WO2016059982A1 - Chemical heat storage device - Google Patents

Chemical heat storage device Download PDF

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WO2016059982A1
WO2016059982A1 PCT/JP2015/078081 JP2015078081W WO2016059982A1 WO 2016059982 A1 WO2016059982 A1 WO 2016059982A1 JP 2015078081 W JP2015078081 W JP 2015078081W WO 2016059982 A1 WO2016059982 A1 WO 2016059982A1
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Prior art keywords
reaction
chemical
medium
reaction medium
heat storage
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PCT/JP2015/078081
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French (fr)
Japanese (ja)
Inventor
鈴木　秀明
山内　崇史
青木　正和
志満津　孝
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株式会社豊田自動織機
株式会社豊田中央研究所
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Priority to JP2016554038A priority Critical patent/JP6320551B2/en
Publication of WO2016059982A1 publication Critical patent/WO2016059982A1/en

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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.
  • the chemical heat storage device described in Patent Document 1 includes a first container that stores an adsorbent that generates heat and absorbs heat by adsorption and desorption of an adsorbed medium, a second container that stores an adsorbed medium, a first container, And a communication pipe communicating with the two containers.
  • the exothermic reaction characteristics of the reaction material (corresponding to the above-mentioned conventional adsorbent) contained in the reactor (corresponding to the above-mentioned prior art first container) depend on the type of the reaction material used. For this reason, depending on the reaction material used, desired exothermic reaction characteristics may not be obtained.
  • the pressure of the reaction medium (corresponding to the adsorbed medium of the prior art) inside the reactor and the reservoir (corresponding to the second container of the prior art) during the exothermic reaction is defined in the specification, There may be a problem that the exothermic temperature of the reaction material does not match the target temperature, and a problem that the exothermic time of the reaction material is short.
  • An object of the present invention is to provide a chemical heat storage device using a reaction material having desired exothermic reaction characteristics.
  • the present inventors As a result of intensive studies on the material of the reaction material, the present inventors, as a result, have a high maximum exothermic temperature associated with a chemical reaction between the reaction medium and the material having a fast reaction time in which the reaction rate with the reaction medium is a predetermined value or more. It was found that desired exothermic reaction characteristics can be obtained at the time of chemical reaction with the reaction medium. Further, the present inventors have further studied that if the mixing ratio of the first material in the mixed material of the reaction material is higher than the mixing ratio of the second material, the reaction material generates heat similar to that of the material having a high mixing ratio. It has been found that exothermic reaction characteristics of materials with low mixing ratio are added while having reaction characteristics. The present inventors have completed the present invention based on such examination results.
  • the chemical heat storage device includes a reactor having a reaction material that generates heat by chemical reaction with the reaction medium and desorbs the reaction medium by heat storage, and the reaction medium through the reactor and the flow path. And a reservoir for storing the reaction medium, the reaction material including a mixed material obtained by mixing the first material and the second material having different exothermic reaction characteristics, and the reaction medium in the first material.
  • the reaction time at which the reaction rate is 90% or more is earlier than the reaction time at which the reaction rate of the second material with the reaction medium is 90% or more, and the maximum exothermic temperature associated with the chemical reaction with the reaction medium of the second material is
  • the first material is higher in temperature than the maximum exothermic temperature associated with the chemical reaction with the reaction medium, and the mixing ratio of the first material in the mixed material is higher than the mixing ratio of the second material in the mixed material.
  • the exothermic reaction characteristics are different.
  • a reaction material including a mixed material obtained by mixing one material and the second material is obtained.
  • the reaction material having the excellent characteristics of the first material and the second material, that is, the reaction medium A reaction material can be obtained in which the reaction time at which the reaction rate is 90% or more is accelerated and the maximum exothermic temperature associated with the chemical reaction with the reaction medium is increased.
  • the first material is MgBr 2
  • the second material is MgI 2
  • the mixing ratio of the first material in the mixed material is 80% or more
  • the mixing ratio of the second material in the mixed material is 20% or less, Also good.
  • a reaction material having desired exothermic reaction characteristics can be obtained with certainty.
  • a chemical heat storage device using a reaction material having desired exothermic reaction characteristics is provided.
  • FIG. 1 is a schematic configuration diagram illustrating an exhaust purification system including an embodiment of a chemical heat storage device.
  • FIG. 2 is a graph showing an example of the relationship between the equilibrium temperature at which the chemical reaction between the reaction material and NH 3 (reaction medium) reaches an equilibrium state, and the pressure of NH 3 (reaction medium).
  • FIG. 3 is a graph showing an example of the relationship between the elapsed time from the start of the exothermic reaction and the temperature of the reactive material as the exothermic reaction characteristics of the reactant, and (b) the elapsed time from the start of the exothermic reaction. It is a graph which shows an example of the relationship between the reaction rate of a reaction material.
  • FIG. 1 is a schematic configuration diagram illustrating an exhaust purification system including an embodiment of a chemical heat storage device.
  • an exhaust purification system 1 is provided in an exhaust system of a diesel engine 2 (hereinafter simply referred to as “engine 2”) of a vehicle, and purifies harmful substances (environmental pollutants) contained in exhaust gas discharged from the engine 2. To do.
  • the exhaust purification system 1 includes a heat exchanger 3, a diesel oxidation catalyst (DOC) 4, a diesel exhaust particulate removal filter (DPF) 5, a selective reduction catalyst (SCR) 6 and an ammonia slip.
  • a catalyst (ASC: Ammonia Slip Catalyst) 7 is provided.
  • the heat exchanger 3, the DOC 4, the DPF 5, the SCR 6, and the ASC 7 are sequentially arranged from the upstream side toward the downstream side in the exhaust passage 8 connected to the engine 2.
  • the heat exchanger 3 performs heat exchange between the exhaust gas and the reaction material 15 (described later).
  • the DOC 4 oxidizes and purifies HC and CO contained in the exhaust gas.
  • the DPF 5 collects particulate matter (PM) contained in the exhaust gas and removes PM from the exhaust gas.
  • the SCR 6 reduces and purifies NOx contained in the exhaust gas with urea or ammonia (NH 3 ).
  • ASC7 oxidizes NH 3 passing through the SCR6.
  • the exhaust purification system 1 includes a chemical heat storage device 10 that heats (warms up) the heat exchanger 3 that is a heating target without using external energy by using a reversible chemical reaction.
  • the chemical heat storage device 10 stores the heat (exhaust heat) of the exhaust gas inside by separating the reaction material 15 (described later) from the reaction medium.
  • the chemical heat storage device 10 supplies the reaction medium to the reaction material 15 when necessary, and causes the reaction medium and the reaction material 15 to chemically react (chemical adsorption), thereby utilizing the reaction heat during the chemical reaction.
  • the heat exchanger 3 is heated.
  • ammonia (NH 3 ) is used as the reaction medium.
  • Chemical heat storage device 10 includes a ring-shaped reactor 11, and reactor 11 and the NH 3 flow pipe (flow passage) 12 adsorber 13 that is fluidly connected to NH 3 through.
  • the NH 3 flow pipe 12 is provided with an on-off valve 14 that opens and closes a flow path between the reactor 11 and the adsorber 13.
  • the reactor 11 is disposed around the heat exchanger 3.
  • the reactor 11 includes a reaction member 15 which leaves the NH 3 by the heat storage of waste heat while heat by chemical reaction with NH 3.
  • a mixed material of a halide represented by the composition formula MXa is used as a material of the reaction material 15.
  • 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 a number specified by the valence of M, and is 2 to 3. The material of the reaction material 15 will be described in detail later.
  • the adsorber 13 has an adsorbent 16 that can be held and desorbed by physical adsorption of NH 3 .
  • adsorbent 16 activated carbon, carbon black, mesoporous carbon, nanocarbon, zeolite, or the like is used.
  • the adsorber 13 constitutes a reservoir for storing NH 3 by physically adsorbing NH 3 on the adsorbent 16.
  • the on-off valve 14 is opened when the temperature of the exhaust gas discharged from the engine 2 is relatively low, such as when the engine 2 is cold started. Control. Then, NH 3 desorbed from the adsorbent 16 of the adsorber 13 due to the pressure difference between the adsorber 13 and the reactor 11 is supplied to the reactor 11 through the NH 3 flow pipe 12. Then, the reaction material 15 and NH 3 in the reactor 11 by a chemical reaction, heat is generated from the reaction material 15 (exothermic reaction). Then, heat generated from the reaction material 15 is transmitted to the heat exchanger 3. Thereby, the heat exchanger 3 is heated, and the exhaust gas flowing through the heat exchanger 3 is heated accordingly. Then, the heated exhaust gas raises the DOC 4 to an activation temperature suitable for purification of pollutants.
