WO2015186604A1 - Appareil d'accumulation de chaleur chimique - Google Patents

Appareil d'accumulation de chaleur chimique Download PDF

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Publication number
WO2015186604A1
WO2015186604A1 PCT/JP2015/065441 JP2015065441W WO2015186604A1 WO 2015186604 A1 WO2015186604 A1 WO 2015186604A1 JP 2015065441 W JP2015065441 W JP 2015065441W WO 2015186604 A1 WO2015186604 A1 WO 2015186604A1
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WO
WIPO (PCT)
Prior art keywords
heat
heat storage
storage material
press
transfer member
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Application number
PCT/JP2015/065441
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English (en)
Japanese (ja)
Inventor
研二 森
鈴木　秀明
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株式会社豊田自動織機
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Publication date
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 WO2015186604A1 publication Critical patent/WO2015186604A1/fr

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Classifications

    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
    • F01N3/24—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by constructional aspects of converting apparatus
    • 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
    • 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 that heats an object to be heated, for example.
  • the chemical heat storage device described in Patent Document 1 includes a heat storage material that generates heat by chemically reacting with ammonia (NH 3 ), a reactor that heats the oxidation catalyst, and the reactor and the NH 3 supply pipe. And a reservoir for storing NH 3 .
  • NH 3 is supplied from the reservoir to the reactor, NH 3 and the heat storage material chemically react to generate heat from the heat storage material, and the oxidation catalyst is heated by the heat.
  • a chemical heat storage device is a chemical heat storage device that heats an object to be heated.
  • the chemical heat storage device is disposed around the object to be heated, generates a heat by chemically reacting with the reaction medium, and stores the reaction medium by storing the heat.
  • a reactor having a heat storage material portion composed of a heat storage material to be desorbed and a heat transfer member having a heat conductivity higher than that of the heat storage material, and a reactor and the reaction medium are connected so as to be able to circulate.
  • the heat transfer member has a sheet-like main body part for transmitting heat generated from the heat storage material part toward the object to be heated, and the main surface of the main body part is formed of a press-molded body. The surface is perpendicular to the pressing direction.
  • the reactor is disposed around the object to be heated, and generates a heat by chemically reacting with the reaction medium, and also stores a heat storage material portion that stores the heat by storing the heat.
  • a heat transfer member having a higher heat conductivity than the heat storage material.
  • the heat-transfer member has a sheet-like main-body part for conveying the heat which generate
  • the heat conductivity of the press-molded body is increased.
  • the press molding body containing a heat storage material part and a heat-transfer member is produced by press molding.
  • the main surface of the sheet-like main body portion is a surface perpendicular to the pressing direction of the press-molded body.
  • the heat transfer member may further include an auxiliary portion provided so as to be bent with respect to the main body at the end of the main body on the heating object side.
  • the press-molded body may be formed by alternately laminating a plurality of heat storage material portions and heat transfer members. By providing a plurality of heat transfer members in this manner, the heat generated from the heat storage material part can easily reach the heat transfer member, so that heat can be more efficiently transferred from the reactor to the object to be heated.
  • a plurality of through holes through which the reaction medium passes may be formed in the main body.
  • the reaction medium introduced into the heat storage material portion of the reactor moves through the through holes of the main body portion and moves through the heat storage material portion, the reaction medium is rapidly supplied to most of the heat storage material portion. be able to.
  • This chemical heat storage device can efficiently transfer heat from the reactor to the object to be heated by improving the thermal conductivity of the reactor.
  • FIG. 1 is a schematic configuration diagram illustrating an exhaust purification system including a chemical heat storage device according to an embodiment.
  • FIG. 2 is a front view of a configuration including the heat exchanger and the reactor shown in FIG.
  • FIG. 3 is a perspective view of the press-molded body shown in FIG.
  • FIG. 4 is a perspective view of the heat transfer member shown in FIG.
  • FIG. 5 is a cross-sectional view showing a method for producing the press-molded body shown in FIG. 2 by press molding.
  • FIG. 6 is a cross-sectional view showing an ideal example and an actual example of a press-formed body having a structure in which a heat transfer member stands along the pressing direction.
  • FIG. 1 is a schematic configuration diagram showing an exhaust purification system including a chemical heat storage device according to an embodiment.
