WO2016080090A1 - Ammonia absorption/desorption apparatus - Google Patents

Ammonia absorption/desorption apparatus Download PDF

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Publication number
WO2016080090A1
WO2016080090A1 PCT/JP2015/078097 JP2015078097W WO2016080090A1 WO 2016080090 A1 WO2016080090 A1 WO 2016080090A1 JP 2015078097 W JP2015078097 W JP 2015078097W WO 2016080090 A1 WO2016080090 A1 WO 2016080090A1
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Prior art keywords
ammonia
container
storage material
ammonia storage
particles
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PCT/JP2015/078097
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French (fr)
Japanese (ja)
Inventor
浩康 河内
河村　清美
近藤　照明
山内　崇史
研二 森
Original Assignee
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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Publication of WO2016080090A1 publication Critical patent/WO2016080090A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
    • B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
    • C01C1/00—Ammonia; Compounds thereof
    • C01C1/02—Preparation, purification or separation of ammonia
    • 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
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C11/00—Use of gas-solvents or gas-sorbents in vessels

Definitions

  • the present invention relates to an ammonia absorption / release device.
  • a device described in Patent Document 1 is known as a conventional ammonia absorption / release device.
  • the ammonia storage / release device described in Patent Document 1 includes an ammonia storage material that stores ammonia and releases ammonia by heating, an ammonia storage tank that stores the ammonia storage material, and an ammonia storage material that is stored in the ammonia storage tank. And a heater for heating.
  • the ammonia occlusion material When ammonia is occluded in the ammonia occlusion material, the ammonia occlusion material expands in volume and a surface pressure acts on the ammonia occlusion tank. At this time, if the surface pressure acting on the ammonia storage tank is too high, the ammonia storage tank may be damaged. Therefore, it is necessary to increase the thickness of the ammonia storage tank. However, increasing the thickness of the ammonia storage tank increases the size of the ammonia storage tank and increases the weight of the ammonia storage tank.
  • An object of the present invention is to provide an ammonia storage / release device capable of reducing the thickness of the container and reducing the size and weight of the container by reducing the surface pressure acting on the container containing the ammonia storage material. It is.
  • the inventors of the present invention reduced the particle size of the ammonia storage material contained in the container, and when ammonia was stored in the ammonia storage material, the ammonia was stored by volume expansion of the ammonia storage material. The fact that the surface pressure acting on the storage tank is low has been found, and the present invention has been completed.
  • an ammonia storage / release apparatus is an ammonia storage / release apparatus including an ammonia storage material that stores ammonia and releases ammonia by heat, and a container that stores the ammonia storage material.
  • D maximum particle diameter of the occlusion material particles
  • Pal Pal
  • the ammonia storage material when ammonia is stored in the ammonia storage material, the ammonia storage material expands in volume. At this time, since the maximum particle diameter D of the ammonia storage material particles is 58.4 ⁇ Pal 0.51 or less, it is considered that other particles easily enter the gaps between the particles and the surface pressure acting on the container is reduced. It is done. Since the surface pressure acting on the container is reduced in this manner, the thickness of the container can be reduced to reduce the size and weight of the container.
  • the maximum particle diameter D of the ammonia storage material particles may be 102 ⁇ m or less.
  • the surface pressure acting on the container during the volume expansion of the ammonia storage material can be suppressed to 3 MPa or less.
  • the ammonia storage material may contain any of MgCl 2 , SrCl 2 and MgBr 2 .
  • the maximum particle diameter D of the ammonia storage material particles is set to 58.4 ⁇ Pal 0.51 or less, the surface pressure acting on the container can be reliably reduced.
  • An ammonia storage / release apparatus is an ammonia storage / release apparatus including an ammonia storage material that stores ammonia and releases ammonia by heat, and a container that stores the ammonia storage material.
  • an ammonia storage / release apparatus including an ammonia storage material that stores ammonia and releases ammonia by heat, and a container that stores the ammonia storage material.
  • T thickness
  • ⁇ safety factor
  • ⁇ allowable stress of the material of the container
  • ⁇ MPa
  • the maximum particle diameter of the ammonia occlusion material is D ( ⁇ m)
  • T ⁇ ⁇ ⁇ L ⁇ (D / 58.4) (1 / 0.51) / 2 / ⁇ It is characterized by satisfying.
  • the ammonia storage material expands in volume.
  • T ⁇ ⁇ ⁇ L ⁇ (D / 58.4) (1 / 0.51) / 2 / ⁇ is satisfied, by reducing the maximum particle diameter D of the ammonia storage material particles, The lower limit value of the thickness T becomes smaller.
  • the maximum particle diameter D of the ammonia storage material particles is reduced, it is considered that other particles easily enter the gaps between the particles, and the surface pressure acting on the container is reduced. Thereby, thickness of a container can be made small and reduction in size and weight of a container can be achieved.
  • T ⁇ ⁇ ⁇ L ⁇ (D / 58.4) (1 / 0.51) / 2 / ⁇ is satisfied, the strength of the container can be ensured.
  • the maximum particle diameter D of the ammonia storage material particles may be 102 ⁇ m or less. The strength of the container can be reliably ensured.
  • the ammonia absorption-and-release apparatus which can reduce the thickness of a container and can attain the size reduction of a container is provided. .
  • FIG. 1 is a schematic configuration diagram illustrating an exhaust purification system including an embodiment of an ammonia absorption / release device.
  • FIG. 2 is a schematic diagram illustrating a state before and after NH 3 is stored in the ammonia storage material in the ammonia storage / release apparatus illustrated in FIG.
  • FIG. 3 is an image diagram showing a state of change of the ammonia storage material when the ammonia storage material expands in volume and a surface pressure acts on the container.
  • FIG. 4 is a graph showing the relationship between the elapsed time from the start of occlusion of NH 3 in the ammonia occlusion material and the surface pressure acting on the container.
  • FIG. 1 is a schematic configuration diagram illustrating an exhaust purification system including an embodiment of an ammonia absorption / release device.
  • FIG. 2 is a schematic diagram illustrating a state before and after NH 3 is stored in the ammonia storage material in the ammonia storage / release apparatus illustrated in FIG.
  • FIG. 3 is an image diagram
  • FIG. 5 is an image diagram showing a change in the ammonia storage material when the volume of the ammonia storage material expands when the particle size of the particles of the ammonia storage material is reduced.
  • FIG. 6 is a cross-sectional view of the surface pressure measuring device.
  • FIG. 7 is a graph showing the relationship between the particle size of MgCl 2 particles as the ammonia storage material, the elapsed time from the start of storage of NH 3 in the ammonia storage material, and the surface pressure acting on the container.
  • FIG. 8 is a diagram showing sieving using a mesh as an example of a method for defining the maximum particle size of ammonia storage material particles.
  • FIG. 9 is a graph showing the relationship between the maximum particle size of MgCl 2 particles as the ammonia storage material and the maximum surface pressure acting on the container.
  • FIG. 10 is a graph showing the maximum surface pressure acting on the container when the maximum particle diameter of particles of MgCl 2 , SrCl 2 and MgBr 2 that are ammonia storage materials is 210 ⁇ m.
  • FIG. 11 is a schematic configuration diagram showing a modified example of the exhaust purification system shown in FIG. 12 is a cross-sectional view of the heat exchanger with a reaction part shown in FIG.
  • FIG. 1 is a schematic configuration diagram showing an exhaust purification system provided with an embodiment of an ammonia absorption / release 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 diesel oxidation catalyst (DOC) 4, a diesel exhaust particulate filter (DPF) 5, a selective reduction catalyst (SCR: Selective Catalytic Reduction) 6, and an ammonia slip catalyst. (ASC: Ammonia Slip Catalyst) 7.
  • DOC diesel oxidation catalyst
  • DPF diesel exhaust particulate filter
  • SCR Selective Catalytic Reduction
  • ASC Ammonia Slip Catalyst
  • the DOC 4, DPF 5, SCR 6, and ASC 7 are arranged in order from the upstream side to the downstream side in the exhaust passage 8 connected to the engine 2.
  • 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 ammonia (NH 3 ).
  • ASC7 oxidizes NH 3 passing through the SCR6.
  • the exhaust purification system 1 is configured to supply the ammonia absorption / release device 10 of the present embodiment, the ammonia injector 12 for injecting NH 3 into the exhaust gas flowing through the exhaust passage 8, and supplying NH 3 to the ammonia absorption / release device 10.
  • an ammonia introduction pipe 13 for connecting the ammonia absorption / release apparatus 10 to the ammonia supply source 11 and an ammonia lead-out pipe 14 for connecting the ammonia absorption / release apparatus 10 and the ammonia injector 12 are provided.
  • the ammonia inlet pipe 13 and the ammonia outlet pipe 14 are provided with on-off valves 15 and 16 for opening and closing the NH 3 flow path, respectively.
  • Ammonia storage and release device 10 as also shown in FIG. 2, a container 17 as ammonia storage tank is housed within the container 17, powdery ammonia releasing NH 3 by heat as well as absorbing the NH 3 And an occlusion material 18.
  • 2A shows a normal state of the ammonia storage material 18
  • FIG. 2B shows a state in which the ammonia storage material 18 is volume-expanded.
  • the container 17 has a base portion 17b, a cylindrical side wall portion 17a integrated with the base portion 17b, and a lid portion 17c fixed to the upper end of the side wall portion 17a.
  • the side wall portion 17a has a cylindrical shape (a cylindrical shape with a circular cross section) or a rectangular shape (a cylindrical shape with a rectangular cross section).