  • FIG. 2 shows an example of the relationship between the equilibrium temperature at which the chemical reaction between the reactant and the reaction medium, NH 3 , reaches an equilibrium state and the pressure of NH 3 .
  • the equilibrium state is a state where neither an exothermic reaction nor a regeneration reaction is performed.
  • the pressure of NH 3 (hereinafter referred to as NH 3 pressure) is set to P 0 (kPa) according to the system specifications.
  • the reaction material 15 is formed by mixing the main material (first material) and the sub-material (second material) having different exothermic reaction characteristics so that the reaction material has desired exothermic reaction characteristics.
  • the main material one kind of the above-mentioned halide materials is used.
  • the auxiliary material one or more of the above-mentioned halide materials are used.
  • the reaction material 15 obtained by mixing the main material and the sub-material may be a molded body or may be in a powder form.
  • the reaction time in which the reaction rate is 90% or more from the start of the reaction in the main material is earlier than the time in which the reaction rate is 90% or more from the start of the reaction in the secondary material.
  • the reaction rate means the ratio of the portion where an exothermic reaction with the reaction medium occurs with respect to the total amount of the reaction material. That is, the higher the reaction rate (the reaction rate approaches 100%), the more the reaction between the reaction material and the reaction medium proceeds.
  • the maximum exothermic temperature associated with the chemical reaction with the reaction medium in the secondary material is higher than the maximum exothermic temperature associated with the chemical reaction with the reaction medium in the main material.
  • the maximum exothermic temperature here refers to the peak value (maximum value) of the exothermic temperature from the start of the reaction until the reaction rate reaches 100%.
  • the mixing ratio of the main material in the mixed material is higher than the mixing ratio of the sub-material in the mixed material.
  • the main material for example, MgBr 2
  • the secondary material for example, MgI 2 is used.
  • an additive for improving thermal conductivity may be mixed in the reaction material 15.
  • carbon fiber, carbon bead, SiC bead, metal bead, polymer bead, polymer fiber or the like is used as the additive.
  • the metal material of the metal beads include Cu, Ag, Ni, Ci—Cr, Al, Fe, and stainless steel.
  • FIG. 3 (a) is a graph showing an example of the relationship between the elapsed time from the start of the reaction and the temperature of the reaction material as the exothermic reaction characteristics of the reaction material.
  • the exothermic reaction between the reaction material and the reaction medium starts from a state where the reaction material is warmed to about 185 ° C. Therefore, the exothermic temperature of the reaction material is a value obtained by subtracting the temperature of the reaction material in the initial state from the temperature of the reaction material at each time point.
  • FIG. 3B is a graph showing an example of the relationship between the elapsed time from the start of the reaction and the reaction rate of the reaction material as the exothermic reaction characteristic of the reaction material.
  • NH 3 pressure P0 at which NH 3 is chemically react with the reaction material is about 760KPa.
  • a black circled line P is a characteristic when MgBr 2 is used as a reaction material.
  • a line Q with a white circle is a characteristic when MgI 2 is used as a reaction material.
  • the mixing ratio in the case of using a mixed material of MgBr 2 and MgI 2 as the reaction material is represented by a molar ratio.
  • MgBr 2 is a main material and MgI 2 is a secondary material.
  • the reaction material is pelletized by physically mixing MgBr 2 and MgI 2 in a mortar.
  • powdered MgBr 2 and powdered MgI 2 are mixed.
  • the mixed powder is packed into a mold and press-molded by applying a predetermined pressure by a press molding machine.
  • mixing respect MgBr 2 powder is a main material as MgI 2 powder is a secondary material is uniformly dispersed.
  • a pressure of a magnitude necessary for the powder mixture material to be compacted into a pellet molded body is applied.
  • the pressure applied during molding is approximately 40 to 300 MPa.
  • the exothermic reaction characteristic of MgBr 2 is shown by a curve P in FIGS. 3 (a) and 3 (b). Specifically, immediately after the start of the reaction, the reaction rate becomes about 20% and the exothermic temperature becomes 75 ° C. Thereafter, the reaction proceeds at a constant reaction rate (the slope of the reaction rate curve) with the passage of time, and the reaction rate reaches 90% or more after about 150 seconds from the start of the reaction. Since MgBr 2 maintains a relatively high reaction rate from the start of the reaction until the reaction rate reaches 100%, it can maintain a high temperature state for a relatively long time.
  • the exothermic reaction characteristics of MgI 2 are shown by the curve Q in FIGS. 3 (a) and 3 (b). Specifically, immediately after the start of the reaction, the reaction rate becomes about 50% and the exothermic temperature becomes 130 ° C. Thereafter, the reaction proceeds more slowly than MgBr 2 , and about 250 seconds have elapsed since the start of the reaction. The reaction rate becomes 90% or more. MgI 2 is temporarily in a high temperature state due to its high reaction rate immediately after the start of the reaction, but since the subsequent reaction rate is slow, heat is taken away to the surroundings and the high temperature state cannot be maintained for a long time. .
  • the maximum exothermic temperature of the mixed material is higher than the maximum exothermic temperature of MgBr 2 as shown by the curve R in FIG. .
  • the reaction rate immediately after the start of the reaction of the mixed material is 40% or more, which is higher than the reaction rate immediately after the start of the reaction of MgBr 2 .
  • the temperature of the mixed material cannot be kept high. That is, the mixed material cannot maintain a high temperature state for a long time like MgBr 2 .
  • the mixing ratio of MgBr 2 and MgI 2 is 9: 1
  • the maximum exothermic temperature of the mixed material is higher than the maximum exothermic temperature of MgBr 2 as shown by the curve S in FIG. . 3B
  • the reaction rate immediately after the start of the reaction of the mixed material is about 20%, similar to the reaction rate immediately after the start of the MgBr 2 reaction.
  • the reaction proceeds at the same reaction rate as the MgBr 2 (the slope of the reaction rate curve) with the passage of time, and the reaction rate reaches 90% or more after about 170 seconds from the start of the reaction.
  • the mixed material Since the mixed material maintains a relatively high reaction rate from the start of the reaction until the reaction rate reaches 100%, similarly to MgBr 2 , it can maintain a high temperature state for a relatively long time. At this time, since the maximum exothermic temperature of the mixed material is higher than the maximum exothermic temperature of MgBr 2 , the temperature of the mixed material is maintained higher than the temperature of MgBr 2 until about 200 seconds from the start of the reaction.
  • the mixing ratio of the main material in the mixed material was 80% or more, the mixing ratio of the sub-material in the mixed material more than 20%
  • the mixing ratio of the main material in the mixed material is preferably 80% to 95%, and the mixing ratio of the sub-material in the mixed material is more preferably 5% to 20%.
  • the reaction material 15 of the reactor 11 includes a mixed material obtained by mixing a main material and a submaterial having different exothermic reaction characteristics.
  • the reaction time in which the reaction rate with the reaction medium in the main material is 90% or more is earlier than the reaction time in which the reaction rate with the reaction medium in the secondary material is 90% or more.
  • the maximum exothermic temperature associated with the chemical reaction with the reaction medium in the secondary material is higher than the maximum exothermic temperature associated with the chemical reaction with the reaction medium in the main material.
  • reaction material 15 in which the reaction time at which the reaction rate with the reaction medium is 90% or more is shortened and the maximum exothermic temperature associated with the chemical reaction with the reaction medium is increased.
  • the chemical heat storage apparatus 10 using the reaction material 15 which has a desired exothermic reaction characteristic can be provided.
  • an exothermic reaction due to a chemical reaction between the reaction material 15 and the reaction medium is promoted, so that the heat exchanger 3 can be effectively heated.
  • the main material is MgBr 2
  • the sub material is MgI 2
  • the mixing ratio of the main material in the mixed material is 80% or more
  • the mixing ratio of the sub material in the mixed material is 20% or less.
  • the present invention is not limited to the above embodiment.
  • a main material (first material) using MgBr 2 but using MgI 2 as an auxiliary material (second material), as the main material and secondary material used, especially its Is not limited.
