are equalized. Therefore, the laminated internal heat exchange reactor of the present invention has a high heat exchange function while being compact.

It is explanatory drawing which shows the manufacturing method of the unit corrugated sheet which concerns on one Example of this invention. It is a perspective view of the lamination | stacking precursor (laminate) which concerns on one Example of this invention. It is a disassembled perspective view of the lamination | stacking internal heat exchange type reactor which concerns on one Example of this invention. It is sectional drawing of the lamination | stacking internal heat exchange type reactor which concerns on one Example of this invention. It is sectional drawing of the inflow side edge part of the lamination | stacking internal heat exchange type reactor which concerns on one Example of this invention. It is sectional drawing of the communication space side edge part of the lamination | stacking internal heat exchange type reactor which concerns on one Example of this invention. It is principal part sectional drawing of the lamination | stacking internal heat exchange type reactor which concerns on one Example of this invention. It is explanatory drawing which shows the flow of the waste gas in the lamination | stacking internal heat exchange type reactor which concerns on one Example of this invention. It is a disassembled perspective view of the lamination | stacking internal heat exchange type reactor which concerns on the 2nd Example of this invention. It is explanatory drawing which shows the manufacturing method of the unit laminated body which concerns on the 3rd Example of this invention. It is a perspective view of the lamination | stacking precursor (laminate) which concerns on the 3rd Example of this invention. It is sectional drawing of the inflow side edge part which shows the other aspect of the lamination | stacking precursor (laminate) which concerns on the 3rd Example of this invention. It is sectional drawing which shows the other aspect of the lamination | stacking precursor (laminate) which concerns on the 3rd Example of this invention. It is a schematic plan view which shows the other aspect of the unit laminated body which concerns on the 3rd Example of this invention. It is a perspective view which shows the manufacturing method of the lamination | stacking precursor (laminate) which concerns on the 4th Example of this invention. It is a perspective view which shows the other aspect of the unit laminated body which concerns on the 4th Example of this invention. It is a perspective view which shows the other aspect of the unit laminated body which concerns on the 4th Example of this invention. It is explanatory drawing which shows the manufacturing method of the unit laminated body which concerns on the 5th Example of this invention. It is explanatory drawing which shows the manufacturing method of the unit laminated body which concerns on the 5th Example of this invention. It is a perspective view of the lamination | stacking precursor (laminate) which concerns on the 5th Example of this invention. It is sectional drawing of the lamination | stacking internal heat exchange type reactor which concerns on the 5th Example of this invention. It is a front view of the inflow side edge which shows the other aspect of the lamination | stacking precursor (laminate) which concerns on the 5th Example of this invention.

  In the production method of the present invention, a flat plate made of an organic porous material and a corrugated plate made of an organic porous material are used as starting materials. The porosity and pore distribution of the flat plate and the corrugated plate can be variously selected according to the purpose, and may be the same or different. As the organic porous body, porous bodies made of various organic materials such as paper, non-woven fabric, woven fabric, knitted fabric, and urethane foam can be used. The material of the flat plate and the corrugated plate may be the same or different.

  For example, double-sided corrugated paper and single-sided corrugated paper are preferably used because a porous flat plate and a corrugated plate formed from the flat plate are joined to each other, and are more porous than copy paper. be able to. For example, in order to form a corrugated sheet from cloth, the corrugated sheet may be shaped and then impregnated with an organic binder such as resin to fix the corrugated sheet.

  The flat plate and the corrugated plate preferably contain carbon powder. The carbon powder is preferably contained in an amount of 50% by mass or more, and preferably 70% by mass or more. By including the carbon powder, a sufficient silicon carbide skeleton can be formed even when the amount of impregnation of the slurry described later is small, and volume shrinkage in the carbonization step and the firing step can be suppressed. Therefore, a silicon carbide laminate having the same shape as the laminate precursor can be easily produced.

  In the precursor forming step, a laminated precursor is formed by alternately laminating inflow side units and outflow side units. The inflow side unit includes a flat plate and a corrugated plate, and has a forward path at least between the peak portion of the corrugated plate and the flat plate. The outflow side unit has a flat plate and a corrugated plate, and has a return path between at least a trough of the corrugated plate and the flat plate. Since the corrugated plate has alternating peaks and valleys, a plurality of forward paths and multiple return paths are formed. Both the forward path and the return path are opened on one end surface on the downstream side of the forward path, and a regulating wall is formed in front of the return path on the other end surface opposite to the one end surface. This regulating wall regulates the flow direction of the fluid flowing in the return path and guides it to the outflow opening of the casing, and is composed of a clogging portion, a crushing portion, or a wall portion.

  For example, if a double-faced corrugated paper having a sandwich structure in which flat plates are laminated on both sides of a corrugated sheet, a flow path constituted by corrugated crests and flat plates, corrugated troughs and flat plates, Is already separated from the flow path. Therefore, if one end of one flow path is closed to form a regulating wall, and an outflow opening communicating with the outside is formed in the closed flow path, the flow path that is not closed becomes the forward path and the closed flow path Therefore, the inflow side unit and the outflow side unit can be formed with a single sheet of corrugated paper. In order to close the flow path and form the regulation wall, there are a method of filling one end portion with a slurry having high viscosity, a method of physically crushing the flow passage at one end portion, and closing the flow path.

  In addition, when using a single-sided corrugated cardboard in which flat plates are laminated on one side of one corrugated sheet, if the paper flat plate is laminated on the corrugated sheet of single-sided corrugated paper, the corrugated cardboard has the sandwich structure described above. Similarly, an inflow side unit and an outflow side unit can be formed. If it is single-sided corrugated paper, it is easy to physically crush and close the corrugated sheet at one end, or it is easy to fill the trough with slurry, so the man-hours for forming the above-mentioned regulation wall Can be reduced.

  When single-sided cardboard is used, it is also preferable to stack flat plates via a plurality of strip-shaped paper spacers. In this way, a planar space is formed between the top surface of the crest of the corrugated plate or the bottom surface of the trough and the flat plate, whereby the flow path of the crest or trough parallel to each other in the forward or return path. You can communicate between them. This makes it possible to equalize the flow velocity between the flow paths, or to connect all the flow paths to the outflow opening in the return path. Further, this planar space can reduce the pressure loss of the fluid flowing in the forward path or the return path. In order to form a planar space between the crest and the flat plate of the corrugated plate, it is possible to reduce the peak height or trough depth by crushing a part of the top of the crest or the bottom of the trough. Good.