  • the shape of the side wall part 17a is cylindrical
  • the shape of the base part 17b and the cover part 17c is circular.
  • the shape of the side wall portion 17a is a quadrangular cylindrical shape
  • the shape of the base portion 17b and the lid portion 17c is a quadrangular shape.
  • the container 17 is made of, for example, stainless steel. The thickness of the container 17 will be described later in detail.
  • magnesium chloride (MgCl 2 ), strontium chloride (SrCl 2 ), or magnesium bromide (MgBr 2 ) is used as the ammonia storage material 18.
  • MgCl 2 magnesium chloride
  • strontium chloride (SrCl 2 ) strontium chloride
  • MgBr 2 magnesium bromide
  • the ammonia storage material 18 may contain an additive such as a carbon fiber that improves thermal conductivity. The particles of the ammonia storage material 18 will be described in detail later.
  • a filter 19 for preventing the ammonia storage material 18 from escaping from the ammonia introduction pipe 13 and the ammonia discharge pipe 14 to the outside of the container 17 is attached to the upper portion of the container 17.
  • a heater 29 for heating the ammonia storage material 18 accommodated in the container 17 is disposed around the side wall portion 17 a of the container 17.
  • NH 3 is released from the ammonia storage material 18.
  • the released NH 3 is supplied to the ammonia injector 12 through the ammonia outlet pipe 14. Then, NH 3 is injected into the exhaust gas by the ammonia injector 12, and NOx is reduced by NH 3 in the SCR 6.
  • a porous member (not shown) for spreading NH 3 as a whole may be arranged.
  • a porous member for example, a sheet-like metal fiber (stainless steel fiber or the like) is used.
  • a partition wall extending from the base portion 17 b toward the lid portion 17 c may be disposed in the container 17.
  • the ammonia storage material 18 is filled so that a free space J exists in the container 17 as shown in FIG.
  • the total amount of ammonia storage material 18 is filled into the container 17 before storage of NH 3 to the ammonia storage material 18, the bulk density at the time of full storage on the NH 3 ammonia absorber 18 NH 3 Is an amount that is smaller than the true density when fully occluded in the ammonia occlusion material 18. That is, the following formula is obtained.
  • NH 3 When NH 3 is introduced into the container 17 by connecting the ammonia introduction pipe 13 to the ammonia supply source 11, NH 3 is occluded in the ammonia occlusion material 18, and as shown in FIG. The occlusion material 18 expands in volume. At this time, there is almost no free space J in the container 17, the ammonia storage material 18 is pressed against the inner wall surface of the container 17, and a surface pressure acts on the container 17. Note that NH 3 may be introduced into the container 17 by connecting the ammonia introduction pipe 13 to the ammonia supply source 11 with the container 17 removed from the exhaust purification system 1.
  • FIG. 3 is an image diagram showing a state of change of the ammonia storage material 18 when the ammonia storage material 18 undergoes volume expansion.
  • FIG. 4 is a graph showing an example of the relationship between the elapsed time from the start of occlusion of NH 3 in the ammonia occlusion material and the surface pressure acting on the container 17.
  • FIG. 3A shows the state of the ammonia storage material 18 before storing NH 3 .
  • the reduced particle 18a When the particle 18a is collapsed and reduced in diameter, as shown in FIG. 3D, the reduced particle 18a enters the gap K between the particles 18a. Thus, it weakens the pressing force of the container 17 by the particles 18a, the surface pressure acting on the container 17 is low (see time T 3 in FIG. 4). Then, as shown in FIG. 3E, when the particle 18a is sufficiently reduced in diameter and the gap K between the particles 18a is filled, the container 17 is prevented from being pressed by the particle 18a. surface pressure almost ceases to act on (see the time T 4 in FIG. 4).
  • the ammonia storage material 18 When the ammonia storage material 18 expands in volume, the ammonia storage material 18 changes as described above. Therefore, when the particle size of the particles 18a of the ammonia storage material 18 is reduced, other particles 18a enter the gap K between the particles 18a. It is considered that the surface pressure acting on the container 17 becomes low.
  • FIG. 5 is an image diagram showing a change in the ammonia storage material 18 when the ammonia storage material 18 undergoes volume expansion when the particle size of the particles 18a of the ammonia storage material 18 is reduced.
  • FIG. 5A shows the state of the ammonia storage material 18 before storing NH 3 .
  • the surface pressure measuring device 20 includes a container 21 having a cylindrical shape.
  • a plunger 22 and a load cell 23 for measuring a load applied to the plunger 22 are arranged inside the container 21.
  • An upper region of the load cell 23 inside the container 21 is an ammonia storage material storage portion 24 in which the ammonia storage material 18 is stored.
  • the inner diameter of the ammonia storage material container 24 is 15 mm, and the depth of the ammonia storage material container 24 is 5 mm.
  • An ammonia introduction pipe 25 for introducing NH 3 into the ammonia storage material accommodating portion 24 is fixed to the lid portion 21 a of the container 21.
  • the ammonia introduction pipe 25 is provided with an on-off valve 26 for opening and closing the NH 3 flow path.
  • a filter 27 for preventing the ammonia storage material 18 from escaping to the outside of the container 21 when the ammonia storage material 18 undergoes volume expansion is disposed at the upper portion of the container 21.
  • anhydrous MgCl 2 was used as the ammonia storage material 18.
  • 0.969 g of Mg (NH 3 ) 6 Cl 2 is generated.
  • the bulk density of Mg (NH 3 ) 6 Cl 2 is 1.1 g / cm 3 .
  • the true density of Mg (NH 3 ) 6 Cl 2 is about 1.25 g / cm 3 . That is, the bulk density under the experimental conditions corresponds to about 0.9 times the true density.
  • the reason why the bulk density has a margin of about 10% with respect to the true density is to suppress the fluctuation of the bulk density due to the influence of disturbance.
  • the result of measuring the surface pressure using the surface pressure measuring device 20 is shown in FIG.
  • the horizontal axis represents the elapsed time from the start of storing NH 3 in the ammonia storage material 18, and the vertical axis represents the surface pressure acting on the container 21.
  • the thick solid line Pa is a measurement result when the particle size of the particles 18a of the ammonia storage material 18 is 40 ⁇ m or less.
  • a thin solid line Qa is a measurement result when the particle size of the particles 18a of the ammonia storage material 18 is larger than 40 ⁇ m and 75 ⁇ m or less.
  • a broken line Ra is a measurement result when the particle size of the particles 18a of the ammonia storage material 18 is larger than 75 ⁇ m and 106 ⁇ m or less.
  • a dotted line Sa is a measurement result when the particle size of the particles 18a of the ammonia storage material 18 is larger than 106 ⁇ m and 150 ⁇ m or less.
  • a one-dot chain line Ta is a measurement result when the particle size of the particles 18a of the ammonia storage material 18 is larger than 150 ⁇ m and equal to or smaller than 210 ⁇ m.
  • the particle diameter of the particles 18a of the ammonia storage material 18 is represented by a value classified by sieving using five types of meshes having different mesh opening sizes. As shown in FIG. 8, the mesh 30 used has a square mesh. As the mesh 30, five kinds of mesh opening sizes M of 40 ⁇ m, 75 ⁇ m, 106 ⁇ m, 150 ⁇ m, and 210 ⁇ m are prepared. By passing the particles 18a through these meshes 30, the particle size of the particles 18a is classified.
  • FIG. 9 is a graph showing the relationship between the maximum particle diameter of the particles 18 a of the ammonia storage material 18 and the maximum surface pressure acting on the container 17.
  • the horizontal axis represents the maximum particle diameter D of the particles 18 a of the ammonia storage material 18, and the vertical axis represents the maximum surface pressure P acting on the container 17.
  • the maximum surface pressure P acting on the container 17 is obtained from the graph shown in FIG.
  • the maximum particle diameter D of the particles 18a is determined by the mesh through which the particles 18a pass among the above five types of meshes. Specifically, the maximum particle diameter D of the particle 18a is the mesh size of a mesh having the smallest mesh size among meshes through which the particle 18a passes. For example, when the particle 18a passes through all five types of meshes, the maximum particle diameter D of the particle 18a is 40 ⁇ m. When the particle 18a passes through a mesh having an opening size of 75 ⁇ m, 106 ⁇ m, 150 ⁇ m, and 210 ⁇ m among the five types of meshes, the maximum particle diameter D of the particle 18a is 75 ⁇ m.
  • the maximum particle diameter D of the particle 18a is 106 ⁇ m.
  • the maximum particle diameter D of the particle 18a is 150 ⁇ m.
  • the maximum particle diameter D of the particle 18a is 210 ⁇ m.
  • the maximum surface pressure P acting on the container 17 is 3 MPa or less.
  • the maximum particle diameter D of the particles 18a may be set to 102 ⁇ m or less.
  • the maximum surface pressure P acting on the container 17 is more preferably 1 MPa or less, and for this purpose, the maximum particle diameter D of the particles 18a may be 58 ⁇ m or less.
  • the maximum surface pressure P acting on the container 17 is more preferably 0.5 MPa or less, and for this purpose, the maximum particle diameter D of the particles 18a may be 40 ⁇ m or less.
  • a resin such as polytetrafluoroethylene (PTFE) that is lighter than stainless steel can be used as the material of the container 17.
  • the thickness T (mm) of the container 17 only needs to satisfy the relationship of the following formula.
  • ⁇ is the safety factor of the container 17
  • ⁇ is the allowable stress (MPa) of the material of the container 17
  • L is the distance (mm) between the opposing inner wall surfaces of the side wall portion 17 a of the container 17.