  • an exhaust purification system 1 is provided in an exhaust system of a diesel engine 2 (hereinafter simply referred to as an engine 2) of a vehicle, and removes harmful substances (environmental pollutants) contained in exhaust gas discharged from the engine 2. It is a purification system.
  • the exhaust purification system 1 includes a heat exchanger 4 provided in an exhaust pipe 3 connected to an engine 2, a diesel oxidation catalyst (DOC) 5, a diesel exhaust particulate removal filter (DPF: DieselDParticulate Filter) 6, A selective reduction catalyst (SCR) 7 and an ammonia slip catalyst (ASC: Ammonia ⁇ ⁇ Slip Catalyst) 8 are provided.
  • DOC diesel oxidation catalyst
  • DPF diesel exhaust particulate removal filter
  • ASC ammonia slip catalyst
  • ASC Ammonia ⁇ ⁇ Slip Catalyst
  • the heat exchanger 4 exchanges heat between the exhaust gas flowing in the exhaust pipe 3 and a reactor 11 described later.
  • the heat exchanger 4 includes an outer cylinder 4a and a heat exchange member 4b disposed inside the outer cylinder 4a.
  • the heat exchange member 4b has a honeycomb structure.
  • the heat exchange member 4b is not particularly limited to a honeycomb structure, and a known heat exchange structure can be used.
  • the heat exchanger 4 is a heating object.
  • the heat exchanger 4 does not need to be provided with the outer cylinder 4a.
  • the DOC 5 is a catalyst that oxidizes and purifies HC and CO contained in the exhaust gas.
  • the DPF 6 is a filter that collects and removes particulate matter (PM) contained in the exhaust gas.
  • the SCR 7 is a catalyst that reduces and purifies NOx contained in the exhaust gas with urea or ammonia (NH 3 ).
  • ASC8 is a catalyst for oxidizing the NH 3 having passed through the SCR7.
  • the exhaust purification system 1 includes the chemical heat storage device 10 of the present embodiment.
  • the chemical heat storage device 10 is a device that heats the heat exchanger 4 that is an object to be heated without energy by storing heat (exhaust heat) of exhaust gas and using the exhaust heat when necessary. is there.
  • Chemical heat storage device 10 as shown in FIGS. 1 and 2, a reactor 11 disposed outside the exhaust pipe 3, the NH 3 is the reaction medium through the reactor 11 and the NH 3 supply pipe 12 And an adsorber 13 connected to be able to circulate.
  • the NH 3 supply pipe 12 is provided with a valve 14 for opening and closing a flow path between the reactor 11 and the adsorber 13.
  • the reactor 11 is provided in the position corresponding to the part in which the heat exchanger 4 of the exhaust pipe 3 was provided so that it may be arrange
  • the adsorber 13 includes an adsorbent 13a that can be held and desorbed by physical adsorption of NH 3 .
  • the adsorbent 13a any one of activated carbon, carbon black, mesoporous carbon, nanocarbon, zeolite and the like is used.
  • the adsorber 13 is a reservoir that stores NH 3 by physically adsorbing NH 3 on the adsorbent 13a.
  • the reactor 11 includes a ring-shaped case 15 provided so as to surround the exhaust pipe 3, and a press-molded body accommodated in the case 15 so as to contact the outer peripheral surface of the exhaust pipe 3. 16.
  • An NH 3 supply pipe 12 is connected to the case 15. Between the casing 15 and the press-molded body 16, although not shown, a porous sheet for conducting the entire periphery of NH 3 supplied from the NH 3 supply pipe 12 to the press-molded body 16 is arranged .
  • the press-molded body 16 has a ring shape by connecting a plurality of curved section-shaped press molded bodies 16A.
  • Press molding body 16A as shown in FIG. 3, which both generates the heat for heating the NH3 and heat exchanger 4 by a chemical reaction, pellets for the NH 3 desorbed with heat storage undergoing heat
  • the heat storage material part 17 which consists of this heat storage material, and the sheet-like L-shaped heat-transfer member 18 with a heat conductivity higher than this heat storage material are included.
  • the press-molded body 16A (press-molded body 16) has a structure in which a plurality of such heat storage material portions 17 and heat transfer members 18 are alternately stacked.
  • a material having a composition MXa of a halide is used as the heat storage material.
  • M is an alkaline earth metal such as Mg, Ca, or Sr, or a transition metal such as Cr, Mn, Fe, Co, Ni, Cu, or Zn.
  • X is Cl, Br, I or the like.
  • a is 2 to 3.
  • the heat transfer member 18 is made of a material having high thermal conductivity such as a metal such as aluminum or a graphite sheet.
  • the heat transfer member 18 includes a main body portion 19 for transferring heat generated from the heat storage material portion 17 toward the heat exchanger 4, and an inner side (heat exchanger) of the main body portion 19.
  • the auxiliary portion 20 is provided so as to be bent at a right angle with respect to the main body portion 19 at the end portion on the (4 side).
  • the inner surface of the auxiliary portion 20 is in contact with the outer peripheral surface of the exhaust pipe 3.
  • the main body 19 extends from the outer peripheral surface of the press molded body 16A (the surface on the opposite side of the heat exchanger 4) to the inner peripheral surface of the press molded body 16A (the surface on the heat exchanger 4 side).
  • the main surface (front surface and back surface) 19a of the main body 19 is a surface perpendicular to the pressing direction of the press-molded body 16A.
