WO2016017428A1 - 化学蓄熱装置 - Google Patents

化学蓄熱装置 Download PDF

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Publication number
WO2016017428A1
WO2016017428A1 PCT/JP2015/070282 JP2015070282W WO2016017428A1 WO 2016017428 A1 WO2016017428 A1 WO 2016017428A1 JP 2015070282 W JP2015070282 W JP 2015070282W WO 2016017428 A1 WO2016017428 A1 WO 2016017428A1
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WIPO (PCT)
Prior art keywords
heat storage
porous body
storage material
reaction medium
ammonia
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PCT/JP2015/070282
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English (en)
French (fr)
Japanese (ja)
Inventor
研二 森
鈴木　秀明
聡 針生
野口　幸宏
山内　崇史
志満津　孝
Original Assignee
株式会社豊田自動織機
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Application filed by 株式会社豊田自動織機 filed Critical 株式会社豊田自動織機
Publication of WO2016017428A1 publication Critical patent/WO2016017428A1/ja

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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28D—HEAT-EXCHANGE APPARATUS, NOT PROVIDED FOR IN ANOTHER SUBCLASS, IN WHICH THE HEAT-EXCHANGE MEDIA DO NOT COME INTO DIRECT CONTACT
    • F28D20/00—Heat storage plants or apparatus in general; Regenerative heat-exchange apparatus not covered by groups F28D17/00 or F28D19/00
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
    • F28F23/00—Features relating to the use of intermediate heat-exchange materials, e.g. selection of compositions
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/14—Thermal energy storage

Definitions

  • the present invention relates to a chemical heat storage device.
  • An exhaust system of a vehicle or the like is provided with various catalysts, filters, and the like inside the piping in order to purify environmental pollutants (HC, CO, NOx, etc.) contained in the exhaust gas discharged from the engine. .
  • the catalyst has an optimum temperature (activation temperature) for exerting the purification ability.
  • the catalyst is warmed by the exhaust gas and reaches the activation temperature.
  • the temperature of the exhaust gas is low, so it takes a long time for the catalyst to reach the activation temperature. Therefore, it is conceivable to provide a heating device for warming up the catalyst so that the temperature of the catalyst is raised to the activation temperature in a short time even when the temperature of the exhaust gas is low, such as when the engine is started. ing.
  • a chemical heat storage device using a reversible chemical reaction between a reaction medium and a heat storage material, which can warm up by reducing energy loss (fuel consumption loss), is known.
  • a chemical heat storage device for example, in Patent Document 1, a heat storage material (heat storage material) is arranged on the outer periphery of a catalyst that is a heating target, and reaction heat due to a chemical reaction between the heat storage material and a reaction medium is used.
  • a catalyst warm-up device for warming up the catalyst is disclosed.
  • the reaction medium introduction port when the reaction medium introduction port is arranged on the outer peripheral surface of the heater having an annular cross section, when the reaction medium is introduced into the heater from the reaction medium introduction port, the heat storage material is close to the reaction medium introduction port (outer periphery). Chemical reaction with the reaction medium in order from the side part) expands the volume. However, before the reaction medium reaches the entire heat storage material, if the outer peripheral portion of the heat storage material chemically reacts and expands the volume, it compresses the inner peripheral portion of the heat storage material. The reaction medium becomes difficult to diffuse. That is, the reactivity with the reaction medium is reduced in the inner peripheral portion of the heat storage material.
  • the volume of the heat storage material is expanded, the volume of the heat storage material is kept expanded even after the heat is stored and the reaction medium is desorbed. For this reason, after the heat storage material has undergone volume expansion during the first chemical reaction, the inner peripheral side portion of the heat storage material is always pressed by the outer peripheral side portion. For this reason, even during the second and subsequent chemical reactions, the reaction medium is difficult to diffuse in the inner peripheral side portion of the heat storage material, and the reactivity decreases.
  • the reaction between the heat storage material near and far from the reaction medium inlet is increased only by increasing the size of the heat storage material in the thickness direction. There was a difference in reactivity with the medium.
  • the present invention has been made in view of the above, and even when the thickness of the heat storage material is increased in order to increase the amount of the heat storage material mounted in the heater, the entire heat storage material is made uniform.
  • An object of the present invention is to provide a chemical heat storage device capable of efficiently extracting heat by chemically reacting with a reaction medium.
  • a chemical heat storage device is a chemical heat storage device that heats an object to be heated, and includes a heat storage material that reversibly generates heat due to a chemical reaction with a reaction medium and desorption of the reaction medium due to heat storage.
  • a heater provided inside the casing, a reservoir for storing the reaction medium, and a connecting pipe for allowing the reaction medium to flow between the heater and the reservoir, and the heat storage material transfer heat to the object to be heated.
  • the heater is divided into a plurality of layers along the heat direction, and the heater diffuses the reaction medium introduced from the reaction medium introduction port into at least one reaction medium introduction port connected to the connecting pipe and forms a heat storage material.
  • the porous body is disposed between adjacent layers in the heat storage material disposed in a plurality of layers along the heat transfer direction.
  • the first porous body has an internal flow path, Connecting ⁇ body inlet and a first porous body.
  • This chemical heat storage device includes a heater disposed at a location where the object to be heated can be heated and a reservoir disposed at other locations, and the heater and the reservoir are connected by a connecting pipe.
  • the storage medium stores the reaction medium, and supplies the reaction medium to the heater through the connecting pipe when heating of the object to be heated is necessary.
  • the heater has a heat storage material inside the casing, and when the reaction medium is introduced from the reaction medium introduction port connected to one end of the connecting pipe, the heat storage material and the reaction medium react chemically to generate heat. And the object to be heated is heated.
  • the heat storage material is arranged in a plurality of layers along the heat transfer direction for transferring heat to the object to be heated.
  • the heater is provided with a porous body that diffuses the reaction medium introduced from the reaction medium inlet and supplies the diffused reaction medium to the heat storage material.