  • L is the inner diameter of the side wall portion 17a.
  • L is the distance between the inner side surfaces which oppose the long side direction of the side wall part 17a.
  • the container 17 When the container 17 is mounted on a vehicle as in this embodiment, it is desirable to set the safety factor ⁇ of the container 17 to 1.2 or more.
  • the maximum surface pressure P acting on the container 17 can be suppressed to 3 MPa or less, so that the safety factor ⁇ of the container 17 is ensured to be 1.2 or more.
  • the thickness T of the container 17 may satisfy the following formula. T ⁇ 1.8 ⁇ L / ⁇ (6)
  • the maximum surface pressure P acting on the container 17 can be suppressed to 1 MPa or less, so that the safety factor ⁇ of the container 17 is ensured to be 1.2 or more.
  • the thickness T of the container 17 may satisfy the following formula. T ⁇ 0.6 ⁇ L / ⁇ (7)
  • the maximum surface pressure P acting on the container 17 can be suppressed to 0.5 MPa or less, and therefore the safety factor ⁇ of the container 17 is secured to 1.2 or more.
  • thickness T of such a container 17 the following formula may be satisfied. T ⁇ 0.3 ⁇ L / ⁇ (8)
  • the measurement result at that time is shown in FIG.
  • the graph shown in FIG. 10 corresponds to the graph shown in FIG.
  • the maximum surface pressure P acting on the container 17 was about 12 MPa (see circle X).
  • the maximum surface pressure P acting on the container 17 is about 10 MPa (see rhombus Y) and about 5 MPa (square mark), respectively. Z). That is, the maximum surface pressure P acting on the container 17 when using SrCl 2 and MgBr 2 is lower than the maximum surface pressure P acting on the container 17 when using MgCl 2 .
  • the maximum particle diameter of the particles 18a of the ammonia storage material 18 is D ( ⁇ m) and the allowable surface pressure of the container 17 is Pal (MPa)
  • the container 17 can be reduced in size and weight. Further, the bulk density when NH 3 is fully occluded in the ammonia occlusion material 18 can be increased by the amount by which the surface pressure acting on the container 17 becomes lower. In this case, since the inner volume of the container 17 can be reduced, the container 17 can be reduced in size and weight.
  • the maximum particle diameter D of the particles 18a of the ammonia storage material 18 is set to 102 ⁇ m or less, the maximum surface pressure P acting on the container 17 during the volume expansion of the ammonia storage material 18 can be suppressed to 3 MPa or less.
  • the ammonia storage material 18 contains any of MgCl 2 , SrCl 2 and MgBr 2 , when the maximum particle diameter D of the particles 18a of the ammonia storage material 18 is 58.4 ⁇ Pal 0.51 or less, the container The surface pressure acting on 17 can be reliably reduced.
  • the thickness of the container 17 is T (mm)
  • the safety factor of the container 17 is ⁇
  • the allowable stress of the material of the container 17 is ⁇ (MPa)
  • the inner side of the side wall portion 17a of the container 17 is opposed.
  • L (mm) is the distance between the wall surfaces
  • D ( ⁇ m) is the maximum particle size of the particles 18a of the ammonia storage material 18. Since / 2 / ⁇ is satisfied, the lower limit value of the thickness T of the container 17 is reduced by reducing the maximum particle diameter D of the particles 18a of the ammonia storage material 18.
  • the present invention is not limited to the above embodiment.
  • the powdery ammonia storage material 18 is accommodated in the container 17, but is not particularly limited thereto, and the powdery ammonia storage material 18 is compression-molded and pelletized.
  • the ammonia storage material 18 may be accommodated in the container 17.
  • ammonia absorption / release device of the present invention may be applied to a reaction part of a chemical heat storage device.
  • An example in which the ammonia absorption / release device is applied to the reaction section of a chemical heat storage device is shown in FIG.
  • FIG. 11 is a schematic configuration diagram showing a modification of the exhaust purification system 1 shown in FIG.
  • the exhaust purification system 1 includes a chemical heat storage device 40.
  • Chemical heat storage device 40 includes a reaction section with the heat exchanger 3 disposed between the engine 2 and the DOC4 in the exhaust passage 8, the holding and NH 3 by physical adsorption of NH 3 desorption of activated carbon can be the adsorber 42 having an adsorbent 41, a reaction part with the heat exchanger 3 with connecting the adsorber 42, the NH 3 supply pipe 43 is NH 3 flows, is disposed in the NH 3 supply pipe 43, And a valve 44 for opening and closing the NH 3 flow path.
  • the heat exchanger 3 with a reaction unit surrounds a laminate 47 in which a plurality of heat exchange units 45 and a plurality of reaction units 46 are alternately laminated, and surrounds the laminate 47. It has a cylindrical pipe 48 arranged. A circular lid member (not shown) is fixed to both ends of the pipe 48 so as to expose the heat exchange units 45 and cover the reaction units 46.
  • the heat exchanging unit 45 forms a flow path through which the exhaust gas flows, and performs heat exchange between the exhaust gas and the reaction unit 46.
  • the heat exchanging part 45 includes a tube 49 having a rectangular cross section and a wave-like fin 50 disposed in the tube 49.
  • the tube 49 is opened on the upstream side and the downstream side.
  • the reaction unit 46 includes ammonia storage material 51 that emits NH 3 by exhaust heat of exhaust gas while occluding and NH 3. In a state where the ammonia storage material 51 does not store NH 3 , a free space is formed in the reaction unit 46.
  • the ammonia storage material 51 is configured by pelletizing the atomized material.
  • a heat insulating material 52 is disposed between the ammonia storage material 51 and the pipe 48.
  • the pipe 48, the tube 49, the heat insulating material 52, and the lid member constitute a container that accommodates the ammonia storage material 51.
  • the thickness of the tube 49 and the lid member (not shown) constituting a part of the container for storing the ammonia storage material 51 is used.
  • the size of the component can be reduced and the weight can be reduced.
  • ammonia absorption / release apparatus 10 is arrange
  • the ammonia absorption / release apparatus of this invention may be arrange
  • the ammonia adsorption / desorption device is applied to the reaction unit of the chemical heat storage device that heats the exhaust gas, but the present invention is a reaction unit of the chemical heat storage device that heats a heating target other than the exhaust system of the engine. It is also applicable to.
  • Such heating object may be various heat media such as engine oil, transmission oil, cooling water, or air.
  • the reaction part of the chemical heat storage device may be disposed on the outer peripheral part (a part of the outer peripheral part or the entire outer periphery 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. .
  • 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 through the heat exchanger in the reaction unit.
  • a heat exchange unit integrated heater 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 exchanger integrated heater is heated. You may arrange
  • the present invention can also be applied to a chemical heat storage device arranged other than the engine.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
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Abstract

An ammonia absorption/desorption apparatus 10 is equipped with: an ammonia-absorbing material 18 which can absorb and can desorb ammonia upon the application of heat; and a container 17 in which the ammonia-absorbing material 18 is housed. In the ammonia absorption/desorption apparatus 10, the requirement represented by the formula: D ≤ 58.4 × Pal0.51 is satisfied, wherein D (μm) represents the largest particle diameter of particles of the ammonia-absorbing material 18 and Pal (MPa) represents a contact pressure which the container 17 can tolerate.

Description

アンモニア吸放出装置Ammonia absorption / release device
　本発明は、アンモニア吸放出装置に関する。 The present invention relates to an ammonia absorption / release device.
　従来のアンモニア吸放出装置としては、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に記載のアンモニア吸放出装置は、アンモニアを吸蔵すると共に加熱によりアンモニアを放出するアンモニア吸蔵材と、アンモニア吸蔵材を収容するアンモニア吸蔵タンクと、アンモニア吸蔵タンクに収容されたアンモニア吸蔵材を加熱するヒータと、を備えている。 For example, a device described in Patent Document 1 is known as a conventional ammonia absorption / release device. The ammonia storage / release device described in Patent Document 1 includes an ammonia storage material that stores ammonia and releases ammonia by heating, an ammonia storage tank that stores the ammonia storage material, and an ammonia storage material that is stored in the ammonia storage tank. And a heater for heating.
特開２０１２－４７１５６号公報JP 2012-47156 A
　アンモニア吸蔵材にアンモニアが吸蔵されると、アンモニア吸蔵材が体積膨張し、アンモニア吸蔵タンクに面圧が作用する。このとき、アンモニア吸蔵タンクに作用する面圧が高すぎると、アンモニア吸蔵タンクが破損するおそれがあるため、アンモニア吸蔵タンクの厚さを大きくする必要がある。しかし、アンモニア吸蔵タンクの厚さを大きくすると、アンモニア吸蔵タンクが大型化すると共に、アンモニア吸蔵タンクの重量が増加する。 When ammonia is occluded in the ammonia occlusion material, the ammonia occlusion material expands in volume and a surface pressure acts on the ammonia occlusion tank. At this time, if the surface pressure acting on the ammonia storage tank is too high, the ammonia storage tank may be damaged. Therefore, it is necessary to increase the thickness of the ammonia storage tank. However, increasing the thickness of the ammonia storage tank increases the size of the ammonia storage tank and increases the weight of the ammonia storage tank.
　本発明の目的は、アンモニア吸蔵材を収容する容器に作用する面圧を低減することにより、容器の厚さを小さくして容器の小型軽量化を図ることができるアンモニア吸放出装置を提供することである。 An object of the present invention is to provide an ammonia storage / release device capable of reducing the thickness of the container and reducing the size and weight of the container by reducing the surface pressure acting on the container containing the ammonia storage material. It is.