  Further, as shown in FIGS. 10 and 11, two single-sided cardboards are laminated so that the corrugated sheets face each other and the ridges face each other, and the valleys facing each other are formed on the inflow side. Even if clogged at the end, the inflow side unit and the outflow side unit can be formed. In this case, the space where the valleys facing each other are not clogged becomes the return path. Also in this case, if two single-sided cardboards are stacked via a spacer, a planar space that communicates the return paths can be formed.

  In addition, as shown in FIG. 12, if two sheets of single-sided corrugated paper are laminated so that the corrugated sheets face each other and the crests and troughs face each other with a gap therebetween, A corrugated passage that connects the return paths is formed between them, or if single-sided corrugated cardboard is laminated so that the ridges of the peaks cross each other, a path that connects the adjacent upper and lower troughs to each other is formed. Therefore, the pressure loss can be reduced without using a spacer.

  Various other lamination forms are conceivable as the lamination precursor formed in the precursor formation step, and will be described in detail in the examples described later.

  In the impregnation step in the first manufacturing method of the present invention, a slurry in which a resin and silicon powder are contained and in which the resin is dissolved or a slurry containing silicon carbide powder is further impregnated into the laminated precursor to obtain an impregnated body. In the impregnation step in the second production method, the laminated precursor is impregnated with a solution containing the resin in a dissolved state or a slurry containing silicon carbide powder in the solution. By impregnating the resin, the shape of the carbonaceous laminated precursor formed in the carbonization step can be maintained. As the resin, a resin that dissolves in a solvent to form a solution can be used, and examples thereof include phenolic resins, furan resins, and organometallic polymers such as polycarbosilane. One kind selected from these may be used, or a plurality of kinds may be mixed and used, but those which are thermosetting, contain many carbon atoms and become a carbon source are preferred, and phenol resins are particularly preferred.

  In the second production method, a silicon melt impregnation step is required as described later. However, if a slurry obtained by adding silicon powder to a resin is used as in the first production method, the silicon melt impregnation step is not performed. However, a silicon carbide laminate can be formed, and when the silicon melt impregnation step is performed, the melt impregnation step can be more easily performed. In addition, carbon powder, graphite powder, carbon black may be added as an additive in the slurry, and silicon carbide is most preferable as an aggregate or antioxidant, but silicon nitride, zirconia, zircon, alumina, silica, Mullite, molybdenum disilicide, boron carbide, boron powder and the like can also be added. In order to impregnate the lamination precursor with the slurry, it may be simply dipped and pulled up, or it is preferably impregnated under reduced pressure.

  When using a slurry containing silicon powder, the silicon powder is preferably a fine powder having an average particle size of 30 μm or less. Those having a large particle size are preferably used after being pulverized by a ball mill or the like. The silicon powder may be a pure silicon powder, or a silicon alloy powder containing a metal such as Mg, Al, Ti, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Nb, Mo, W, Alternatively, a mixed powder of pure silicon powder and these metal powders can be used.

  When a slurry containing silicon powder is used, the mixing ratio of the resin and silicon powder in the slurry is preferably in the range of Si / C <5.00 in terms of atomic ratio. When this atomic ratio exceeds 5.00, the amount of silicon powder in the slurry increases and precipitation tends to occur. Moreover, when using the slurry which mixed silicon powder and the silicon carbide powder as an aggregate, it is preferable to make silicon carbide powder into the range within 3 times the weight of silicon powder. If the silicon carbide powder exceeds 3 times the weight of the silicon powder, mixing may be insufficient.

  The solid content concentration in the slurry is not particularly limited as long as it is a viscosity capable of impregnating the slurry into the flat plate and the corrugated plate of the lamination precursor. The solvent used for the slurry is not particularly limited, but a solvent capable of dissolving the resin is used. In order to impregnate the lamination precursor with the slurry, it may be simply dipped and pulled up, or it is preferably impregnated under reduced pressure.

  After the impregnation step, it is desirable to perform a removal step of removing excess slurry adhering to the lamination precursor. The reason why the excess slurry is removed from the laminated precursor is to remove the excess slurry filled in the forward path and the backward path to prevent the blockage of the flow path, and can be performed by centrifugation or suction. Moreover, it is desirable to perform the drying process which dries the solvent in the slurry adhering to the lamination | stacking precursor before the next carbonization process. The drying step can be performed in the atmosphere, and it is sufficient to hold at 70 ° C. for about 3 hours.

  Before the impregnation step or after the impregnation step, it is desirable to perform a clogging step for forming a return path, forming a regulating wall, or filling a gap. As the filling material, a clay-like paste containing various ceramic powders having heat resistance as a main component and containing an organic binder such as a phenol resin can be used. It is preferable to use a paste mainly composed of silicon carbide powder that is firmly bonded to the silicon carbide laminate formed in the firing step. In addition, if a paste containing silicon powder is used, the filling material becomes silicon carbide in the firing step described later, so that the bonding strength between the filling material and the silicon carbide laminate is further improved. Organic materials such as paper clay and resin powder can also be used as the filling material. In this case, the plugging material is carbonized in the carbonization step described later, and becomes silicon carbide in the firing step.

  Moreover, it can replace with a clogging process and can also perform a crushing process before an impregnation process or after an impregnation process. If one end part of the peak part of a corrugated sheet is crushed, the part will be obstruct | occluded and it can replace with clogging. Moreover, a part of the return path can be crushed to form an outflow opening, and a mountain space can be crushed to reduce the height to form a planar space.

  In the carbonization step, the impregnated body is heated in a vacuum or in a non-oxidizing atmosphere to carbonize the impregnated resin and thermally decompose the laminated precursor to obtain a carbonaceous laminated precursor. As the non-oxidizing atmosphere, an inert gas atmosphere such as argon gas is preferable. In the carbonization process by thermal decomposition of the resin, tar-like substances and vaporized substances are generated, so that it is not preferable to perform in a vacuum. Further, when the impregnation step is performed using a slurry containing silicon powder, the carbonization step in a nitrogen gas atmosphere is not preferable because silicon nitride may be generated.

  The firing temperature in the carbonization step can be in the range of 900 to 1350 ° C. By heating in the range of 900 to 1350 ° C, the resin adhering to the surface of the lamination precursor is carbonized, and the organic components of the lamination precursor are pyrolyzed and carbonized while maintaining the three-dimensional skeleton. . Therefore, a carbonaceous laminate precursor that maintains the skeleton of the laminate precursor is formed.