  • the porous body has a large number of holes through which the reaction medium can flow, and becomes a path through which the reaction medium flows.
  • the porous body has a first porous body. A 1st porous body is arrange
  • the heater is provided with at least one internal flow path that connects the reaction medium introduction port and the first porous body so that the reaction medium can flow. Therefore, when the reaction medium is introduced into the heater from the reaction medium introduction port, the reaction medium can be circulated from the reaction medium introduction port to the first porous body by the internal flow path. Further, the reaction medium is diffused between the heat storage material of one layer and the heat storage material of the other layer by the first porous body, and the reaction medium is respectively applied to the heat storage material of one layer and the heat storage material of the other layer. Can be supplied. As a result, the reaction medium can be quickly supplied to the heat storage material far from the reaction medium introduction port among the heat storage materials housed in the casing of the heater. It rapidly reacts with the reaction medium without swelling and expands.
  • the reaction medium introduced from the reaction medium inlet also directly diffuses in the portion of the heat storage material near the reaction medium introduction port, the heat storage material in the vicinity of the reaction medium rapidly reacts with the reaction medium and expands. Therefore, the volume of the heat storage material in the portion close to the reaction medium inlet and the heat storage material in the far portion expand substantially uniformly.
  • the state in which the heat storage material of each layer is almost uniformly volume-expanded is maintained even after the reaction medium is desorbed, and the pressure by the heat storage material of each layer that has been substantially uniformly volume-expanded is almost uniformly applied to the periphery.
  • the chemical heat storage device provides the first porous body between the heat storage materials of each layer even when the amount of the heat storage material mounted on the heater is increased by laminating the heat storage materials in a plurality of layers.
  • the reaction medium introduction port by providing an internal flow path for circulating the reaction medium introduced from the reaction medium introduction port to the first porous body, among the heat storage materials formed in a plurality of layers, particularly from the reaction medium introduction port A decrease in reactivity at a distant portion can be suppressed.
  • the entire heat storage material can be uniformly chemically reacted with the reaction medium to efficiently extract heat.
  • the porous body has a second porous body disposed in the internal flow path.
  • the porous body has a third porous body disposed between the inner peripheral surface of the casing provided with the reaction medium inlet and the layer of the heat storage material adjacent to the casing.
  • the porous body further has a third porous body.
  • the third porous body is disposed between the inner peripheral surface of the casing and the heat storage material layer adjacent to the casing. This third porous body also becomes a path through which the reaction medium flows, like the first porous body.
  • the reaction medium is introduced into the heater from the reaction medium inlet, the third porous body can quickly diffuse and supply the reaction medium to each part of the heat storage material in the layer closest to the casing.
  • the reactivity can be improved.
  • the reactivity between the heat storage material and the reaction medium can be improved by providing the third porous body between the heat storage material in the layer closest to the casing and the casing.
  • the porous body has at least one fourth porous body that is connected at one end to the first porous body and extends from the first porous body toward the object to be heated.
  • the porous body further has a fourth porous body.
  • One end of the fourth porous body is connected to the first porous body, and extends from the first porous body toward the object to be heated.
  • This fourth porous body also becomes a path through which the reaction medium flows, like the first porous body.
  • the reaction medium diffuses into the first porous body, the reaction medium is rapidly diffused and supplied from the first porous body to the inside of the layer of the heat storage material arranged on the heated object side by the fourth porous body. can do.
  • the reactivity of a thermal storage material and a reaction medium can further be improved.
  • the heat storage material and the reaction medium The reactivity can be improved.
  • the porous body has a porosity of 10% or more and an average pore diameter of 150 ⁇ m or less in a state where pressure is received from the heat storage material expanded by a chemical reaction with the reaction medium.
  • each porous body is a porous body having a porosity of 10% or more and an average pore diameter of 150 ⁇ m or less when pressure is applied by the volume-expanded heat storage material.
  • porosity is 10% or more, a sufficient amount of the reaction medium necessary for the chemical reaction of each part of the heat storage material can be quickly circulated and diffused through the porous body.
  • the average pore diameter is 150 ⁇ m or less, it is possible to prevent particles of the heat storage material (for example, those in which a part of the heat storage material molding is chipped and powdered) enter the pores of the porous body. Therefore, even when the porous body is under pressure by the heat storage material that has undergone volume expansion, the porous body can function as a path through which the reaction medium flows.
  • the entire heat storage material in the heater can be uniformly chemically reacted with the reaction medium to efficiently extract heat.
  • FIG. 1 is a schematic configuration diagram of an exhaust gas purification system including a chemical heat storage device according to an embodiment.
  • FIG. 2 is a cross-sectional view around the heater and the heat exchanger according to the first embodiment, (a) is a front cross-sectional view, and (b) is a side cross-section along the line AA in the front cross-sectional view.
  • FIG. 3 is a perspective view of the porous sheet, in which (a) is a state before being assembled in the heater, and (b) is a state after being assembled in the heater.
  • FIG. 4 is a front sectional view of the vicinity of the heater and the heat exchanger according to the second embodiment.
  • the chemical heat storage device is applied to a chemical heat storage device provided in an exhaust gas purification system provided in an exhaust system of a vehicle engine.
  • An exhaust gas purification system is a system that purifies harmful substances (environmental pollutants) contained in exhaust gas discharged from an engine (particularly a diesel engine), and is a catalyst DOC [Diesel Oxidation Catalyst]. SCR [SelectiveSelectCatalytic Reduction], ASC [Ammonia Slip Catalyst] and DPF [Diesel Particulate Filter] of the filter.
  • the exhaust gas purification system includes a chemical heat storage device for warm-up.
  • FIG. 1 is a schematic configuration diagram of an exhaust gas purification system 1 according to an embodiment.
  • FIG. 2 is a cross-sectional view around the heater and the heat exchanger according to the first embodiment, (a) is a front cross-sectional view, and (b) is a side cross-sectional view along the line AA in the front cross-sectional view. It is.