  • NH 3 and a reaction member 15 which includes a main material and mixed mixed material sub material expressed by a composition formula MXa by chemical reaction is caused to generate heat is the reaction medium.
  • the reaction medium is not particularly limited to NH 3 , and for example, CO 2 or H 2 O may be used.
  • CO 2 is used as the reaction medium
  • the material of the reaction material that chemically reacts with CO 2 is MgO, CaO, BaO, Ca (OH) 2 , Mg (OH) 2 , Fe (OH) 2 , Fe (OH) 3 , FeO, Fe 2 O 3 or Fe 3 O 4 can be used.
  • the reaction material includes a mixed material obtained by mixing a main material (first material) and a sub material (second material) having different exothermic reaction characteristics.
  • the said embodiment is the chemical heat storage apparatus 10 which heats the heat exchanger 3
  • this invention is applicable also to the chemical heat storage apparatus which heats catalysts, such as DOC4.
  • the present invention is a chemical heat storage device that heats the heating object disposed in the exhaust system of the gasoline engine, or other than the exhaust system of the engine.
  • the present invention can also be applied to a chemical heat storage device that heats an object to be heated disposed in an oil distribution system or the like.
  • the heating object of the chemical heat storage device of the present invention is not limited to a heat exchanger or a catalyst provided in the exhaust system of the engine, but may be an exhaust pipe itself through which exhaust gas flows.
  • the reactor of a chemical thermal storage apparatus is applicable also to what heats the piping etc. which were provided in the distribution system of oil other than an engine exhaust system, for example.
  • the reactor of the chemical heat storage device may heat various heat media in the vehicle such as engine oil, transmission oil, cooling water, or air.
  • the reactor of the chemical heat storage device may be disposed on the outer periphery (a part of the outer periphery or the entire periphery of the outer periphery) of the heat medium channel through which the heat medium flows to heat the heat medium channel itself.
  • a heat exchanger may be disposed in the heat medium flow path through which the heat medium flows, and the heat medium may be heated via the heat exchanger by a reactor disposed on the outer periphery of the heat medium flow path.
  • a heat exchange unit integrated reactor is configured in which a plurality of reaction units including heat storage materials and heat exchange units such as heat exchange fins are alternately stacked, and the heat exchange unit integrated reactor is heated. You may arrange

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Abstract

Provided is a chemical heat storage device which uses a reaction material having desired heat generation reaction characteristics. This chemical heat storage device 10 is provided with: a reactor 11 comprising a reaction material 15 that generates heat through a chemical reaction with a reaction medium and detaches the reaction medium through heat storage; and a storage unit 13 which stores the reaction medium and is connected to the reactor 11 via a flow path 12 such that the reaction medium is able to be transferred therebetween. The reaction material 15 contains a mixed material that is obtained by mixing a first material and a second material having heat generation reaction characteristics different from each other. The reaction time at which the reaction rate between the first material and the reaction medium reaches 90% or more is shorter than the reaction time at which the reaction rate between the second material and the reaction medium reaches 90% or more. The maximum exothermic temperature associated with a chemical reaction between the second material and the reaction medium is higher than the maximum exothermic temperature associated with a chemical reaction between the first material and the reaction medium. The mixing ratio of the first material in the mixed material is higher than the mixing ratio of the second material in the mixed material.

Description

化学蓄熱装置Chemical heat storage device
　本発明は、化学蓄熱装置に関する。 The present invention relates to a chemical heat storage device.
　従来の化学蓄熱装置としては、例えば特許文献１に記載されている装置が知られている。特許文献１に記載の化学蓄熱装置は、被吸着媒体の吸着・脱離により発熱・吸熱する吸着剤を収納する第１容器と、被吸着媒体を収納する第２容器と、第１容器と第２容器とを連通する連通管とを備えている。 As a conventional chemical heat storage device, for example, a device described in Patent Document 1 is known. The chemical heat storage device described in Patent Document 1 includes a first container that stores an adsorbent that generates heat and absorbs heat by adsorption and desorption of an adsorbed medium, a second container that stores an adsorbed medium, a first container, And a communication pipe communicating with the two containers.
特開平１１－３１１１１７号公報JP-A-11-3111117
　ところで、反応器（上記従来技術の第１容器に相当）に含まれる反応材（上記従来技術の吸着剤に相当）の発熱反応特性は、使用する反応材の種類に依存する。このため、使用する反応材によっては、所望の発熱反応特性が得られない場合がある。例えば、発熱反応時の反応器及び貯蔵器（上記従来技術の第２容器に相当）の内部の反応媒体（上記従来技術の被吸着媒体に相当）の圧力が仕様で定められている場合に、反応材の発熱温度が目標温度と合致しないといった問題、及び反応材の発熱時間が短いといった問題が生じることがある。 Incidentally, the exothermic reaction characteristics of the reaction material (corresponding to the above-mentioned conventional adsorbent) contained in the reactor (corresponding to the above-mentioned prior art first container) depend on the type of the reaction material used. For this reason, depending on the reaction material used, desired exothermic reaction characteristics may not be obtained. For example, when the pressure of the reaction medium (corresponding to the adsorbed medium of the prior art) inside the reactor and the reservoir (corresponding to the second container of the prior art) during the exothermic reaction is defined in the specification, There may be a problem that the exothermic temperature of the reaction material does not match the target temperature, and a problem that the exothermic time of the reaction material is short.
　本発明の目的は、所望の発熱反応特性を有する反応材を使用する化学蓄熱装置を提供することである。 An object of the present invention is to provide a chemical heat storage device using a reaction material having desired exothermic reaction characteristics.
　本発明者等は、反応材の材料について鋭意検討を重ねた結果、反応媒体との反応率が所定値以上となる反応時間が早い材料と反応媒体との化学反応に伴う最大発熱温度が高い材料とを適切な割合で混合することにより、反応媒体との化学反応時に所望の発熱反応特性を得ることができることを見出した。また、本発明者等は、更に検討したところ、反応材の混合材料における第１材料の混合割合を第２材料の混合割合よりも高くすると、反応材は混合割合の高い材料と同じような発熱反応特性を有しつつ、混合割合の低い材料の発熱反応特性が付加されることが分かった。本発明者等は、そのような検討結果に基づいて本発明を完成させるに至った。 As a result of intensive studies on the material of the reaction material, the present inventors, as a result, have a high maximum exothermic temperature associated with a chemical reaction between the reaction medium and the material having a fast reaction time in which the reaction rate with the reaction medium is a predetermined value or more. It was found that desired exothermic reaction characteristics can be obtained at the time of chemical reaction with the reaction medium. Further, the present inventors have further studied that if the mixing ratio of the first material in the mixed material of the reaction material is higher than the mixing ratio of the second material, the reaction material generates heat similar to that of the material having a high mixing ratio. It has been found that exothermic reaction characteristics of materials with low mixing ratio are added while having reaction characteristics. The present inventors have completed the present invention based on such examination results.
　即ち、本発明一側面に係る化学蓄熱装置は、反応媒体との化学反応により発熱すると共に蓄熱により反応媒体を脱離する反応材を有する反応器と、反応器と流通路を介して反応媒体を流通可能に接続され、反応媒体を貯蔵する貯蔵器と、を備え、反応材は、発熱反応特性が異なる第１材料及び第２材料を混合した混合材料を含み、第１材料における反応媒体との反応率が９０％以上となる反応時間は、第２材料における反応媒体との反応率が９０％以上となる反応時間よりも早く、第２材料における反応媒体との化学反応に伴う最大発熱温度は、第１材料における反応媒体との化学反応に伴う最大発熱温度よりも高く、混合材料における第１材料の混合割合は、混合材料における第２材料の混合割合よりも高いことを特徴とする。 That is, the chemical heat storage device according to one aspect of the present invention includes a reactor having a reaction material that generates heat by chemical reaction with the reaction medium and desorbs the reaction medium by heat storage, and the reaction medium through the reactor and the flow path. And a reservoir for storing the reaction medium, the reaction material including a mixed material obtained by mixing the first material and the second material having different exothermic reaction characteristics, and the reaction medium in the first material. The reaction time at which the reaction rate is 90% or more is earlier than the reaction time at which the reaction rate of the second material with the reaction medium is 90% or more, and the maximum exothermic temperature associated with the chemical reaction with the reaction medium of the second material is The first material is higher in temperature than the maximum exothermic temperature associated with the chemical reaction with the reaction medium, and the mixing ratio of the first material in the mixed material is higher than the mixing ratio of the second material in the mixed material.