  • the press direction of the press-molded body 16A is a direction in which the heat storage material is pressed when the press-molded body 16A is produced by press molding (described later).
  • the main body 19 is formed with a plurality of through holes 21 through which NH 3 introduced from the NH 3 supply pipe 12 into the heat storage material portion 17 is passed.
  • the shape and dimensions of the through hole 21 are not particularly limited.
  • a heat transfer member 18 for example, a single curved original plate is prepared, and a plurality of through holes 21 are formed in a region to be the main body portion 19 of the curved original plate. It is produced by bending it.
  • the heat transfer member 18 may be manufactured by configuring the main body 19 and the auxiliary portion 20 as separate members and joining the auxiliary portion 20 to the main body 19 in which the plurality of through holes 21 are formed.
  • the auxiliary unit 20 does not necessarily have to be a sheet.
  • the press-molded body 16A is manufactured by press molding using a mold. Specifically, as shown in FIG. 5, a lower mold 22 having a concave cavity 22a and an upper mold 23 to be inserted into the cavity 22a are prepared. Then, the heat transfer member 18 and the powdered heat storage material are put into the cavity 22a in order. At this time, the heat transfer member 18 is disposed in the cavity 22 a so that the auxiliary portion 20 contacts the inner surface of the lower mold 22 and the tip of the auxiliary portion 20 faces the upper side of the lower mold 22. In this state, the upper mold 23 is set in the cavity 22a, and the heat storage material is pressed simultaneously with the heat transfer member 18 by the upper mold 23, whereby the heat storage material is pressed and hardened. Thereby, the press molding 16A in which the heat-transfer member 18 and the pellet-shaped heat storage material part 17 are laminated
  • NH 3 is passed from the adsorber 13 to the reactor 11 through the NH 3 supply pipe 12 by opening the valve 14.
  • the heat storage material for example, MgCl 2
  • the heat storage material that is supplied and forms the heat storage material portion 17 of the reactor 11 and NH 3 chemically react and chemically adsorb (coordinate bond), and heat is generated from the heat storage material portion 17. That is, a reaction from the left side to the right side (exothermic reaction) in the following reaction formula (A) occurs. Then, the heat generated from the heat storage material portion 17 is transmitted to the heat exchanger 4 through the exhaust pipe 3.
  • the reactor 11 includes the press-molded body 16 including the heat storage material portion 17 made of the heat storage material and the heat transfer member 18 having a higher thermal conductivity than the heat storage material. Further, the heat transfer member 18 has a main body 19 for transmitting heat generated by a chemical reaction between the heat storage material and NH 3 toward the inside of the press-molded body 16 (on the heat exchanger 4 side). Thereby, the thermal conductivity of the press-molded body 16 of the reactor 11 can be increased.
  • the heat transfer member 51 has a structure standing along the pressing direction of the press-molded body 50.
  • the following problems occur in such a structure. That is, when a powdery heat storage material is pressed simultaneously with the heat transfer member 51 using a mold, the heat transfer member 51 is actually crushed as shown in FIG. For this reason, the heat transfer member 51 does not extend to the outer peripheral surface of the press-molded body 50. Therefore, the heat generated from the region on the outer peripheral surface side of the press-molded body 50 in the heat storage material portion 17 becomes difficult to reach the heat transfer member 51, and the high thermal conductivity of the press-molded body 50 cannot be ensured.
  • the main surface 19a of the main body 19 of the heat transfer member 18 is a surface perpendicular to the pressing direction of the press-molded body 16. That is, when the press-molded body 16 ⁇ / b> A is manufactured by press molding, the main surface 19 a of the main body 19 is pressed together with the heat storage material 17. Thereby, it is prevented that the main-body part 19 is crushed at the time of press molding.
  • the auxiliary portion 20 of the heat transfer member 18 stands along the pressing direction of the press-molded body 16. However, the press molding process is performed in a state where the auxiliary portion 20 is in contact with the inner surface of the lower mold 22 forming the cavity 22a as described above. For this reason, the auxiliary
  • the effective thermal conductivity of the press-molded body 16 can be set to about 40 W / m ⁇ K, for example.
  • the effective thermal conductivity of the press-molded body 16 is, for example, 1 W / m ⁇ K or less. Therefore, the chemical heat storage device 10 having a high heat output can be obtained.
  • the heat generated from the heat storage material portion 17 of the reactor 11 can be efficiently transmitted to the heat exchanger 4.
  • the heat exchanger 4 can be efficiently heated, and the exhaust gas can be efficiently heated.
  • the heat of the exhaust gas can be efficiently transmitted to the heat storage material portion 17.
  • the NH 3 regeneration speed can be increased.