  • the exhaust gas purification system 1 includes a heat exchanger 4, a diesel oxidation catalyst (DOC) 5, a diesel exhaust particulate removal filter (DPF) from the upstream side to the downstream side of the exhaust pipe 3 connected to the exhaust side of the engine 2. 6.
  • a selective reduction catalyst (SCR) 7 and an ammonia slip catalyst (ASC) 8 are provided.
  • Each part where these heat exchangers 4, DOC5, DPF6, SCR7, and ASC8 are arranged is larger than the diameter of the exhaust pipe 3 where the parts are not arranged.
  • Exhaust gas discharged from the engine 2 flows inside the exhaust pipe 3 and the heat exchanger 4, DOC5, DPF6, SCR7, and ASC8, and the upstream side and the downstream side are defined by the flow direction of the exhaust gas.
  • the heat exchanger 4 is a device that exchanges (transmits) heat between exhaust gas discharged from the engine 2 and a heater 11 described later.
  • the heat exchanger 4 is formed of, for example, a high thermal conductivity material such as metal or ceramic, and the inside of a cylindrical outer cylinder 4a is a honeycomb structure 4b as shown in FIG.
  • the heat exchanger 4 is not limited to the honeycomb structure, and a known heat exchange structure can be applied.
  • the DOC 5 is a catalyst that oxidizes HC, CO, etc. contained in the exhaust gas.
  • the DPF 6 is a filter that collects and removes PM [Particulate Matter] contained in the exhaust gas.
  • SCR 7 When SCR 7 is supplied with ammonia (NH 3 ) or urea water (hydrolyzed into ammonia) to the upstream side of the exhaust pipe 3 by the injector 7 a, the SCR 7 chemically reacts with NOx contained in the exhaust gas. This is a catalyst that reduces and purifies NOx.
  • the ASC 8 is a catalyst that oxidizes ammonia that has passed through the SCR 7 and has flowed downstream.
  • Each of the catalysts 5, 7, 8 has a temperature range (that is, an activation temperature) that can exhibit a purification ability against environmental pollutants.
  • the temperature of the exhaust gas immediately after being discharged from the engine 2 is relatively low and may be lower than its activation temperature. Therefore, in order for the catalysts 5, 7, and 8 to exhibit the purification capability even immediately after the engine 2 is started, it is necessary to quickly bring the temperatures of the catalysts 5, 7, and 8 to the activation temperatures.
  • the exhaust gas purification system 1 includes a chemical heat storage device 10 that heats the exhaust gas via the most upstream heat exchanger 4 and warms up the catalyst.
  • the chemical heat storage device 10 is a chemical heat storage device that warms up an object to be heated without external energy. Specifically, the chemical heat storage device 10 stores heat by separating the heat storage material and the reaction medium, and supplies the reaction medium to the heat storage material when necessary to store the heat storage material and the reaction medium. Are heated, and the object to be heated is heated using reaction heat (heat radiation) during the chemical reaction. That is, the chemical heat storage device 10 stores heat using a reversible chemical reaction and supplies heat to the object to be heated again. In this embodiment, the chemical heat storage device 10 heats the exhaust gas via the heat exchanger 4 arranged on the upstream side of the DOC 5 that is the catalyst located on the most upstream side.
  • the heat exchanger 4 corresponds to the heating object described in the claims.
  • the chemical heat storage device 10 includes a heater 11, a storage 12, a connecting pipe 13, a valve 14, and the like.
  • the heater 11 corresponds to the heater described in the claims
  • the storage 12 corresponds to the reservoir described in the claims
  • the connecting pipe 13 corresponds to the claims.
  • the heater 11 is provided on the entire circumference of the outer peripheral portion of the heat exchanger 4, and the cross-sectional shape is an annular shape surrounding the heat exchanger 4.
  • the heater 11 has a large number of heat storage materials 11a (11a 1 , 11a 2 ) that generate heat by a chemical reaction with the reaction medium, and the large number of heat storage materials 11a are housed inside the casing 11b.
  • ammonia is used as the reaction medium.
  • ammonia and the heat storage material 11 a chemically react (chemical adsorption or coordinate bond) to generate heat.
  • the heat storage material 11a that has received the exhaust heat of the exhaust gas through the heat exchanger 4 reaches a predetermined temperature or higher, ammonia is separated (desorbed) from the heat storage material 11a.
  • This predetermined temperature is determined by the combination of the heat storage material 11a used in the heater 11 and the reaction medium.
  • the heat storage material 11 a is disposed so as to be in contact with the entire circumference of the outer peripheral surface of the outer cylinder 4 a of the heat exchanger 4.
  • a material that generates heat by chemically reacting with ammonia as a reaction medium and can raise the exhaust gas passing through the heat exchanger 4 to the activation temperature of the catalyst (DOC5 or the like) is used.
  • the additive which improves thermal conductivity with the thermal storage material 11a.
  • the additive include carbon fiber, carbon bead, SiC bead, Cu, Ag, Ni, Ci—Cr, Al, Fe, stainless steel and other metal beads, polymer beads, and polymer fibers.
  • the casing 11 b is disposed so as to cover the entire outer peripheral side of the heater 11 and the entire upstream end and downstream end of the heater 11, and is sealed between the outer peripheral surface of the outer cylinder 4 a of the heat exchanger 4.
  • a space is formed, and the heat storage material 11a is enclosed therein.
  • a heat insulating material may be provided between the heat storage material 11a and the casing 11b, or a heat conductive sheet formed of a metal sheet such as a graphite sheet or aluminum is provided between the heat storage material 11a and the outer cylinder 4a. May be.
  • heat transfer direction (direction from the outer peripheral side to the inner peripheral side) for transferring heat to the heat exchanger 4 in order to increase the generated heat quantity by increasing the thickness of the heat storage material as a whole.
  • heat storage material 11a is divided into two layers (thermal storage material 11a 2 on the inner circumferential side of the layer heat storage material 11a 1 and the outer layer of) along the are disposed.