　このように本発明の一側面に係る化学蓄熱装置においては、発熱反応特性（反応媒体との反応率が９０％以上となる反応時間及び反応媒体との化学反応に伴う最大発熱温度）が異なる第１材料及び第２材料を混合した混合材料を含む反応材が得られる。ここで、混合材料における第１材料の混合割合を混合材料における第２材料の混合割合よりも高くすることにより、第１材料及び第２材料の優れた特性を併せ持った反応材、即ち反応媒体との反応率が９０％以上となる反応時間が早くなると共に反応媒体との化学反応に伴う最大発熱温度が高くなるような反応材を得ることができる。これにより、所望の発熱反応特性を有する反応材を使用する化学蓄熱装置を提供することができる。 Thus, in the chemical heat storage device according to one aspect of the present invention, the exothermic reaction characteristics (the reaction time when the reaction rate with the reaction medium is 90% or more and the maximum exothermic temperature associated with the chemical reaction with the reaction medium) are different. A reaction material including a mixed material obtained by mixing one material and the second material is obtained. Here, by making the mixing ratio of the first material in the mixed material higher than the mixing ratio of the second material in the mixed material, the reaction material having the excellent characteristics of the first material and the second material, that is, the reaction medium, A reaction material can be obtained in which the reaction time at which the reaction rate is 90% or more is accelerated and the maximum exothermic temperature associated with the chemical reaction with the reaction medium is increased. Thereby, the chemical heat storage apparatus which uses the reaction material which has a desired exothermic reaction characteristic can be provided.
　第１材料はＭｇＢｒ２であり、第２材料はＭｇＩ２であり、混合材料における第１材料の混合割合が８０％以上であり、混合材料における第２材料の混合割合が２０％以下であってもよい。この場合には、所望の発熱反応特性を有する反応材を確実に得ることができる。 The first material is MgBr 2 , the second material is MgI 2 , the mixing ratio of the first material in the mixed material is 80% or more, and the mixing ratio of the second material in the mixed material is 20% or less, Also good. In this case, a reaction material having desired exothermic reaction characteristics can be obtained with certainty.
　本発明によれば、所望の発熱反応特性を有する反応材を使用する化学蓄熱装置が提供される。 According to the present invention, a chemical heat storage device using a reaction material having desired exothermic reaction characteristics is provided.
図１は、化学蓄熱装置の一実施形態を備えた排気浄化システムを示す概略構成図である。FIG. 1 is a schematic configuration diagram illustrating an exhaust purification system including an embodiment of a chemical heat storage device. 図２は、反応材とＮＨ３（反応媒体）との化学反応が平衡状態となる平衡温度とＮＨ３（反応媒体）の圧力との関係の一例を示すグラフである。FIG. 2 is a graph showing an example of the relationship between the equilibrium temperature at which the chemical reaction between the reaction material and NH 3 (reaction medium) reaches an equilibrium state, and the pressure of NH 3 (reaction medium). 図３は、反応材の発熱反応特性として、（ａ）は発熱反応開始からの経過時間と反応材の温度との関係の一例を示すグラフであり、（ｂ）は発熱反応開始からの経過時間と反応材の反応率との関係の一例を示すグラフである。FIG. 3 is a graph showing an example of the relationship between the elapsed time from the start of the exothermic reaction and the temperature of the reactive material as the exothermic reaction characteristics of the reactant, and (b) the elapsed time from the start of the exothermic reaction. It is a graph which shows an example of the relationship between the reaction rate of a reaction material.
　以下、本発明の実施形態について、図面を参照して詳細に説明する。なお、図面において、同一または同等の要素には同じ符号を付し、重複する説明を省略する。 Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. In the drawings, the same or equivalent elements are denoted by the same reference numerals, and redundant description is omitted.
　図１は、化学蓄熱装置の一実施形態を備えた排気浄化システムを示す概略構成図である。図１において、排気浄化システム１は、車両のディーゼルエンジン２（以下、単にエンジン２という）の排気系に備えられ、エンジン２から排出される排気ガスに含まれる有害物質（環境汚染物質）を浄化する。 FIG. 1 is a schematic configuration diagram illustrating an exhaust purification system including an embodiment of a chemical heat storage device. In FIG. 1, an exhaust purification system 1 is provided in an exhaust system of a diesel engine 2 (hereinafter simply referred to as “engine 2”) of a vehicle, and purifies harmful substances (environmental pollutants) contained in exhaust gas discharged from the engine 2. To do.
　排気浄化システム１は、熱交換器３、ディーゼル酸化触媒（ＤＯＣ：DieselOxidation Catalyst）４、ディーゼル排気微粒子除去フィルタ（ＤＰＦ：Diesel Particulate Filter）５、選択還元触媒（ＳＣＲ：Selective Catalytic Reduction）６及びアンモニアスリップ触媒（ＡＳＣ：Ammonia Slip Catalyst）７を備えている。熱交換器３、ＤＯＣ４、ＤＰＦ５、ＳＣＲ６及びＡＳＣ７は、エンジン２と接続された排気通路８の途中に、上流側から下流側に向けて順に配置されている。 The exhaust purification system 1 includes a heat exchanger 3, a diesel oxidation catalyst (DOC) 4, a diesel exhaust particulate removal filter (DPF) 5, a selective reduction catalyst (SCR) 6 and an ammonia slip. A catalyst (ASC: Ammonia Slip Catalyst) 7 is provided. The heat exchanger 3, the DOC 4, the DPF 5, the SCR 6, and the ASC 7 are sequentially arranged from the upstream side toward the downstream side in the exhaust passage 8 connected to the engine 2.
　熱交換器３は、排気ガスと反応材１５（後述）との間で熱交換を行う。ＤＯＣ４は、排気ガス中に含まれるＨＣ及びＣＯ等を酸化して浄化する。ＤＰＦ５は、排気ガス中に含まれる粒子状物質（ＰＭ：Particulate Matter）を捕集し、排気ガスからＰＭを取り除く。ＳＣＲ６は、尿素またはアンモニア（ＮＨ３）によって、排気ガス中に含まれるＮＯｘを還元して浄化する。ＡＳＣ７は、ＳＣＲ６を通過したＮＨ３を酸化する。 The heat exchanger 3 performs heat exchange between the exhaust gas and the reaction material 15 (described later). The DOC 4 oxidizes and purifies HC and CO contained in the exhaust gas. The DPF 5 collects particulate matter (PM) contained in the exhaust gas and removes PM from the exhaust gas. The SCR 6 reduces and purifies NOx contained in the exhaust gas with urea or ammonia (NH 3 ). ASC7 oxidizes NH 3 passing through the SCR6.
　また、排気浄化システム１は、可逆的な化学反応を利用して、外部エネルギーレスで加熱対象物である熱交換器３を加熱（暖機）する化学蓄熱装置１０を備えている。具体的には、化学蓄熱装置１０は、反応材１５（後述）と反応媒体とを分離した状態にすることで、排気ガスの熱（排熱）を内部に蓄えておく。そして、化学蓄熱装置１０は、必要なときに反応媒体を反応材１５に供給して、反応媒体と反応材１５とを化学反応（化学吸着）させることで、化学反応時の反応熱を利用して熱交換器３を加熱する。なお、本実施形態では、反応媒体としてアンモニア（ＮＨ３）が用いられる。 Further, the exhaust purification system 1 includes a chemical heat storage device 10 that heats (warms up) the heat exchanger 3 that is a heating target without using external energy by using a reversible chemical reaction. Specifically, the chemical heat storage device 10 stores the heat (exhaust heat) of the exhaust gas inside by separating the reaction material 15 (described later) from the reaction medium. The chemical heat storage device 10 supplies the reaction medium to the reaction material 15 when necessary, and causes the reaction medium and the reaction material 15 to chemically react (chemical adsorption), thereby utilizing the reaction heat during the chemical reaction. The heat exchanger 3 is heated. In the present embodiment, ammonia (NH 3 ) is used as the reaction medium.
　化学蓄熱装置１０は、リング状の反応器１１と、この反応器１１とＮＨ３流通管（流通路）１２を介してＮＨ３を流通可能に接続された吸着器１３とを備えている。ＮＨ３流通管１２には、反応器１１と吸着器１３との間の流路を開閉させる開閉弁１４が設けられている。 Chemical heat storage device 10 includes a ring-shaped reactor 11, and reactor 11 and the NH 3 flow pipe (flow passage) 12 adsorber 13 that is fluidly connected to NH 3 through. The NH 3 flow pipe 12 is provided with an on-off valve 14 that opens and closes a flow path between the reactor 11 and the adsorber 13.
