JP2010106735A - Heating element, exhaust emission control device for internal combustion engine, and fuel reformer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a heating element easy to be manufactured, high in degree of freedom of molding, resistant to oxidation, which can be heated to a higher temperature range than metal and locally heated, small in size as a heating means and high in heat efficiency, and higher in strength than constructional material constituted only by silicon carbide, and to provide an exhaust emission control device for an internal combustion engine, and to provide a fuel reformer. <P>SOLUTION: The heating element 100 includes: a porous compound body 110 having a shaped skeleton made from material containing silicon carbide and silicon; and electrodes 120 disposed to the compound body to apply electric current to the compound body. In the heating element 100, the compound body generates heat when the electric current is applied between the electrodes, so that substances such as particles and fluid existing in or around the compound body are heated. The heating element is incorporated in the exhaust emission control device 300 for an internal combustion engine or the fuel reformer 400. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention belongs to the technical field of an exhaust gas purification device for an internal combustion engine and a fuel reforming device, and relates to these devices improved by a heating element.

  As an exhaust purification device that collects particulate matter (also referred to as particulate matter) contained in exhaust gas of an internal combustion engine, a particulate filter that collects particulate matter contained in exhaust gas is provided in the exhaust passage. Is known (see, for example, Patent Document 1 and Patent Document 2). In such an exhaust purification device, when the particulate filter is clogged, particulate matter collected by a burner or an electric heater is oxidized and burned to regenerate the particulate filter.

  Non-Patent Document 3 discloses various catalysts provided in an exhaust gas purification apparatus for an internal combustion engine as an exhaust gas purification catalyst. Among these, three-way catalysts, NOx trap catalysts (NOx occlusion reduction type catalysts), and HC trap catalysts are disclosed as gasoline engine catalysts, and DOC (diesel oxidation catalyst), PM post-treatment as diesel engine catalysts. Catalysts, selective reduction catalysts (SCR catalysts), NOx trap catalysts (NAC) and the like are disclosed.

  Patent Document 4 discloses a fuel reformer that can stably supply fuel gas. The fuel reformer includes a cylindrical container filled with a reforming catalyst, a heater disposed so as to surround a side portion of the container, an inlet temperature sensor on the inlet side of the container, And a controller that monitors the deterioration state of the reforming catalyst based on the temperature detected by the inlet temperature sensor.

JP-A-2-185611 JP-A-10-131740 Hideaki Muraki, “Exhaust Gas Treatment System: Catalyst”, Automotive Technology, Vol. 59, no. 2,2005, P65-69 JP 2007-26927 A Japanese Patent No. 3699992 JP 2007-44674 A

  In order to regenerate the clogged particulate filter, regenerating means such as the burner or electric heater is required, and the structure becomes complicated. There is also a demand to reduce the energy consumed by such reproducing means.

  In order for the catalyst to exhibit activity, the catalyst needs to be heated to a predetermined temperature. However, when it is difficult to provide a means for heating the catalyst, for example, in an internal combustion engine for automobiles, it is necessary to wait for the catalyst to be heated to a predetermined temperature by the exhaust gas, until a sufficient exhaust purification function is obtained. It takes a certain amount of time. Moreover, sufficient activity of the catalyst cannot be obtained in the operation region where the temperature of the exhaust gas is low.

  In the fuel reformer, the heater for heating the reforming catalyst is disposed so as to surround the side portion of the container. Therefore, there is a problem that the fuel reformer is enlarged and bulky. In addition, since the reforming catalyst inside the container is indirectly heated by heat conduction or the like by the heater outside the container, the thermal efficiency is not good.

One of the inventors of the present invention comprises molten carbon and silicon carbide with good wettability, and at the same time, the carbonized porous structure sintered body in which open pores resulting from the volume reduction reaction are melt-impregnated with silicon, When the carbonized porous structure sintered body is one sponge-like porous structure selected from resin, rubber, and paper forming a tangible skeleton, the atomic ratio of silicon to carbon is Si / C = 0.05. The amount of the mixture is set so as to be ˜4, and the slurry containing the resin as the carbon source and the silicon powder is impregnated into the tangible skeleton of the sponge-like porous structure, and then the slurry is squeezed. By impregnating the sponge-like porous structure within a range in which the continuous pores are not blocked, the resins are fired and carbonized to form a carbonized porous structure. Reactive sintering of silicon on the body A silicon carbide-based heat-resistant ultralight porous structural material formed by melt impregnation with silicon, and the silicon carbide-based heat-resistant ultralight porous structural material is a sponge-like porous structure A silicon carbide-based heat-resistant ultralight porous structure having the same structure as the continuous pores of No. 1, having a pore diameter of 500 μm to 2 mm, an open porosity of 95 to 97%, and a density of 0.06 to 0.1 g / cm ³ Invented materials and the like (see Patent Document 5). According to the present invention, it is possible to easily manufacture a silicon carbide-based heat-resistant ultralight porous structure material that retains the shape of the first porous structure, and therefore easily manufacture even a complicated shape. Can do. Furthermore, since this structure material is filled with silicon between the silicon carbide particles, the structure material has higher strength than that constituted only by silicon carbide.

  Furthermore, this inventor is used for purification of pollutant removal, and a sponge-like carbonized porous structure sintered impregnated with a slurry containing resins and silicon powder within a range where continuous pores are not blocked. This sponge-like carbonized porous structure sintered body is made into a plurality of structures having different densities, then carbonized at 900 ° C. to 1350 ° C., reacted and sintered at 1350 ° C. or higher, and 1300 ° C. to 1800 Invented a porous structure filter manufactured by melt impregnation of silicon at 0 ° C. (see Patent Document 6). This porous structure filter is similar to the above-mentioned silicon carbide heat-resistant ultralight porous structure material. However, for example, one three-dimensional fine cell structure filter of the sponge-like porous structure is made into a flexible structure, and the other Compared to the former three-dimensional fine cell structure filter, the three-dimensional fine cell structure filter has a higher density and is harder, which makes it easier to handle and results in two different filter structures with different sizes. It can be captured efficiently, thereby increasing the purification efficiency and increasing the work efficiency.

  The present invention covers a wide range of porous composites having a tangible skeleton containing silicon carbide and silicon, including the above-mentioned silicon carbide heat-resistant ultralight porous structure material and sponge-like carbonized porous structure sintered body. As mentioned above, it was made paying attention to generating heat when energized. The object of the present invention is to provide an electrode on a porous composite having a tangible skeleton containing silicon carbide and silicon, so that it is easy to manufacture, has a high degree of freedom in molding, and is resistant to oxidation. An object of the present invention is to provide a heating element that can be heated to a higher temperature range than metal, can be locally heated, is small in size and has high thermal efficiency as a heating means, and has higher strength than a structural material composed only of silicon carbide. A further object of the present invention is to use the above-mentioned heating element, without requiring a separate regeneration means, having a simple structure, excellent energy saving, and continuously removing particulate matter from exhaust gas. An object of the present invention is to provide an exhaust emission control device for an internal combustion engine. Furthermore, a further object of the present invention is to exhaust the internal combustion engine whose exhaust purification function is improved by activating an exhaust purification catalyst provided on the downstream side with the heat obtained by the heating element that performs this exhaust purification. It is to provide a purification device. A further object of the present invention is to improve the exhaust purification function by suppressing or preventing clogging of the particulate filter provided on the downstream side with the heat obtained by the heating element that performs the exhaust purification. An object of the present invention is to provide an exhaust emission control device for an engine. Furthermore, a further object of the present invention is to provide a fuel reformer that is small and has high thermal efficiency by using the above-mentioned heating element carrying a catalyst as a reforming catalyst.

In order to achieve the above object, a first heating element of the present invention includes a porous composite having a tangible skeleton composed of a material containing silicon carbide and silicon, and
An electrode provided on the composite so that the composite can be energized,
When an electric current is passed between the electrodes, the complex generates heat, and a substance such as particles or fluid existing inside or around the complex is heated.

  Since the composite includes silicon carbide and silicon and has conductivity, when a current is passed between the electrodes of the first heating element, a current flows through the skeleton of the composite and Joule heat is generated. Then, a substance such as particles or fluid existing inside the complex, that is, in the pores formed between the skeletons or around the complex is heated. In that case, since the composite includes silicon carbide and silicon, the composite is resistant to oxidation and can be heated to a higher temperature range than the metal. Further, as compared with the case where a substance such as particles or fluid inside the container or passage component is heated from the outside of the container or passage component, the composite is disposed while the substance floats or flows, Since the substance is heated by heat conduction or radiation from a short distance, local heating can be performed, the heating means is downsized, and the thermal efficiency is high. Furthermore, since the silicon carbide fills between the silicon carbide particles, the composite has higher strength than a structural material composed only of silicon carbide, and has improved vibration resistance, for example, and is suitable for mounting on a vehicle.

  The composite in the first heating element includes a resin or rubber sponge-like porous structure having a tangible skeleton, a slurry containing a resin as a carbon source and silicon powder, or an aggregate in the slurry. The slurry is impregnated to such an extent that the continuous pores of the sponge-like porous structure are not blocked, and the resins are fired and carbonized to form a carbonized porous structure. It may be composed of a silicon carbide-based heat-resistant ultralight porous structure material formed by reacting and sintering carbon of the porous structure and silicon powder of the slurry, and then melt-impregnating silicon.

  Thus, when the composite in the first heating element is composed of the silicon carbide heat-resistant ultralight porous structure material, the tangible skeleton of the foamed resin is impregnated with resins and silicon powder, Porous silicon carbide and residual carbon parts are produced by the silicon carbide production reaction accompanied by volume reduction with silicon powder and carbon from the sponge. When this porous skeleton part is melt-impregnated with silicon, silicon carbide type Even if the composite made of a heat-resistant ultralight porous structural material has a complicated shape, it is easily produced while maintaining the shape of the tangible skeleton of the sponge. When the electrode is provided on the composite made of the silicon carbide-based heat resistant ultralight porous structure material thus obtained, the first heating element can be obtained. Therefore, manufacture of this 1st heat generating body is easy, and the freedom degree of shaping | molding is high.

  In the second heating element of the present invention, in the first heating element, the composite carries a catalyst.

  In this way, in addition to obtaining the same action as that obtained with the first heating element, when the substance causes a chemical reaction inside or around the complex, the reaction is a catalyst. Promoted by. In that case, when the complex generates heat, the catalyst exhibits activity, and the chemical reaction by the catalyst is further promoted.

In the exhaust gas purification apparatus for a first internal combustion engine of the present invention, an internal passage constituting at least a part of an exhaust passage having one end connected to the combustion chamber of the internal combustion engine and the other end opened to the atmosphere is provided inside. An exhaust passage component;
The composite is housed in an internal passage of the exhaust passage constituting member, and the electrode includes the first or second heating element led out to the outside of the exhaust passage constituting member.

Since the composite contains silicon carbide and silicon and has conductivity, when an electric current is passed between the electrodes of the first or second heating element, an electric current flows through the skeleton of the composite and Joule heat is generated. . When the exhaust gas passes through the composite of the first or second heating element, the soot that occupies most of the particulate matter contained in the exhaust gas is composed of silicon carbide and silicon. Adsorbed on the above skeleton. The soot receives heat from the skeleton and is decomposed into finer particles by HC in the exhaust gas. The fine particles receive heat from the skeleton and oxidize to become CO ₂ or the like. In the second heating element, this oxidation reaction is promoted by the catalyst. Therefore, the particulate matter contained in the exhaust gas is reduced by the first or second heating element. In addition, combustible components such as unburned fuel in the exhaust gas receive heat from the skeleton, and oxidation and combustion are promoted. Therefore, there is no need for a separate regeneration means for regenerating from clogging, the structure is simple, the energy is saved, and particulate matter can be continuously removed from the exhaust gas.

  According to a second internal combustion engine exhaust gas purification apparatus of the present invention, in the first internal combustion engine exhaust gas purification apparatus, the first or second heating element in the internal passage of the exhaust passage constituent member is more complex than the composite body. An exhaust gas purification catalyst is provided on the exhaust downstream side.

  By so doing, the temperature of the exhaust gas rises due to oxidation of fine particles, oxidation of combustible components, combustion, etc. in the first or second heating element, and this high-temperature exhaust gas flows into the exhaust gas purification catalyst. Therefore, the exhaust gas purification catalyst is activated and exhaust gas purification is promoted by an oxidation reaction or the like.

  According to a third aspect of the present invention, there is provided an exhaust gas purification apparatus for an internal combustion engine according to the first aspect of the present invention, wherein the exhaust gas purification apparatus for the first internal combustion engine is more complex than the complex of the first or second heating element in the internal passage of the exhaust passage component. A particulate filter that collects particulate matter contained in the exhaust gas is provided on the exhaust downstream side.

By so doing, the temperature of the exhaust gas rises due to oxidation of fine particles in the first or second heating element, oxidation of the combustible component, combustion, etc., and this high-temperature exhaust gas is passed to the particulate filter. As it flows in, soot that occupies most of the particulate matter collected in the particulate filter receives heat from the high-temperature exhaust gas, and is decomposed into finer particles by HC in the exhaust gas. It becomes like CO ₂ oxidized by receiving heat from the. Further, since the first or second heating element reduces the particulate matter contained in the exhaust gas, the progress of clogging of the particulate filter becomes slow or clogging is prevented.