  • the heat storage materials 11a 1 and 11a 2 are molded bodies in which the material of the heat storage material is consolidated into a pellet shape by pressing.
  • a plurality of heat storage materials 11a 1 are arranged on the outer peripheral surface of the outer cylinder 4a of the heat exchanger 4 along the direction in which the exhaust gas flows as shown in FIG. It is set (in the case of the example shown in FIGS. 2 (a), 8 pieces) plurality along in the circumferential direction as shown in FIG. 2 (a) is the heat storage material 11a 1 is arranged disposed of.
  • a plurality of heat storage materials 11a 2 (the same number as the inner layer) are provided on the outer peripheral side of the inner peripheral layer along the exhaust gas flow direction as shown in FIG. 2B. It is aligned with arranged (in the example shown in FIGS.
  • the thermal storage material 11a 2 are arranged disposed of
  • the side cross-sectional shape of each of the heat storage materials 11a 1 and 11a 2 is substantially rectangular as shown in FIG. 2B, and the front cross-sectional shape has a predetermined thickness as shown in FIG. It has a substantially arc shape.
  • the plurality of heat storage materials 11a 1 and 11a 2 are arranged in a two-layered shape surrounding the entire outer periphery of the outer cylinder 4a of the heat exchanger 4.
  • the length of each heat storage material 11a 2 on the inner circumferential side (length in the direction of flow of exhaust gas)
  • the length of each heat storage material 11a 1 layer and the outer peripheral side of the layer is substantially the same length.
  • the inner peripheral side of the width of each heat storage material 11a 2 and the outer peripheral side of the layer (the width in the circumferential direction) width each heat storage material 11a 1 layer, with wider towards the thermal storage material 11a 2 of the outer peripheral side of the layer is there.
  • the inner peripheral side of the thickness of each heat storage material 11a 2 and the outer peripheral side of the layer (thickness at the heat transfer direction) the thermal storage material 11a 1 of the thickness of the layer is substantially the same thickness.
  • the thickness of the heater 11 as a whole is increased.
  • the amount of heat storage material mounted in the heater 11 increases, and the amount of heat that can be generated by the heater 11 increases.
  • FIG. 2 shows the heat storage materials 11a 1 and 11a 2 before expansion that have never chemically reacted with ammonia, and there are voids around the heat storage materials 11a 1 and 11a 2 .
  • the heat storage material 11a 1, 11a 2 is inflated with ammonia and chemical reaction, the void is filled with the heat storage material 11a 1, 11a 2 that volume expansion, additional pressure due to volume expansion in the periphery of the heat storage material 11a 1, 11a 2 To do.
  • thermal storage material 11a 1, 11a 2 is volume expansion, so that the heat storage material 11a 1 in a state in which volumetric expansion, 11a 2 continues to add pressure to the periphery.
  • the heater 11A is a first porous body that serves as an ammonia flow path as a porous body for diffusing the ammonia introduced from the ammonia inlet 13a and supplying it uniformly to the heat storage materials 11a 1 and 11a 2 of the two layers.
  • 11c, a second porous body 11d, a third porous body 11e, and a fourth porous body 11f are a first porous body that serves as an ammonia flow path as a porous body for diffusing the ammonia introduced from the ammonia inlet 13a and supplying it uniformly to the heat storage materials 11a 1 and 11a 2 of the two layers.
  • 11c a second porous body 11d
  • a third porous body 11e corresponds to the second porous body recited in the claims.
  • the third porous body 11e corresponds to the third porous body recited in the claims
  • the fourth porous body 11f corresponds to the fourth porous body recited in the claims.
  • the first porous member 11c is disposed between the thermal storage material 11a 2 to form a layer of the heat storage material 11a 1 and the outer periphery side to form a layer on the inner circumferential side.
  • the first porous member 11c has a cylindrical shape having a predetermined thickness, has a length substantially the same length of the column comprising a plurality of thermal storage material 11a 1 which is disposed in a direction that the exhaust gas flows Yes.
  • the ammonia through the second porous body 11d is supplied (where ammonia is also supplied through the thermal storage material 11a 2 to form a layer on the outer peripheral side), the inner peripheral Ammonia diffuses quickly and uniformly between the heat storage material 11a 1 forming the side layer and the heat storage material 11a 2 forming the outer layer. Therefore, the first porous body 11c functions as a path for supplying ammonia to the heat storage material 11a 1 of the inner peripheral side of the layer, also serves as a path for supplying ammonia to the thermal storage material 11a 2 on the outer circumferential side of the layer.
  • the third porous member 11e is disposed between the thermal storage material 11a 2 to form a layer of the inner peripheral surface and the outer side of the casing 11b.
  • the third porous body 11e has a cylindrical shape having a predetermined thickness, has a length substantially the same length of the column comprising a plurality of thermal storage material 11a 2 which are arranged along the direction in which the exhaust gas flows Yes.
  • the third porous body 11e is connected to an ammonia introduction port 13a opened on the inner peripheral surface of the casing 11b. When ammonia is introduced from the ammonia introduction port 13a, a layer on the outer peripheral side is formed with the casing 11b. Ammonia diffuses rapidly and uniformly between the heat storage material 11a 2 to be performed.
  • the third porous member 11e functions as a path for supplying ammonia to the thermal storage material 11a 2 on the outer circumferential side of the layer.
  • the second porous body 11d is provided between the first porous body 11c and the third porous body 11e, and connects the first porous body 11c and the third porous body 11e.
  • the second porous body 11d, a plurality of heat storage material consisting of 11a 2 rows and a plurality of the adjacent exhaust gas of the thermal storage material 11a 2 to form a layer on the outer periphery side is arranged along the direction of flow It is disposed between the columns of the thermal storage material 11a 2.
  • the second porous body 11d is disposed between the rows closest to the ammonia inlet 13a. In the case of the example shown in FIG. 2, the second porous body 11d is disposed immediately below the ammonia inlet 13a.