　反応器１１は、熱交換器３の周囲に配置されている。反応器１１は、ＮＨ３との化学反応により発熱すると共に排熱の蓄熱によりＮＨ３を脱離する反応材１５を有している。反応材１５の材料としては、組成式ＭＸａで表されるハロゲン化物の混合材料が用いられる。Ｍは、Ｍｇ、ＣａまたはＳｒ等のアルカリ土類金属、若しくはＣｒ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、ＣｕまたはＺｎ等の遷移金属である。Ｘは、Ｃｌ、ＢｒまたはＩ等である。ａは、Ｍの価数により特定される数であり、２～３である。なお、反応材１５の材料については、後で詳述する。 The reactor 11 is disposed around the heat exchanger 3. The reactor 11 includes a reaction member 15 which leaves the NH 3 by the heat storage of waste heat while heat by chemical reaction with NH 3. As a material of the reaction material 15, a mixed material of a halide represented by the composition formula MXa is used. 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 a number specified by the valence of M, and is 2 to 3. The material of the reaction material 15 will be described in detail later.
　吸着器１３は、ＮＨ３の物理吸着による保持及び脱離が可能な吸着材１６を有している。吸着材１６としては、活性炭、カーボンブラック、メソポーラスカーボン、ナノカーボンまたはゼオライト等が用いられる。吸着器１３は、ＮＨ３を吸着材１６に物理吸着させることで、ＮＨ３を貯蔵する貯蔵器を構成している。 The adsorber 13 has an adsorbent 16 that can be held and desorbed by physical adsorption of NH 3 . As the adsorbent 16, activated carbon, carbon black, mesoporous carbon, nanocarbon, zeolite, or the like is used. The adsorber 13 constitutes a reservoir for storing NH 3 by physically adsorbing NH 3 on the adsorbent 16.
　このような化学蓄熱装置１０を備えた排気浄化システム１では、エンジン２のコールドスタート時などのようにエンジン２から排出される排気ガスの温度が比較的低いときに、開閉弁１４を開くように制御する。すると、吸着器１３と反応器１１との圧力差によって、吸着器１３の吸着材１６から脱離したＮＨ３がＮＨ３流通管１２を通って反応器１１に供給される。そして、反応器１１の反応材１５とＮＨ３とが化学反応して、反応材１５から熱が発生する（発熱反応）。そして、反応材１５から発生した熱が熱交換器３に伝えられる。これにより、熱交換器３が加熱され、これに伴って熱交換器３を流れる排気ガスが加熱される。そして、暖められた排気ガスによってＤＯＣ４が汚染物質の浄化に適した活性温度まで上昇する。 In the exhaust purification system 1 having such a chemical heat storage device 10, the on-off valve 14 is opened when the temperature of the exhaust gas discharged from the engine 2 is relatively low, such as when the engine 2 is cold started. Control. Then, NH 3 desorbed from the adsorbent 16 of the adsorber 13 due to the pressure difference between the adsorber 13 and the reactor 11 is supplied to the reactor 11 through the NH 3 flow pipe 12. Then, the reaction material 15 and NH 3 in the reactor 11 by a chemical reaction, heat is generated from the reaction material 15 (exothermic reaction). Then, heat generated from the reaction material 15 is transmitted to the heat exchanger 3. Thereby, the heat exchanger 3 is heated, and the exhaust gas flowing through the heat exchanger 3 is heated accordingly. Then, the heated exhaust gas raises the DOC 4 to an activation temperature suitable for purification of pollutants.
　一方、エンジン２から排出される排気ガスの温度が十分（例えば触媒の活性温度以上）に高くなると、排気ガスの熱（排熱）が熱交換器３から反応器１１の反応材１５に与えられることで、反応器１１内では再生反応が生じ、反応材１５からＮＨ３が脱離する。そして、反応器１１と吸着器１３との圧力差によって、反応材１５から脱離したＮＨ３がＮＨ３流通管１２を通って吸着器１３に戻り、吸着器１３の吸着材１６にＮＨ３が物理吸着される。これにより、ＮＨ３が吸着器１３に回収される。 On the other hand, when the temperature of the exhaust gas discharged from the engine 2 becomes sufficiently high (for example, higher than the activation temperature of the catalyst), the heat (exhaust heat) of the exhaust gas is given from the heat exchanger 3 to the reaction material 15 of the reactor 11. Thus, a regeneration reaction occurs in the reactor 11, and NH 3 is desorbed from the reaction material 15. Then, due to the pressure difference between the reactor 11 and the adsorber 13, NH 3 desorbed from the reaction material 15 returns to the adsorber 13 through the NH 3 flow pipe 12, and NH 3 is adsorbed on the adsorbent 16 of the adsorber 13. Physically adsorbed. Thereby, NH 3 is recovered in the adsorber 13.
　ここで、反応材と反応媒体であるＮＨ３との化学反応が平衡状態となる平衡温度とＮＨ３の圧力との関係の一例を図２に示す。なお、平衡状態とは、発熱反応も再生反応も行われない状態である。図２において、ＮＨ３の圧力（以下、ＮＨ３圧力）がシステムの仕様に応じてＰ０（ｋＰａ）と設定される。その圧力における平衡温度がＴとなるような反応材が所望されたとしても（図中のＣ参照）、既知の反応材の平衡温度が所望する平衡温度Ｔから外れていて（既知の反応材Ａの平衡温度Ｔ１＜Ｔ、既知の反応材Ｂの平衡温度Ｔ２＞Ｔ）、既知の材料からの選択では適切な材料を見つけることができないという場合があった。 Here, FIG. 2 shows an example of the relationship between the equilibrium temperature at which the chemical reaction between the reactant and the reaction medium, NH 3 , reaches an equilibrium state and the pressure of NH 3 . The equilibrium state is a state where neither an exothermic reaction nor a regeneration reaction is performed. In FIG. 2, the pressure of NH 3 (hereinafter referred to as NH 3 pressure) is set to P 0 (kPa) according to the system specifications. Even if a reaction material whose equilibrium temperature at that pressure is T is desired (see C in the figure), the equilibrium temperature of the known reaction material deviates from the desired equilibrium temperature T (known reaction material A). Equilibrium temperature T 1 <T, Equilibrium temperature T 2 of known reaction material B> T), and there is a case where an appropriate material cannot be found by selecting from known materials.
　このように反応材の発熱反応特性は選択する材料に依存するため、所望の発熱反応特性を満たす既存の材料が存在しないことがある。そこで本実施形態では、反応材が所望の発熱反応特性を有するように、発熱反応特性が異なる主材料（第１材料）及び副材料（第２材料）を混合して反応材１５を形成している。主材料としては、上記のハロゲン化物材料の１種類が用いられる。副材料としては、上記のハロゲン化物材料の１種類以上が用いられる。主材料及び副材料を混合して得られる反応材１５は、成型体であってもよいし、粉末状であってもよい。 As described above, since the exothermic reaction characteristic of the reaction material depends on the material to be selected, there may be no existing material that satisfies the desired exothermic reaction characteristic. Therefore, in this embodiment, the reaction material 15 is formed by mixing the main material (first material) and the sub-material (second material) having different exothermic reaction characteristics so that the reaction material has desired exothermic reaction characteristics. Yes. As the main material, one kind of the above-mentioned halide materials is used. As the auxiliary material, one or more of the above-mentioned halide materials are used. The reaction material 15 obtained by mixing the main material and the sub-material may be a molded body or may be in a powder form.
　主材料における反応開始から反応率が９０％以上となる反応時間は、副材料における反応開始から反応率が９０％以上となる時間よりも早い。ここで、反応率とは、反応材の全量に対する反応媒体との発熱反応が生じている部分の割合を意味する。即ち、反応率が高くなる（反応率が１００％に近づく）ほど、反応材と反応媒体との反応が進んでいることになる。 The reaction time in which the reaction rate is 90% or more from the start of the reaction in the main material is earlier than the time in which the reaction rate is 90% or more from the start of the reaction in the secondary material. Here, the reaction rate means the ratio of the portion where an exothermic reaction with the reaction medium occurs with respect to the total amount of the reaction material. That is, the higher the reaction rate (the reaction rate approaches 100%), the more the reaction between the reaction material and the reaction medium proceeds.