  • the heat transfer member 18 has the auxiliary portion 20 provided to bend with respect to the main body portion 19, the contact area of the heat transfer member 18 with respect to the exhaust pipe 3 is increased. Therefore, the heat generated from the heat storage material portion 17 can be transmitted to the heat exchanger 4 more efficiently.
  • the press-molded body 16 has a structure in which a plurality of the heat storage material portions 17 and the heat transfer members 18 are alternately stacked, the position of the heat storage material portion 17 farthest from the heat transfer member 18 and the heat transfer member 18. The distance between is shortened. Therefore, since the heat generated from the heat storage material part 17 can easily reach the heat transfer member 18, the heat generated from the heat storage material part 17 can be transmitted to the heat exchanger 4 more efficiently.
  • the main body portion 19 of the heat transfer member 18 since a plurality of through holes 21 for the passage of NH 3, NH 3 introduced into the heat storage material 17 from the NH 3 supply pipe 12 through holes 21 It moves through the heat storage material part 17 through. Therefore, NH 3 can be rapidly supplied to most of the heat storage material portion 17. Thereby, heat can be effectively generated from the heat storage material portion 17.
  • the present invention is not limited to the above embodiment.
  • the main body portion 19 of the heat transfer member 18 extends from the inner peripheral surface of the press-molded body 16 to the outer peripheral surface. It does not need to extend to an outer peripheral surface.
  • the heat-transfer member 18 has the auxiliary
  • the press-molded body 16 ⁇ / b> A has a plurality of heat transfer members 18, but heat generated from the heat storage material portion 17 of the reactor 11 can be transmitted to the heat exchanger 4.
  • the number of heat transfer members 18 included in the press-molded body 16A may be one.
  • the main body portion 19 of the heat transfer member 18 a plurality of through holes 21 for passing the NH 3 is formed, to supply the NH 3 to the majority of the heat storage material 17 If possible, such a through hole 21 may not be particularly provided.
  • the reactor 11 is disposed around the exhaust pipe 3 in the portion of the exhaust pipe 3 where the heat exchanger 4 is provided.
  • the arrangement location of the reactor 11 is not particularly limited, and may be inside the exhaust pipe 3 as long as it is around the heat exchanger 4.
  • the reactor 11 may be disposed in a part around the heat exchanger 4.
  • only one heat exchanger 4 is arranged inside the exhaust pipe 3, but the number of heat exchangers is not particularly limited to one, and is viewed from the direction in which the exhaust gas flows.
  • a plurality of heat exchangers may be arranged inside the exhaust pipe 3.
  • the reactor is integrally provided around each heat exchanger in the exhaust pipe 3.
  • NH 3 which is a gaseous reaction medium and heat storage material having a composition of MXa are chemically reacted to generate heat.
  • the reaction medium is not particularly limited to NH 3.
  • CO 2 or H 2 O may be used.
  • the heat storage material that chemically reacts with CO 2 includes MgO, CaO, BaO, Ca (OH) 2 , Mg (OH) 2 , Fe (OH) 2 , and Fe (OH) 3.
  • FeO, Fe 2 O 3 , Fe 3 O 4 and the like can be used.
  • H 2 O is used as the reaction medium
  • CaO, MnO, CuO, Al 2 O 3 or the like can be used as the heat storage material that chemically reacts with H 2 O.
  • this invention is what heats catalysts, such as DOC5 provided in the exhaust system of the diesel engine 2, in the exhaust pipe 3.
  • the present invention is also applicable to one that heats a region where the heat exchanger 4 or the DOC 5 or the like is not provided, or one that heats any catalyst or the like provided in an exhaust system of a gasoline engine.
  • the catalyst corresponds to an object to be heated.
  • the exhaust pipe 3 corresponds to a heating object.
  • the present invention can be applied to other than an engine exhaust system, for example, one that heats piping or the like provided in an oil circulation system.
  • the present invention may heat various heat media in vehicles such as engine oil, transmission oil, cooling water, or air.
  • the reactor 11 of the chemical heat storage device 10 is arranged on the outer peripheral part (a part of the outer peripheral part or the entire circumference of the outer peripheral part) of the heat medium flow path through which the heat medium flows to heat the heat medium flow path itself. Also good.
  • the heat medium flow path becomes a heating object.
  • the heat exchanger 4 may be disposed in the heat medium flow path through which the heat medium flows, and the heat exchanger 4 may be heated.
  • the heat exchanger 4 becomes a heating object.
  • a heat exchanger integrated heater in which a plurality of reactors 11 including heat storage materials and heat exchangers such as heat exchange fins are alternately arranged is configured, and the heat exchanger integrated heater is used as a heat medium. May be disposed in the heat medium storage part in which the heat medium is stored or on the heat medium flow path through which the heat medium flows. In this case, a heat exchange part such as a heat exchange fin adjacent to the reactor 11 becomes a heating object.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Combustion & Propulsion (AREA)
  • Exhaust Gas After Treatment (AREA)