  A baking process is performed after a carbonization process. In this firing step, the carbonaceous laminate precursor is heated in a vacuum or in a non-oxidizing atmosphere to react silicon and carbon to form a silicon carbide laminate from the carbonaceous laminate precursor. The firing atmosphere can be the same as in the carbonization step, but is preferably performed in a vacuum atmosphere.

  The firing temperature in the firing step can be 1350 ° C. or higher. By heating to 1350 ° C. or higher, carbon and silicon react to form a silicon carbide laminate having silicon carbide as a main component. This reaction is a reaction in which the volume is reduced because silicon and carbon are present in the system, and when carbon is diffused and reacts with silicon, fine pores are formed in the interior simultaneously with the formation of silicon carbide. This porous silicon carbide has good wettability with molten silicon, and can be easily melted and impregnated with silicon described later. In the case where it is already clogged, the clogging material is also fired and fixed integrally with the silicon carbide laminate.

  The carbonization step and the firing step may be performed separately, but it is desirable to perform the firing step continuously after the carbonization step. In this way, waste of heat energy can be prevented.

  In the second manufacturing method, after the carbonization step, a melt impregnation step of impregnating the silicon laminate precursor with molten silicon in a vacuum or in a non-oxidizing atmosphere is performed. This melt impregnation step can also be performed by the first manufacturing method. This melt impregnation step may be performed by heating metal silicon to a melting point (about 1410 ° C.) or higher to form molten silicon and impregnating the carbonaceous laminated precursor, and it is particularly preferable to perform in a vacuum. The melt-impregnating silicon may be in the form of powder, granules, or lumps.

  In the melt impregnation step, molten silicon enters the fine pores of the carbonaceous laminate precursor formed during the carbonization step, and reacts with carbon to form silicon carbide. This reaction is a reaction in which the volume increases because silicon is added from outside the system, and fine pores formed inside are filled with silicon or silicon carbide. Accordingly, the strength of the carbonaceous laminated precursor is improved.

  In the reaction in the melt impregnation step, if the composition of carbon from silicon and resin and carbon from the organic porous material is Si / C <1 in atomic ratio, silicon carbide and unreacted carbon remain, and Si / C> If it is 1, silicon carbide and unreacted metal silicon remain, but it is preferable that metal silicon remains in terms of strength.

In the case where the silicon carbide laminate includes silicon, it is also preferable to perform an oxidation step in which at least part of the silicon included is oxidized to form SiO ₂ . In SiO ₂ , silanol groups are easily generated and hydrophilicity is improved. Accordingly, it is possible to absorb a large amount of an aqueous solution of the catalyst metal compound, and by firing it, a laminate in which a catalyst metal such as Pt is highly dispersed and supported can be formed. In this way, if it is a laminated internal heat exchange type reactor having a laminated body carrying a catalyst, it becomes possible to oxidize HC and CO by circulating a gas containing HC and CO such as automobile exhaust gas, in a low temperature range. It can be used as a reactor for heating and purifying exhaust gas. In addition, since the laminate is made of silicon carbide, heat can be generated by energization. Therefore, harmful components can be purified by heating the low-temperature exhaust gas at the time of starting.

In this oxidation step, the silicon carbide laminate including silicon may be heated in an oxidizing atmosphere such as the air. It is clear that the higher the heating temperature, the more SiO ₂ is produced with respect to the total amount of silicon, and it is desirable to heat at 400 ° C. or higher. It is sufficient to keep the heating time for about 10 minutes. The amount of SiO ₂ formed can be adjusted by the heating temperature, and the higher the heating temperature, the more SiO ₂ can be formed. Therefore, it is only necessary to select a heating temperature at which the catalyst metal such as Pt can be supported in a highly dispersed state with a sufficient amount of support.

  In the first production method, when carbon remains after the firing step or when the strength is insufficient, melt impregnation is performed by impregnating the silicon carbide laminate with molten silicon in a vacuum or in a non-oxidizing atmosphere after the firing step. It is also preferable to carry out the process. The melt impregnation step may be performed by heating metal silicon to a melting point (about 1410 ° C.) or higher to form molten silicon and impregnating the silicon carbide laminate, and it is particularly preferably performed in a vacuum. The melt-impregnating silicon may be in the form of powder, granules, or lumps.

  In the melt impregnation process, since silicon carbide has good wettability to molten silicon, the molten silicon penetrates into the fine pores formed during the firing process and reacts with the remaining carbon to form silicon carbide. The This reaction is a reaction in which the volume increases because silicon is added from outside the system, and fine pores formed inside are filled with silicon or silicon carbide. Accordingly, the strength of the silicon carbide laminate is improved.

  In the melt impregnation step, since it is exposed to a high temperature of 1410 ° C. in a vacuum or in a non-oxidizing atmosphere, most of the residual carbon is silicon carbide when residual carbon is present. The melt impregnation step can be performed simultaneously with the baking step or continuously with the baking step. In other words, after the carbonization process, silicon for melt impregnation is added and the firing process is performed by setting the temperature to a temperature equal to or higher than the melting point of silicon (about 1410 ° C.) in a vacuum or non-oxidizing atmosphere. The carbon and silicon are reacted. Excess silicon remains as metallic silicon.

  The silicon carbide laminate thus formed is enclosed in a casing. A communication space communicating with the forward path and the return path that opens to the one end surface is formed between the casing and the one end surface where the forward path and the return path of the laminate are exposed. The casing is formed with an inlet that communicates with the forward path of the laminate, and an outlet that communicates with the outlet opening and the return path of the laminate. The inflow port and the outflow port may be formed in parallel on one end face of the casing, or may be formed so that the flow direction of the fluid intersects, but the flow of the forward path and the return path is separated from the wall of the laminate. It is desirable that the channel lengths facing each other be as long as possible.

  Heat generating means is formed in at least one of the inside of the communication space and the laminated body in the vicinity of the communication space. This heat generating means directly or indirectly heats the fluid flowing in the forward path, the return path, and the communication space, and may be, for example, an electric heater, a combustion burner, or a catalytic combustor disposed in the communication space. Or, an oxidation catalyst such as Pt or Pd is supported on the surface of the laminate near the communication space, or the wall surface of the outbound path or return path near the communication space, and oxidizes the oxidizable substances contained in the fluid and generates heat from the combustion heat. Can also be used.