  • the second porous body 11d has a rectangular shape with a predetermined thickness, and has approximately the same length as the lengths of the first porous body 11c and the third porous body 11e.
  • the second porous body 11d when ammonia is introduced from the ammonia introduction port 13a and the ammonia is supplied through the third porous body 11e, the ammonia rapidly diffuses in the direction of the first porous body 11c. .
  • the second porous body 11d functions as a path (flow path) for flowing ammonia from the third porous body 11e to the first porous body 11c, and the heat storage material 11a existing around the second porous body 11d. 2 also functions as a path for supplying ammonia to the tank.
  • the flow path formed by the second porous body 11d corresponds to the internal flow path described in the claims.
  • the fourth porous body 11f is provided between the first porous body 11c and the outer peripheral surface of the outer cylinder 4a of the heat exchanger 4, and connects the first porous body 11c and the outer cylinder 4a.
  • the fourth porous body 11f is an inner circumferential side of the columns comprising a plurality of thermal storage material 11a 1 of the exhaust gas is disposed along a flow direction of the heat storage material 11a 1 to form a layer and a plurality of the adjacent The heat storage material 11a 1 is provided between the columns.
  • the fourth porous body 11f is provided between the rows closest to the second porous body 11d. In the case of the example shown in FIG.
  • the fourth porous body 11 f is arranged at a position slightly deviated from directly below the second porous body 11 d (ammonia introduction port 13 a), but the heat storage material of the inner peripheral side layer depending on the arrangement of 11a 1 may be located directly under the second porous body 11d (ammonia inlet 13a).
  • the fourth porous body 11f has a rectangular shape with a predetermined thickness, and has substantially the same length as the length of the first porous body 11c. In the fourth porous body 11f, when ammonia is supplied through the first porous body 11c, the ammonia rapidly diffuses in the direction of the outer cylinder 4a.
  • the fourth porous body 11f serves as a path for supplying ammonia to the heat storage material 11a 1 existing around the fourth porous body 11f.
  • Each of the porous bodies 11c to 11f has a diameter that allows gaseous ammonia to sufficiently flow and does not contain particles of the heat storage material 11a (for example, a part of the heat storage material molded body lacking powder). Has many holes. Further, even when the porous bodies 11c to 11f are subjected to pressure by the heat storage material 11a having undergone volume expansion, the outer shape is substantially maintained (particularly, the thickness is ensured), and the pores are not crushed (however, ammonia If it can be distributed, it may be somewhat crushed). Further, each of the porous bodies 11c to 11f does not prevent this heat transfer when transferring heat generated by the chemical reaction of the heat storage material 11a with ammonia along the heat transfer direction.
  • the porous bodies 11c to 11f when the heat storage material 11a chemically reacts with ammonia, its volume expands, and this volume expanded state is maintained even if ammonia is desorbed from the heat storage material 11a. Therefore, when the heat storage material 11a is first subjected to volume expansion, the porous bodies 11c to 11f provided at each position by the volume expansion heat storage material 11a thereafter receive pressure (surface pressure) due to volume expansion. Therefore, as described above, even when each of the porous bodies 11c to 11f is subjected to pressure by the volume-expanded heat storage material 11a, the porous bodies 11c to 11f have a strength that prevents the holes from being crushed in order to function as an ammonia flow path. .
  • each of the porous bodies 11c to 11f preferably has a porosity of 10% or more and an average pore diameter of 150 ⁇ m or less when pressure is applied by the volume-expanded heat storage material 11a.
  • the porosity is 10% or more, a sufficient amount of ammonia necessary for the chemical reaction can be quickly diffused.
  • the average pore diameter is 150 ⁇ m or less, it is possible to prevent a part of the heat storage material 11a from being in the hole.
  • the pressure (surface pressure) received by the porous bodies 11c to 11f by the volume-expanded heat storage material 11a is the density of the porous material used for the porous bodies 11c to 11f, the space volume in the casing 11b of the heater 11A, and the heater. It is defined by the loading amount of all the heat storage materials 11a 1 and 11a 2 accommodated in 11A.
  • the pressure (surface pressure) is, for example, about 0.2 MPa to 20 MPa.
  • the porous material used in each of the porous bodies 11c to 11f has corrosion resistance against ammonia.
  • the porous material is preferably excellent in thermal conductivity.
  • the porous material is a porous material made of metal (particularly, fibrous material), ceramic, or the like.
  • metal it is stainless steel, for example, aluminum, copper, etc. may be sufficient.
  • the porous material include a felt-like material formed of a very thin wire (stainless steel fiber) of stainless steel or a foam metal.
  • the thickness of each of the porous bodies 11c to 11f is a thickness that can sufficiently retain the outer shape even when pressure is applied by the volume-expanded heat storage material 11a.
  • the thickness of each of the porous bodies 11c to 11f is desirably a thickness that does not make it difficult for heat to be transmitted.
  • the thickness of each porous body 11c to 11f is, for example, about 0.1 mm to 3 mm, preferably about 0.2 mm to 2 mm.
  • FIG. 3 is a perspective view of the porous sheet, in which (a) is a state before being assembled in the heater 11A, and (b) is a state after being assembled in the heater 11A.
  • the porous sheet 15 forms the first porous body 11c and the fourth porous body 11f or the third porous body 11e and the second porous body 11d.
  • the porous sheet 15 is a rectangular sheet formed of the above-described porous material and having the above thickness.
  • the porous sheet 15 has a main body portion 15a and bent end portions 15b obtained by vertically bending both end portions of the main body portion 15a.
  • the width of the main body 15a is a width corresponding to the circumferential length of the cylindrical first porous body 11c or the third porous body 11e.
  • the width of the bent end portion 15b is a width corresponding to the length in the heat transfer direction of the second porous body 11d and the fourth porous body 11f (the thickness of the heat storage materials 11a 1 and 11a 2 ).