　本発明者等は、鋭意検討を重ねた結果、容器に収容されるアンモニア吸蔵材の粒子の粒径を小さくすると、アンモニア吸蔵材にアンモニアが吸蔵されたときに、アンモニア吸蔵材の体積膨張によりアンモニア吸蔵タンクに作用する面圧が低くなるという事実を見出し、本発明を完成させるに至った。 As a result of intensive studies, the inventors of the present invention reduced the particle size of the ammonia storage material contained in the container, and when ammonia was stored in the ammonia storage material, the ammonia was stored by volume expansion of the ammonia storage material. The fact that the surface pressure acting on the storage tank is low has been found, and the present invention has been completed.
　即ち、本発明の一側面に係るアンモニア吸放出装置は、アンモニアを吸蔵すると共に熱によりアンモニアを放出するアンモニア吸蔵材と、アンモニア吸蔵材を収容する容器と、を備えたアンモニア吸放出装置において、アンモニア吸蔵材の粒子の最大粒径をＤ（μｍ）、容器に許容される面圧をＰａｌ（ＭＰａ）としたときに、Ｄ≦５８．４×Ｐａｌ０．５１を満たすことを特徴とする。 That is, an ammonia storage / release apparatus according to one aspect of the present invention is an ammonia storage / release apparatus including an ammonia storage material that stores ammonia and releases ammonia by heat, and a container that stores the ammonia storage material. When the maximum particle diameter of the occlusion material particles is D (μm) and the surface pressure allowed for the container is Pal (MPa), D ≦ 58.4 × Pal 0.51 is satisfied.
　以上のような本発明の一側面に係るアンモニア吸放出装置においては、アンモニア吸蔵材にアンモニアが吸蔵されると、アンモニア吸蔵材が体積膨張する。このとき、アンモニア吸蔵材の粒子の最大粒径Ｄが５８．４×Ｐａｌ０．５１以下であるため、粒子間の隙間に他の粒子が入り込みやすくなり、容器に作用する面圧が低くなると考えられる。このように容器に作用する面圧が低減されるため、容器の厚さを小さくして容器の小型軽量化を図ることができる。 In the ammonia storage / release device according to one aspect of the present invention as described above, when ammonia is stored in the ammonia storage material, the ammonia storage material expands in volume. At this time, since the maximum particle diameter D of the ammonia storage material particles is 58.4 × Pal 0.51 or less, it is considered that other particles easily enter the gaps between the particles and the surface pressure acting on the container is reduced. It is done. Since the surface pressure acting on the container is reduced in this manner, the thickness of the container can be reduced to reduce the size and weight of the container.
　アンモニア吸蔵材の粒子の最大粒径Ｄは、１０２μｍ以下であってもよい。この場合には、アンモニア吸蔵材の体積膨張時に容器に作用する面圧を３ＭＰａ以下に抑えることができる。 The maximum particle diameter D of the ammonia storage material particles may be 102 μm or less. In this case, the surface pressure acting on the container during the volume expansion of the ammonia storage material can be suppressed to 3 MPa or less.
　アンモニア吸蔵材は、ＭｇＣｌ２、ＳｒＣｌ２及びＭｇＢｒ２のいずれかを含んでもよい。この場合には、アンモニア吸蔵材の粒子の最大粒径Ｄを５８．４×Ｐａｌ０．５１以下としたときに、容器に作用する面圧を確実に低減することができる。 The ammonia storage material may contain any of MgCl 2 , SrCl 2 and MgBr 2 . In this case, when the maximum particle diameter D of the ammonia storage material particles is set to 58.4 × Pal 0.51 or less, the surface pressure acting on the container can be reliably reduced.
　また、本発明の一側面に係るアンモニア吸放出装置は、アンモニアを吸蔵すると共に熱によりアンモニアを放出するアンモニア吸蔵材と、アンモニア吸蔵材を収容する容器と、を備えたアンモニア吸放出装置において、容器は、筒状の側壁部を有し、容器の厚さをＴ（ｍｍ）、容器の安全率をα、容器の材料の許容応力をσ（ＭＰａ）、側壁部の対向する内壁面間の距離をＬ（ｍｍ）、アンモニア吸蔵材の粒子の最大粒径をＤ（μｍ）としたときに、Ｔ≧α×Ｌ×（Ｄ／５８．４）（１／０．５１）／２／σを満たすことを特徴とする。 An ammonia storage / release apparatus according to one aspect of the present invention is an ammonia storage / release apparatus including an ammonia storage material that stores ammonia and releases ammonia by heat, and a container that stores the ammonia storage material. Has a cylindrical side wall, the thickness of the container is T (mm), the safety factor of the container is α, the allowable stress of the material of the container is σ (MPa), and the distance between the opposing inner wall surfaces of the side wall is Is L (mm) and the maximum particle diameter of the ammonia occlusion material is D (μm), T ≧ α × L × (D / 58.4) (1 / 0.51) / 2 / σ It is characterized by satisfying.
　以上のような本発明の一側面に係るアンモニア吸放出装置においては、アンモニア吸蔵材にアンモニアが吸蔵されると、アンモニア吸蔵材が体積膨張する。このとき、Ｔ≧α×Ｌ×（Ｄ／５８．４）（１／０．５１）／２／σを満たしているため、アンモニア吸蔵材の粒子の最大粒径Ｄを小さくすることで、容器の厚さＴの下限値が小さくなる。アンモニア吸蔵材の粒子の最大粒径Ｄを小さくすると、粒子間の隙間に他の粒子が入り込みやすくなり、容器に作用する面圧が低くなると考えられる。これにより、容器の厚さを小さくして容器の小型軽量化を図ることができる。また、Ｔ≧α×Ｌ×（Ｄ／５８．４）（１／０．５１）／２／σを満たしているため、容器の強度を確保することができる。 In the ammonia storage / release device according to one aspect of the present invention as described above, when ammonia is stored in the ammonia storage material, the ammonia storage material expands in volume. At this time, since T ≧ α × L × (D / 58.4) (1 / 0.51) / 2 / σ is satisfied, by reducing the maximum particle diameter D of the ammonia storage material particles, The lower limit value of the thickness T becomes smaller. When the maximum particle diameter D of the ammonia storage material particles is reduced, it is considered that other particles easily enter the gaps between the particles, and the surface pressure acting on the container is reduced. Thereby, thickness of a container can be made small and reduction in size and weight of a container can be achieved. Moreover, since T ≧ α × L × (D / 58.4) (1 / 0.51) / 2 / σ is satisfied, the strength of the container can be ensured.
　Ｔ≧１．８×Ｌ／σを満たしてもよい。この場合には、例えば容器の安全率αを１．２以上に確保しつつ、容器に作用する面圧を３ＭＰａ以下に抑えるために、アンモニア吸蔵材の粒子の最大粒径Ｄを１０２μｍ以下としても、容器の強度を確実に確保することができる。 It may satisfy T ≧ 1.8 × L / σ. In this case, for example, in order to suppress the surface pressure acting on the container to 3 MPa or less while securing the safety factor α of the container to 1.2 or more, the maximum particle diameter D of the ammonia storage material particles may be 102 μm or less. The strength of the container can be reliably ensured.
　本発明によれば、アンモニア吸蔵材を収容する容器に作用する面圧を低減することにより、容器の厚さを小さくして容器の小型軽量化を図ることができるアンモニア吸放出装置が提供される。 ADVANTAGE OF THE INVENTION According to this invention, by reducing the surface pressure which acts on the container which accommodates an ammonia occlusion material, the ammonia absorption-and-release apparatus which can reduce the thickness of a container and can attain the size reduction of a container is provided. .
図１は、アンモニア吸放出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 an ammonia absorption / release device. 図２は、図１に示されたアンモニア吸放出装置においてアンモニア吸蔵材にＮＨ３が吸蔵される前後の状態を示す概略図である。FIG. 2 is a schematic diagram illustrating a state before and after NH 3 is stored in the ammonia storage material in the ammonia storage / release apparatus illustrated in FIG. 図３は、アンモニア吸蔵材が体積膨張して容器に面圧が作用する時のアンモニア吸蔵材の変化の様子を示すイメージ図である。FIG. 3 is an image diagram showing a state of change of the ammonia storage material when the ammonia storage material expands in volume and a surface pressure acts on the container. 図４は、ＮＨ３をアンモニア吸蔵材に吸蔵開始からの経過時間と容器に作用する面圧との関係を示すグラフである。FIG. 4 is a graph showing the relationship between the elapsed time from the start of occlusion of NH 3 in the ammonia occlusion material and the surface pressure acting on the container. 図５は、アンモニア吸蔵材の粒子の粒径を小さくした場合に、アンモニア吸蔵材が体積膨張する時のアンモニア吸蔵材の変化の様子を示すイメージ図である。FIG. 5 is an image diagram showing a change in the ammonia storage material when the volume of the ammonia storage material expands when the particle size of the particles of the ammonia storage material is reduced. 図６は、面圧測定装置の断面図である。FIG. 6 is a cross-sectional view of the surface pressure measuring device. 図７は、アンモニア吸蔵材であるＭｇＣｌ２の粒子の粒径とＮＨ３をアンモニア吸蔵材に吸蔵開始からの経過時間と容器に作用する面圧との関係を示すグラフである。FIG. 7 is a graph showing the relationship between the particle size of MgCl 2 particles as the ammonia storage material, the elapsed time from the start of storage of NH 3 in the ammonia storage material, and the surface pressure acting on the container. 図８は、アンモニア吸蔵材の粒子の最大粒径を規定する方法の一例として、メッシュを用いたふるい分けを示す図である。FIG. 8 is a diagram showing sieving using a mesh as an example of a method for defining the maximum particle size of ammonia storage material particles. 図９は、アンモニア吸蔵材であるＭｇＣｌ２の粒子の最大粒径と容器に作用する最大面圧との関係を示すグラフである。FIG. 9 is a graph showing the relationship between the maximum particle size of MgCl 2 particles as the ammonia storage material and the maximum surface pressure acting on the container. 図１０は、アンモニア吸蔵材であるＭｇＣｌ２、ＳｒＣｌ２及びＭｇＢｒ２の粒子の最大粒径を２１０μｍとした場合における容器に作用する最大面圧を示すグラフである。FIG. 10 is a graph showing the maximum surface pressure acting on the container when the maximum particle diameter of particles of MgCl 2 , SrCl 2 and MgBr 2 that are ammonia storage materials is 210 μm. 図１１は、図１に示された排気浄化システムの変形例を示す概略構成図である。FIG. 11 is a schematic configuration diagram showing a modified example of the exhaust purification system shown in FIG. 図１２は、図１１に示された反応部付き熱交換器の断面図である。12 is a cross-sectional view of the heat exchanger with a reaction part shown in FIG.