  According to a fourth internal combustion engine exhaust gas purification apparatus of the present invention, in the second internal combustion engine exhaust gas purification apparatus, the exhaust gas is disposed on the exhaust downstream side of the exhaust gas purification catalyst in the internal passage of the exhaust passage constituent member. A particulate filter for collecting the particulate matter contained therein is provided.

In this way, the exhaust gas whose temperature has risen due to the oxidation reaction or the like in the first or second heating element further rises in temperature due to the oxidation reaction or the like in the exhaust gas purification catalyst, and this high-temperature exhaust gas becomes the particulate filter. The soot occupying most of the particulate matter collected by the particulate filter receives heat from the high-temperature exhaust gas and is decomposed into finer particles by the HC in the exhaust gas. It receives heat from the skeleton and oxidizes to CO ₂ . Further, since the first or second heating element reduces the particulate matter contained in the exhaust gas, the progress of clogging of the particulate filter becomes slow or clogging is prevented.

  The fuel reformer of the present invention includes a container having an inlet into which a mixture containing a raw fuel mainly composed of hydrocarbons and an oxygen-containing compound is introduced, and an outlet from which a combustible reformed gas is taken out. The composite is housed inside the container, and the second heating element is provided with the electrode led out to the outside of the container.

  Since the composite contains silicon carbide and silicon and has conductivity, when an electric current is passed between the electrodes of the second heating element, an electric current flows through the skeleton of the composite and Joule heat is generated. The mixture that has entered the container from the inlet of the container undergoes a predetermined reforming reaction by the action of the catalyst heated by the skeleton, and combustible reformed fuel is generated. In that case, the mixture inside the container is not heated by a heater provided so as to surround the side portion of the container as in the conventional case, but from the heat conduction or short distance by the skeleton of the composite. Since the heating is performed by this radiation, the rise of the heating is good, the thermal efficiency is high, and the entire apparatus is downsized.

The exhaust gas purification apparatus for an internal combustion engine of the fifth aspect of the present invention is provided with an internal passage that constitutes at least a part of an exhaust passage having one end connected to the combustion chamber of the internal combustion engine and the other end open to the atmosphere. An exhaust passage component;
A particulate filter accommodated in the internal passage of the exhaust passage constituent member and collecting particulate matter contained in the exhaust gas;
Comprising the fuel reformer of the present invention described above,
The outlet of the container of the fuel reformer is connected to the internal passage of the exhaust passage component, and the combustible reformed fuel is supplied to the particulate filter.

  When the reformed fuel generated by the fuel reformer is supplied to the particulate filter, the particulate matter collected by the particulate filter is promoted to oxidize and burn, and the particulate filter is clogged. Progression is slowed or clogging is prevented.

  The first heating element of the present invention includes a composite having a tangible skeleton made of a material containing silicon carbide and silicon, and an electrode. When a current is passed between the electrodes, the composite generates heat, Since it is configured to heat particles, fluids, and other substances present in or around the composite, it is easy to manufacture, has a high degree of freedom in forming, is resistant to oxidation, can be heated to a higher temperature range than metal, and is locally It can be heated, is small as a heating means, has high thermal efficiency, and has higher strength than a structural material composed only of silicon carbide. By using the first heating element, the first to fourth internal combustion engine exhaust purification apparatuses of the present invention are established.

  In the second heating element of the present invention, since the catalyst is supported on the composite, the same effect as that obtained by the first heating element can be obtained. When a chemical reaction occurs inside or around, the chemical reaction can be further promoted. By using this second heating element, the fuel reforming apparatus of the present invention or the exhaust purification apparatus of the fifth internal combustion engine is established.

  In the exhaust gas purification apparatus for a first internal combustion engine of the present invention, the composite of the first or second heating element is provided in the exhaust passage constituting member, so that the exhaust gas is exhausted by the composite of the first or second heating element. Particulate matter, unburned fuel, etc. contained in the gas can be reduced. Therefore, it is possible to provide an exhaust emission control device for an internal combustion engine that does not require a separate regeneration means, has a simple structure, is excellent in energy saving, and can continuously remove particulate matter from exhaust gas.

  According to a second internal combustion engine exhaust gas purification apparatus of the present invention, an exhaust gas purification catalyst is provided on the exhaust downstream side of the first or second heating element composite in the first internal combustion engine exhaust gas purification apparatus. Therefore, in addition to obtaining the effect of the exhaust gas purification device of the first internal combustion engine, the exhaust gas purification can be promoted by activating the exhaust gas purification catalyst.

  In the exhaust gas purification apparatus for a third internal combustion engine of the present invention, in the exhaust gas purification apparatus for the first internal combustion engine, the particulate filter is provided on the exhaust downstream side of the composite body of the first or second heating element. In addition to obtaining the effect of the exhaust gas purification apparatus for the first internal combustion engine, clogging of the particulate filter can be suppressed or prevented.

  In the exhaust gas purification apparatus for a fourth internal combustion engine of the present invention, since the particulate filter is provided on the exhaust downstream side of the exhaust gas purification catalyst in the exhaust gas purification apparatus for the second internal combustion engine, the second internal combustion engine is provided. In addition to obtaining the effect of the exhaust gas purification device, clogging of the particulate filter can be further suppressed or prevented.

  The fuel reformer of the present invention includes a container having an inlet into which a mixture containing a raw fuel mainly composed of hydrocarbons and an oxygen-containing compound is introduced, and an outlet from which a combustible reformed fuel is taken out. Since the composite of the two heating elements is accommodated, the rise of heating can be improved, the thermal efficiency can be improved, and the entire apparatus can be downsized.

  According to a fifth internal combustion engine exhaust gas purification apparatus of the present invention, a particulate filter is provided in an exhaust passage constituting member, and the combustible reformed fuel from the fuel reforming apparatus of the present invention is supplied to the particulate filter. Therefore, clogging of the particulate filter can be suppressed or prevented.

  FIG. 1 shows an embodiment of the first heating element of the present invention. The first heating element 100 of this embodiment includes a porous composite 110 having a tangible skeleton made of a material containing silicon carbide and silicon, and the composite 110 so that the composite 110 can be energized. And an electrode 120 provided. In the first heating element 100, when a current is passed between the electrodes 120, the complex 110 generates heat, and heats substances such as particles and fluid existing in or around the complex 110. It is configured. The material constituting the tangible skeleton may be a material containing silicon carbide and silicon, but may be a material composed only of silicon carbide and silicon, or a material mainly composed of silicon carbide and silicon. Also good. In the case of this embodiment, the composite 110 includes a resin-like sponge-like porous structure having a tangible skeleton and a slurry containing a resin and carbon powder as a carbon source. After impregnation to such an extent that the pores are not blocked, the resins are fired and carbonized to form a carbonized porous structure, and the carbon of the carbonized porous structure reacts with the silicon powder of the slurry. It is composed of a silicon carbide-based heat resistant ultralight porous structure formed by sintering and further impregnating silicon. The resin constituting the sponge-like porous structure of this embodiment is a urethane foam resin, but the sponge-like porous structure may be constituted by other forms or other types of resins, Instead, rubber may be used. The resin contained in the slurry of this embodiment is a phenol resin, but the slurry may be composed of other types of resin, or the resin may be composed of a carbon compound other than the resin. Or a mixture thereof. The slurry may contain a resin as a carbon source and silicon powder, and further may be a slurry in which an aggregate is further added. In this case, the strength of the skeleton is increased by the aggregate. This aggregate includes silicon carbide, silicon nitride, zirconia, zircon, alumina, silica, mullite, molybdenum disilicide, boron carbide, boron, etc., which are added as powders, but added in other forms May be. Of these, silicon carbide is preferable because it has good wettability with molten silicon. May also function as an antioxidant. The resin may be a natural resin or a synthetic resin.

The silicon carbide-based heat-resistant ultralight porous structure material of the above-mentioned embodiment includes carbonized porous structure sintered material that contains molten silicon and silicon carbide with good wettability, and at the same time, generated open pores due to a volume reduction reaction. The body is melt impregnated with silicon. And this silicon carbide heat-resistant ultralight porous structure material has the above-mentioned carbonized porous structure sintered body in which a foamed resin sponge-like porous structure forming a tangible skeleton has an atomic ratio of silicon to carbon. The mixing amount is set so that the ratio of Si / C is 0.05 to 4, and the tangible skeleton of the sponge-like porous structure is impregnated with a slurry containing a resin as a carbon source and silicon powder. After squeezing the slurry after impregnation to such an extent that the continuous pores of the sponge-like porous structure are not blocked, the resins are baked and carbonized to make a carbonized porous structure, This is a silicon carbide-based heat-resistant ultralight porous structure material formed by reacting and sintering carbon of this carbonized porous structure and silicon powder in the slurry, and further melt-impregnating silicon. The silicon carbide-based heat resistant ultralight porous structure has the same structure as the continuous pores of the sponge-like porous structure, and has a pore diameter of 500 μm to 2 mm, an open porosity of 95 to 97%, and a density of 0.06 to 0.00. 1 g / cm ³ .

That is, this silicon carbide heat-resistant ultralight porous structure material is tangible as a sponge-like porous structure of the silicon carbide heat-resistant ultralight porous structure material according to claim 1 of Japanese Patent No. 36999992. A sponge-like porous structure of resin or rubber having a skeleton is used. The ratio of the atomic ratio of silicon to carbon described above is not limited to Si / C = 0.05 to 4 and may be less than Si / C = 0.05 or more than 4. The method of impregnating the above-described slurry to such an extent that the continuous pores of the sponge-like porous structure are not blocked is a method of squeezing the slurry after impregnating the slurry with the tangible skeleton of the sponge-like porous structure. It is not limitedly interpreted, and other methods may be used. For example, the tangible skeleton of the sponge-like porous structure may be simply impregnated with the slurry. The pore diameter of the silicon carbide-based heat-resistant ultralight porous structural material described above is not limited to 500 μm to 2 mm, and may be less than 500 μm or may exceed 2 mm. The open porosity of the silicon carbide-based heat-resistant ultralight porous structural material described above is not limited to 95 to 97%, and may be less than 95% or more than 97%. The density of the silicon carbide-based refractory super lightweight porous structure material described above is not restricted interpreted 0.06~0.1g / cm ^3, even less than 0.06g / cm ^3, 0.1g / Cm ³ may be exceeded.

  Citing with a slight supplement from Japanese Patent No. 36999992, the inventor of the silicon carbide-based heat-resistant ultralight porous structure material of the same patent invented the silicon melt impregnation method in the silicon melt impregnation method. Is added from outside the system, resulting in a volume increase reaction, and the dense amorphous carbon-only matrix resulting from the carbonization of the phenol resin hardly reacts with the molten silicon, but a mixture of silicon powder and carbon carbonized from the phenol resin. Found that silicon carbide with good wettability with molten silicon produced by reactive sintering (volume reduction reaction) and porous amorphous carbon matrix can easily penetrate and react with molten silicon. (Japanese Patent Laid-Open No. 2000-313676).

The invention of Japanese Patent No. 3699992 was made based on such knowledge, overcomes various drawbacks in the previous silicon carbide-based heat resistant lightweight porous material and its production method, and has a tangible skeleton of the porous structure. The silicon carbide-based heat-resistant superficially uniform pores with an open pore ratio of 80% or more and a density of 0.3 g / cm ³ or less, which can be easily manufactured even in complicated shapes by keeping the shape as it is molded A lightweight porous structural material and a method for producing the same.

  That is, the inventor of the patent No. 3699992 has conducted extensive research on a silicon carbide-based heat-resistant ultralight porous structure material. As a result, the tangible skeleton of a porous structure such as a sponge is impregnated with silicon powder and resin. The porous silicon carbide and the residual carbon part are generated by the silicon carbide generation reaction accompanied by the volume reduction with the silicon powder and the carbon from the structure, and the porous skeleton part is melt impregnated with silicon. It has been found that a silicon carbide-based heat-resistant ultralight porous structure material can be easily produced while maintaining the shape of the tangible skeleton of the porous structure, even if it has a complicated shape. The invention has been completed.

The silicon carbide heat-resistant ultralight porous structure material of the invention of Patent No. 3699992 completed as described above contains molten silicon and silicon carbide with good wettability, and at the same time, open pores due to volume reduction reaction were generated. A carbonized porous structure sintered body is melt-impregnated with silicon,
When the carbonized porous structure sintered body is one sponge-like porous structure selected from resin, rubber, and paper forming a tangible skeleton, the atomic ratio of silicon to carbon is Si / C = 0.05. The amount of the mixture is set so as to be ˜4, and the slurry containing the resin as the carbon source and the silicon powder is impregnated into the tangible skeleton of the sponge-like porous structure, and then the slurry is squeezed. By impregnating the sponge-like porous structure to such an extent that the continuous pores are not blocked, the resins are fired and carbonized to form a carbonized porous structure. A silicon carbide-based heat-resistant ultralight porous structure material that is formed by reaction-sintering silicon and then melting and impregnating silicon.
The silicon carbide-based heat resistant ultralight porous structure has the same structure as the continuous pores of the sponge-like porous structure, and has a pore diameter of 500 μm to 2 mm, an open porosity of 95 to 97%, and a density of 0.06 to 0.00. 1 g / cm ³ .
In addition, the method for producing a silicon carbide-based heat-resistant ultralight porous structure material according to the invention of Japanese Patent No. 3699992 includes a carbon source on a tangible skeleton of one sponge-like porous structure selected from resin, rubber, and paper. A carbonized porous structure obtained by impregnating a tangible skeleton of the sponge-like porous structure with a slurry containing the above resins and silicon powder and then carbonizing at 900 to 1350 ° C. in a vacuum or an inert atmosphere Make
This carbonized porous structure is subjected to reactive sintering in a vacuum or an inert atmosphere at a temperature of 1350 ° C. or higher to produce molten silicon and silicon carbide with good wettability, and at the same time due to a volume reduction reaction. The silicon carbide system is characterized in that the open pores are generated, and the silicon carbide and the open pores are melt impregnated with silicon at a temperature of 1300 to 1800 ° C. in a vacuum or in an inert atmosphere. In the method of manufacturing a heat-resistant ultralight porous structure material,
After impregnating the slurry containing the resin and silicon powder into the tangible skeleton of the sponge-like porous structure, the slurry is squeezed to close the continuous pores of the sponge-like porous structure. It is characterized by impregnation to the extent that it does not occur.
In the above method, the reactive sintering treatment of silicon and carbon and the melt impregnation of silicon may be performed by the same heat treatment, or all the heat treatments including carbonization may be performed by the same heat treatment. According to such a method of the invention of Japanese Patent No. 3699992, even a large structure having a complicated shape can be easily manufactured, and the processing of the porous structure can be easily performed after carbonization.