  The fluid flowing in from the inflow port passes through the forward path, enters the communication space, reverses in the communication space, is introduced into the return path, and is heated by the heating means during this period, and then is formed in front of the return path (downstream side). It is guided by the wall and flows out from the outlet of the casing through the outflow opening. At that time, heat is transferred (heat exchange) from the fluid that has risen in temperature by the heat generating means and flows into the return path to the forward path fluid through the silicon carbide laminate. As a result, the reciprocating fluid can be remarkably heated in the vicinity of the communication space by the heating action by heat exchange with the heat generating means. In this way, the temperature of the fluid is increased, and a catalyst that promotes the target reaction is disposed in the vicinity of the fluid. The reaction rate can be significantly accelerated.

  As the fluid flowing in the communication space with the forward path and the return path, both liquid and gas can be used.

  Hereinafter, the present invention will be described specifically by way of examples. The present embodiment relates to a stacked internal heat exchange reactor that can purify the exhaust gas from an automobile by raising the temperature.

<Precursor formation step>
First, a flat plate (corresponding to a flat plate of single-sided corrugated paper) having a thickness of about 0.3 mm and weighing about 110 g / m ² containing 70% by mass of activated carbon, and a corrugated plate (single-sided corrugated paper) formed by corrugating this flat plate And a number of corrugated sheet equivalent products). As shown in FIG. 1 (a), the corrugated plate 1 is formed with ridges 10 and valleys 11 alternately.

  Next, the mixing amount of the phenol resin and silicon powder having an average particle size of about 20 μm is set at a ratio where the atomic ratio of carbon to silicon by the carbonization of the phenol resin is Si / C = 1.5. A 3 μm silicon carbide powder was added in the same amount as the silicon powder, and the phenol resin was dissolved in ethyl alcohol having a weight of about 0.6 times the weight of the silicon powder to prepare a clay-like paste. Using this paste, as shown by the hatched portion in FIG. 1 (b), the valley portion 11 was filled with the paste at one end portion of the corrugated plate 1 to form a clogging portion 12. In addition, the peak portion 10 was filled with the paste at both end portions in the direction perpendicular to the direction in which the mountain and valley portions extend. Since the valley portion 11 has a substantially U-shaped cross section and has a large opening, the paste can be easily and uniformly filled using a spatula or the like. Next, the crests 10 at both ends filled with the paste were cut out at portions close to one end of the corrugated plate 1 to form a pair of left and right outflow openings 13.

  A plurality of strip-shaped flat plates (corresponding to single-sided corrugated paper) containing 70% by mass of activated carbon are prepared and laminated to a thickness of about 2 mm. As shown in FIG. A spacer 14 was formed by adhering to the top of the peak portion 10 with a paper adhesive so as to cross the peak portion 10. Thus, the unit corrugated plate 1 ′ shown in FIG. 1 (c) was manufactured.

  The obtained unit corrugated plate 1 ′ and the flat plate 2 were alternately laminated using a paper adhesive to form a lamination precursor 3 shown in FIG. Each unit corrugated plate 1 ′ is laminated so that the clogging portions 12 are exposed on the same end face, and the pair of left and right outflow openings 13 are also exposed at the same position in the longitudinal direction. A passage defined by the peak portion 10 and the flat plate 2 is opened on one end surface where the clogging portion 12 is exposed, and a passage defined by the peak portion 10 and the flat plate 2 is formed on the other end surface on the opposite side. A passage defined by the portion 11 and the flat plate 2 is opened.

  Since the gap due to the spacer 14 is formed between the unit corrugated plate 1 ′ and the flat plate 2 on both side surfaces where the outflow opening 13 is opened, the paste described above except for the portion of the outflow opening 13. Filled with.

<Impregnation process>
Next, the mixing amount of the phenol resin and silicon powder having an average particle diameter of about 20 μm is set at a ratio where the atomic ratio of carbon to silicon by the carbonization of the phenol resin is Si / C = 3. A phenol resin is dissolved in 0.9 times the weight of ethyl alcohol to prepare a slurry, which is mixed with a ball mill for one day in order to reduce the particle size of the silicon powder. Further, silicon carbide powder having an average particle size of about 3 μm is added to the silicon powder. A dispersion slurry was prepared by adding 0.33 times the weight. Then, the dispersion precursor 3 was impregnated with the dispersion slurry, and excess slurry was blown off, followed by drying at 70 ° C. for 3 hours.

<Carbonization process>
Then, it carbonized by heating at 1000 degreeC under argon gas atmosphere. At this time, the corrugated plate 1, the flat plate 2, and the spacer 14 are pyrolyzed and carbonized, and the impregnated slurry and the phenolic resin in the plugging portion 12 are carbonized to form the same shape as the laminated precursor 3. None A carbonaceous laminate precursor having an equivalent porous structure was formed.

<Baking process>
Next, this carbonaceous laminated precursor was fired at 1450 ° C. for 1 hour in a vacuum. In this firing, carbon reacts with silicon at a temperature below the melting point of silicon (about 1410 ° C.) to form a silicon carbide laminate having a three-dimensional skeleton composed of silicon carbide and having the same three-dimensional skeleton as the carbonaceous laminate precursor. It was.

  This silicon carbide laminate has the same shape as the laminate precursor 3 shown in FIG. Therefore, for the sake of convenience, in the following description, the laminated body is denoted by the reference numeral 3, and each part of the laminated body 3 is denoted by the same reference numeral as the corresponding part of the laminated precursor 3.

<Encapsulation process>
Next, the casing 4 shown in FIG. 3 was prepared. The casing 4 has a rectangular parallelepiped storage space 40, and has an inlet 41 communicating with the storage space 40 on one end surface in the longitudinal direction. In addition, an outlet 42 is formed in the vicinity of the inlet 41 on each of a pair of side surfaces connecting the one end surface and the other end surface. The storage space 40 is configured to be sealed by the lid 43 using a fastener (not shown).

  The above laminate 3 was stored in the casing 4. At this time, as shown in FIG. 4, a pair of left and right outflow openings 13 are formed such that one end face where the passage defined by the clogging portion 12 is exposed and divided by the peak portion 10 and the flat plate 2 is opposed to the inflow port 41. The laminated body 3 was disposed so as to face the pair of outlets 42, respectively. A communication space 44 is formed between the other end surface of the laminate 3 and the casing 4. A heater 100 that can be heated by a power source (not shown) is fixed to the surface of the casing 4 facing the other end surface of the laminate 3.