　副材料における反応媒体との化学反応に伴う最大発熱温度は、主材料における反応媒体との化学反応に伴う最大発熱温度よりも高い。ここでの最大発熱温度は、反応開始から反応率が１００％となるまでの間における発熱温度のピーク値（最大値）をいう。 The maximum exothermic temperature associated with the chemical reaction with the reaction medium in the secondary material is higher than the maximum exothermic temperature associated with the chemical reaction with the reaction medium in the main material. The maximum exothermic temperature here refers to the peak value (maximum value) of the exothermic temperature from the start of the reaction until the reaction rate reaches 100%.
　混合材料における主材料の混合割合は、混合材料における副材料の混合割合よりも高くなっている。主材料としては、例えばＭｇＢｒ２が用いられ、副材料としては、例えばＭｇＩ２が用いられる。 The mixing ratio of the main material in the mixed material is higher than the mixing ratio of the sub-material in the mixed material. As the main material, for example, MgBr 2 is used, and as the secondary material, for example, MgI 2 is used.
　なお、反応材１５には、熱伝導性を向上させる添加物が混合されていてもよい。添加物としては、カーボンファイバ、カーボンビーズ、ＳｉＣビーズ、金属ビーズ、高分子ビーズまたは高分子ファイバ等が用いられる。金属ビーズの金属材料としては、Ｃｕ、Ａｇ、Ｎｉ、Ｃｉ－Ｃｒ、Ａｌ、Ｆｅまたはステンレス鋼等が挙げられる。 Note that an additive for improving thermal conductivity may be mixed in the reaction material 15. As the additive, carbon fiber, carbon bead, SiC bead, metal bead, polymer bead, polymer fiber or the like is used. Examples of the metal material of the metal beads include Cu, Ag, Ni, Ci—Cr, Al, Fe, and stainless steel.
　図３（ａ）は、反応材の発熱反応特性として、反応開始からの経過時間と反応材の温度との関係の一例を示すグラフである。なお、図３（ａ）では、反応材と反応媒体との発熱反応は、反応材を１８５℃程度に暖めた状態から開始している。従って、反応材の発熱温度は、各時点における反応材の温度から初期状態の反応材の温度を引いた値となる。 FIG. 3 (a) is a graph showing an example of the relationship between the elapsed time from the start of the reaction and the temperature of the reaction material as the exothermic reaction characteristics of the reaction material. In FIG. 3A, the exothermic reaction between the reaction material and the reaction medium starts from a state where the reaction material is warmed to about 185 ° C. Therefore, the exothermic temperature of the reaction material is a value obtained by subtracting the temperature of the reaction material in the initial state from the temperature of the reaction material at each time point.
　図３（ｂ）は、反応材の発熱反応特性として、反応開始からの経過時間と反応材の反応率との関係の一例を示すグラフである。なお、ＮＨ３が反応材と化学反応する時のＮＨ３圧力Ｐ０は、７６０ｋＰａ程度である。 FIG. 3B is a graph showing an example of the relationship between the elapsed time from the start of the reaction and the reaction rate of the reaction material as the exothermic reaction characteristic of the reaction material. Incidentally, NH 3 pressure P0 at which NH 3 is chemically react with the reaction material is about 760KPa.
　図３において、黒丸印付き線Ｐは、反応材としてＭｇＢｒ２を使用した時の特性である。白丸印付き線Ｑは、反応材としてＭｇＩ２を使用した時の特性である。×印付き線Ｒは、反応材としてＭｇＢｒ２及びＭｇＩ２の混合材料（ＭｇＢｒ２：ＭｇＩ２＝５：５）を使用した時の特性である。三角印付き線Ｓは、反応材としてＭｇＢｒ２及びＭｇＩ２の混合材料（ＭｇＢｒ２：ＭｇＩ２＝９：１）を使用した時の特性である。 In FIG. 3, a black circled line P is a characteristic when MgBr 2 is used as a reaction material. A line Q with a white circle is a characteristic when MgI 2 is used as a reaction material. The line marked with X is a characteristic when a mixed material of MgBr 2 and MgI 2 (MgBr 2 : MgI 2 = 5: 5) is used as a reaction material. A line S with a triangle mark is a characteristic when a mixed material of MgBr 2 and MgI 2 (MgBr 2 : MgI 2 = 9: 1) is used as a reaction material.
　ここで、反応材としてＭｇＢｒ２及びＭｇＩ２の混合材料を使用する場合の混合比は、モル比で表されている。反応材としてＭｇＢｒ２及びＭｇＩ２の混合材料を使用する場合、ＭｇＢｒ２が主材料であり、ＭｇＩ２が副材料である。また、反応材としてＭｇＢｒ２及びＭｇＩ２の混合材料を使用する場合、反応材は、ＭｇＢｒ２及びＭｇＩ２を乳鉢で物理混合してペレット成型されている。なお、ここで、ペレット成形は、まず粉末のＭｇＢｒ２と粉末のＭｇＩ２とを混合する。その混合粉末を型の中に詰め込み、プレス成型機によって所定の圧力をかけてプレス成型することで行われる。混合工程では、主材料である粉末のＭｇＢｒ２に対して副材料である粉末のＭｇＩ２が均一に分散されるように混合する。プレス成型加工工程では、粉末の混合材料が押し固められてペレット成型体となるために必要な大きさの圧力を加える。成型時に加える圧力としてはおよそ４０～３００ＭＰａである。 Here, the mixing ratio in the case of using a mixed material of MgBr 2 and MgI 2 as the reaction material is represented by a molar ratio. When a mixed material of MgBr 2 and MgI 2 is used as a reaction material, MgBr 2 is a main material and MgI 2 is a secondary material. Further, when a mixed material of MgBr 2 and MgI 2 is used as the reaction material, the reaction material is pelletized by physically mixing MgBr 2 and MgI 2 in a mortar. Here, in the pellet molding, first, powdered MgBr 2 and powdered MgI 2 are mixed. The mixed powder is packed into a mold and press-molded by applying a predetermined pressure by a press molding machine. In the mixing step, mixing respect MgBr 2 powder is a main material as MgI 2 powder is a secondary material is uniformly dispersed. In the press molding process, a pressure of a magnitude necessary for the powder mixture material to be compacted into a pellet molded body is applied. The pressure applied during molding is approximately 40 to 300 MPa.
　ＭｇＢｒ２の発熱反応特性は、図３（ａ）、（ｂ）の曲線Ｐに示される。具体的には、反応開始直後に、反応率が約２０％となると共に発熱温度が７５℃となる。その後、時間の経過と共に一定の反応速度（反応率曲線の傾き）で反応が進行し、反応開始から約１５０秒経過時点で反応率が９０％以上となる。ＭｇＢｒ２は、反応開始から反応率が１００％になるまで比較的高い反応速度を維持しているので、比較的長い時間、高温状態を維持することができる。 The exothermic reaction characteristic of MgBr 2 is shown by a curve P in FIGS. 3 (a) and 3 (b). Specifically, immediately after the start of the reaction, the reaction rate becomes about 20% and the exothermic temperature becomes 75 ° C. Thereafter, the reaction proceeds at a constant reaction rate (the slope of the reaction rate curve) with the passage of time, and the reaction rate reaches 90% or more after about 150 seconds from the start of the reaction. Since MgBr 2 maintains a relatively high reaction rate from the start of the reaction until the reaction rate reaches 100%, it can maintain a high temperature state for a relatively long time.
　ＭｇＩ２の発熱反応特性は図３（ａ）、（ｂ）の曲線Ｑに示される。具体的には、反応開始直後に、反応率が約５０％となると共に発熱温度が１３０℃となるが、その後、反応はＭｇＢｒ２に比較して緩やかに進み、反応開始から約２５０秒経過時点で反応率が９０％以上となる。ＭｇＩ２は、反応開始直後の反応率が高いため一時的に高温状態となるが、その後の反応速度が緩やかであるため、周囲に熱を奪われてしまい高温状態を長時間維持することができない。 The exothermic reaction characteristics of MgI 2 are shown by the curve Q in FIGS. 3 (a) and 3 (b). Specifically, immediately after the start of the reaction, the reaction rate becomes about 50% and the exothermic temperature becomes 130 ° C. Thereafter, the reaction proceeds more slowly than MgBr 2 , and about 250 seconds have elapsed since the start of the reaction. The reaction rate becomes 90% or more. MgI 2 is temporarily in a high temperature state due to its high reaction rate immediately after the start of the reaction, but since the subsequent reaction rate is slow, heat is taken away to the surroundings and the high temperature state cannot be maintained for a long time. .