　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、アンモニア吸放出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 showing an exhaust purification system provided with an embodiment of an ammonia absorption / release 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、ディーゼル酸化触媒（ＤＯＣ：Diesel Oxidation Catalyst）４と、ディーゼル排気微粒子除去フィルタ（ＤＰＦ：Diesel Particulate Filter）５と、選択還元触媒（ＳＣＲ：Selective Catalytic Reduction）６と、アンモニアスリップ触媒（ＡＳＣ：Ammonia Slip Catalyst）７と、を備えている。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 diesel oxidation catalyst (DOC) 4, a diesel exhaust particulate filter (DPF) 5, a selective reduction catalyst (SCR: Selective Catalytic Reduction) 6, and an ammonia slip catalyst. (ASC: Ammonia Slip Catalyst) 7. The DOC 4, DPF 5, SCR 6, and ASC 7 are arranged in order from the upstream side to the downstream side in the exhaust passage 8 connected to the engine 2.
　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、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 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 ammonia (NH 3 ). ASC7 oxidizes NH 3 passing through the SCR6.
　また、排気浄化システム１は、本実施形態のアンモニア吸放出装置１０と、排気通路８を流れる排気ガスにＮＨ３を注入するアンモニア注入器１２と、アンモニア吸放出装置１０にＮＨ３を供給する際にアンモニア吸放出装置１０をアンモニア供給源１１に接続するためのアンモニア導入管１３と、アンモニア吸放出装置１０とアンモニア注入器１２とを接続するアンモニア導出管１４と、を備えている。アンモニア導入管１３及びアンモニア導出管１４には、ＮＨ３の流路を開閉する開閉弁１５，１６がそれぞれ配設されている。 Further, the exhaust purification system 1 is configured to supply the ammonia absorption / release device 10 of the present embodiment, the ammonia injector 12 for injecting NH 3 into the exhaust gas flowing through the exhaust passage 8, and supplying NH 3 to the ammonia absorption / release device 10. In addition, an ammonia introduction pipe 13 for connecting the ammonia absorption / release apparatus 10 to the ammonia supply source 11 and an ammonia lead-out pipe 14 for connecting the ammonia absorption / release apparatus 10 and the ammonia injector 12 are provided. The ammonia inlet pipe 13 and the ammonia outlet pipe 14 are provided with on-off valves 15 and 16 for opening and closing the NH 3 flow path, respectively.
　アンモニア吸放出装置１０は、図２にも示されるように、アンモニア吸蔵タンクとしての容器１７と、この容器１７内に収容され、ＮＨ３を吸蔵すると共に熱によりＮＨ３を放出する粉末状のアンモニア吸蔵材１８とを備えている。なお、図２（ａ）は、アンモニア吸蔵材１８の通常状態を示し、図２（ｂ）は、アンモニア吸蔵材１８が体積膨張した状態を示している。 Ammonia storage and release device 10, as also shown in FIG. 2, a container 17 as ammonia storage tank is housed within the container 17, powdery ammonia releasing NH 3 by heat as well as absorbing the NH 3 And an occlusion material 18. 2A shows a normal state of the ammonia storage material 18, and FIG. 2B shows a state in which the ammonia storage material 18 is volume-expanded.
　容器１７は、基部１７ｂと、この基部１７ｂと一体化された筒状の側壁部１７ａと、この側壁部１７ａの上端に固定された蓋部１７ｃとを有している。側壁部１７ａは、円筒状（断面円形の筒状）または四角形筒状（断面四角形の筒状）を呈している。側壁部１７ａの形状が円筒状である場合、基部１７ｂ及び蓋部１７ｃの形状は円形状である。側壁部１７ａの形状が四角形筒状である場合、基部１７ｂ及び蓋部１７ｃの形状は四角形状である。蓋部１７ｃには、容器１７の内部にＮＨ３を導入するための上記のアンモニア導入管１３の一端部と、容器１７の外部にＮＨ３を導出するための上記のアンモニア導出管１４の一端部とが固定されている。容器１７は、例えばステンレス鋼で形成されている。なお、容器１７の厚さについては、後で詳述する。 The container 17 has a base portion 17b, a cylindrical side wall portion 17a integrated with the base portion 17b, and a lid portion 17c fixed to the upper end of the side wall portion 17a. The side wall portion 17a has a cylindrical shape (a cylindrical shape with a circular cross section) or a rectangular shape (a cylindrical shape with a rectangular cross section). When the shape of the side wall part 17a is cylindrical, the shape of the base part 17b and the cover part 17c is circular. When the shape of the side wall portion 17a is a quadrangular cylindrical shape, the shape of the base portion 17b and the lid portion 17c is a quadrangular shape. One end of the ammonia introduction pipe 13 for introducing NH 3 into the interior of the container 17 and one end of the ammonia delivery pipe 14 for deriving NH 3 to the outside of the container 17 are provided on the lid portion 17c. And are fixed. The container 17 is made of, for example, stainless steel. The thickness of the container 17 will be described later in detail.
　アンモニア吸蔵材１８としては、塩化マグネシウム（ＭｇＣｌ２）、塩化ストロンチウム（ＳｒＣｌ２）または臭化マグネシウム（ＭｇＢｒ２）が用いられる。アンモニア吸蔵材１８の通常状態（図２（ａ）参照）において、アンモニア吸蔵材１８にＮＨ３が吸蔵されると、アンモニア吸蔵材１８が体積膨張する（図２（ｂ）参照）と共に、アンモニア吸蔵材１８から熱が発生する。なお、アンモニア吸蔵材１８には、熱伝導性を向上させるカーボンファイバ等の添加物が含まれていてもよい。アンモニア吸蔵材１８の粒子については、後で詳述する。 As the ammonia storage material 18, magnesium chloride (MgCl 2 ), strontium chloride (SrCl 2 ), or magnesium bromide (MgBr 2 ) is used. In the normal state of the ammonia storage material 18 (see FIG. 2A), when NH 3 is stored in the ammonia storage material 18, the ammonia storage material 18 expands in volume (see FIG. 2B) and ammonia storage. Heat is generated from the material 18. The ammonia storage material 18 may contain an additive such as a carbon fiber that improves thermal conductivity. The particles of the ammonia storage material 18 will be described in detail later.
　容器１７の上部には、アンモニア吸蔵材１８が体積膨張した時にアンモニア吸蔵材１８がアンモニア導入管１３及びアンモニア導出管１４から容器１７の外部に逃げることを防ぐためのフィルタ１９が取り付けられている。 A filter 19 for preventing the ammonia storage material 18 from escaping from the ammonia introduction pipe 13 and the ammonia discharge pipe 14 to the outside of the container 17 is attached to the upper portion of the container 17.
　容器１７の側壁部１７ａの周囲には、容器１７内に収容されたアンモニア吸蔵材１８を加熱するヒータ２９が配置されている。アンモニア吸蔵材１８にＮＨ３が吸蔵されている状態で、ヒータ２９によりアンモニア吸蔵材１８が加熱されると、アンモニア吸蔵材１８からＮＨ３が放出される。放出されたＮＨ３がアンモニア導出管１４を通ってアンモニア注入器１２に供給される。そして、アンモニア注入器１２によって排気ガスにＮＨ３が注入され、ＳＣＲ６においてＮＨ３によりＮＯｘが還元される。 A heater 29 for heating the ammonia storage material 18 accommodated in the container 17 is disposed around the side wall portion 17 a of the container 17. When the ammonia storage material 18 is heated by the heater 29 in a state where NH 3 is stored in the ammonia storage material 18, NH 3 is released from the ammonia storage material 18. The released NH 3 is supplied to the ammonia injector 12 through the ammonia outlet pipe 14. Then, NH 3 is injected into the exhaust gas by the ammonia injector 12, and NOx is reduced by NH 3 in the SCR 6.
　なお、容器１７内には、ＮＨ３を全体的に行き渡らせるための多孔質部材（図示せず）が配置されていてもよい。多孔質部材としては、例えばシート状の金属繊維（ステンレス鋼繊維等）が用いられる。また、ヒータ２９で発生した熱をアンモニア吸蔵材１８に効果的に伝えるために、容器１７内に基部１７ｂから蓋部１７ｃに向けて延びる隔壁を配置してもよい。 In the container 17, a porous member (not shown) for spreading NH 3 as a whole may be arranged. As the porous member, for example, a sheet-like metal fiber (stainless steel fiber or the like) is used. In order to effectively transmit the heat generated by the heater 29 to the ammonia storage material 18, a partition wall extending from the base portion 17 b toward the lid portion 17 c may be disposed in the container 17.