  • the length of the porous sheet 15 is the length of each of the porous bodies 11c to 11d in the direction in which the exhaust gas flows (a row of a plurality of heat storage materials 11a 1 and 11a 2 arranged along the direction in which the exhaust gas flows). Length).
  • the porous sheet 15 is bent on the outer side of the heat storage material 11a 1 forming the inner peripheral layer or the heat storage material 11a 2 forming the outer peripheral layer as shown in FIG. Round with 15b, 15b inside.
  • the 1st porous body 11c or the 3rd porous body 11e is comprised by forming a cylinder with the main-body part 15a.
  • the side surface of one bent end portion 15b at both ends is matched with the side surface of the other bent end portion 15b.
  • the storage 12 includes an adsorbent 12a that can hold (adsorb) and separate (release) ammonia as a reaction medium.
  • adsorbent 12a for example, activated carbon capable of storing ammonia by physical adsorption is used.
  • ammonia is separated from the adsorbent 12 a and supplied to the heater 11, and after the warm-up is completed, the exhaust heat of exhaust gas is received and the ammonia desorbed from the heat storage material 11 a is physically adsorbed to the adsorbent 12 a. Collect again.
  • the adsorbent 12a is not limited to activated carbon, and for example, mesoporous material having mesopores such as mesoporous silica, mesoporous carbon, or mesoporous alumina, zeolite, or silica gel may be used.
  • mesoporous material having mesopores such as mesoporous silica, mesoporous carbon, or mesoporous alumina, zeolite, or silica gel may be used.
  • the connecting pipe 13 is a pipe that connects the heater 11 and the storage 12, and serves as a flow path through which the reaction medium (ammonia) flows between the heater 11 and the storage 12.
  • One end of the connecting pipe 13 on the heater 11 side passes through the casing 11b of the heater 11 and is connected to an opening on the inner peripheral surface of the casing 11b. This opening is the ammonia inlet 13a.
  • ammonia introduction port 13a Through the ammonia introduction port 13a, ammonia is introduced into the heater 11 from the outermost peripheral side (third porous body 11e) of the internal space of the casing 11b.
  • the ammonia inlet 13a corresponds to the reaction medium inlet described in the claims.
  • one ammonia inlet 13a is provided, but a plurality of ammonia inlets 13a may be provided.
  • the valve 14 is a valve disposed in the middle of the connecting pipe 13 to open and close the ammonia flow path between the heater 11 and the storage 12. When the valve 14 is opened, ammonia can be transferred between the heater 11 and the storage 12 via the connecting pipe 13.
  • the opening / closing control of the valve 14 is performed by a dedicated controller of the chemical heat storage device 10 or an ECU such as an ECU (Electronic Control Unit) that controls the engine 2.
  • the valve 14 is an electromagnetic normally closed valve and opens when a voltage is applied.
  • the valve 14 may be a current-driven valve or a valve other than an electromagnetic valve.
  • the operation of the chemical heat storage device 10 including the heater 11A configured as described above will be described.
  • the valve 14 is opened when a voltage is applied to the valve 14.
  • ammonia can be moved in the connecting pipe 13.
  • the pressure in the storage 12 is higher than the pressure in the heater 11 ⁇ / b> A
  • the ammonia in the storage 12 flows in the connection pipe 13, and the heater 11 ⁇ / b> A passes through the ammonia inlet 13 a of the connection pipe 13. It is introduced into the casing 11b.
  • the third porous member 11e When ammonia inlet 13a ammonia is introduced into the third porous member 11e, the third porous member 11e, rapidly and uniformly between the thermal storage material 11a 2 of ammonia to form a layer of casing 11b and the outer periphery side To spread. This uniformly diffused ammonia is supplied uniformly to the heat storage material 11a 2 forming the outer peripheral layer. Further, when ammonia is rapidly supplied to the second porous body 11d disposed near the ammonia introduction port 13a via the third porous body 11e, the second porous body 11d has the first porous body 11c. Ammonia diffuses quickly in the direction of.
  • ammonia When ammonia is supplied to the first porous body 11c, ammonia diffuses quickly and uniformly between the thermal storage material 11a 2 to form a layer of the heat storage material 11a 1 and the outer periphery side to form a layer on the inner circumferential side .
  • the uniformly diffused ammonia is uniformly supplied to the heat storage material 11a 1 forming the inner peripheral layer and also supplied to the heat storage material 11a 2 forming the outer peripheral layer.
  • ammonia when ammonia is supplied to the fourth porous body 11f via the first porous body 11c, the ammonia rapidly diffuses in the direction of the outer cylinder 4a of the heat exchanger 4 in the fourth porous body 11f. .
  • the heater 11A not only the thermal storage material 11a 2 side to form a layer on the outer peripheral side closer to the ammonia inlet 13a, in the heat storage material 11a 1 that forms an inner peripheral side of the layer furthest from the ammonia inlet 13a Ammonia is supplied uniformly and rapidly.
  • the supplied ammonia and the heat storage materials 11a 1 and 11a 2 of each layer chemically react to generate heat.
  • the heat storage material 11a 2 forming the outer layer is chemically reacted with ammonia, in parallel, the heat storage material 11a 1 forming the inner layer is also chemically reacted with ammonia. .
  • the thermal storage material 11a 2 When ammonia from the storage 12 is first supplied to the heater 11A is, the thermal storage material 11a 2 to form a layer on the outer peripheral side, the volume expands by ammonia and chemical reaction. In parallel with this, the volume of the heat storage material 11a 1 forming the inner peripheral layer also expands due to a chemical reaction with ammonia. Therefore, the heat storage material 11a 2 that forms the outer peripheral layer and the heat storage material 11a 1 that forms the inner peripheral layer chemically react almost uniformly, and the volume expands.
  • the heat generated by the chemical reaction between the heat storage materials 11a 1 and 11a 2 and ammonia is transferred to the outer cylinder 4a of the heat exchanger 4 and is transferred to the honeycomb structure 4b inside the heat exchanger 4 by the heat transfer effect.