  As shown in FIG. 5, a path (hereinafter referred to as the forward path 30) defined by the peak portion 10 and the flat plate 2 is opened at one end surface of the laminate 3 where the clogging portion 12 is exposed. It communicates with the inlet 41. On the other hand, on the other end surface facing the communication space 44, as shown in FIG. 6, a passage (hereinafter referred to as a return path 31) defined by the valley 11 and the flat plate 2 and an outward path 30 are opened. Further, since the spacer 14 is interposed between the corrugated plate 1 and the flat plate 2, as shown in FIG. 7, a planar space 15 is formed between the ridge line of the peak portion 10 and the flat plate 2, and the surface The space 15 communicates with the return path 31. Further, a sealing material (not shown) is interposed between the pair of side surfaces of the laminate 3 and the casing 4.

  That is, as schematically shown in FIG. 8, the exhaust gas flowing in from the inflow port 41 flows into the forward path 30 and then enters the communication space 44, and after being heated by the heater 100, flows into the return path 31 from the communication space 44. Then, the exhaust gas passing through the return path 31 and the planar space 15 and whose flow is regulated by the clogging portion 12 (regulation wall) flows out from the outflow port 42 through the outflow opening 13. Therefore, in the laminate 3 according to the present embodiment, an inflow side unit having an outward path 30 is formed between the peak portion 10 of the corrugated plate 1 and the flat plate 2, and between the trough portion 11 of the corrugated plate 1 and the flat plate 2. An outflow side unit having a return path 31 is formed, and inflow side units and outflow side units are alternately stacked.

  The exhaust gas flowing in the forward path 30 is heated by receiving heat from the exhaust gas flowing in the backward path 31 (heat exchange) through a thin silicon carbide wall having excellent thermal conductivity that partitions the backward path 31 and the outbound path 30. . That is, the temperature of the exhaust gas flowing into the communication space 44 from the forward path 30 is increased, and the exhaust gas is further heated and heated by the heater 100 to reach the maximum temperature. After that, the exhaust gas flowing into the return path 31 is heat-exchanged with the exhaust gas flowing in the outward path, and the temperature is lowered. Finally, the temperature rises by the amount of net heating (adiabatic increase temperature) by the heater 100 as compared to when flowing into the outbound path 30. And flows out from the outlet 42.

  Therefore, a catalyst that promotes a target reaction, such as an exhaust gas purifying catalyst, may be disposed in the communication space of the reactor according to the present embodiment or in the inside of the reciprocating path in the vicinity thereof or on the surface of the laminate forming the reciprocating path. For example, the temperature of the catalyst is remarkably increased by the heat generating means and the heat exchange function, so that the exhaust gas temperature can be increased to the activation temperature of the catalyst even in a low temperature range such as at the time of starting, and the emission of harmful substances can be greatly suppressed. it can.

  FIG. 9 shows the stacked internal heat exchange reactor of this example. Since this laminated internal heat exchange reactor is the same as that of Example 1 except that the materials used in the precursor forming step are different, only the different parts will be described.

In this example, a flat plate having a thickness of about 0.3 mm and a weight of about 110 g / m ² containing 70% by mass of activated carbon and a corrugated plate formed by corrugating the flat plate were laminated one by one. A plurality of single-sided corrugated paper 32 was prepared. Then, the clogging portion 12 was formed in the same manner as in Example 1. In addition, the peak portion 10 was filled with the paste at both end portions in the direction perpendicular to the direction in which the mountain and valley portions extend. Since the valley portion 11 has a substantially U-shaped cross section and has a large opening, the paste can be easily and uniformly filled using a spatula or the like. Next, the crests 10 at both ends filled with the paste were cut out at portions close to one end of the corrugated plate 1 to form a pair of left and right outflow openings 13. And as in Example 1, a flat plate containing 70% by mass of activated carbon with a paper adhesive at the top of the peak 10 so as to cross the peak 10 at three locations in the longitudinal direction (a flat plate equivalent of single-sided cardboard) Was pasted to form a spacer 14.

  A plurality of single-sided cardboards 32 formed in this way were laminated using a paper adhesive, and only the flat plate 2 was laminated on the uppermost part to form the lamination precursor 3 of this example. Each single-sided cardboard 32 is laminated so that the clogging portion 12 is exposed on the same end face, and the pair of left and right outflow openings 13 are also exposed at the same position in the longitudinal direction. A passage (outward path 30) defined by the peak portion 10 and the flat plate 2 is opened on one end surface where the clogging portion 12 is exposed, and the peak portion 10 and the flat plate 2 are defined on the other end surface on the opposite side. A passage (outward passage 30) and a passage (return passage 31) defined by the valley 11 and the flat plate 2 are opened.

<Impregnation process / carbonization process>
Next, the mixing amount of the phenol resin and silicon powder having an average particle size of about 20 μm is set at a ratio where the atomic ratio of carbon to silicon by the carbonization of the phenol resin is Si / C = 0.6. A phenol resin is dissolved in 2.5 times the weight of ethyl alcohol to prepare a slurry, which is mixed with a ball mill for one day to reduce the particle size of the silicon powder. Further, silicon carbide powder having an average particle size of about 3 μm is added to the silicon powder. The dispersion slurry was prepared by adding 0.5 times the weight. Then, the dispersion precursor 3 was impregnated with the dispersion slurry, and excess slurry was blown off, followed by drying at 70 ° C. for 3 hours.

  Using this laminated precursor 3, a carbonization step was performed in the same manner as in Example 1 to form a carbonaceous laminated precursor.

<Baking process and melt impregnation process>
Next, an appropriate amount of silicon granules was placed on the surface of the carbonaceous laminated precursor and fired at 1450 ° C. for 1 hour in a vacuum. In this firing, first, carbon reacts with the silicon powder at a temperature lower than the melting point of silicon (about 1410 ° C.) to form a laminate 3 made of silicon carbide and unreacted carbon. Furthermore, silicon granules are melt-impregnated into the laminate 3 at a temperature equal to or higher than the melting point of silicon, react with unreacted carbon to produce silicon carbide, and the laminate 3 is reinforced with excess metal silicon.

  The obtained laminate 3 was subjected to an encapsulation step in the same manner as in Example 1 to obtain a laminated internal heat exchange reactor of this example. According to the laminated internal heat exchange type reactor of this example, the strength and density of the laminate 3 are higher than those of the laminated internal heat exchange type reactor of Example 1. Moreover, at the time of manufacture of the lamination | stacking precursor 3, the effort which laminates | stacks a corrugated sheet and a flat plate alternately can be saved, and a man-hour can further be reduced.