  In the above method, the material constituting the tangible skeleton of the sponge-like porous structure to be used is preferably a porous structure capable of holding slurry, and the material constituting the porous structure is made of resin or rubber. Sponges or sponge-shaped plastics or paper are suitable.

In addition, as a resin as a carbon source to be impregnated into the tangible skeleton of the porous structure in the above method, a phenol resin, a furan resin, an organometallic polymer such as polycarbosilane, or sucrose is preferable. One of these resins may be used, or two or more thereof may be used in combination. Furthermore, carbon powder, graphite powder, carbon black is added as an additive, or silicon carbide, silicon nitride, zirconia, zircon, alumina, silica, mullite, molybdenum disilicide, carbonized as an aggregate or antioxidant. Boron, boron powder, or the like may be added.
The silicon powder contained in the slurry used in the above method is at least one silicon alloy selected from magnesium, aluminum, titanium, chromium, manganese, iron, cobalt, nickel, copper, zinc, zirconium, niobium, molybdenum, or tungsten. Or a mixture of these and silicon powder. Silicon for melt impregnation may be pure silicon metal, magnesium, aluminum, titanium, chromium, manganese, iron, cobalt, nickel, copper, zinc, zirconium, niobium, molybdenum, tungsten, or other silicon alloys, or A mixture of silicon may be used.

  According to the silicon carbide-based heat-resistant ultralight porous structure material of the invention of this patent No. 3699992 and the manufacturing method thereof, the tangible skeleton of the sponge-like porous structure contains a resin serving as a carbon source and silicon powder. After impregnating the slurry so that the continuous pores of the porous structure are not blocked, molten silicon, silicon carbide with good wettability and open pores are generated using reactive sintering, and silicon is added to this part. Silicon carbide-based heat-resistant lightweight porous composites that retain the shape of the original porous structure by melt impregnation can be easily manufactured, so even complex shapes can be manufactured easily. It can be used for many applications such as high-temperature filters, high-temperature structural members, heat insulating materials, molten metal filter media, burner plates, heater materials, and high-temperature silencers.

Next, preferred embodiments of the silicon carbide-based heat-resistant ultralight porous structure material of the invention of Japanese Patent No. 36999992 and a method for producing the same will be described.
In the method of the invention of Japanese Patent No. 3699992, first, a slurry in which a phenol resin as a dissolved carbon source and silicon powder are mixed is sufficiently applied to the tangible skeleton of the sponge-like porous structure, or the slurry is porous. After soaking and impregnating the porous structure, the slurry is squeezed to such an extent that the continuous pores are not blocked and dried. This drying is desirably performed at about 70 ° C. for about 12 hours.

As described above, a sponge made of resin or rubber, sponge-shaped plastics, paper, or the like can be used for the porous structure.
In addition, as the resin impregnated into the tangible skeleton of the porous structure, at least one selected from phenol resin, furan resin, organometallic polymer or sucrose can be used, and if necessary, the above additives and the like Can be added.
Furthermore, fine powder is suitable as the silicon powder used for producing silicon carbide, and fine powder having an average particle size of 30 μm or less is particularly suitable. What has a large particle diameter should just pulverize and pulverize with a ball mill etc.

  Next, the porous structure thus obtained is carbonized at a temperature of about 900 to 1350 ° C. under an inert atmosphere such as vacuum or argon. In the carbonized composite obtained in this manner, the porous structure of the sponge is lost by thermal decomposition, and the skeleton part is in a state where the carbon part obtained by carbonization of the phenol resin and the silicon powder are mixed, and the skeleton part The shape of is the same as the original shape. Moreover, the carbonized porous structure has a processable strength.

  This carbonized porous structure is fired at a temperature of 1350 ° C. or higher under an inert atmosphere such as vacuum or argon, and carbon and silicon are reacted to form molten silicon and porous silicon carbide having good wettability. It is formed on the tangible skeleton part of the structure. At the same time, since this reaction is a volume reduction reaction, open pores resulting from the volume reduction reaction are generated. As a result, a porous structure sintered body in which the matrix portion is formed of silicon carbide having pores and residual carbon is obtained.

Next, this porous structure sintered body is heated to a temperature of about 1300 to 1800 ° C. in a vacuum or in an inert atmosphere, and the porous silicon carbide and carbon portions on the skeleton are melt-impregnated with silicon. A silicon carbide-based heat-resistant ultralight porous material is obtained.
Note that the mixing ratio of silicon powder and carbon from the resin used in the method of the invention of Japanese Patent No. 3699992 is selected so that the atomic ratio of silicon to carbon is Si / C = 0.05-4. desirable.

[Examples of silicon carbide-based heat resistant ultralight porous structure]
Next, the method of the invention of Japanese Patent No. 3699992 will be described in more detail by way of examples, but the invention of Japanese Patent No. 3699992 is not limited in any way by these examples.

[Example 1]
The mixing ratio of the phenol resin and the silicon powder is set to a ratio of 5: 3 of carbon and silicon by carbonization of the phenol resin, and the slurry is prepared by dissolving the phenol resin with ethyl alcohol. In order to reduce the particle size, ball mill mixing was performed for 1 day, and they were impregnated into a polyurethane sponge having pores of 500 to 600 μm. After the slurry liquid was squeezed to such an extent that the continuous pores were not blocked, it was dried. At this time, the sponge expanded about 20% in the axial direction.
Next, this sponge was carbonized by firing at 1000 ° C. for 1 hour in an argon atmosphere. The obtained carbonaceous porous body was simultaneously subjected to reactive sintering and silicon melt impregnation in vacuum at 1450 ° C. for 1 hour to obtain a sponge-shaped silicon carbide heat resistant ultralight porous composite material. The sponge contracted during carbonization, and was slightly smaller with about 12% contraction in the axial direction than before carbonization.
The obtained silicon carbide-based heat-resistant ultralight porous structure has the same structure as a sponge, has a pore diameter of 500 to 600 μm, an open porosity of 97%, and a density of 0.07 g / cm ³ , and no collapsed pores are found. It was.

[Example 2]
The mixing ratio of the phenol resin and the silicon powder is set to a ratio of 5: 3 of carbon and silicon by carbonization of the phenol resin, and the slurry is prepared by dissolving the phenol resin with ethyl alcohol. In order to reduce the particle size, ball mill mixing was performed for one day, and they were impregnated into a polyurethane sponge having pores of about 1 mm, and the slurry liquid was squeezed to such an extent that the continuous pores were not covered, and then dried. At this time, the sponge expanded about 20% in the axial direction.
Next, this sponge was carbonized by firing at 1000 ° C. for 1 hour in an argon atmosphere. The obtained carbonaceous porous body was simultaneously subjected to reactive sintering and silicon melt impregnation in vacuum at 1450 ° C. for 1 hour to obtain a sponge-shaped silicon carbide heat resistant ultralight porous composite material. The sponge contracted during carbonization, and was slightly smaller with about 12% contraction in the axial direction than before carbonization.
The obtained silicon carbide heat-resistant ultralight porous structural material had the same structure as the sponge, and had a pore diameter of about 1 mm, an open porosity of 97%, and a density of 0.06 g / cm ³ .

[Example 3]
The mixing ratio of the phenol resin and the silicon powder is set to a ratio of 5: 3 of carbon and silicon by carbonization of the phenol resin, and the slurry is prepared by dissolving the phenol resin with ethyl alcohol. In order to reduce the particle size, the mixture was ball milled for 1 day, impregnated in a polyurethane sponge having pores of about 1.5 to 2 mm, squeezed to such an extent that the slurry liquid did not cover the continuous pores, and then dried. It was. In this case, there was almost no expansion of the sponge.
Next, this sponge was carbonized by firing at 1000 ° C. for 1 hour in an argon atmosphere. The obtained carbonaceous porous body was simultaneously subjected to reactive sintering and silicon melt impregnation in vacuum at 1450 ° C. for 1 hour to obtain a sponge-shaped silicon carbide heat-resistant ultralight porous composite material. The sponge shrunk during carbonization and eventually became slightly smaller with about 12% shrinkage in the axial direction.
The obtained silicon carbide heat-resistant ultralight porous structural material had the same structure as the sponge, had a pore diameter of 1.5 to 2 mm, an open porosity of 95%, and a density of 0.1 g / cm ³ .

[Comparative Example 1]
When the sponge used in Example 1 was baked at 1000 ° C. for 1 hour in an argon atmosphere, there was no trace.

[Comparative Example 2]
A phenol resin was dissolved in ethyl alcohol to prepare a slurry, impregnated into a polyurethane sponge having 500 to 600 μm pores, and squeezed to such an extent that the slurry liquid did not cover the continuous pores, and then dried.
Next, this sponge was carbonized by firing at 1000 ° C. for 1 hour in an argon atmosphere. The obtained carbonaceous porous body was simultaneously subjected to reactive sintering and silicon melt impregnation in vacuum at 1450 ° C. for 1 hour, but no silicon impregnation occurred, and the carbonaceous porous body remained as it was.

  The composite of the first heating element of the present invention may be a porous structure filter according to the invention of Japanese Patent Application No. 2005-234608 (Japanese Patent Laid-Open No. 2007-44674). That is, as a modification of the first heating element 100 of the above embodiment, instead of the silicon carbide-based heat-resistant ultralight porous structure material, a porous structure filter according to the invention of the Japanese Patent Application No. 2005-234608 is used. There is a first heating element 100 as another embodiment of the present invention in which a porous composite body 110 having a tangible skeleton composed of the silicon carbide and the material containing silicon is configured. This porous structure filter is used for purification of contaminant removal, and is a sponge-like carbonized porous structure sintered impregnated with slurry containing resin and silicon powder to such an extent that continuous pores are not blocked. This sponge-like carbonized porous structure sintered body is made into a plurality of structures having different densities, then carbonized at 900 ° C. to 1350 ° C., reacted and sintered at 1350 ° C. or higher, and 1300 ° C. to 1800 It is a porous structure filter manufactured by melt impregnating silicon at 0 ° C. In that case, the composite 110 of the first heating element 100 of the present invention is not limited to being interpreted as being used for purification of contaminant removal, and is not limited to a filter.

  Cited from Japanese Patent Application Laid-Open No. 2007-44674, the object of the invention of Japanese Patent Application No. 2005-234608 is to provide a porous structure filter for removing contaminants that facilitates handling and enhances purification efficiency, and a method for manufacturing the same. There is to do.

  The invention of Japanese Patent Application No. 2005-234608 takes the following means in order to achieve the above object.

  The porous structure filter of the invention 1 of Japanese Patent Application No. 2005-234608 is used for purification of contaminant removal, and is impregnated with a slurry containing resins and silicon powder to such an extent that continuous pores are not blocked. A sponge-like carbonized porous structure sintered body, wherein the sponge-like carbonized porous structure sintered body is made into a plurality of structures having different densities, then carbonized at 900 ° C. to 1350 ° C., and above 1350 ° C. It is a porous structure filter manufactured by reaction sintering and melt impregnating silicon at 1300 ° C to 1800 ° C.

  The porous structure filter of invention 2 of Japanese Patent Application No. 2005-234608 is characterized in that, in Invention 1 of Japanese Patent Application No. 2005-234608, the slurry contains SiC powder.

  The porous structure filter of invention 3 of Japanese Patent Application No. 2005-234608 is the invention 1 or 2 of Japanese Patent Application No. 2005-234608, wherein the carbonized porous structure sintered body is a three-dimensional Si / SiC porous ceramic. It is characterized by being.

  The porous structure filter of invention 4 of Japanese Patent Application No. 2005-234608 is the same as the invention 1 or 2 of Japanese Patent Application No. 2005-234608, wherein the carbonized porous structure sintered body is a sponge-like porous material made of plastic or nonwoven fabric. It is a structure.

  The porous structure filter of invention 5 of Japanese Patent Application No. 2005-234608 is the same as that of Invention 1 or 2 of Japanese Patent Application No. 2005-234608, wherein the carbonized porous structure sintered body comprises two three-dimensional fine cells having different densities. It is a sintered body in which a structural filter is overlapped and bonded into two layers.

  The porous structure filter of the invention 6 of Japanese Patent Application No. 2005-234608 is the same as that of the invention 1 or 2 of the Japanese Patent Application No. 2005-234608, wherein the carbonized porous structure sintered body is a columnar body and has an outer sponge-like porous structure. The density of the porous structure is higher than that of the inner sponge-like porous structure.