  • the heat exchanger 4 is heated, the temperature of the exhaust gas flowing through the honeycomb structure 4b of the heat exchanger 4 rises. Further, the heated exhaust gas flows downstream, and the temperature of each catalyst of DOC5, SCR7, and ASC8 rises. And when the temperature of each catalyst becomes more than the activation temperature, the exhaust gas can be suitably purified.
  • the chemical heat storage device 10 provided with the heater 11A, even when increasing the thickness of the entire heat storage material by the heat storage material 11a 1, 11a 2 of two layers, the first between the heat storage material 11a 1, 11a 2 of the two layers 1
  • the porous body 11c and the second porous body 11d for diffusing the ammonia introduced from the ammonia inlet 13a into the first porous body 11c are provided, so that the inner peripheral layer is formed.
  • Ammonia can also be supplied quickly and uniformly to the heat storage material 11a 1 to be formed.
  • the reduction of the heat storage material 11a 1 of each layer, reactivity at 11a 2 (in particular, the reactivity of the heat storage material 11a 1 on the far side of the layer from the ammonia inlet 13a) can be suppressed. Therefore, in the chemical heat storage device 10, since the chemical reaction (chemical adsorption) with ammonia occurs quickly and uniformly in the heat storage materials 11a 1 and 11a 2 of each layer, the heat storage materials 11a 1 and 11a 2 are efficiently adapted to the mounting amount of the heat storage materials 11a 1 and 11a 2 . Much heat can be extracted.
  • the chemical heat storage device 10 by providing the third porous member 11e between the thermal storage material 11a 2 and the casing 11b to form a layer on the outer peripheral side close to the casing 11b, to form a layer on the outer peripheral side Since ammonia can be supplied to the heat storage material 11a 2 quickly and uniformly, the reactivity can be further improved. Further, according to the chemical heat storage device 10, the reactivity can be further improved by providing the fourth porous body 11 f between the first porous body 11 c and the outer peripheral surface of the outer cylinder 4 a of the heat exchanger 4.
  • the chemical heat storage device 10 by providing the second porous body 11d between the first porous body 11c and the third porous body 11e, even when the heat storage material 11a is volume-expanded, An internal flow path for diffusing ammonia to the porous body 11c can be ensured.
  • the porosity of the porous bodies 11c to 11f is 10% or more. Further, since the average pore diameter is 150 ⁇ m or less, each of the porous bodies 11c to 11f can sufficiently function as an ammonia flow path.
  • the ammonia inlet can be provided at a plurality of locations. Even if the ammonia introduction port 13a becomes one place in consideration of the mountability to the vehicle and the number of parts, the ammonia introduced from the ammonia introduction port 13a by the third porous body 11e is quickly diffused in the circumferential direction. it can. It is also conceivable that the connecting pipe is inserted into the heater, and the ammonia introduction port is provided inside the heater (for example, a position close to the heat exchanger). There is a possibility that the missing part enters the ammonia inlet. Therefore, in the chemical heat storage device 10, the ammonia introduction port 13a is provided at the position of the outermost peripheral portion (third porous body 11e) of the heater 11.
  • FIG. 4 is a front sectional view of the vicinity of the heater and the heat exchanger according to the second embodiment.
  • the heater 11B is different from the heater 11A described above in that it has only the first porous body 11c as a porous body and an internal flow path 11g.
  • the first porous body 11c corresponds to the first porous body described in the claims
  • the internal flow path 11g corresponds to the internal flow path described in the claims.
  • the heater 11B Since the heater 11B is not provided the third porous member 11e, it is arranged thermal storage material 11a 2 of the outer peripheral side of the layer between the casing 11b and the first porous body 11c as shown in FIG. 4 . Further, since the heater 11B not provided a fourth porous body 11f, all of the heat storage material 11a 1 of the inner peripheral side of the layer along the circumferential direction as shown in FIG. 4 are arranged without an interval ing.
  • the internal flow path 11g is a flow path for diffusing ammonia by connecting the first porous body 11c and the ammonia inlet 13a.
  • the internal flow path 11g is disposed between the row closest to the ammonia introduction port 13a. In the case of the example shown in FIG. 4, the internal flow path 11g is disposed immediately below the ammonia inlet 13a.
  • the internal flow path 11g is a space having a predetermined width, and has substantially the same length as the length of the first porous body 11c.
  • the internal flow path 11g functions as a flow path for flowing ammonia from the ammonia introduction port 13a to the first porous body 11c.
  • the internal flow path 11g is formed by, for example, providing a groove in the casing 11b, or by forming a space between the heat storage materials 11a 2 and 11a 2 arranged in the circumferential direction slightly wider.
  • ammonia When ammonia is introduced from the ammonia inlet 13a, the ammonia is diffused toward the first porous body 11c by the internal flow path 11g formed near the ammonia inlet 13a, and the ammonia is supplied to the first porous body 11c. Is done.
  • ammonia When ammonia is supplied to the first porous body 11c, ammonia diffuses quickly and uniformly between the thermal storage material 11a 2 to form a layer of the heat storage material 11a 1 and the outer periphery side to form a layer on the inner circumferential side .
  • the uniformly diffused ammonia is uniformly supplied to the heat storage material 11a 1 forming the inner peripheral layer and also supplied to the heat storage material 11a 2 forming the outer peripheral layer.
  • ammonia is introduced from an ammonia inlet 13a is supplied directly to the thermal storage material 11a 2 to form a layer on the outer peripheral side.
  • the chemical heat storage device 10 provided with the heater 11B even when increasing the thickness of the entire heat storage material by the heat storage material 11a 1, 11a 2 of two layers, the first between the heat storage material 11a 1, 11a 2 of the two layers 1 of the porous body 11c provided with by providing an internal flow path 11g for diffusing ammonia to the first porous body 11c, the ammonia in the heat storage material 11a 1 to form a layer on the inner circumferential side quickly and uniformly Can supply. Therefore, a reduction in reactivity in each layer of the heat storage material 11a 1, 11a 2 can be suppressed.