  10 and 11 show the laminate used in the laminated internal heat exchange reactor of this example. Since this laminated body is the same as that of Example 2 except that the materials used in the precursor forming step are different, only different parts will be described.

 In this example, a plurality of single-sided cardboards 32 similar to those in Example 2 were prepared. In the same manner as in Example 2, the clogging portion 12 was formed, and a pair of left and right outflow openings 13 were formed. A first single-sided cardboard paper 33 having spacers 14 and a second single-sided cardboard paper 34 identical to the first single-sided cardboard paper 33 except that the spacers 14 were not formed were prepared.

  A unit laminated body 35 is formed by laminating the first single-sided cardboard 33 and the second single-sided cardboard 34 so that the crests 10 face each other and the outflow openings 13 communicate with each other. The laminated bodies 35 were laminated in the same direction to form the laminated precursor 3 of this example.

  Using this laminated precursor 3, the impregnation step, the carbonization step, the firing step and the melt impregnation step are carried out in the same manner as in Example 2 to form the silicon carbide laminate 3, and further in the same manner as in Example 1. An encapsulation process was performed to obtain a stacked internal heat exchange reactor of this example.

  In this laminate 3, the forward path 30 is opened at one end surface where the clogging portion 12 is exposed, and the forward path 30 and the return path 31 are opened at the other end face on the opposite side. Therefore, the exhaust gas flowing in from the inflow port 41 flows into the forward path 30, enters the communication space 44, is heated by the heater 100, and then flows from the communication space 44 into the return path 31. Then, the exhaust gas that passes through the planar space 15 secured by the return path 31 and the spacer 14 and whose flow is regulated by the clogging portion 12 (regulation wall) flows out from the outflow port 42 through the outflow opening 13. Therefore, in the laminated body 3 according to the present embodiment, an inflow side unit having a forward path 30 is formed at the peak portion of the first single-sided cardboard 33 and the second single-sided cardboard 34, and the first single-sided cardboard 33 and the second single-sided cardboard 33 are formed. An outflow side unit having a return path 31 is formed in a valley portion of the corrugated paper 34, and the inflow side unit and the outflow side unit are alternately stacked.

  In the present embodiment, the planar space 15 in which the return paths 31 communicate with each other is formed by the spacers 14, but the thick spacers 14 used for forming the gaps can be dispensed with as shown in FIGS. 12 and 13. . FIG. 12 shows a cross-sectional view at the site of the clogging portion 12, and FIG. 13 shows a cross-sectional view at the site of the outflow opening 13.

  That is, the first single-sided corrugated paper 33 and the second single-sided corrugated paper 34 are aligned with the same paste so that the crests 10 and the troughs 11 face each other with a space therebetween. Pack and stack. At this time, the unit laminated body 35 is formed by crushing a part of the second single-sided corrugated paper 34 to form the outflow opening 13. A plurality of unit laminated bodies 33 are laminated in the same direction to form a laminated body 3. By doing so, a planar return path 31 having a corrugated cross section is formed between the first single-sided cardboard paper 33 and the second single-sided cardboard paper 34, so that the spacers 14 are unnecessary and all the return paths 31 are passed. Communication with the outflow opening 13 is possible.

  In order to prevent deformation of the forward path 30 or the backward path 31 due to a pressure difference between the reciprocating paths, it is desirable to reinforce the peak portion 10 using the spacer 14. In this case, the spacer 14 may be thin.

  Further, as shown in a schematic plan view in FIG. 14, if the unit laminated body 35 is formed by overlapping the first single-sided cardboard paper 33 and the second single-sided cardboard paper 34 so that the ridge lines of the mountain portions 10 intersect each other. Since the portions where the ridge lines of the mountain portions 10 overlap each other are reduced, the return paths 31 communicate with each other. Therefore, all the return paths 31 can be communicated with the outflow opening 13 without using the spacer 14. Even if the heights of the peaks 10 other than the peaks 10 on both the left and right sides are partially reduced, the planar space 15 can be formed without using the spacers 14.

  FIG. 15 shows a laminate used in the laminated internal heat exchange reactor of this example. Since this laminated body is the same as that of Example 2 except that the materials used in the precursor forming step are different, only different parts will be described.

In this embodiment, the plate comprises a flat plate 2 containing 70% by mass of activated carbon having a thickness of about 0.3 mm and a weight of about 110 g / m ² , and a corrugated plate 1 formed by corrugating the flat plate 2. Double-sided corrugated paper in which flat plates 2 are laminated on both sides of 1 is used.

  First, two double-sided corrugated papers are laminated with a paper adhesive so that the ridges of the crests 10 of the corrugated sheet 1 are parallel to each other. At this time, the upper cardboard 50 is laminated so that one end surface thereof is separated from the one end surface of the lower cardboard 51 and the other end surfaces are aligned. Then, the unit cardboard 52 having one peak 10 of the corrugated sheet 1 is laminated on one end of the lower cardboard 51 so that the ridge line of the peak 10 is orthogonal to the ridge line of the peak 10 of the lower cardboard 51. . Accordingly, a passage 53 that extends in the left-right direction is formed between one end surface of the upper cardboard 50 and the unit cardboard 52 and communicates with the peaks and valleys of the upper cardboard 50.

  A plurality of unit laminated bodies 54 thus configured were laminated so as to be in the same direction, and the flat plate 2 was laminated on the uppermost unit laminated body 54 to form the laminated precursor 5 of this example. Using this laminated precursor 5, the impregnation step, the carbonization step, the firing step and the melt impregnation step are carried out in the same manner as in Example 2 to form the silicon carbide laminate 5, and further in the same manner as in Example 1. An encapsulation process was performed to obtain a stacked internal heat exchange reactor of this example.

  According to the laminated internal heat exchange type reactor of the present embodiment, the exhaust gas flowing in from the valley portion opened at one end surface of the lower cardboard 51 flows into the communication space 44, and the mountain valley of the upper cardboard 50 from the communication space 44. Flows into the section and exits from the top and bottom of the upper corrugated paper 50, and then is guided by the unit corrugated paper 52 and flows into the passage 53. That is, the unit corrugated paper 52 functions as a restriction wall. Since the passage 53 communicates with the outlet 42 of the casing 4, the exhaust gas is guided by the passage 53 and flows out from the outlet 42. Therefore, in the laminated body 5 according to the present embodiment, an inflow side unit having the forward path 30 is formed in the peak portion of the lower cardboard 51, and an outflow side unit having the return path 31 is formed in the peak portion of the upper cardboard 50, Inflow side units and outflow side units are alternately stacked.