  The porous structure filter of the invention 7 of Japanese Patent Application No. 2005-234608 is the structure of the invention 6 of the Japanese Patent Application No. 2005-234608, wherein the outer sponge-like porous structure is a structure in which nonwoven fabrics are wound. It is characterized by.

  The method for producing a porous structure filter of invention 8 of Japanese Patent Application No. 2005-234608 is such that continuous pores are not clogged with a slurry containing a resin and silicon powder as a carbon source in a tangible skeleton of a sponge-like porous structure. Impregnating the sponge-like porous structure into a plurality of structures having different densities, and carbonizing the sponge-like porous structure at 900 ° C. to 1350 ° C. in an inert atmosphere. A step of reacting and sintering the sponge-like porous structure at 1350 ° C. or higher in a vacuum or an inert atmosphere, and 1300 ° C. to 1800 ° C. in a vacuum or an inert atmosphere of the sponge-like porous structure. And a step of melt impregnating silicon.

  The method for producing a porous structure filter according to Invention 9 of Japanese Patent Application No. 2005-234608 is characterized in that, in Invention 8 of Japanese Patent Application No. 2005-234608, the slurry contains SiC powder.

  For example, when the filter has a two-layer structure, the two-stage reaction sintering method in which silicon (Si) is melted and impregnated can be used for easy joining. The two-stage reaction sintering method is a reaction sintering method and a silicon melt impregnation method, and refers to a reaction in which silicon (Si) and carbon (C) react to generate silicon carbide (SiC). In the reaction sintering method, a phenol resin is used as a carbon source and silicon powder is used as a silicon source. Phenol resin powder is dissolved in alcohol and silicon powder is added to form a mixed slurry. Soak sponge or cardboard in this mixed slurry.

  In the case of sponge, squeeze well enough not to block the cell. The phenol resin enters the inside of the polyurethane skeleton of the sponge as a solution. The silicon powder is stuck into the polyurethane skeleton. When this is baked at 900 ° C. to 1350 ° C., for example, about 1000 ° C. in an inert atmosphere such as argon gas, the phenol resin is thermally decomposed into carbon (amorphous). This state is a state where silicon powder is scattered in amorphous carbon. When the temperature is raised to 1350 ° C. or higher in this state, for example, amorphous carbon diffuses into the silicon powder from about 1320 ° C. and silicon carbide (SiC) is generated from the outside of the silicon powder.

This reaction continues to 1410 ° C. and the reaction between the silicon powder and carbon is complete. This is reaction sintering. The feature is that the reaction between silicon and carbon occurs at a silicon melting point (1410 ° C.) or lower. Volume reduction reaction (Volume required for reaction at 1 mol is Si: 28 g / 2.33 g / cm ³ = 12 cm ³ , C: 12 g / 1.5 g / cm ³ = 8 cm ³ , SiC: 40 g / 3.2 g / cm ³ = 12.5 cm ³ and 12 + 8 = 20 cm ³ is reduced in volume to 12.5 cm ³ ), and the generated silicon carbide becomes porous. This reaction is also slow due to carbon diffusion.

The silicon melt impregnation method is, for example, a reaction in which silicon is placed on a carbon material in a vacuum, and when the temperature is higher than the melting point of silicon (1410 ° C.), the silicon melts and enters into the carbon to produce silicon carbide. It is. The characteristic is that a temperature higher than the melting point of silicon is required, and the reaction occurs rapidly. Further, since silicon is placed on the carbon material, the silicon is out of the system, and in terms of volume, the carbon is changed to silicon carbide, resulting in a volume increase reaction in which 8 cm ³ becomes 12.5 cm ³ . Therefore, the reaction does not proceed when the carbon material is dense and the volume cannot be increased.

  In the two-step reactive sintering method, when the Si / C ratio is set to 1 in the reactive sintering method, only SiC is generated. If the composition is excessive in carbon, amorphous carbon and porous SiC are generated. Molten silicon has good wettability with porous SiC. Amorphous carbon is scattered in porous SiC, is not dense, and reacts with molten silicon. At this time, the volume increases, but since there are pores formed by the reactive sintering method, there is a volume that can be increased and the reaction proceeds. In this embodiment, this phenomenon is used for bonding. For this reason, a lightweight porous Si / SiC ceramic is formed with the sponge as it is. This porous Si / SiC ceramic has good workability and can easily perform filter shape processing.

  As a method for strengthening the outside of the filter by making it dense in the form of a skin, resin and silicon powder, or a slurry containing SiC powder in addition to these is applied to the outside of the Si / SiC ceramic porous body, and two-step reaction sintering is performed. The other method is a method in which a resin / silicon powder or a water-absorbing non-woven fabric containing SiC powder is wound around the outer peripheral portion of the Si / SiC ceramic porous body, and two-step reaction sintering is performed. By such a method, the outer peripheral portion of the ceramic porous body is hardened and strengthened.

  As a result, the filter has a sponge structure inside and a dense structure outside. Furthermore, from the realization of such a configuration, the supply-side filter in the exhaust gas passage is a low-density or coarse mesh sponge filter, and the exhaust-side filter is a high-density or fine sponge filter. The outer peripheral portion can be made into a filter having an outer skin structure in which the strength is precisely increased by the above-described method. As a result, the filter has a double structure, and fine contaminants having different sizes can be removed, and the filter is strengthened as a single body and is difficult to break.

  As described above, in the invention of Japanese Patent Application No. 2005-234608, for example, one three-dimensional fine cell structure filter of a sponge-like porous structure is made a sparse structure or a rough structure, and the other three-dimensional fine cell structure is used. Since the density of the filter is higher than that of the former three-dimensional fine cell structure filter, it is easy to handle, and as a result, two different filter structures with different densities can efficiently capture contaminants of different sizes. . As a result, the purification efficiency was increased and the work efficiency was increased.

  Hereinafter, embodiments of the purification technology for removing contaminants relating to the invention of Japanese Patent Application No. 2005-234608 will be described in detail with reference to the drawings. The target object including the pollutant to be treated in this embodiment is a gas such as an exhaust gas including the pollutant and a liquid such as polluted water. Prior to the description of the invention of Japanese Patent Application No. 2005-234608, in order to facilitate understanding of the invention of Japanese Patent Application No. 2005-234608, a basic configuration as a single filter will be described.

  The filter relating to the purification technique of the invention of Japanese Patent Application No. 2005-234608 may be any filter as long as it has a sponge-like porous structure. For example, the following is applied. One is porous Si in which polyurethane sponge is made as it is by combining reaction sintering method (Si + C = SiC) of silicon (Si) and carbon (C) and silicon melt impregnation method. / SiC ceramics. This porous Si / SiC ceramic has good workability and can be formed in any shape.

It has good light permeability and is excellent as a carrier for photocatalysts. This porous Si / SiC ceramic has a light bulk density of 0.05 to 0.13 g / cm ³ and a porosity of 95 to 98%. In addition, it is possible to reduce the porosity to about 50% by adding SiC powder to increase the strength of the sponge structure and loosening the slurry. The sponge in the present embodiment is a foamed polyurethane material, and is used for cushions, packing materials, impact absorbing materials, and the like.

  This high-porosity filter was processed into a donut shape and stacked, and the result of NOx decomposition experiment covering a 15 W lamp installed at the center is, for example, 15 ppm NOx treated at 1 L / min. In a germicidal lamp and a black light ultraviolet lamp, it became almost 0 ppm by one treatment, and could be decomposed with high efficiency. Further, in the case of a visible fluorescent lamp, 15 ppm NOx is obtained to be 5 ppm or less. The filter will be described in more detail. The above-mentioned filter is effective as a visible light responsive type three-dimensional fine cell structure photocatalytic filter, and is a sponge-like structure in which a three-dimensional Si / SiC porous ceramic is coated with a photocatalyst (titanium oxide). However, it can also be applied to purification of exhaust gas and the like.

  In addition, the sponge-like porous structure of the filter is manufactured by immersing in a solution containing or generating titanium oxide and drying, followed by firing at 100 ° C. to 800 ° C. in an oxidizing atmosphere. Furthermore, after impregnating a prototype structure with a sponge skeleton and thermally decomposing during carbonization with a slurry containing a resin as a carbon source, silicon powder, and a silicon alloy, the prototype structure under an inert atmosphere, Carbonization is performed by carbonizing at 800 ° C. to 1300 ° C. and further by reactive sintering at 1300 ° C. or higher.

  Alternatively, in a nitrogen atmosphere, heat treatment is performed at 800 ° C. to 1500 ° C. to perform carbonization and silicon nitridation to form a porous structure.

  The porous structure after reaction sintering is melt impregnated with silicon at a temperature of 1300 ° C. to 1800 ° C. in a vacuum or in an inert atmosphere. As a result, even if the porous structure has a complicated shape, it can be easily manufactured while maintaining the shape of the tangible skeleton of the porous structure.

  Others that can be applied as sponge filters have been described above, but there are various types such as amorphous carbon, carbon + Si, carbon + Ti, carbon + SiC, carbon + silicon nitride, or combinations thereof. Further, the resin to be impregnated may be phenol resin, furan resin, organometallic polymer, sucrose, or the like, and the slurry to be impregnated is silicon carbide, silicon nitride, zirconia, zircon, alumina, silica, mullite, two Additives such as molybdenum silicide, boron carbide, and boron powder may be used.

  Furthermore, as a silicon powder to be included in the slurry, a silicon alloy such as magnesium, aluminum, titanium, chromium, manganese, iron, cobalt, nickel, copper, zinc, zirconium, niobium, molybdenum, tungsten, or a mixture with silicon may be used. Good.

  Furthermore, silicon alloys such as magnesium, aluminum, titanium, chromium, manganese, iron, cobalt, nickel, copper, zinc, zirconium, niobium, molybdenum, tungsten, or a mixture with silicon may be used as silicon for melt impregnation. . As described above, the filter may be any filter as long as it has a sponge-like porous structure.

  Next, a configuration example of the filter of the invention of Japanese Patent Application No. 2005-234608 will be described. FIG. 2 is a front view of the entire structure of the porous structure filter of the invention of Japanese Patent Application No. 2005-234608, and shows a porous structure filter having a double structure of an outer porous structure and an inner porous structure. It is a front view. FIG. 3 is a cross-sectional view of the porous structure filter of FIG. FIG. 4 is an explanatory view showing a state in which the outer porous structure is wound around the inner porous structure. In this embodiment, a filter having a sponge-like porous structure three-dimensional fine cell structure is doubled in a cylindrical shape, and is configured for purifying exhaust gas from a diesel engine vehicle. This filter is inserted between a muffler of a diesel engine vehicle and an engine as an exhaust gas purification filter, and purifies pollutants contained in the exhaust gas.

  The structure of this filter is a two-layer filter structure of an outer porous structure 1 and an inner porous structure 2, and the outer porous structure 1 is higher in density than the inner porous structure 2 in the form of a sponge. The porous structure has a three-dimensional fine cell structure. In addition, before the outer porous structure 1 is melt-impregnated with silicon, the outer peripheral portion of the filter is coated with a resin and silicon powder or a slurry containing SiC powder in addition to these, or a nonwoven fabric coated with this slurry. Is wound and impregnated with silicon to form a strong outer skin (see FIG. 4). Although this embodiment has been described with a double configuration, a triple configuration or more may be used as shown in FIG.

  FIG. 5 is a cross-sectional view of a porous structure filter having a triple structure of an outer porous structure and an inner porous structure. In this embodiment, two types of sponge-like porous structures having different densities from the supply side to the discharge side are arranged on the inner side as inner porous structures 2a and 2b, and the outer side is hard and has a high density such as a nonwoven fabric. The outer porous structure 1 is wound around. Thus, the filter of the structure which changes a density continuously is applied similarly in other embodiment.

  FIG. 6 is a diagram showing another embodiment of the invention of Japanese Patent Application No. 2005-234608, and is a cross-sectional view of a porous structure filter in which disc-shaped porous structures having different densities are overlapped. In another embodiment, a cylindrical sponge-like porous structure 3 having a low density, a supply-side porous structure 3 that is a three-dimensional fine cell structure filter, and a high-density cylindrical sponge-like porous structure 3 are used. The discharge-side porous structure 4 that is a three-dimensional fine cell structure filter is joined in a disk shape. If the outer side is wound as a hard and dense outer porous structure 5 such as a non-woven fabric, the form becomes easy to handle. For example, the exhaust gas is discharged from the low density side to the high density side as indicated by an arrow.

  A contaminant having a large size is first captured by the supply-side porous structure 3, and a contaminant having a small size that has passed through the supply-side porous structure 3 is captured by the discharge-side porous structure 4. . Since the method for generating the junction is the same as described above, the description thereof is omitted. In this case, the ratio of the supply-side porous structure 3 and the discharge-side porous structure 4 is determined by conditions such as exhaust gas. The degree of density difference is as described above.

  FIG. 7 is a view showing still another embodiment of the invention of Japanese Patent Application No. 2005-234608, and is a filter in which porous structures having different densities are formed in a spiral shape. The plate-like outer porous structure 6 having a higher density and the inner porous structure 7 having a lower density are superposed and formed into a spirally wound filter. According to this configuration, since the filter is held in a strong configuration including the inside, the filter can be partially processed and easily handled.