Abstract

Selon la présente invention, un appareil d'accumulation de chaleur chimique est pourvu d'un réacteur et d'un adsorbeur raccordé au réacteur par l'intermédiaire d'un tube d'alimentation en NH3. Le réacteur comporte une pluralité de corps moulés à la presse (16A) ayant des sections transversales incurvées. Les corps moulés à la presse (16A) comprennent : des parties de matériau d'accumulation de chaleur (17) comprenant un matériau d'accumulation de chaleur en forme de pastille qui réagit chimiquement avec le NH3 pour générer de la chaleur ; et des éléments thermo-conducteurs (18) ayant une section transversale en forme de L, les éléments ayant une conductivité thermique plus élevée que le matériau d'accumulation de chaleur. Les éléments thermo-conducteurs (18) sont composés d'une partie de corps (19) permettant de conduire la chaleur générée à partir de la partie de matériau d'accumulation de chaleur (17), et d'une partie auxiliaire (20) disposée au niveau de la partie d'extrémité sur le côté interne de la partie de corps (19) de manière à fléchir par rapport à la partie de corps (19). Une surface principale (19a) de la partie de corps (19) est une surface perpendiculaire à la direction de pression des corps moulés à la presse (16A).
PCT/JP2015/065441 2014-06-02 2015-05-28 Appareil d'accumulation de chaleur chimique WO2015186604A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2014-114005 2014-06-02
JP2014114005A JP2017133697A (ja) 2014-06-02 2014-06-02 化学蓄熱装置

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WO2015186604A1 true WO2015186604A1 (fr) 2015-12-10

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009132844A (ja) * 2007-11-30 2009-06-18 Toyota Central R&D Labs Inc 化学蓄熱材成形体及びその製造方法
JP2013137125A (ja) * 2011-12-28 2013-07-11 Aisin Seiki Co Ltd 化学蓄熱装置
JP2013234625A (ja) * 2012-05-10 2013-11-21 Toyota Industries Corp 排気浄化装置

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009132844A (ja) * 2007-11-30 2009-06-18 Toyota Central R&D Labs Inc 化学蓄熱材成形体及びその製造方法
JP2013137125A (ja) * 2011-12-28 2013-07-11 Aisin Seiki Co Ltd 化学蓄熱装置
JP2013234625A (ja) * 2012-05-10 2013-11-21 Toyota Industries Corp 排気浄化装置

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