  • the porous body since the porous body includes only the first porous body 11c, the number of constituent members of the heater 11B is small, and the manufacture of the heater 11B is facilitated.
  • the present invention is applied to an exhaust gas purification system including DOC, SCR, and ASC as a catalyst and DPF as a filter.
  • the present invention may be applied to an exhaust gas purification system having other configurations, for example, DOC, SCR, ASC.
  • the present invention may be applied to an exhaust gas purification system that does not include any one or two of these catalysts, or an exhaust gas purification system that includes a catalyst other than DOC, SCR, and ASC.
  • the vehicle is a diesel engine vehicle, it can also be applied to a gasoline engine vehicle. Further, the present invention can also be applied to other mounted objects such as ships and generators using an engine as a drive source.
  • a heater may be attached to a pipe through which oil, water, or other heat medium flows, and the heat medium flowing through the pipe may be heated. In this case, the piping becomes an object to be heated.
  • the heater is provided on the entire outer periphery of the heat exchanger.
  • the heater may be provided only on a part of the outer periphery of the heating object.
  • reaction medium is ammonia in the above embodiment
  • other reaction medium such as alcohol or water
  • each material of the heat storage material and the adsorbent when the reaction medium is ammonia is exemplified, but depending on the reaction medium used in the chemical heat storage device, other materials may be used as appropriate for the heat storage material and the adsorbent. Used.
  • segmented into 2 layers along a heat transfer direction it applies to the heater by which a thermal storage material is arrange
  • a fourth porous body is provided between the adjacent first outer porous body and the inner first porous body provided along the heat transfer direction, and the first outer body is provided by the fourth porous body. The porous body and the inner first porous body are connected.
  • the reaction medium When ammonia diffuses into the outer first porous body, the reaction medium can be quickly diffused to the inner first porous body by the fourth porous body, and ammonia is added to the heat storage material in the inner layer. It can be diffused quickly and the reactivity can be improved.
  • one end of the fourth porous body is connected to the first porous body, extends to the outer cylinder of the heat exchanger, and the other end is connected to the outer cylinder of the heat exchanger.
  • it does not extend to the outer cylinder of the heat exchanger, and the other end may not be connected to the outer cylinder of the heat exchanger.
  • the second porous body is provided only at one location between the first porous body and the third porous body. However, between the first porous body and the third porous body. It is good also as a structure which provides a 2nd porous body in 2 or more places (for example, all the places between the thermal storage materials divided
  • the fourth porous body is provided only at one location between the first porous body and the outer peripheral surface of the heat exchanger (heating target). It is good also as a structure which provides a 4th porous body in two or more places (for example, all the places between the thermal storage materials divided
  • the 1st porous body and the 4th porous body or the 3rd porous body are rounded by rounding the porous sheet which bent both ends into the cylindrical shape, and match
  • the example which forms a body and a 2nd porous body was shown, you may form each porous body with another method.
  • the porous material is sandwiched and pressed between the heat storage material of the outer peripheral side layer and the heat storage material of the inner peripheral side layer. A two-layer heat storage material in a sandwiched state is formed.
  • the second porous body is provided over the entire area of the internal flow path between the first porous body and the ammonia inlet (third porous body).
  • the second porous body may be provided.
  • the second porous body may be provided only in one internal channel, and some or all of the plurality of internal channels may be provided with the second porous body.
  • Two porous bodies may be provided.
  • the chemical heat storage device is configured by arranging the annular heater so as to surround the periphery of the cylindrical heat exchanger as the heating object, but is not limited thereto, A plurality of corrugated plate-shaped heat exchange members as heating objects and a plurality of flat tube-shaped heating chambers as heaters may be alternately stacked.
  • heat storage materials are arranged in a plurality of layers along the laminating direction of the corrugated plate-like heat exchange members, and the heat storage materials are arranged between the layers of the heat storage materials.
  • 1 porous body is provided.
  • the header part as an internal flow path which connects a reaction medium so that distribution
  • the porous body not only diffuses the reaction medium introduced into the heater from the reaction medium introduction port of the heater and supplies it to the heat storage material, but also removes the reaction medium desorbed from the heat storage material. It also functions as a reaction medium flow path leading to the inlet. That is, the first porous body provided between the layers of the heat storage material not only enables the uniform supply of the reaction medium to each part of the heat storage material, but also efficiently removes the reaction medium desorbed from each part of the heat storage material. To the reaction medium inlet.

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  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Exhaust Gas After Treatment (AREA)
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CN109556439A (zh) * 2019-01-10 2019-04-02 合肥职业技术学院 一种余热回收节能环保设备

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JP2018059681A (ja) * 2016-10-06 2018-04-12 株式会社豊田自動織機 化学蓄熱装置
JP2018179450A (ja) * 2017-04-19 2018-11-15 株式会社豊田自動織機 化学蓄熱装置

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JPS55165496A (en) * 1979-04-30 1980-12-23 Wallsten Hans Ivar Unit containing absorbant
JP2013253212A (ja) * 2012-06-08 2013-12-19 Shibaura Institute Of Technology 化学蓄熱材成形体およびその製造方法ならびに化学蓄熱装置
JP2014085093A (ja) * 2012-10-26 2014-05-12 Toyota Industries Corp 蓄熱装置

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JPS55165496A (en) * 1979-04-30 1980-12-23 Wallsten Hans Ivar Unit containing absorbant
JP2013253212A (ja) * 2012-06-08 2013-12-19 Shibaura Institute Of Technology 化学蓄熱材成形体およびその製造方法ならびに化学蓄熱装置
JP2014085093A (ja) * 2012-10-26 2014-05-12 Toyota Industries Corp 蓄熱装置

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CN109556439A (zh) * 2019-01-10 2019-04-02 合肥职业技术学院 一种余热回收节能环保设备

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