  FIG. 8 is a diagram showing still another embodiment of the invention of Japanese Patent Application No. 2005-234608, and a plurality of lower-density inner porous structures are added to a higher-density outer porous structure. It is a perspective view which shows the filter inserted and comprised. FIG. 8 shows a state before the inner porous structure is inserted into the outer porous structure. As shown in FIG. 8, the external shape of this filter is a circular cylindrical shape in plan view. The outer porous structure 10 which is harder and has a higher density is formed with an outer skin portion 10a and a lattice-like inner wall portion 10b. A square-shaped or fan-shaped hole 10c is formed between the outer skin portion 10a, the inner wall portion 10b, and the inner wall portion 10b. In each of the plurality of holes 10c of the outer porous structure 10, inner porous structures 11, 11,... Having the same shape as the hole 10c and the outer periphery are inserted. That is, the filter of this embodiment includes the outer porous structure 10 having a higher density and the plurality of inner porous structures having a lower density inserted into the plurality of holes 10c of the outer porous structure 10. 11. In this embodiment, a filter having a high honeycomb structure can be used, and a filter with a large size can be easily manufactured.

  FIG. 9 is a diagram showing still another embodiment of the invention of Japanese Patent Application No. 2005-234608. Similarly to FIG. 8, a plurality of lower density structures are formed on the outer porous structure having a higher density. It is a perspective view which shows the filter which inserts and comprises an inner porous structure. FIG. 9 shows a state before the inner porous structure is inserted into the outer porous structure. As shown in FIG. 9, the external shape of this filter is a rectangular parallelepiped in plan view. The outer porous structure 12 which is harder and has a higher density is formed with an outer skin portion 12a and a lattice-like inner wall portion 12b. A square hole 12c is formed between the outer skin portion 12a, the inner wall portion 12b, and the inner wall portion 12b. In each of the plurality of holes 12c of the outer porous structure 12, inner porous structures 13, 13, 13,... In which the shape of the hole 12c and the shape of the outer periphery coincide with each other are inserted. That is, the filter according to this embodiment includes an outer porous structure 12 having a higher density and a plurality of inner porous structures having a lower density inserted into the plurality of holes 12c of the outer porous structure 12. It consists of a body 13. In this embodiment, a filter having a high honeycomb structure can be used, and a filter with a large size can be easily manufactured.

  In the description of the embodiment shown in FIGS. 8 and 9, the shape of the hole formed in the outer porous structure is described as a quadrangle, but other shapes may be used. For example, it may be a hexagonal hole. In this case, the outer peripheral shape of the inner porous structure is also a hexagonal shape, and the honeycomb structure is formed.

  Although various embodiments of the invention of Japanese Patent Application No. 2005-234608 have been described above, it goes without saying that the invention of Japanese Patent Application No. 2005-234608 is not limited to these forms. For example, the shape of the filter is described as a columnar body (cylindrical body), but it may be a prismatic filter or a plate-like filter, and further deformed according to the shape of the object to be attached. It goes without saying that examples can be made.

  Making this sponge-like carbonized porous structure sintered body into a plurality of structures having different densities means that a plurality of structures having different densities are combined to form a sponge-like carbonized porous structure sintered body. Therefore, it includes the combination of the plurality of parts after sintering, and the combination of the plurality of parts before sintering before sintering the whole. As described in the embodiment, the method includes sintering a part of the plurality of parts and combining the other parts before sintering. In any case, in order to reinforce the outer peripheral portion of the sponge-like carbonized porous structure sintered body, only the density of the outer peripheral portion can be increased or become dense.

  The composite 110 of the present invention is not a so-called thin two-dimensional shape, but a three-dimensional shape having a sufficient thickness, and a three-dimensional shape. In other words, when the depth direction, the width direction, and the thickness direction orthogonal to each other are set, the dimension along one direction is not extremely smaller than the dimension along the other two. In the case of the said embodiment, the composite_body | complex 110 is formed in the substantially column shape. As described above, the electrode 120 is provided on the composite 110 so that the composite 110 can be energized. The electrode 120 is in contact with the complex 110 and is connected to the complex 110. The electrode 120 is made of a material containing silicon carbide and silicon. This is the same material configuration as that of the composite 110, but it is not always necessary to match the material configurations of both. The electrode 120 is connected to the composite 110 via a fixed layer made of a material containing silicon carbide and silicon. This fixed layer is formed by carbonization of a slurry containing resins and silicon powder and reaction sintering of the carbon and silicon. That is, a slurry containing a resin as a carbon source and silicon powder or a slurry further containing an aggregate in this slurry is applied to the surface of the connecting portion in the composite 110 and the electrode 120, and the surfaces are brought into contact with each other. After holding the composite 110 and the electrode 120 via the slurry, heating the slurry, firing the resin of the slurry, and carbonizing the carbon, and reacting and sintering the carbon and the silicon powder of the slurry Further, if silicon is further melted and impregnated, a fixed layer is formed.

  The electrode 120 includes a plate-shaped connecting plate 121 and a rod-shaped terminal 122 that rises from the surface of the connecting plate 121. As described above, both the connection plate 121 and the terminal 122 are formed of a material containing silicon carbide and silicon. The back surface of the connection plate 121 is connected to the skeleton forming the curved surface on the outer periphery of the composite 110 via the fixed layer. Therefore, the terminal 122 rises in a direction away from the composite 110. There are two electrodes 120, and these connecting plates 121 are connected to a curved surface on the outer periphery of the composite 110 at a position facing the composite 110. And the electric wire from a power supply and a ground part, or another conductor is each connected to the terminal 122 of these electrodes 120 via a connector. You may perform the connection of the electric wire etc. to this terminal by bolt fastening, soldering, or other well-known connection forms. With the above configuration, when a current flows between the electrodes 120 in the first heating element 100, a current flows through the skeleton of the composite 110, Joule heat is generated, the composite 110 generates heat, A substance such as particles and fluid existing in or around the composite 110 is heated.

  Here, two electrodes are connected to the composite, but this electrode is used as one, a housing member for housing the composite as exemplified by an exhaust passage constituting member described later, or an adjoining adjacent to the composite. By using a conductive member as the member, the housing member, the adjacent member, and the like may exhibit the same function as the electrode. In short, the electrode has only to be conductive and has one end mechanically and electrically connected to the composite. The electrode may be connected to any part as long as it is a skeleton that forms the surface of the composite. The terminal may be formed of a flexible member such as a core wire of an electric wire. Further, the electrode may be constituted only by the connection plate without providing the terminal. In that case, the connection plate is connected to the composite, and an electric wire or other conductor from the power source or the grounding portion may be connected to the connection plate. Further, the electrode may be constituted by only the terminal without providing the connection plate. In that case, for example, a hole recessed inward from the surface is formed in the composite, the terminal is inserted into the hole, and the terminal is inserted into the skeleton forming the surface of the hole of the composite via the fixing layer. May be connected. Although the electrode is formed of a material containing silicon carbide and silicon, the electrode may be formed of a metal or other material as long as it is a conductive material. In that case, the electrode is connected to the composite by, for example, metal spraying, electroless plating, or the like. This is the same when the electrode is constituted by only the connecting plate or only by the terminal. In this embodiment, the composite 110 is formed in a substantially cylindrical shape. However, the shape of the composite of the present invention is not limited to this, and the shape of the composite is utilized to take advantage of the characteristics of the composite and can be freely formed according to the application. Can be formed.

  Therefore, in the case of the first heating element 100 of this embodiment, the composite 110 includes silicon carbide and silicon and has conductivity. Therefore, when a current is passed between the electrodes of the first heating element 100, the composite 110 is electrically conductive. An electric current flows through the skeleton of the composite 110, and Joule heat is generated. Then, a substance such as particles or fluid existing inside the composite 110, that is, in the pores formed between the skeletons, or around the composite 110 is heated. In that case, since the composite 110 includes silicon carbide and silicon, the composite 110 is resistant to oxidation and can be heated to a higher temperature range than the metal. For example, in the case of an iron alloy, when heated to 600 degrees Celsius, it becomes difficult to maintain its original form because it oxidizes. However, the composite 110 is oxidized even if it generates heat up to 1000 degrees Celsius, for example. It is possible to maintain the original shape without any problems. Further, as compared with the case where a substance such as a particle or a fluid inside the container or passage constituent member is heated from the outside of the container or passage constituent member, the substance is suspended or flowing in the first heating element 100. When arranged, the substance is heated by heat conduction or radiation from a short distance, so that local heating is possible, the heating means is miniaturized, and the thermal efficiency is high. Furthermore, since the silicon | silicone between the silicon carbide particles fills the composite 110, the strength is higher than that of a structural material composed only of silicon carbide, and the vibration resistance is improved, for example. Then, by using the first heating element 100, the first to fourth internal combustion engine exhaust gas purification apparatuses of the present invention are established.

  The composite in the first heating element of the present invention may be a porous composite having a tangible skeleton composed of a material containing silicon carbide and silicon. Among such various embodiments, the composite 110 in the first heating element 100 of the above embodiment includes a resin having a tangible skeleton or a sponge-like porous structure of rubber and a resin as a carbon source. And impregnating the slurry containing silicon powder or the slurry further containing aggregate into the slurry to such an extent that the continuous pores of the sponge-like porous structure are not blocked, and then firing the resins. Carbonized heat-resistant structure formed by carbonizing to make a carbonized porous structure, reacting and sintering the carbon of this carbonized porous structure and the silicon powder of the slurry, and then melt-impregnating silicon. It was composed of a porous ultralight porous material. Thus, when the composite 110 in the first heating element 100 is composed of the silicon carbide heat-resistant ultralight porous structural material, the tangible skeleton of the foamed resin is impregnated with resins and silicon powder. Porous silicon carbide and residual carbon part are generated by the silicon carbide formation reaction accompanied by volume reduction with the silicon powder and carbon from the resin, and when the porous skeleton part is melt impregnated with silicon, Even if the composite 110 made of a silicon-based heat-resistant ultralight porous structure material has a complicated shape, it is easily manufactured while maintaining the shape of the tangible skeleton of the sponge. When the electrode is provided on the composite 110 made of the silicon carbide-based heat-resistant ultralight porous structure material thus obtained, the first heating element 100 can be obtained. Therefore, manufacture of this 1st heat generating body is easy, and the freedom degree of shaping | molding is high.

  The electrode in the 1st heat generating body of this invention should just be formed with the electroconductive material, and the electrode should just be provided in the said composite body so that it can supply with electricity to the said composite body. In such various embodiments, the electrode 120 of the first heating element 100 of the above embodiment is formed of a material containing silicon carbide and silicon, and the electrode 120 is made of a material containing silicon carbide and silicon. It connected to the said composite_body | complex 110 through the fixed layer which becomes. In this way, since the composite 110, the electrode 120, and the fixed layer are made of the same material, there is no difference in the coefficient of thermal expansion. Therefore, the connection strength between the composite 110 and the electrode 120 is high due to the difference in thermal expansion, and the possibility of peeling at the boundary surface can be reduced as much as possible. In addition, since the fixed layer can be distributed widely and deeply at the interface between the composite 110 and the electrode 120 by adhering and infiltrating the slurry, the contact area between the composite 110 and the electrode 120 is sufficient. Secured. Therefore, it is possible to reduce the possibility that the boundary surface between the composite 110 and the electrode 120 at the time of energization becomes extremely higher than other parts due to heat generation, and the heat generation at this boundary surface becomes a bottleneck. The composite 110 can sufficiently generate heat without suppressing the amount, and the composite 110 can stably generate heat up to, for example, 400 degrees Celsius or more. Moreover, since a sufficient contact area between the composite 110 and the electrode 120 is ensured, current flows through a large number of skeletons, which is preferable for improving thermal efficiency. Further, when the terminal 122 is provided, an electric wire from the power source and the grounding part, or other conductors can be arranged away from the composite 110 by the length of the terminal 122, so that the conductor receives The thermal load is reduced, the difference in thermal expansion between the terminal 122 and the conductor is reduced, and the thermal stress generated between them is suppressed.

  Next, an embodiment of the second heating element of the present invention will be described. In the second heating element 100 of this embodiment, the composite 110 carries a catalyst in the first heating element 100 of the above embodiment. Therefore, the description regarding the composite 110 and the electrode 120 of the first heating element 100 of the above-described embodiment, and the description regarding the modifications thereof are the same as the composite 110 and the electrode 120 of the second heating element 100 of the present embodiment. It is quoted as an explanation concerning the above, as well as an explanation concerning those modifications.

  The catalyst supported on the second heating element 100 of this embodiment is platinum (Pt). In this catalyst loading method, the composite 110 of the first heating element 100 is applied to the liquid containing the catalyst, whereby the catalyst is supported on the composite 110. In addition to this, for example, the catalyst may be supported by spraying a powdered catalyst on the composite, or the catalyst may be applied by applying a slurry containing the catalyst to the composite and firing again. It may be supported. The electrode 120 may be attached after the catalyst is supported on the composite 110, or the catalyst may be supported on the composite 110 after the electrode 120 is attached to the composite 110. According to this embodiment, the catalyst supported by the complex is not limited to platinum, and any catalyst suitable for promoting the chemical reaction of a substance can be supported by the complex.