　ＭｇＢｒ２とＭｇＩ２との混合比を５：５とした場合、図３（ａ）の曲線Ｒに示されるように、当該混合材料の最大発熱温度は、ＭｇＢｒ２の最大発熱温度よりも高くなる。また、図３（ｂ）の曲線Ｒに示されるように、当該混合材料の反応開始直後の反応率は４０％以上となっており、ＭｇＢｒ２の反応開始直後の反応率よりも高くなっている。しかしながら、その後の反応は非常に緩やかに進むため、当該混合材料の温度は高温を維持することができない。即ち、当該混合材料は、ＭｇＢｒ２のように高温状態を長時間維持することができない。 When the mixing ratio of MgBr 2 and MgI 2 is 5: 5, the maximum exothermic temperature of the mixed material is higher than the maximum exothermic temperature of MgBr 2 as shown by the curve R in FIG. . Moreover, as shown by the curve R in FIG. 3B, the reaction rate immediately after the start of the reaction of the mixed material is 40% or more, which is higher than the reaction rate immediately after the start of the reaction of MgBr 2 . . However, since the subsequent reaction proceeds very slowly, the temperature of the mixed material cannot be kept high. That is, the mixed material cannot maintain a high temperature state for a long time like MgBr 2 .
　ＭｇＢｒ２とＭｇＩ２との混合比を９：１とした場合、図３（ａ）の曲線Ｓに示されるように、当該混合材料の最大発熱温度は、ＭｇＢｒ２の最大発熱温度よりも高くなる。また、図３（ｂ）の曲線Ｓに示されるように、当該混合材料の反応開始直後の反応率はＭｇＢｒ２の反応開始直後の反応率と同様に約２０％となっている。その後、時間の経過と共にＭｇＢｒ２と同様の反応速度（反応率曲線の傾き）で反応が進行し、反応開始から約１７０秒経過時点で反応率が９０％以上となる。当該混合材料は、ＭｇＢｒ２と同様に、反応開始から反応率が１００％になるまで比較的高い反応速度を維持しているので、比較的長い時間、高温状態を維持することができる。このとき、当該混合材料の最大発熱温度はＭｇＢｒ２の最大発熱温度よりも高いため、当該混合材料の温度は、反応開始から約２００秒経過時点まではＭｇＢｒ２の温度よりも高い状態に維持される。 When the mixing ratio of MgBr 2 and MgI 2 is 9: 1, the maximum exothermic temperature of the mixed material is higher than the maximum exothermic temperature of MgBr 2 as shown by the curve S in FIG. . 3B, the reaction rate immediately after the start of the reaction of the mixed material is about 20%, similar to the reaction rate immediately after the start of the MgBr 2 reaction. Thereafter, the reaction proceeds at the same reaction rate as the MgBr 2 (the slope of the reaction rate curve) with the passage of time, and the reaction rate reaches 90% or more after about 170 seconds from the start of the reaction. Since the mixed material maintains a relatively high reaction rate from the start of the reaction until the reaction rate reaches 100%, similarly to MgBr 2 , it can maintain a high temperature state for a relatively long time. At this time, since the maximum exothermic temperature of the mixed material is higher than the maximum exothermic temperature of MgBr 2 , the temperature of the mixed material is maintained higher than the temperature of MgBr 2 until about 200 seconds from the start of the reaction. The
　以上により、主材料としてＭｇＢｒ２を使用し、副材料としてＭｇＩ２を使用する場合には、混合材料における主材料の混合割合を８０％以上とし、混合材料における副材料の混合割合を２０％以下とするのが好ましく、混合材料における主材料の混合割合を８０％～９５％とし、混合材料における副材料の混合割合を５％～２０％とするのがより好ましい。 By the above, using MgBr 2 as a main material, when using MgI 2 as an auxiliary material, the mixing ratio of the main material in the mixed material was 80% or more, the mixing ratio of the sub-material in the mixed material more than 20% The mixing ratio of the main material in the mixed material is preferably 80% to 95%, and the mixing ratio of the sub-material in the mixed material is more preferably 5% to 20%.
　以上のように本実施形態にあっては、反応器１１の反応材１５は、発熱反応特性が異なる主材料及び副材料を混合した混合材料を含んでいる。主材料における反応媒体との反応率が９０％以上となる反応時間は、副材料における反応媒体との反応率が９０％以上となる反応時間よりも早い。副材料における反応媒体との化学反応に伴う最大発熱温度は、主材料における反応媒体との化学反応に伴う最大発熱温度よりも高い。ここで、混合材料における主材料の混合割合を混合材料における副材料の混合割合よりも高くすることにより、主材料及び副材料の優れた特性を併せ持った反応材１５を得ることができる。即ち反応媒体との反応率が９０％以上となる反応時間が早くなると共に反応媒体との化学反応に伴う最大発熱温度が高くなるような反応材１５を得ることができる。これにより、所望の発熱反応特性を有する反応材１５を使用する化学蓄熱装置１０を提供することができる。その結果、反応材１５と反応媒体との化学反応による発熱反応が促進されるため、熱交換器３を効果的に加熱することが可能となる。 As described above, in the present embodiment, the reaction material 15 of the reactor 11 includes a mixed material obtained by mixing a main material and a submaterial having different exothermic reaction characteristics. The reaction time in which the reaction rate with the reaction medium in the main material is 90% or more is earlier than the reaction time in which the reaction rate with the reaction medium in the secondary material is 90% or more. The maximum exothermic temperature associated with the chemical reaction with the reaction medium in the secondary material is higher than the maximum exothermic temperature associated with the chemical reaction with the reaction medium in the main material. Here, by making the mixing ratio of the main material in the mixed material higher than the mixing ratio of the sub-material in the mixed material, it is possible to obtain the reaction material 15 having both excellent characteristics of the main material and the sub-material. That is, it is possible to obtain a reaction material 15 in which the reaction time at which the reaction rate with the reaction medium is 90% or more is shortened and the maximum exothermic temperature associated with the chemical reaction with the reaction medium is increased. Thereby, the chemical heat storage apparatus 10 using the reaction material 15 which has a desired exothermic reaction characteristic can be provided. As a result, an exothermic reaction due to a chemical reaction between the reaction material 15 and the reaction medium is promoted, so that the heat exchanger 3 can be effectively heated.
　また、主材料をＭｇＢｒ２とし、副材料をＭｇＩ２とすると共に、混合材料における主材料の混合割合を８０％以上とし、混合材料における副材料の混合割合を２０％以下とすることにより、所望の発熱反応特性を有する反応材１５を確実に得ることができる。 Further, the main material is MgBr 2 , the sub material is MgI 2 , the mixing ratio of the main material in the mixed material is 80% or more, and the mixing ratio of the sub material in the mixed material is 20% or less. The reaction material 15 having the exothermic reaction characteristics can be obtained with certainty.
　なお、本発明は、上記実施形態には限定されない。例えば、上記実施形態では、主材料（第１材料）としてＭｇＢｒ２を使用し、副材料（第２材料）としてＭｇＩ２を使用しているが、使用する主材料及び副材料としては、特にそれには限られない。 The present invention is not limited to the above embodiment. For example, in the above embodiment, as a main material (first material) using MgBr 2, but using MgI 2 as an auxiliary material (second material), as the main material and secondary material used, especially its Is not limited.