  For example, as shown in FIG. 16, the upper cardboard 50 may be partially cut out in the thickness direction for each unit laminate 54 to form a frame shape. Moreover, in the laminated body 5 of the present embodiment, the cross-sectional area of the passage 53 is smaller than the total opening area of the return path 31, so that the return path near the center is more outflowed than the return path near the side surface. Pressure loss may increase. In such a case, as shown in FIG. 17, if each unit laminated body 54 has a structure in which one end surface of the upper cardboard 50 facing the passage 53 is notched in a V shape, Since the exhaust gas flowing out from the return path 31 is guided along the V-shaped end face, the pressure loss can be reduced. It is also possible to form at least one of upper cardboard 50, lower cardboard 51, and unit cardboard 52 from single-sided cardboard.

  First, a single-sided corrugated paper similar to that in Example 2 is prepared, and using the same paste as in Example 1, half of the plurality of valleys from the left side are clogged at one end as shown in FIG. Part 60 was formed. Next, in the same manner as in Example 2, a spacer 14 that crosses the ridge line of the crest portion of the corrugated sheet 2 was stuck to form a first unit laminate 61. On the other hand, using the same paste as in Example 1, as shown in FIG. 19, half of the plurality of peaks and valleys from the right side was clogged at one end surface to form a clogged portion 62. Next, in the same manner as in Example 2, a spacer 14 that crosses the ridgeline of the peak portion of the corrugated sheet 2 was pasted to form a second unit laminate 63.

  As shown in FIG. 20, the first unit laminated body 61 and the second unit laminated body 63 are alternately laminated so that the clogging portions 60 and the clogging portions 62 are on the same end face side, and the uppermost unit lamination is obtained. A flat plate 2 was laminated on the body to form a lamination precursor 6 of this example. As shown in FIG. 20, a clogging portion 60 and a clogging portion 62 are formed in a staggered pattern on one end surface of the laminated precursor 6, and the rightmost cuffing portion 60 a and the cuffing portion 62 of the cuffing portion 60 The leftmost clogged portion 62a overlaps in the thickness direction in each layer. In addition, the clogging part does not exist in the other end surface.

  Using this laminated precursor 6, an impregnation step, a carbonization step, a firing step, and a melt impregnation step were performed in the same manner as in Example 2 to form a silicon carbide laminate 6. The enclosing process of housing this laminate in the casing 7 shown in FIG. 21 was performed to obtain a laminated internal heat exchange reactor of this example.

  The casing 7 shown in FIG. 21 has an inlet 70 and an outlet 71 on one end face, and a partition wall 72 that partitions the inlet 70 and outlet 71 is formed in an internal space continuous with the one end face. In the accommodated laminated body 6, the clogging portion 60 a and the clogging portion 62 a abut against the partition wall 72, and a communication space 73 is formed between the other end surface and the inner wall surface of the casing 7. In the laminated body 6, the opening of the return path 65 on the clogging portion 60 side (outflow block) communicates with the outflow port 71, and the opening of the outward path 64 on the clogging portion 62 side (inflow block) communicates with the inflow port 70. .

  That is, the exhaust gas flowing in from the inflow port 70 flows into the forward path 64 opened to the clogging portion 62 side (inflow block) on one end surface of the first unit laminate 61, and is a planar space formed by the forward path 64 and the spacer 14. It flows through 15 and flows into the communication space 73. The exhaust gas heated by the heater 100 flows into the opening other than the forward path 64 of the laminate 6 from the communication space 73 and flows through the planar space 15 toward the return path 65 opened to the clogging portion 60 side (outflow block). It flows out from the outlet 71. That is, the crests that open to the clogging portion 62 side (inflow block) of the laminate 6 form the inflow side unit, and the crests that open to the clogging portion 60 side (outflow block) form the outflow side unit. Side units and outflow side units are alternately stacked.

  Therefore, according to the laminated internal heat exchange type reactor of the present embodiment, since the counter flow occurs in the entire length of the laminated body 6, the heat exchange performance can be improved and the size can be further reduced. Also, using a large single-sided corrugated cardboard, as shown in FIG. 22, if a plurality of clogged portions and a plurality of non-clogged portions are alternately formed in the left-right direction for each sheet, a plurality of inflow blocks in the width direction and Since an outflow block can be formed, a large stacked internal heat exchange reactor can also be easily manufactured.

  Also in the case of the present embodiment, as in FIG. 16, if the peak portion 10 of the first unit laminate 61 and / or the second unit laminate 63 is partially cut away, the spacer 14 is not required. You can also.

  The laminated internal heat exchange reactor of the present invention can remarkably raise the temperature of a flowing gas or liquid inside thereof, and can be used in various fields such as an automobile exhaust gas purification device and the chemical industry.

1: Corrugated plate 2: Flat plate 3: Laminated precursor (laminate) 4: Casing
10: Yamabe 11: Tanibe
12: Clogging section 13: Outflow opening
14: Spacer 15: Planar space
30: Outbound 31: Return
41: Inlet 42: Outlet
44: Communication space 100: Heater (heating means)

Claims (10)