  Therefore, in the case of the second heating element 100 of this embodiment, the composite 110 contains silicon carbide and silicon and has conductivity. Therefore, when a current is passed between the electrodes of the second heating element 100, An electric current flows through the skeleton of the composite 110, and Joule heat is generated. Then, a substance such as particles or fluid existing inside the composite 110, that is, in the pores formed between the skeletons, or around the composite 110 is heated. In that case, since the composite 110 includes silicon carbide and silicon, the composite 110 is resistant to oxidation and can be heated to a higher temperature range than the metal. For example, in the case of an iron alloy, when heated to 600 degrees Celsius, it becomes difficult to maintain its original form because it oxidizes. However, the composite 110 is oxidized even if it generates heat up to 1000 degrees Celsius, for example. It is possible to maintain the original shape without any problems. Further, as compared with the case where a substance such as a particle or a fluid inside the container or passage constituent member is heated from the outside of the container or passage constituent member, the second heating element 100 is suspended or flowing. When arranged, the substance is heated by heat conduction or radiation from a short distance, so that local heating is possible, the heating means is miniaturized, and the thermal efficiency is high. By using the second heating element 100, the fuel reformer of the present invention or the exhaust gas purification device of the fifth internal combustion engine is established.

  When a substance such as particles or fluid existing inside or around the complex 110 causes a chemical reaction inside or around the complex 110, the reaction is promoted by the catalyst. In that case, when the composite 100 generates heat, the catalyst exhibits activity, and the chemical reaction by the catalyst is further promoted.

  The composite in the second heating element of the present invention may be a porous composite having a tangible skeleton composed of a material containing silicon carbide and silicon. Among such various embodiments, the composite 110 in the second heating element 100 of the above embodiment includes a resin having a tangible skeleton or a sponge-like porous structure of rubber and a resin as a carbon source. And impregnating the slurry containing silicon powder or the slurry further containing aggregate into the slurry to such an extent that the continuous pores of the sponge-like porous structure are not blocked, and then firing the resins. Carbonized heat-resistant structure formed by carbonizing to make a carbonized porous structure, reacting and sintering the carbon of this carbonized porous structure and the silicon powder of the slurry, and then melt-impregnating silicon. It was composed of a porous ultralight porous material. Thus, when the composite 110 in the second heating element 100 is composed of the silicon carbide-based heat resistant ultralight porous structure material, the tangible skeleton of the foamed resin is impregnated with resins and silicon powder. Porous silicon carbide and residual carbon part are generated by the silicon carbide formation reaction accompanied by volume reduction with the silicon powder and carbon from the resin, and when the porous skeleton part is melt impregnated with silicon, Even if the composite 110 made of a silicon-based heat-resistant ultralight porous structure material has a complicated shape, it is easily manufactured while maintaining the shape of the tangible skeleton of the sponge. When the composite 110 made of the silicon carbide-based heat resistant ultralight porous structure material thus obtained is provided with electrodes and the composite 110 catalyst is supported before and after the composite 110, the second heating element 100 can be formed. Therefore, the production of the second heating element is easy and the degree of freedom in molding is high.

  Next, an embodiment of the exhaust gas purification apparatus for a first internal combustion engine of the present invention will be described. As shown in FIG. 10, the exhaust gas purification apparatus 300 for the first internal combustion engine of this embodiment includes an exhaust passage constituting member 310 and a first heating element 100 provided in the exhaust passage constituting member 310. Yes.

  In FIG. 11, reference numeral 200 denotes an internal combustion engine, and the internal combustion engine 200 is a known diesel engine provided with a reciprocating piston mechanism. The internal combustion engine 200 includes a cylinder and a piston slidably inserted into the cylinder, and a combustion chamber is formed on the top surface side of the piston in the cylinder (the cylinder, the piston, and the piston). (The combustion chamber is not shown). The internal combustion engine 200 is provided with an intake passage (not shown) for supplying fresh air to the combustion chamber with one end connected to the combustion chamber and the other end open to the atmosphere. Further, the internal combustion engine 200 is provided with an exhaust passage 210 that has one end connected to the combustion chamber and the other end open to the atmosphere, and exhausts exhaust gas discharged from the combustion chamber to the outside. The exhaust passage 210 is constituted by a series of internal passages of a plurality of exhaust passage members such as an exhaust manifold and an exhaust pipe from the side close to the cylinder. One of the plurality of exhaust passage members is the exhaust passage constituting member 310 provided with the first heating element 100. Therefore, an internal passage 311 constituting a part of the exhaust passage 210 is provided inside the exhaust passage constituting member 310. When the exhaust passage is constituted by an internal passage of a single exhaust passage member, the first heating element is provided in the single exhaust passage member. In short, regardless of the configuration of the exhaust passage, the exhaust passage member provided with the first heating element has at least one of the exhaust passages having one end connected to the combustion chamber of the internal combustion engine and the other end open to the atmosphere. It is sufficient if the internal passage constituting the part is an exhaust passage constituent member provided inside. Although the internal combustion engine is a known diesel engine having a reciprocating piston mechanism, the internal combustion engine targeted by the exhaust gas purification apparatus of the first internal combustion engine of the present invention is not limited to this. The internal combustion engines targeted by the exhaust gas purification apparatus of the first internal combustion engine of the present invention include, for example, a rotary engine and a gasoline engine, and the gasoline engine includes one in which fuel is directly injected into a cylinder. The internal combustion engine targeted by the exhaust gas purification apparatus of the first internal combustion engine of the present invention includes an internal combustion engine mounted on an automobile or other transportation equipment, such as an internal combustion engine for driving a power generator. Also included are internal combustion engines that are stationary. The concept of the internal combustion engine targeted by the exhaust gas purification apparatus of the first internal combustion engine of the present invention described here is the concept of the internal combustion engine targeted by the exhaust gas purification apparatus of the second to fifth internal combustion engines of the present invention as it is. Means.

  The composite 110 of the first heating element 100 is accommodated in the internal passage 311 of the exhaust passage constituting member 310. The electrode 120 of the first heating element 100 is led out to the outside of the exhaust passage constituting member 310. The first heating element 100 of this embodiment is the same as the first heating element 100 of the above embodiment. Therefore, the description related to the composite 110 and the electrode 120 of the first heating element 100 of the above-described embodiment and the description related to the modifications thereof are the same as those used in the exhaust gas purification apparatus 300 of the first internal combustion engine of this embodiment. It is referred to as an explanation about the composite 110 and the electrode 120 of one heating element 100, and an explanation about a modification thereof. The same applies to the second heating element 100. In this embodiment, the terminal 122 of the electrode 120 passes through the exhaust passage constituting member 310 and is led out to the outside. The terminal 122 and the exhaust passage constituting member 310 are insulated. However, when the exhaust passage constituent member is a conductive member, the ground-side terminal may be brought into contact with the exhaust passage constituent member. In addition, the various modifications of the electrode have been described above. However, in each modification, the electrode may be led out of the exhaust passage constituent member. In that case, when the terminal is provided, it is preferable that a part of the terminal is provided so as to penetrate the exhaust passage constituting member because the wiring is simplified. The same applies when a rod-shaped electrode bar is provided instead of the connection plate. Further, when the electrode is configured only by the connection plate without providing the terminal, for example, a terminal may be provided on the exhaust passage constituting member, and the connection plate may be brought into contact with the terminal. The two electrodes 120 are connected to an anode and a ground electrode of a power supply 500, respectively, so that the composite 110 of the first heating element 100 can be energized. A control device 600 is connected to the power source 500, and the control device 600 controls energization and non-energization of the electrode 120. You may control the voltage applied between electrodes, or the electric current sent between electrodes by this control apparatus. This control device includes an electric circuit assembled so as to perform a predetermined processing procedure, and is configured to perform control along a predetermined flow by a computer including a storage unit, a calculation unit, and the like. Also good. When one electrode is grounded, the anode of the power source is connected to the other electrode. A capacitor is connected between the two electrodes as necessary. Switching between energization and de-energization of the electrode 120 by the control device 600 can be performed manually, but energization is performed in conjunction with the start of the internal combustion engine 200, and de-energization is performed in conjunction with the stop of the internal combustion engine 200. The control method by the control device is not limited to this. You may provide the manual switch which turns on / off electricity to the electrode of a power supply, without providing a control apparatus.

  The exhaust gas purification apparatus 300 for the first internal combustion engine of the above embodiment has an internal passage 311 that constitutes at least a part of the exhaust passage 210 having one end connected to the combustion chamber of the internal combustion engine 200 and the other end open to the atmosphere. The exhaust passage constituting member 310 provided inside and the composite 110 are accommodated in the internal passage 311 of the exhaust passage constituting member 310, and the electrode 120 is led out to the outside of the exhaust passage constituting member 310. The heating element 100 was provided. As a modified example, there is a first internal combustion engine exhaust gas purification apparatus 300 provided with a second heating element 100 instead of the first heating element 100. The second heating element 100 of this modification is the same as the second heating element 100 of the above embodiment.

Therefore, since the composite 110 includes silicon carbide and silicon and has conductivity, when a current is passed between the electrodes of the first or second heating element 100, a current flows through the skeleton of the composite 110, Joule heat is generated. And, when the exhaust gas passes through the composite 110 of the first or second heating element 100, soot that occupies most of the particulate matter contained in the exhaust gas, because the composite 110 contains silicon carbide and silicon, Adsorbed to the skeleton of the complex 110. The soot receives heat from the skeleton and is decomposed into finer particles by HC in the exhaust gas. The fine particles receive heat from the skeleton and oxidize to become CO ₂ or the like. In the second heating element 100, this oxidation reaction is promoted by the catalyst. Therefore, the particulate matter contained in the exhaust gas is reduced by the first or second heating element 100. In addition, combustible components such as unburned fuel in the exhaust gas receive heat from the skeleton, and oxidation and combustion are promoted. Therefore, there is no need for a separate regeneration means for regenerating from clogging, the structure is simple, the energy is saved, and particulate matter can be continuously removed from the exhaust gas.

  Next, an embodiment of an exhaust emission control device for a second internal combustion engine of the present invention will be described. As shown in FIG. 12, the second internal combustion engine exhaust gas purification apparatus 300 of this embodiment is the same as the exhaust gas purification apparatus 300 of the first internal combustion engine of the above embodiment, in the internal passage 311 of the exhaust passage structural member 310. An exhaust gas purification device 320 is provided on the exhaust downstream side of the first heating element 100 or the complex 110 of the second heating element 100. Therefore, the internal combustion engine 200, the exhaust passage constituting member 310, the power source 500 and the control device 600, the first heating element 100, and the second heating element in the exhaust gas purification apparatus 300 of the first internal combustion engine of the embodiment. As for the explanation regarding 100 and the explanation regarding the modified examples, the internal combustion engine 200, the exhaust passage constituting member 310, the power source 500 and the control device 600 in the exhaust purification apparatus 300 of the second internal combustion engine are used as they are. It is quoted as the explanation about the heating element 100 of No. 2 and the explanation about those modified examples.

The exhaust gas purification device 320 is a DOC (diesel oxidation catalyst). This DOC is a catalyst that oxidizes CO, HC, SOF, SO _{2 and the} like. In addition to this embodiment, the exhaust gas purification catalyst is a PM aftertreatment catalyst, a selective reduction catalyst (SCR catalyst), or a NOx trap catalyst (NAC) as a second internal combustion engine exhaust gas purification device according to a modification. 2 is an exhaust purification device for an internal combustion engine. The PM post-treatment catalyst is a catalyst provided with a DOC and a particulate filter that is provided downstream of the exhaust gas and collects particulate matter contained in the exhaust gas. The particulate matter accumulated in the particulate filter is burned and removed. The selective reduction catalyst (SCR catalyst) is a catalyst that reduces NOx in the exhaust gas, and includes a urea SCR catalyst. The NOx trap catalyst (NAC) is a catalyst that uses Ba as the NOx storage agent and oxides such as alkali, alkaline earth, and rare earth. When the target internal combustion engine is a gasoline engine, the exhaust gas purification catalyst is a three-way catalyst, a NOx trap catalyst (NOx occlusion reduction type catalyst), or An exhaust purification device for a second internal combustion engine which is an HC trap catalyst is exemplified. The three-way catalyst is a catalyst on which Rh excellent in NOx reduction performance, Pt excellent in oxidation performance, and noble metals Pt / Rh, Pd / Rh, and Pt / Pd / Rh added with Pd are supported. The NOx trap catalyst (NOx occlusion reduction type catalyst) is a catalyst using Ba as the NOx occlusion agent and oxides such as alkali, alkaline earth, and rare earth. The HC trap catalyst is a catalyst that oxidizes HC desorbed from the adsorbent that traps HC when the exhaust gas temperature rises to the activation temperature of the catalyst.

Therefore, since the composite 110 includes silicon carbide and silicon and has conductivity, when a current is passed between the electrodes of the first or second heating element 100, a current flows through the skeleton of the composite 110, Joule heat is generated. And, when the exhaust gas passes through the composite 110 of the first or second heating element 100, soot that occupies most of the particulate matter contained in the exhaust gas, because the composite 110 contains silicon carbide and silicon, Adsorbed to the skeleton of the complex 110. The soot receives heat from the skeleton and is decomposed into finer particles by HC in the exhaust gas. The fine particles receive heat from the skeleton and oxidize to become CO ₂ or the like. In the second heating element 100, this oxidation reaction is promoted by the catalyst. Therefore, the particulate matter contained in the exhaust gas is reduced by the first or second heating element 100. In addition, combustible components such as unburned fuel in the exhaust gas receive heat from the skeleton, and oxidation and combustion are promoted. Therefore, there is no need for a separate regeneration means for regenerating from clogging, the structure is simple, the energy is saved, and particulate matter can be continuously removed from the exhaust gas.