　このようなアンモニア吸放出装置１０において、アンモニア吸蔵材１８は、図２（ａ）に示されるように、容器１７内に自由空間Ｊが存在するように充填されている。具体的には、アンモニア吸蔵材１８へのＮＨ３の吸蔵前に容器１７内に充填されるアンモニア吸蔵材１８の総量は、ＮＨ３をアンモニア吸蔵材１８にフル吸蔵した時のかさ密度がＮＨ３をアンモニア吸蔵材１８にフル吸蔵した時の真密度よりも小さくなるような量である。つまり、下記式が得られる。
 
　　　　ＮＨ３をフル吸蔵した時のかさ密度＝（ＮＨ３をフル吸蔵した時のアンモニア吸蔵材の重量／ＮＨ３をフル吸蔵した時のアンモニア吸蔵材の体積）＜ＮＨ３をフル吸蔵した時の真密度 In such an ammonia storage / release device 10, the ammonia storage material 18 is filled so that a free space J exists in the container 17 as shown in FIG. In particular, the total amount of ammonia storage material 18 is filled into the container 17 before storage of NH 3 to the ammonia storage material 18, the bulk density at the time of full storage on the NH 3 ammonia absorber 18 NH 3 Is an amount that is smaller than the true density when fully occluded in the ammonia occlusion material 18. That is, the following formula is obtained.

Bulk density when NH 3 was full occlusion = (volume of ammonia storage material when the weight / NH 3 was full occlusion of ammonia storage material when NH 3 was full occlusion) <true when NH 3 was full occlusion density
　アンモニア供給源１１にアンモニア導入管１３を接続することで、容器１７内にＮＨ３が導入されると、アンモニア吸蔵材１８にＮＨ３が吸蔵され、図２（ｂ）に示されるように、アンモニア吸蔵材１８が体積膨張する。このとき、容器１７内の自由空間Ｊが殆ど無くなり、アンモニア吸蔵材１８が容器１７の内壁面に押し付けられ、容器１７に面圧が作用する。なお、容器１７を排気浄化システム１から取り外した状態で、アンモニア導入管１３をアンモニア供給源１１に接続することで、容器１７にＮＨ３を導入するようにしてもよい。 When NH 3 is introduced into the container 17 by connecting the ammonia introduction pipe 13 to the ammonia supply source 11, NH 3 is occluded in the ammonia occlusion material 18, and as shown in FIG. The occlusion material 18 expands in volume. At this time, there is almost no free space J in the container 17, the ammonia storage material 18 is pressed against the inner wall surface of the container 17, and a surface pressure acts on the container 17. Note that NH 3 may be introduced into the container 17 by connecting the ammonia introduction pipe 13 to the ammonia supply source 11 with the container 17 removed from the exhaust purification system 1.
　図３は、アンモニア吸蔵材１８が体積膨張した時のアンモニア吸蔵材１８の変化の様子を示すイメージ図である。図４は、ＮＨ３をアンモニア吸蔵材に吸蔵開始からの経過時間と容器１７に作用する面圧との関係の一例を示すグラフである。図３（ａ）は、ＮＨ３吸蔵前のアンモニア吸蔵材１８の状態を示している。ＮＨ３吸蔵前は、アンモニア吸蔵材１８の粒子１８ａが容器１７の内壁面を押し付けないため、容器１７には面圧が殆ど作用しない（図４中の時間Ｔ０参照）。 FIG. 3 is an image diagram showing a state of change of the ammonia storage material 18 when the ammonia storage material 18 undergoes volume expansion. FIG. 4 is a graph showing an example of the relationship between the elapsed time from the start of occlusion of NH 3 in the ammonia occlusion material and the surface pressure acting on the container 17. FIG. 3A shows the state of the ammonia storage material 18 before storing NH 3 . NH 3 storage before, since the particles 18a of ammonia absorber 18 is not pressed against the inner wall surface of the container 17, hardly acts surface pressure in the vessel 17 (see time T 0 in Figure 4).
　図３（ａ）に示される状態から、ＮＨ３がアンモニア吸蔵材１８に吸蔵されると、図３（ｂ）に示されるように、アンモニア吸蔵材１８の粒子１８ａが体積膨張する。そして、アンモニア吸蔵材１８の粒子１８ａが容器１７の内壁面を押し付けると、粒子１８ａ同士が押し合うことで、容器１７に面圧が作用する（図４中の時間Ｔ１参照）。このとき、一部の粒子１８ａが容器１７の内壁面を押し付けており、粒子１８ａ間には隙間Ｋが存在する。 When NH 3 is occluded in the ammonia occlusion material 18 from the state shown in FIG. 3A, the particles 18a of the ammonia occlusion material 18 expand in volume as shown in FIG. 3B. When the particles 18a of ammonia absorber 18 presses the inner wall surface of the container 17, that mutually push the particles 18a together, the surface pressure is exerted on the container 17 (see time T 1 of the in Figure 4). At this time, some of the particles 18a press against the inner wall surface of the container 17, and a gap K exists between the particles 18a.
　その後、アンモニア吸蔵材１８の更なる体積膨張によってアンモニア吸蔵材１８の粒子１８ａによる容器１７の押付力が強くなることで、容器１７に作用する面圧が更に高くなる（図４中の時間Ｔ２参照）。粒子１８ａが自身の形状を保持できなくなると、図３（ｃ）に示されるように、粒子１８ａが崩壊し始める。 Thereafter, the pressing force of the container 17 by the particles 18a of the ammonia storage material 18 is increased by the further volume expansion of the ammonia storage material 18, so that the surface pressure acting on the container 17 is further increased (time T 2 in FIG. 4). reference). When the particle 18a cannot maintain its own shape, the particle 18a starts to collapse as shown in FIG.
　粒子１８ａが崩壊して細径化されると、図３（ｄ）に示されるように、粒子１８ａ間の隙間Ｋに、細径化された粒子１８ａが入り込む。これにより、粒子１８ａによる容器１７の押付力が弱くなり、容器１７に作用する面圧が低くなる（図４中の時間Ｔ３参照）。そして、図３（ｅ）に示されるように、粒子１８ａが十分に細径化されて、粒子１８ａ間の隙間Ｋが埋め尽くされると、粒子１８ａによる容器１７の押し付けが抑えられるため、容器１７に面圧が殆ど作用しなくなる（図４中の時間Ｔ４参照）。 When the particle 18a is collapsed and reduced in diameter, as shown in FIG. 3D, the reduced particle 18a enters the gap K between the particles 18a. Thus, it weakens the pressing force of the container 17 by the particles 18a, the surface pressure acting on the container 17 is low (see time T 3 in FIG. 4). Then, as shown in FIG. 3E, when the particle 18a is sufficiently reduced in diameter and the gap K between the particles 18a is filled, the container 17 is prevented from being pressed by the particle 18a. surface pressure almost ceases to act on (see the time T 4 in FIG. 4).
　アンモニア吸蔵材１８が体積膨張すると、上記のようにアンモニア吸蔵材１８が変化することから、アンモニア吸蔵材１８の粒子１８ａの粒径を小さくすると、粒子１８ａ間の隙間Ｋに他の粒子１８ａが入り込みやすくなり、容器１７に作用する面圧が低くなると考えられる。 When the ammonia storage material 18 expands in volume, the ammonia storage material 18 changes as described above. Therefore, when the particle size of the particles 18a of the ammonia storage material 18 is reduced, other particles 18a enter the gap K between the particles 18a. It is considered that the surface pressure acting on the container 17 becomes low.
　図５は、アンモニア吸蔵材１８の粒子１８ａの粒径を小さくした場合に、アンモニア吸蔵材１８が体積膨張した時のアンモニア吸蔵材１８の変化の様子を示すイメージ図である。図５（ａ）は、ＮＨ３吸蔵前のアンモニア吸蔵材１８の状態を示している。 FIG. 5 is an image diagram showing a change in the ammonia storage material 18 when the ammonia storage material 18 undergoes volume expansion when the particle size of the particles 18a of the ammonia storage material 18 is reduced. FIG. 5A shows the state of the ammonia storage material 18 before storing NH 3 .
　図５（ａ）に示される状態から、ＮＨ３がアンモニア吸蔵材１８に吸蔵されると、図５（ｂ）に示されるように、アンモニア吸蔵材１８の粒子１８ａが体積膨張する。このとき、粒子１８ａの粒径が小さいため、粒子１８ａ間の隙間Ｋに他の粒子１８ａが入り込みやすくなり、図５（ｃ）に示されるように、粒子１８ａ間の隙間Ｋの大部分が埋まる。その結果、粒子１８ａが容器１７の内壁面を押し付ける力が弱くなるため、容器１７に作用する面圧が低くなる。 When NH 3 is occluded in the ammonia occlusion material 18 from the state shown in FIG. 5A, the particles 18a of the ammonia occlusion material 18 expand in volume as shown in FIG. 5B. At this time, since the particle diameter of the particles 18a is small, other particles 18a can easily enter the gaps K between the particles 18a, and as shown in FIG. 5C, most of the gaps K between the particles 18a are filled. . As a result, since the force with which the particles 18a press the inner wall surface of the container 17 becomes weak, the surface pressure acting on the container 17 becomes low.