An inflow side in which a flat plate made of an organic porous material and a corrugated plate made of an organic porous material and having crests and troughs formed alternately are laminated and has a forward path at least between the crests of the corrugated plate and the flat plate Units, the flat plate and the corrugated plate are laminated, and at least an outflow side unit having a return path between the trough portion of the corrugated plate and the flat plate is laminated alternately, and the forward path is formed on one end surface. A precursor forming step of forming a laminated precursor having both of the return paths open and a regulating wall in front of the return path on the other end surface opposite to the one end face;
An impregnation step of impregnating the laminated precursor by impregnating the slurry containing the resin and silicon powder with the resin dissolved or the slurry containing the silicon carbide powder into the slurry;
Carbonization by heating the impregnated body in a vacuum or in a non-oxidizing atmosphere to carbonize the resin and pyrolyzing the laminated precursor to form a carbonaceous laminated precursor having substantially the same shape as the laminated precursor Process,
The carbonaceous laminate precursor is heated in a vacuum or in a non-oxidizing atmosphere to cause silicon and carbon to react to form a silicon carbide laminate having the same shape as the laminate precursor from the carbonaceous laminate precursor. A firing step for forming a body,
The laminated body obtained in a casing having an inlet and an outlet, such that the forward path opened to the other end surface communicates with the inlet and the fluid flowing through the return path is guided to the outlet by the restriction wall A communication space is formed between the one end surface of the laminate and the casing, and a communication space communicating with the forward path and the return path is formed in the one end surface, and the communication space and the vicinity of the communication space are formed. A method for producing a laminated internal heat exchange reactor, wherein a heating means is formed on at least one of the laminated bodies. An inflow side in which a flat plate made of an organic porous material and a corrugated plate made of an organic porous material and having crests and troughs formed alternately are laminated and has a forward path at least between the crests of the corrugated plate and the flat plate Units, the flat plate and the corrugated plate are laminated, and at least an outflow side unit having a return path between the trough portion of the corrugated plate and the flat plate is laminated alternately, and the forward path is formed on one end surface. A precursor forming step of forming a laminated precursor having a restriction wall in front of the return path on the other end face opposite to the one end face, the return path being open;
An impregnation step in which a solution containing a resin in a dissolved state or a slurry containing a silicon carbide powder in the solution is further impregnated into the laminated precursor to form an impregnated body;
Carbonization by heating the impregnated body in a vacuum or in a non-oxidizing atmosphere to carbonize the resin and pyrolyzing the laminated precursor to form a carbonaceous laminated precursor having substantially the same shape as the laminated precursor Process,
The carbonaceous laminated precursor is impregnated with molten silicon in a vacuum or in a non-oxidizing atmosphere, and silicon and carbon are reacted to form a silicon carbide-like material having substantially the same shape as the laminated precursor from the carbonaceous laminated precursor. Performing a melt impregnation step to form a laminate,
The laminated body obtained in a casing having an inlet and an outlet, such that the forward path opened to the other end surface communicates with the inlet and the fluid flowing through the return path is guided to the outlet by the restriction wall A communication space is formed between the one end face of the laminate and the casing, and a communication space communicating with the forward path and the return path is opened at the one end face, and the communication space and the laminate in the vicinity of the communication space are formed. A method for producing a laminated internal heat exchange reactor, wherein a heat generating means is formed on at least one of the above.   The method for producing a laminated internal heat exchange reactor according to claim 1 or 2, wherein the flat plate made of an organic porous material and the corrugated plate made of an organic porous material are corrugated paper.   The method for producing a laminated internal heat exchange reactor according to any one of claims 1 to 3, wherein the flat plate and the corrugated plate contain 50% by mass or more of carbon powder.   The method for producing a laminated internal heat exchange reactor according to claim 1, wherein a melt impregnation step of impregnating the silicon carbide laminate with molten silicon in a vacuum or in a non-oxidizing atmosphere is performed after the firing step. A flat plate made of silicon carbide-based ceramics and a corrugated plate made of silicon carbide-based ceramics and having ridges and valleys formed alternately are laminated by the manufacturing method according to claim 1. A laminated body having a large number of flow paths partitioned by the crests and valleys of the corrugated sheet and the flat plate, and a casing having an inlet and an outlet in which the laminated body is enclosed. A laminated internal heat exchange reactor,
The laminated body is formed by laminating the flat plate and the corrugated plate and at least the inflow side unit having a forward path between the peak portion of the corrugated plate and the flat plate, and the flat plate and the corrugated plate are laminated. Outflow side units having a return path between the valleys of the plate and the flat plate are alternately stacked,
The forward path and the return path are open at one end face of the laminate, and the other end face opposite to the one end face has a regulating wall in front of the return path, and the one end face of the laminate and the casing A communication space communicating with the forward path and the return path is formed between, and at least one of the stacked body in the vicinity of the communication space and in the vicinity of the communication space has a heating means,
The fluid flowing in from the inflow port flows into the communication space from the forward path opened at the other end surface, and receives the heat from the fluid flowing in the return path before flowing into the communication space in the forward path, and the temperature rises. The temperature further rises due to heating by the heat generating means when flowing into the return path from the communication space, and the temperature gradually decreases by passing heat to the forward path in the return path, and is guided by the regulation wall from the outlet. A laminated internal heat exchange reactor characterized by flowing out.   The inflow side unit includes the corrugated plate and a first flat plate that forms the forward path together with the peak portion of the corrugated plate, and the outflow side unit includes the corrugated plate and the corrugated plate common to the inflow side unit. It comprises a second flat plate that constitutes the return path together with a trough, and the gap between the trough and the second flat plate of the corrugated plate is blocked at the inflow side end of the forward path to form the restriction wall. The corrugated plate has an outflow opening that opens in a direction intersecting with the extending direction of the forward path and the backward path and communicates with the backward path, and a plurality of the trough portions are formed between the second flat plate and the trough portion. The stacked internal heat exchange reactor according to claim 6, wherein a planar space communicating with the outflow opening is formed.   The inflow side unit includes the corrugated plate and a pair of flat plates laminated on both the crest and trough sides of the corrugated plate, and the outflow side unit includes the corrugated plate and at least the crest side. The at least one corrugated plate of the outflow side unit is formed with an outflow opening that opens in a direction intersecting with the extending direction of the forward path and the backward path, and the outflow side unit has the trough portion. The laminated internal heat exchange type according to claim 6, wherein a guide flow path for guiding fluid to the outflow opening is formed in front of the opening on the outflow side of the return path, the side being laminated on the flat plate of the inflow side unit. Reactor. The laminated body is formed by alternately laminating the flat plate and the corrugated plate, and each corrugated plate has a plurality of adjacent crest portions and closed portions in which the trough portions are blocked, and a plurality of adjacent crest portions. Each of the one end face side, and the laminated body is alternately formed with the closed portions and the open portions in a checkered pattern in the stacking direction,
The inlet and the outlet of the casing are formed in parallel to each other, and an inflow block in which the closed portions and the open portions are alternately formed in the stacking direction communicates with the inflow port and is adjacent to the inflow block. The stacked internal heat exchange reactor according to claim 6, wherein an outflow block in which the open portions and the closed portions are alternately formed in the stacking direction communicates with the outflow port.   Between the crest and the flat plate of the corrugated plate, a planar space is formed that communicates with the plurality of troughs, communicates with the communication space, and communicates with the inlet or the outlet. The laminated internal heat exchange reactor according to claim 9.

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