  Furthermore, since the exhaust gas purification device 320 is provided in the internal passage 311 of the exhaust passage constituting member 310 on the exhaust downstream side of the first heating element 100 or the complex 110 of the second heating element 100, the first heating element 100 is provided. The temperature of the exhaust gas rises due to oxidation of fine particles in the heating element 100 or the second heating element 100, oxidation of the combustible component, combustion, etc., and this high-temperature exhaust gas flows into the exhaust gas purification device 320. The exhaust gas purification device 320 is activated and the exhaust gas purification is promoted by an oxidation reaction or the like.

  Next, an embodiment of an exhaust gas purification apparatus for a third internal combustion engine of the present invention will be described. As shown in FIG. 13, the third internal combustion engine exhaust gas purification apparatus 300 of this embodiment is the same as that of the first internal combustion engine exhaust gas purification apparatus 300 of the above embodiment in the internal passage 311 of the exhaust passage configuration member 310. A particulate filter 330 is provided on the exhaust downstream side of the first heating element 100 or the complex 110 of the second heating element 100. Therefore, the internal combustion engine 200, the exhaust passage constituting member 310, the power source 500 and the control device 600, the first heating element 100, and the second heating element in the exhaust gas purification apparatus 300 of the first internal combustion engine of the embodiment. The description regarding 100, and the description regarding these modifications, are the same as the internal combustion engine 200, the exhaust passage constituting member 310, the power supply 500 and the control device 600 in the third exhaust purification device 300 of the third internal combustion engine, the first heating element 100 and the first. It is quoted as the explanation about the heating element 100 of No. 2 and the explanation about those modified examples.

  The particulate filter 330 is a so-called sealing type. This particulate filter 330 is a so-called honeycomb body made of ceramic and having a plurality of cells partitioned by partition walls, in which the honeycombs are alternately closed one by one, and the exhaust gas passes through the wall. Particulate matter is collected as it passes through. On one end face of the particulate filter 330, the end faces of the cells are alternately closed in a checkered pattern by a sealing material, and on the other end face, the cells closed by the one end face are opened, The cell opened at one end face has a structure closed by a sealing material. One end face communicates with the inlet of the particulate filter 330 and the other end face communicates with the outlet of the particulate filter 330. Other particulate filters include porous and fiber types, which are made of materials such as metal, for example, and particulate matter is collected by exhaust gas colliding with porous or fiber components. Is configured to do. However, the structure of the particulate filter in the present invention is not limited to these. The particulate filter 330 is housed and held in the internal passage 311 of the exhaust passage constituting member 310. However, the particulate filter may be detachably attached to the exhaust passage constituent member so that the clogged particulate filter can be replaced with a new or regenerated one, or the particulate filter of the exhaust passage constituent member can be replaced. A heater may be provided in the vicinity, and the particulate filter in the particulate filter clogged by the heater may be oxidized and burned to regenerate the particulate filter. The present invention hinders the establishment of these modifications. is not.

Therefore, since the composite 110 includes silicon carbide and silicon and has conductivity, when a current is passed between the electrodes of the first or second heating element 100, a current flows through the skeleton of the composite 110, Joule heat is generated. And, when the exhaust gas passes through the composite 110 of the first or second heating element 100, soot that occupies most of the particulate matter contained in the exhaust gas, because the composite 110 contains silicon carbide and silicon, Adsorbed to the skeleton of the complex 110. The soot receives heat from the skeleton and is decomposed into finer particles by HC in the exhaust gas. The fine particles receive heat from the skeleton and oxidize to become CO ₂ or the like. In the second heating element 100, this oxidation reaction is promoted by the catalyst. Therefore, the particulate matter contained in the exhaust gas is reduced by the first or second heating element 100. In addition, combustible components such as unburned fuel in the exhaust gas receive heat from the skeleton, and oxidation and combustion are promoted. Therefore, there is no need for a separate regeneration means for regenerating from clogging, the structure is simple, the energy is saved, and particulate matter can be continuously removed from the exhaust gas.

Further, since the particulate filter 330 is provided on the exhaust downstream side of the first heating element 100 or the complex 110 of the second heating element 100 in the internal passage 311 of the exhaust passage constituting member 310, The exhaust gas temperature rises due to oxidation of fine particles in the heating element 100 or the second heating element 100, oxidation of flammable components, combustion, etc., and this high-temperature exhaust gas flows into the particulate filter 330. The soot occupying most of the particulate matter collected in the curate filter 330 receives heat from the high-temperature exhaust gas and is decomposed into finer particles by HC in the exhaust gas, and these fine particles generate heat from the skeleton. It receives and oxidizes to CO ₂ etc. Further, since the first heating element 100 or the second heating element 100 reduces the particulate matter contained in the exhaust gas, the progress of the clogging of the particulate filter 330 becomes slow or clogging is prevented. The clogging of the particulate filter 330 can be suppressed or prevented.

  Next, a fourth embodiment of the exhaust gas purification apparatus for an internal combustion engine of the present invention will be described. As shown in FIG. 14, the fourth internal combustion engine exhaust gas purification apparatus 300 of this embodiment is the same as the exhaust gas purification apparatus 300 of the second internal combustion engine of the above embodiment, in the internal passage 311 of the exhaust passage configuration member 310. A particulate filter 330 that collects particulate matter contained in the exhaust gas is provided on the exhaust downstream side of the exhaust gas purification device 320. Therefore, the internal combustion engine 200, the exhaust passage constituting member 310, the power source 500 and the control device 600, the first heating element 100, and the second heating element in the exhaust gas purification apparatus 300 of the first internal combustion engine of the embodiment. As for the explanation about 100 and the explanation about those modified examples, the internal combustion engine 200, the exhaust passage constituting member 310, the power source 500 and the control device 600, the first heating element 100 and the first in the fourth exhaust gas purification apparatus 300 of the fourth internal combustion engine. It is quoted as the explanation about the heating element 100 of No. 2 and the explanation about those modified examples. In addition, the description regarding the exhaust gas purification device 320 in the exhaust purification device 300 of the second internal combustion engine of the above embodiment and the description regarding the modifications thereof are the same as the exhaust gas in the exhaust purification device 300 of the fourth internal combustion engine. It quotes as description regarding the purification apparatus 320, and description regarding those modifications. Further, the particulate filter 330 of the exhaust gas purification apparatus 300 of the fourth internal combustion engine of this embodiment is the same as the particulate filter 330 of the exhaust gas purification apparatus 300 of the third internal combustion engine of the above embodiment. Therefore, the description of the particulate filter 330 in the exhaust purification device 300 of the third internal combustion engine of the above embodiment and the description of the modifications thereof are the same as those in the exhaust purification device 300 of the fourth internal combustion engine of this embodiment. It will be cited as an explanation about the curate filter 330 and an explanation thereof.

Therefore, since the composite 110 includes silicon carbide and silicon and has conductivity, when a current is passed between the electrodes of the first or second heating element 100, a current flows through the skeleton of the composite 110, Joule heat is generated. Then, when the exhaust gas passes through the composite 110 of the first or second heating element 100, soot that occupies most of the particulate matter contained in the exhaust gas is because the composite 110 contains silicon carbide and silicon. Adsorbed to the skeleton of the complex 110. The soot receives heat from the skeleton and is decomposed into finer particles by HC in the exhaust gas. The fine particles receive heat from the skeleton and oxidize to become CO ₂ or the like. In the second heating element 100, this oxidation reaction is promoted by the catalyst. Therefore, the particulate matter contained in the exhaust gas is reduced by the first or second heating element 100. In addition, flammable components such as unburned fuel in the exhaust gas receive heat from the skeleton to promote oxidation and combustion. Therefore, there is no need for a separate regeneration means for regenerating from clogging, the structure is simple, the energy is saved, and particulate matter can be continuously removed from the exhaust gas.

  Furthermore, since the exhaust gas purification device 320 is provided in the internal passage 311 of the exhaust passage constituting member 310 on the exhaust downstream side of the first heating element 100 or the complex 110 of the second heating element 100, the first heating element 100 is provided. The temperature of the exhaust gas rises due to oxidation of fine particles in the heating element 100 or the second heating element 100, oxidation of the combustible component, combustion, etc., and this high-temperature exhaust gas flows into the exhaust gas purification device 320. The exhaust gas purification device 320 is activated and the exhaust gas purification is promoted by an oxidation reaction or the like.

In addition, since the particulate filter 330 is provided in the internal passage 311 of the exhaust passage constituting member 310 on the exhaust downstream side of the exhaust gas purification device 320, the first heat generating body 100 or the second heat generating body 100 oxidizes. The exhaust gas whose temperature has risen due to the reaction or the like further rises in temperature by an oxidation reaction or the like in the exhaust gas purification device 320, and this high-temperature exhaust gas flows into the particulate filter 330, so that the particulate matter collected by the particulate filter 330 The soot occupying most of the material receives heat from the high-temperature exhaust gas, and is decomposed into finer particles by HC in the exhaust gas. The fine particles receive heat from the skeleton and oxidize to become CO ₂ or the like. . Further, since the first heating element 100 or the second heating element 100 reduces the particulate matter contained in the exhaust gas, the progress of the clogging of the particulate filter 330 becomes slow or clogging is prevented. The clogging of the particulate filter 330 can be suppressed or prevented.

Next, an embodiment of the fuel reformer of the present invention will be described. As shown in FIG. 15, the fuel reformer 400 of this embodiment includes a container 410 and the second heating element 100 in which the composite 110 is accommodated in the container 410. As shown in FIG. 16, the container 410 is formed in a cylindrical shape or a tubular shape. One end of the container 410 has an inlet 411 into which a mixture containing a raw fuel mainly composed of hydrocarbon and an oxygen-containing compound is introduced, and a combustible reformed fuel is taken out at the other end. The outlet 412 is opened. The inlet 411 is connected to an introduction pipe 420 for supplying a mixture containing the raw fuel mainly composed of hydrocarbons and the oxygen-containing compound, and the outlet 412 is provided with an outlet pipe 430 for discharging the reformed fuel. Each is connected. The shape of the container is not limitedly interpreted by this embodiment. The container has an inlet into which a mixture containing a raw fuel mainly composed of hydrocarbons and an oxygen-containing compound is introduced, and a combustible reformed fuel. A mixture containing a raw fuel mainly composed of hydrocarbons and an oxygen-containing compound and a combustible reformed fuel can be circulated in the interior of the outlet so that they do not leak to the outside. As long as it is comprised, the shape and structure are not ask | required. Both the raw fuel and the reformed fuel may be gas or liquid. As exemplified by H ₂ O, O ₂ , and O ₃ , the oxygen-containing compound is a compound in which an oxygen element is combined with another element or a compound composed of an oxygen element.

In the fuel reformer 400 of this embodiment, the raw fuel mainly composed of the hydrocarbon is methane, the oxygen-containing compound is H ₂ O in the form of water vapor, and the combustible reformed fuel obtained is Hydrogen is a rich gas. Steam is supplied from a steam generator or the like. In this fuel reformer 400, hydrogen is produced if the methane and steam react with each other in a high temperature atmosphere of about 350 ° C. or higher. Preferably, the methane and water vapor are generated in a high temperature atmosphere of about 800 ° C. or higher. The reaction produces more hydrogen. That is, in the container 410, the methane and water vapor first react to generate hydrogen and carbon monoxide, and further, the carbon monoxide and water vapor react to generate hydrogen together with carbon dioxide. . If this is shown by the reaction formula, CH ₄ + H ₂ O → 3H ₂ + CO, CO + H ₂ O → H ₂ + CO ₂ . That is, a reformed fuel is obtained by a steam reforming reaction. This steam reforming reaction is an endothermic reaction that requires a large amount of heat, and the amount of heat necessary for this is obtained by heat exchange with the heat generated by the composite 110 of the second heating element 100. City gas may be used in place of methane as the raw fuel. The reformed fuel obtained by the fuel reformer 400 is introduced into a fuel cell, for example, and used as a reaction gas in the fuel cell. In that case, the reformed fuel is filtered through a hydrogen permselective membrane as necessary to increase the hydrogen concentration. Further, as a modification of this embodiment, the raw fuel mainly composed of hydrocarbons is light oil, the oxygen-containing compound is air, and the combustible reformed fuel obtained contains carbon monoxide and water. There is a fuel reformer 400 which is In the fuel reformer 400 of this modification, hydrogen is produced by reacting the light oil and air in a high temperature atmosphere of 350 ° C. or higher. That is, in the container 410, the light oil and water vapor first react to generate hydrogen and carbon monoxide, and further, the carbon monoxide and water vapor react to generate hydrogen together with carbon dioxide. . That is, a reformed fuel is obtained by a steam reforming reaction. This steam reforming reaction is an endothermic reaction that requires a large amount of heat, and the amount of heat necessary for this is obtained by heat exchange with the heat generated by the composite 110 of the second heating element 100. Gasoline, kerosene or other liquid fuel may be used as the raw fuel instead of light oil. The reformed fuel obtained by the fuel reformer 400 can be introduced into the fuel cell, for example, as in the above embodiment.