　そのような事実を確認するために、アンモニア吸蔵材１８の粒子１８ａの粒径と容器１７に作用する面圧との関係について実験を行った。このとき、面圧の測定は、図６に示されるような面圧測定装置２０を用いて行った。 In order to confirm such a fact, an experiment was conducted on the relationship between the particle size of the particles 18 a of the ammonia storage material 18 and the surface pressure acting on the container 17. At this time, the surface pressure was measured using a surface pressure measuring device 20 as shown in FIG.
　面圧測定装置２０は、円筒状を有する容器２１を備えている。容器２１の内部には、プランジャ２２と、このプランジャ２２に加わる荷重を計測するロードセル２３とが配置されている。容器２１の内部におけるロードセル２３の上側の領域は、アンモニア吸蔵材１８が収容されるアンモニア吸蔵材収容部２４となっている。アンモニア吸蔵材収容部２４の内径は１５ｍｍであり、アンモニア吸蔵材収容部２４の深さは５ｍｍである。 The surface pressure measuring device 20 includes a container 21 having a cylindrical shape. A plunger 22 and a load cell 23 for measuring a load applied to the plunger 22 are arranged inside the container 21. An upper region of the load cell 23 inside the container 21 is an ammonia storage material storage portion 24 in which the ammonia storage material 18 is stored. The inner diameter of the ammonia storage material container 24 is 15 mm, and the depth of the ammonia storage material container 24 is 5 mm.
　容器２１の蓋部２１ａには、アンモニア吸蔵材収容部２４にＮＨ３を導入するためのアンモニア導入管２５が固定されている。アンモニア導入管２５には、ＮＨ３の流路を開閉する開閉弁２６が配設されている。容器２１の上部には、アンモニア吸蔵材１８が体積膨張した時にアンモニア吸蔵材１８が容器２１の外部に逃げることを防ぐためのフィルタ２７が配置されている。 An ammonia introduction pipe 25 for introducing NH 3 into the ammonia storage material accommodating portion 24 is fixed to the lid portion 21 a of the container 21. The ammonia introduction pipe 25 is provided with an on-off valve 26 for opening and closing the NH 3 flow path. A filter 27 for preventing the ammonia storage material 18 from escaping to the outside of the container 21 when the ammonia storage material 18 undergoes volume expansion is disposed at the upper portion of the container 21.
　アンモニア吸蔵材１８にＮＨ３が吸蔵されてアンモニア吸蔵材１８が体積膨張することで、容器２１の内壁面に面圧が作用すると、プランジャ２２が押し下げられる。このとき、プランジャ２２に加わる荷重がロードセル２３によって計測される。容器２１に作用する面圧は、プランジャ２２に加わる荷重からプランジャ２２の断面積を除することによって求められる。 When NH 3 is occluded in the ammonia occlusion material 18 and the ammonia occlusion material 18 undergoes volume expansion, when the surface pressure acts on the inner wall surface of the container 21, the plunger 22 is pushed down. At this time, the load applied to the plunger 22 is measured by the load cell 23. The surface pressure acting on the container 21 is obtained by dividing the cross-sectional area of the plunger 22 from the load applied to the plunger 22.
　ここでは、アンモニア吸蔵材１８として、無水のＭｇＣｌ２を０．４６７ｇ使用した。そのアンモニア吸蔵材１８にＮＨ３がフル吸蔵されると、０．９６９ｇのＭｇ（ＮＨ３）６Ｃｌ２が生成される。このとき、Ｍｇ（ＮＨ３）６Ｃｌ２のかさ密度は、１．１ｇ／ｃｍ３になる。なお、Ｍｇ（ＮＨ３）６Ｃｌ２の真密度は、約１．２５ｇ／ｃｍ３である。つまり、実験した条件でのかさ密度は、真密度の約０．９倍に相当する。なお、真密度に対してかさ密度に１０％程度の余裕を持たせた理由は、外乱の影響によるかさ密度の変動を抑制するためである。なお、アンモニア吸蔵材収容部２４にＮＨ３を供給する際には、アンモニア吸蔵材収容部２４を真空引きした後、０．１ＭＰａの供給圧力でＮＨ３を供給した。 Here, 0.467 g of anhydrous MgCl 2 was used as the ammonia storage material 18. When NH 3 is fully stored in the ammonia storage material 18, 0.969 g of Mg (NH 3 ) 6 Cl 2 is generated. At this time, the bulk density of Mg (NH 3 ) 6 Cl 2 is 1.1 g / cm 3 . The true density of Mg (NH 3 ) 6 Cl 2 is about 1.25 g / cm 3 . That is, the bulk density under the experimental conditions corresponds to about 0.9 times the true density. The reason why the bulk density has a margin of about 10% with respect to the true density is to suppress the fluctuation of the bulk density due to the influence of disturbance. At the time of supplying NH 3 to the ammonia storage material accommodating portion 24, after the ammonia storage material container 24 was evacuated, it was supplied NH 3 in the supply pressure of 0.1 MPa.
　面圧測定装置２０を用いて面圧を測定した結果を図７に示す。図７に示されるグラフにおいて、横軸は、ＮＨ３をアンモニア吸蔵材１８に吸蔵開始からの経過時間を表し、縦軸は、容器２１に作用する面圧を表している。 The result of measuring the surface pressure using the surface pressure measuring device 20 is shown in FIG. In the graph shown in FIG. 7, the horizontal axis represents the elapsed time from the start of storing NH 3 in the ammonia storage material 18, and the vertical axis represents the surface pressure acting on the container 21.
　また、太実線Ｐａは、アンモニア吸蔵材１８の粒子１８ａの粒径が４０μｍ以下のときの測定結果である。細実線Ｑａは、アンモニア吸蔵材１８の粒子１８ａの粒径が４０μｍよりも大きく且つ７５μｍ以下のときの測定結果である。破線Ｒａは、アンモニア吸蔵材１８の粒子１８ａの粒径が７５μｍよりも大きく且つ１０６μｍ以下のときの測定結果である。点線Ｓａは、アンモニア吸蔵材１８の粒子１８ａの粒径が１０６μｍよりも大きく且つ１５０μｍ以下のときの測定結果である。１点鎖線Ｔａは、アンモニア吸蔵材１８の粒子１８ａの粒径が１５０μｍよりも大きく且つ２１０μｍ以下のときの測定結果である。 Moreover, the thick solid line Pa is a measurement result when the particle size of the particles 18a of the ammonia storage material 18 is 40 μm or less. A thin solid line Qa is a measurement result when the particle size of the particles 18a of the ammonia storage material 18 is larger than 40 μm and 75 μm or less. A broken line Ra is a measurement result when the particle size of the particles 18a of the ammonia storage material 18 is larger than 75 μm and 106 μm or less. A dotted line Sa is a measurement result when the particle size of the particles 18a of the ammonia storage material 18 is larger than 106 μm and 150 μm or less. A one-dot chain line Ta is a measurement result when the particle size of the particles 18a of the ammonia storage material 18 is larger than 150 μm and equal to or smaller than 210 μm.
　アンモニア吸蔵材１８の粒子１８ａの粒径は、網目の目開き寸法が異なる５種類のメッシュを用いたふるい分けにより分級された値で表されている。図８に示されるように、使用されるメッシュ３０は、正方形状の網目を有している。メッシュ３０としては、網目の目開き寸法Ｍが４０μｍ、７５μｍ、１０６μｍ、１５０μｍ、２１０μｍという５種類が用意されている。これらのメッシュ３０に粒子１８ａを通過させることで、粒子１８ａの粒径が分級される。 The particle diameter of the particles 18a of the ammonia storage material 18 is represented by a value classified by sieving using five types of meshes having different mesh opening sizes. As shown in FIG. 8, the mesh 30 used has a square mesh. As the mesh 30, five kinds of mesh opening sizes M of 40 μm, 75 μm, 106 μm, 150 μm, and 210 μm are prepared. By passing the particles 18a through these meshes 30, the particle size of the particles 18a is classified.
　図７に示されるグラフから分かるように、アンモニア吸蔵材１８の粒子１８ａの粒径が小さくなるほど、容器２１に作用する最大面圧が低くなる。 As can be seen from the graph shown in FIG. 7, the smaller the particle size of the particles 18a of the ammonia storage material 18, the lower the maximum surface pressure acting on the container 21.
　図９は、アンモニア吸蔵材１８の粒子１８ａの最大粒径と容器１７に作用する最大面圧との関係を示すグラフである。図９に示されるグラフにおいて、横軸は、アンモニア吸蔵材１８の粒子１８ａの最大粒径Ｄを表し、縦軸は、容器１７に作用する最大面圧Ｐを表している。容器１７に作用する最大面圧Ｐは、図７に示されるグラフから得られる。 FIG. 9 is a graph showing the relationship between the maximum particle diameter of the particles 18 a of the ammonia storage material 18 and the maximum surface pressure acting on the container 17. In the graph shown in FIG. 9, the horizontal axis represents the maximum particle diameter D of the particles 18 a of the ammonia storage material 18, and the vertical axis represents the maximum surface pressure P acting on the container 17. The maximum surface pressure P acting on the container 17 is obtained from the graph shown in FIG.