　また、上記実施形態では、反応媒体であるＮＨ３と組成式ＭＸａで表される主材料及び副材料を混合した混合材料を含む反応材１５とを化学反応させて熱を発生させている。ただし、反応媒体としては、特にＮＨ３には限られず、例えばＣＯ２またはＨ２Ｏ等を使用してもよい。反応媒体としてＣＯ２を使用する場合、ＣＯ２と化学反応する反応材の材料としては、ＭｇＯ、ＣａＯ、ＢａＯ、Ｃａ（ＯＨ）２、Ｍｇ（ＯＨ）２、Ｆｅ（ＯＨ）２、Ｆｅ（ＯＨ）３、ＦｅＯ、Ｆｅ２Ｏ３またはＦｅ３Ｏ４等を使用することができる。反応媒体としてＨ２Ｏを使用する場合、Ｈ２Ｏと化学反応する反応材の材料としては、ＣａＯ、ＭｎＯ、ＣｕＯまたはＡｌ２Ｏ３等を使用することができる。何れの場合にも、反応材は、発熱反応特性が異なる主材料（第１材料）及び副材料（第２材料）を混合した混合材料を含んでいる。 In the above embodiment, NH 3 and a reaction member 15 which includes a main material and mixed mixed material sub material expressed by a composition formula MXa by chemical reaction is caused to generate heat is the reaction medium. However, the reaction medium is not particularly limited to NH 3 , and for example, CO 2 or H 2 O may be used. When CO 2 is used as the reaction medium, the material of the reaction material that chemically reacts with CO 2 is MgO, CaO, BaO, Ca (OH) 2 , Mg (OH) 2 , Fe (OH) 2 , Fe (OH) 3 , FeO, Fe 2 O 3 or Fe 3 O 4 can be used. When H 2 O is used as a reaction medium, CaO, MnO, CuO, Al 2 O 3 or the like can be used as a material for a reaction material that chemically reacts with H 2 O. In any case, the reaction material includes a mixed material obtained by mixing a main material (first material) and a sub material (second material) having different exothermic reaction characteristics.
　また、上記実施形態は、熱交換器３を加熱する化学蓄熱装置１０であるが、本発明は、ＤＯＣ４等の触媒を加熱する化学蓄熱装置にも適用可能である。また、本発明は、ディーゼルエンジンの排気系に配設された加熱対象物以外にも、ガソリンエンジンの排気系に配設された加熱対象物を加熱する化学蓄熱装置、或いはエンジンの排気系以外、例えばオイルの流通系等に配設された加熱対象物を加熱する化学蓄熱装置にも適用可能である。 Moreover, although the said embodiment is the chemical heat storage apparatus 10 which heats the heat exchanger 3, this invention is applicable also to the chemical heat storage apparatus which heats catalysts, such as DOC4. In addition to the heating object disposed in the exhaust system of the diesel engine, the present invention is a chemical heat storage device that heats the heating object disposed in the exhaust system of the gasoline engine, or other than the exhaust system of the engine. For example, the present invention can also be applied to a chemical heat storage device that heats an object to be heated disposed in an oil distribution system or the like.
　さらに、本発明の化学蓄熱装置の加熱対象物としては、エンジンの排気系に設けられた熱交換器や触媒に限定されず、排ガスが流れる排気管そのものとしてもよい。あるいは、化学蓄熱装置の反応器は、エンジンの排気系以外、例えばオイルの流通系に設けられた配管等を加熱するものにも適用可能である。更に、化学蓄熱装置の反応器は、例えばエンジンオイル、変速機オイル、冷却水、又は空気等の車両における種々の熱媒体を加熱するものであってもよい。このとき、化学蓄熱装置の反応器を熱媒体が流れる熱媒体流路の外周部（外周部の一部又は外周部の全周）に配置して、熱媒体流路そのものを加熱してもよい。また、熱媒体が流れる熱媒体流路内に熱交換器を配置して、熱媒体流路の外周部に配置した反応器で、その熱交換器を介して熱媒体を加熱してもよい。 Furthermore, the heating object of the chemical heat storage device of the present invention is not limited to a heat exchanger or a catalyst provided in the exhaust system of the engine, but may be an exhaust pipe itself through which exhaust gas flows. Or the reactor of a chemical thermal storage apparatus is applicable also to what heats the piping etc. which were provided in the distribution system of oil other than an engine exhaust system, for example. Furthermore, the reactor of the chemical heat storage device may heat various heat media in the vehicle such as engine oil, transmission oil, cooling water, or air. At this time, the reactor of the chemical heat storage device may be disposed on the outer periphery (a part of the outer periphery or the entire periphery of the outer periphery) of the heat medium channel through which the heat medium flows to heat the heat medium channel itself. . Further, a heat exchanger may be disposed in the heat medium flow path through which the heat medium flows, and the heat medium may be heated via the heat exchanger by a reactor disposed on the outer periphery of the heat medium flow path.
　また、蓄熱材を備える反応部と熱交換フィンなどの熱交換部とを交互に複数個重ねて配置した熱交換部一体型の反応器を構成し、その熱交換部一体型の反応器を熱媒体が貯蔵されている熱媒体貯蔵部内や熱媒体が流れる熱媒体流路上に配置してもよい。さらに、本発明は、エンジン以外に配置される化学蓄熱装置にも適用可能である。 In addition, a heat exchange unit integrated reactor is configured in which a plurality of reaction units including heat storage materials and heat exchange units such as heat exchange fins are alternately stacked, and the heat exchange unit integrated reactor is heated. You may arrange | position in the heat-medium storage part in which the medium is stored, and the heat-medium flow path through which a heat-medium flows. Furthermore, this invention is applicable also to the chemical heat storage apparatus arrange | positioned besides an engine.
　１０…化学蓄熱装置、１１…反応器、１２…ＮＨ３流通管（流通路）、１３…吸着器（貯蔵器）、１５…反応材。 10 ... chemical heat storage device, 11 ... reactor, 12 ... NH 3 flow pipe (passage), 13 ... adsorber (reservoir), 15 ... reaction material.

Claims (2)

  1. 　反応媒体との化学反応により発熱すると共に蓄熱により前記反応媒体を脱離する反応材を有する反応器と、
    　前記反応器と流通路を介して前記反応媒体を流通可能に接続され、前記反応媒体を貯蔵する貯蔵器と、を備え、
    　前記反応材は、発熱反応特性が異なる第１材料及び第２材料を混合した混合材料を含み、
    　前記第１材料における前記反応媒体との反応率が９０％以上となる反応時間は、前記第２材料における前記反応媒体との反応率が９０％以上となる反応時間よりも早く、
    　前記第２材料における前記反応媒体との化学反応に伴う最大発熱温度は、前記第１材料における前記反応媒体との化学反応に伴う最大発熱温度よりも高く、
    　前記混合材料における前記第１材料の混合割合は、前記混合材料における前記第２材料の混合割合よりも高いことを特徴とする化学蓄熱装置。     A reactor having a reaction material which generates heat by chemical reaction with the reaction medium and desorbs the reaction medium by storing heat;
    A reservoir that is connected to the reactor via the flow path so that the reaction medium can be circulated, and stores the reaction medium;
    The reaction material includes a mixed material obtained by mixing a first material and a second material having different exothermic reaction characteristics,
    The reaction time at which the reaction rate with the reaction medium in the first material is 90% or more is earlier than the reaction time at which the reaction rate with the reaction medium in the second material is 90% or more,
    The maximum exothermic temperature associated with the chemical reaction with the reaction medium in the second material is higher than the maximum exothermic temperature associated with the chemical reaction with the reaction medium in the first material,
    The chemical heat storage device, wherein a mixing ratio of the first material in the mixed material is higher than a mixing ratio of the second material in the mixed material.
  2. 　前記第１材料はＭｇＢｒ２であり、
    　前記第２材料はＭｇＩ２であり、
    　前記混合材料における前記第１材料の混合割合が８０％以上であり、前記混合材料における前記第２材料の混合割合が２０％以下であることを特徴とする請求項１記載の化学蓄熱装置。     The first material is MgBr 2 ;
    The second material is MgI 2 ;
    The chemical heat storage device according to claim 1, wherein a mixing ratio of the first material in the mixed material is 80% or more, and a mixing ratio of the second material in the mixed material is 20% or less.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06136357A (en) * 1992-07-15 1994-05-17 Nok Corp Production of chemical heat-storage material
JP2012172901A (en) * 2011-02-21 2012-09-10 Toyota Central R&D Labs Inc Chemical heat storage heat transfer device and heat exchanger type reactor
JP2014051972A (en) * 2012-08-09 2014-03-20 Toyota Central R&D Labs Inc Catalytic reaction device and vehicle

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06136357A (en) * 1992-07-15 1994-05-17 Nok Corp Production of chemical heat-storage material
JP2012172901A (en) * 2011-02-21 2012-09-10 Toyota Central R&D Labs Inc Chemical heat storage heat transfer device and heat exchanger type reactor
JP2014051972A (en) * 2012-08-09 2014-03-20 Toyota Central R&D Labs Inc Catalytic reaction device and vehicle

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