  The complex 110 of the second heating element 100 is accommodated in the container 410. The electrode 120 of the second heating element 100 is led out of the container 410. The second heating element 100 of this embodiment is the same as the second heating element 100 of the above embodiment. Therefore, the description regarding the composite 110 and the electrode 120 of the second heating element 100 of the above-described embodiment, and the description regarding the modifications thereof are the same as those of the second heating element 100 used in the fuel reformer of this embodiment. It is referred as description regarding the composite_body | complex 110 and the electrode 120, and description regarding those modifications. In this embodiment, the terminal 122 of the electrode 120 passes through the container 410 and is led out to the outside. The terminal 122 and the container 410 are insulated. However, when the container is a conductive member, the ground-side terminal may be brought into contact with the container. Moreover, although the various modifications about the electrode have been described above, the electrode may be led out of the container in each modification. In that case, when the terminal is provided, it is preferable that wiring is simplified if a part of the terminal is provided so as to penetrate the container. The same applies when a rod-shaped electrode bar is provided instead of the connection plate. Further, when the electrode is configured only by the connection plate without providing the terminal, for example, a terminal may be provided on the container, and the connection plate may be brought into contact with the terminal. The two electrodes 120 are connected to an anode and a ground electrode of a power source 500, respectively, so that the composite 110 of the second heating element 100 can be energized. A control device 600 is connected to the power source 500, and the control device 600 controls energization and non-energization of the electrode 120. You may control the voltage applied between electrodes, or the electric current sent between electrodes by this control apparatus. When one electrode is grounded, the anode of the power source is connected to the other electrode. A capacitor is connected between the two electrodes as necessary. Switching between energization and de-energization of the electrode 120 by the control device 600 can be performed manually, but energization is performed in conjunction with the start of the internal combustion engine 200, and de-energization is performed in conjunction with the stop of the internal combustion engine 200. The control method by the control device is not limited to this. You may provide the manual switch which turns on / off electricity to the electrode of a power supply, without providing a control apparatus.

  An inlet temperature sensor 440 and an outlet temperature sensor 450 are provided on the end face on the inlet side of the second heating element 100 and on the end face on the outlet side, respectively, and outputs from the inlet temperature sensor 440 and the outlet temperature sensor 450 are provided. The signal is sent to the control device 600. Then, the control device 600 detects the temperature of the second heating element 100 from the signals from the inlet temperature sensor 440 and the outlet temperature sensor 450, and from the power source 500 to the second temperature so that the temperature falls within a predetermined range. The temperature of the second heating element 100 is adjusted by adjusting at least one of the current and voltage supplied to the heating element 100. Thus, the reformed gas having the optimum temperature corresponding to the load condition of the fuel reformer 400 is stably supplied. For example, when the fuel reformed by the fuel reformer 400 is supplied to the fuel cell, the load condition is an output state or an operating state of the fuel cell. This embodiment does not limit the number of temperature sensors, the position where the temperature sensors are provided, and the like. Further, when control can be performed based on an empirical rule or the like, control is not required, and thus a temperature sensor need not be provided.

  Therefore, in the fuel reformer 400, the composite 110 contains silicon carbide and silicon and has conductivity. Therefore, when a current is passed between the electrodes of the second heating element 100, Current flows through the skeleton and Joule heat is generated. The mixture that has entered the container from the inlet of the container 410 undergoes a predetermined reforming reaction by the action of the catalyst heated by the skeleton, and combustible reformed fuel is generated. In that case, the mixture inside the container 410 is not heated by a heater provided so as to surround the side of the container as in the conventional case, but the composite 110 of the second heating element 100 is not heated. Since heating is performed by heat conduction or radiation from a short distance by the skeleton, the rise of the heating is good and the thermal efficiency is high, and the entire apparatus is downsized.

  Next, an embodiment of an exhaust emission control device for a fifth internal combustion engine of the present invention will be described. As shown in FIG. 17, an exhaust purification device 700 for a fifth internal combustion engine of this embodiment is provided with an exhaust passage constituting member 710 and the exhaust passage constituting member 710, and captures particulate matter contained in the exhaust gas. The particulate filter 720 to collect and the fuel reformer 400 of the said embodiment are provided.

  In FIG. 17, reference numeral 200 denotes an internal combustion engine, and this internal combustion engine 200 is the same as the internal combustion engine 200 described in the exhaust gas purification apparatus 300 of the first internal combustion engine of the above embodiment. Therefore, the description regarding the internal combustion engine 200 in the exhaust gas purification apparatus 300 of the first internal combustion engine of the above embodiment and the description regarding the modifications thereof are the same as the description regarding the internal combustion engine 200 in the exhaust gas purification apparatus 700 of the fifth internal combustion engine. , As well as the explanations of these modifications. The internal combustion engine 200 is provided with an intake passage (not shown) that has one end connected to the combustion chamber and the other end open to the atmosphere, and supplies fresh air to the combustion chamber. Further, the internal combustion engine 200 is provided with an exhaust passage 210 that has one end connected to the combustion chamber and the other end open to the atmosphere, and exhausts exhaust gas discharged from the combustion chamber to the outside. The exhaust passage 210 of the internal combustion engine 200 is constituted by a series of internal passages of a plurality of exhaust passage members such as an exhaust manifold and an exhaust pipe from the side close to the cylinder. One of the plurality of exhaust passage members is the exhaust passage constituting member 710 provided with the particulate filter 720. Therefore, an internal passage 711 constituting a part of the exhaust passage 210 is provided in the exhaust passage constituting member 710. The particulate filter 720 is accommodated in the internal passage 711 of the exhaust passage constituting member 710. When the exhaust passage is constituted by an internal passage of a single exhaust passage member, a particulate filter is provided on the single exhaust passage member. In short, regardless of the configuration of the exhaust passage, the exhaust passage member provided with the particulate filter has at least a part of the exhaust passage having one end connected to the combustion chamber of the internal combustion engine and the other end opened to the atmosphere. Any exhaust passage constituent member may be used as long as the internal passage to be configured is provided inside. In addition, the particulate filter 330 of the fifth internal combustion engine exhaust purification apparatus 300 of this embodiment is the same as the particulate filter 330 of the third internal combustion engine exhaust purification apparatus 300 of the above embodiment. Therefore, the description of the particulate filter 330 in the exhaust purification device 300 of the third internal combustion engine of the above embodiment and the description of the modifications thereof are the same as those in the exhaust purification device 300 of the fifth internal combustion engine of this embodiment. It will be cited as an explanation about the curate filter 330 and an explanation thereof. Further, the fuel reformer 400 of the fifth internal combustion engine exhaust purification apparatus 300 of this embodiment is the same as the fuel reformer 400 of the above embodiment. Therefore, the description related to the fuel reformer 400 of the above embodiment and the description thereof are the same as the description of the fuel reformer 400 in the exhaust gas purification apparatus 300 of the fifth internal combustion engine of this embodiment. It quotes as description regarding a modification.

  The outlet 412 of the container 410 of the fuel reformer 400 is connected to the internal passage 711 of the exhaust passage member 710 so that the combustible reformed fuel is supplied to the particulate filter 720. It is composed. Here, the other end of the outlet pipe 430 whose one end is connected to the outlet 412 is connected to the internal passage 711 of the exhaust passage constituting member 710. The connection portion of the outlet pipe 430 to the internal passage 711 is an intermediate portion of the particulate filter 720, but the position of the connection portion is not interpreted in a limited manner.

  Therefore, when the reformed fuel generated by the fuel reformer is supplied to the particulate filter, the particulate matter collected by the particulate filter is promoted to oxidize and burn, and the particulate filter 720 The progress of clogging becomes slow or clogging is prevented, and clogging of the particulate filter 720 can be suppressed or prevented.

  The heating element, the exhaust gas purification apparatus for an internal combustion engine, and the fuel reforming apparatus of the present invention include embodiments that combine the features of the above embodiments. Further, the above embodiments merely show some examples of the heating element, the exhaust gas purification device of the internal combustion engine, and the fuel reforming device of the present invention. Therefore, the description of these embodiments does not limit the interpretation of the heating element, the exhaust purification device of the internal combustion engine, and the fuel reforming device of the present invention.

It is a perspective view which shows the 1st heat generating body of embodiment. It is a front view of the whole structure of the porous structure filter of invention of Japanese Patent Application No. 2005-234608. It is sectional drawing of the porous structure filter of invention of Japanese Patent Application No. 2005-234608, and is sectional drawing of the porous structure filter made into the double structure of an outer porous structure and an inner porous structure. It is explanatory drawing which shows the state which has wound the outer side porous structure to the inner side porous structure of FIG. It is sectional drawing of the porous structure filter made into the triple structure of an outer porous structure and an inner porous structure. Sectional drawing of the porous structure filter which piled up the disk-shaped porous structure from which density differs in the sectional view of the porous structure filter which shows other embodiment of invention of Japanese Patent Application No. 2005-234608 It is. FIG. 11 is a cross-sectional view of a porous structure filter showing still another embodiment of the invention of Japanese Patent Application No. 2005-234608, and is a porous structure in which plate-like porous structures having different densities are stacked and wound in a spiral shape. It is a perspective view which shows a structure filter. FIG. 11 is a diagram showing still another embodiment of the invention of Japanese Patent Application No. 2005-234608, and is configured by inserting a plurality of lower density inner porous structures into a higher density outer porous structure. It is a perspective view which shows the filter to do. FIG. 11 is a diagram showing still another embodiment of the invention of Japanese Patent Application No. 2005-234608, and is configured by inserting a plurality of lower density inner porous structures into a higher density outer porous structure. It is a perspective view which shows the filter to do. 1 is a perspective view showing an exhaust emission control device for a first internal combustion engine of an embodiment. It is explanatory drawing which carried out the cross section which shows a part which shows the internal combustion engine provided with the exhaust gas purification device of the 1st internal combustion engine of embodiment. It is explanatory drawing which carried out the cross section which showed a part which shows the internal combustion engine provided with the exhaust gas purification apparatus of the 2nd internal combustion engine of embodiment. It is explanatory drawing which carried out the cross section which shows a part which shows the internal combustion engine provided with the exhaust gas purification device of the 3rd internal combustion engine of embodiment. It is explanatory drawing which carried out the cross section which showed a part which shows the internal combustion engine provided with the exhaust gas purification apparatus of the 4th internal combustion engine of embodiment. It is the explanatory view which cut a part showing fuel reformer of an embodiment. It is a perspective view which shows the exhaust gas purification apparatus of the 5th internal combustion engine of embodiment. It is explanatory drawing which carried out the cross section which shows a part which shows the internal combustion engine provided with the exhaust gas purification apparatus of the 5th internal combustion engine of embodiment.

Explanation of symbols

1, 5, 6, 10, 12 Outer porous structure 2, 7, 11, 13 Inner porous structure 3 Supply-side porous structure 4 Discharge-side porous structure 100 First heating element, second Heating element 110 Composite 120 Electrode 200 Internal combustion engine 210 Exhaust passage 300 Exhaust purification device 310 of internal combustion engine 310 Exhaust passage component 311 Internal passage 320 Exhaust gas purification device 330 Particulate filter 400 Fuel reformer 410 Container 411 Inlet 412 Outlet 700 Internal combustion Exhaust gas purification device 710 Exhaust passage component 711 Internal passage 720 Particulate filter

Claims (9)

A porous composite with a tangible skeleton composed of silicon carbide and a silicon-containing material;
An electrode provided on the composite so that the composite can be energized,
A heating element configured to generate heat when a current is passed between the electrodes, and to heat substances such as particles and fluid existing in or around the complex.   The composite is a sponge in which a resin or rubber sponge-like porous structure having a tangible skeleton is added to a slurry containing a resin as a carbon source and silicon powder, or a slurry in which an aggregate is further added to the slurry. After impregnating so that the continuous pores of the porous structure are not blocked, the resins are baked and carbonized to form a carbonized porous structure. The carbon of the carbonized porous structure and the carbon 2. The heating element according to claim 1, wherein the heating element is composed of a silicon carbide-based heat-resistant ultralight porous structure formed by reaction-sintering with the silicon powder of the slurry and then melt-impregnating silicon.   The heating element according to claim 1 or 2, wherein the composite carries a catalyst. An exhaust passage constituting member having an internal passage which is at least part of an exhaust passage whose one end is connected to the combustion chamber of the internal combustion engine and the other end is opened to the atmosphere;
The heating element according to any one of claims 1 to 3, wherein the composite is housed in an internal passage of the exhaust passage constituent member, and the electrode is led out of the exhaust passage constituent member. An exhaust purification device for an internal combustion engine.   5. The exhaust gas purification apparatus for an internal combustion engine according to claim 4, wherein an exhaust gas purification catalyst is provided on the exhaust downstream side of the complex of the heating element in the internal passage of the exhaust passage constituent member.   The exhaust gas purification apparatus for an internal combustion engine according to claim 4, wherein the particulate filter contained in the exhaust gas is collected downstream of the complex of the heating element in the internal passage of the exhaust passage component member. An exhaust purification device for an internal combustion engine provided with   6. The exhaust gas purification apparatus for an internal combustion engine according to claim 5, wherein a particulate filter for collecting particulate matter contained in the exhaust gas is provided downstream of the exhaust gas purification catalyst in the internal passage of the exhaust passage constituent member. An exhaust purification device for an internal combustion engine.   A container having an inlet for introducing a mixture containing a raw fuel mainly composed of hydrocarbons and an oxygen-containing compound, an outlet for taking out a combustible reformed fuel, and the composite housed in the container And a heating element according to claim 3, wherein the electrode is led out of the container. An exhaust passage constituting member having an internal passage which is at least part of an exhaust passage whose one end is connected to the combustion chamber of the internal combustion engine and the other end is opened to the atmosphere;
A particulate filter accommodated in the internal passage of the exhaust passage constituent member and collecting particulate matter contained in the exhaust gas;
A fuel reformer according to claim 8,
An exhaust purification device for an internal combustion engine, wherein an outlet of a container of the fuel reformer is connected to an internal passage of the exhaust passage component, and the combustible reformed fuel is supplied to the particulate filter. .

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