　粒子１８ａの最大粒径Ｄは、上記５種類のメッシュのうち粒子１８ａが通過するメッシュによって決まる。具体的には、粒子１８ａの最大粒径Ｄは、粒子１８ａが通過するメッシュのうち網目の目開き寸法が最も小さいメッシュの当該目開き寸法である。例えば、粒子１８ａが５種類のメッシュの全てを通過するときは、当該粒子１８ａの最大粒径Ｄは４０μｍである。５種類のメッシュのうち目開き寸法が７５μｍ、１０６μｍ、１５０μｍ及び２１０μｍのメッシュを粒子１８ａが通過するときは、当該粒子１８ａの最大粒径Ｄは７５μｍである。５種類のメッシュのうち目開き寸法が１０６μｍ、１５０μｍ及び２１０μｍのメッシュを粒子１８ａが通過するときは、当該粒子１８ａの最大粒径Ｄは１０６μｍである。５種類のメッシュのうち目開き寸法が１５０μｍ及び２１０μｍのメッシュを粒子１８ａが通過するときは、当該粒子１８ａの最大粒径Ｄは１５０μｍである。５種類のメッシュのうち目開き寸法が２１０μｍのメッシュのみを粒子１８ａが通過するときは、当該粒子１８ａの最大粒径Ｄは２１０μｍである。 The maximum particle diameter D of the particles 18a is determined by the mesh through which the particles 18a pass among the above five types of meshes. Specifically, the maximum particle diameter D of the particle 18a is the mesh size of a mesh having the smallest mesh size among meshes through which the particle 18a passes. For example, when the particle 18a passes through all five types of meshes, the maximum particle diameter D of the particle 18a is 40 μm. When the particle 18a passes through a mesh having an opening size of 75 μm, 106 μm, 150 μm, and 210 μm among the five types of meshes, the maximum particle diameter D of the particle 18a is 75 μm. When the particle 18a passes through a mesh having an opening size of 106 μm, 150 μm, and 210 μm among the five types of meshes, the maximum particle diameter D of the particle 18a is 106 μm. When the particle 18a passes through a mesh having an opening size of 150 μm and 210 μm among the five types of meshes, the maximum particle diameter D of the particle 18a is 150 μm. When the particle 18a passes only through a mesh having an opening size of 210 μm among the five types of meshes, the maximum particle diameter D of the particle 18a is 210 μm.
　図９に示されるグラフから明らかなように、アンモニア吸蔵材１８の粒子１８ａの最大粒径Ｄが小さくなるほど、容器１７に作用する最大面圧Ｐが低くなる。このとき、以下の関係式が成り立つ。
　　　Ｄ＝５８．４×Ｐ０．５１　　…（１） As is clear from the graph shown in FIG. 9, the maximum surface pressure P acting on the container 17 decreases as the maximum particle diameter D of the particles 18 a of the ammonia storage material 18 decreases. At this time, the following relational expression holds.
D = 58.4 × P 0.51 (1)
　従って、容器１７に作用する最大面圧Ｐ（ＭＰａ）を容器１７の許容面圧Ｐａｌ（ＭＰａ）以下にするには、下記式の関係を満たす最大粒径Ｄ（μｍ）を有する粒子１８ａを使用すればよい。なお、容器１７の許容面圧Ｐａｌは、容器１７の材料等によって決まる。
　　　Ｄ≦５８．４×Ｐａｌ０．５１　　…（２） Therefore, in order to make the maximum surface pressure P (MPa) acting on the container 17 equal to or less than the allowable surface pressure Pal (MPa) of the container 17, particles 18a having a maximum particle diameter D (μm) satisfying the relationship of the following formula are used. do it. The allowable surface pressure Pal of the container 17 is determined by the material of the container 17 and the like.
D ≦ 58.4 × Pal 0.51 (2)
　このとき、容器１７の強度の観点から、容器１７に作用する最大面圧Ｐを３ＭＰａ以下とすることが好ましい。このためには、粒子１８ａの最大粒径Ｄを１０２μｍ以下にすればよい。また、容器１７に作用する最大面圧Ｐを１ＭＰａ以下とすることがより好ましく、このためには粒子１８ａの最大粒径Ｄを５８μｍ以下にすればよい。また、容器１７に作用する最大面圧Ｐを０．５ＭＰａ以下とすることが更に好ましく、このためには粒子１８ａの最大粒径Ｄを４０μｍ以下にすればよい。容器１７に作用する最大面圧Ｐを０．５ＭＰａ以下とした場合には、容器１７の材料として、ステンレス鋼よりも軽いポリテトラフルオロエチレン（ＰＴＦＥ）等の樹脂を使用することが可能となる。 At this time, from the viewpoint of the strength of the container 17, it is preferable that the maximum surface pressure P acting on the container 17 is 3 MPa or less. For this purpose, the maximum particle diameter D of the particles 18a may be set to 102 μm or less. The maximum surface pressure P acting on the container 17 is more preferably 1 MPa or less, and for this purpose, the maximum particle diameter D of the particles 18a may be 58 μm or less. Further, the maximum surface pressure P acting on the container 17 is more preferably 0.5 MPa or less, and for this purpose, the maximum particle diameter D of the particles 18a may be 40 μm or less. When the maximum surface pressure P acting on the container 17 is 0.5 MPa or less, a resin such as polytetrafluoroethylene (PTFE) that is lighter than stainless steel can be used as the material of the container 17.
　また、容器１７の強度を確保するためには、容器１７の厚さＴ（ｍｍ）が下記式の関係を満たせばよい。ここで、αは容器１７の安全率、σは容器１７の材料の許容応力（ＭＰａ）、Ｌは容器１７の側壁部１７ａの対向する内壁面間の距離（ｍｍ）である。容器１７の側壁部１７ａの形状が円筒状である場合、Ｌは側壁部１７ａの内径である。容器１７の側壁部１７ａの形状が四角形筒状である場合、Ｌは側壁部１７ａの長辺方向に対向する内側面間の距離である。
　　　Ｔ≧α×Ｌ×Ｐ／２／σ　　…（３） Further, in order to ensure the strength of the container 17, the thickness T (mm) of the container 17 only needs to satisfy the relationship of the following formula. Here, α is the safety factor of the container 17, σ is the allowable stress (MPa) of the material of the container 17, and L is the distance (mm) between the opposing inner wall surfaces of the side wall portion 17 a of the container 17. When the shape of the side wall portion 17a of the container 17 is cylindrical, L is the inner diameter of the side wall portion 17a. When the shape of the side wall part 17a of the container 17 is a quadrangular cylinder shape, L is the distance between the inner side surfaces which oppose the long side direction of the side wall part 17a.
T ≧ α × L × P / 2 / σ (3)
　上記（１）式により、下記式が得られる。
　　　Ｐ＝（Ｄ／５８．４）（１／０．５１）　　…（４） The following formula is obtained from the formula (1).
P = (D / 58.4) ( 1 / 0.51) ... (4)
　従って、上記（３）式は、下記式で表される。
　　　Ｔ≧α×Ｌ×（Ｄ／５８．４）（１／０．５１）／２／σ　　…（５） Therefore, the above formula (3) is expressed by the following formula.
T ≧ α × L × (D / 58.4) (1 / 0.51) / 2 / σ (5)
　本実施形態のように容器１７を車両に搭載する場合には、容器１７の安全率αを１．２以上に設定することが望ましい。最大粒径Ｄが１０２μｍ以下の粒子１８ａを使用する場合には、容器１７に作用する最大面圧Ｐを３ＭＰａ以下に抑制できることから、容器１７の安全率αを１．２以上に確保するような容器１７の厚さＴとしては、下記式を満たせばよい。
　　　Ｔ≧１．８×Ｌ／σ　　…（６） When the container 17 is mounted on a vehicle as in this embodiment, it is desirable to set the safety factor α of the container 17 to 1.2 or more. When the particles 18a having the maximum particle diameter D of 102 μm or less are used, the maximum surface pressure P acting on the container 17 can be suppressed to 3 MPa or less, so that the safety factor α of the container 17 is ensured to be 1.2 or more. The thickness T of the container 17 may satisfy the following formula.
T ≧ 1.8 × L / σ (6)
　最大粒径Ｄが５８μｍ以下の粒子１８ａを使用する場合には、容器１７に作用する最大面圧Ｐを１ＭＰａ以下に抑制できることから、容器１７の安全率αを１．２以上に確保するような容器１７の厚さＴとしては、下記式を満たせばよい。
　　　Ｔ≧０．６×Ｌ／σ　　…（７） When using the particles 18a having the maximum particle diameter D of 58 μm or less, the maximum surface pressure P acting on the container 17 can be suppressed to 1 MPa or less, so that the safety factor α of the container 17 is ensured to be 1.2 or more. The thickness T of the container 17 may satisfy the following formula.
T ≧ 0.6 × L / σ (7)
　最大粒径Ｄが４０μｍ以下の粒子１８ａを使用する場合には、容器１７に作用する最大面圧Ｐを０．５ＭＰａ以下に抑制できることから、容器１７の安全率αを１．２以上に確保するような容器１７の厚さＴとしては、下記式を満たせばよい。
　　　Ｔ≧０．３×Ｌ／σ　　…（８） When using the particles 18a having a maximum particle diameter D of 40 μm or less, the maximum surface pressure P acting on the container 17 can be suppressed to 0.5 MPa or less, and therefore the safety factor α of the container 17 is secured to 1.2 or more. As thickness T of such a container 17, the following formula may be satisfied.
T ≧ 0.3 × L / σ (8)
　以上は、アンモニア吸蔵材１８としてＭｇＣｌ２を使用した場合の測定結果及び評価であるが、アンモニア吸蔵材１８としてＳｒＣｌ２及びＭｇＢｒ２を使用した場合の測定も行った。具体的には、粒子１８ａの最大粒径Ｄが２１０μｍであるＳｒＣｌ２及びＭｇＢｒ２を使用した場合に、容器１７に作用する最大面圧Ｐを測定した。 The above are the measurement results and evaluation when MgCl 2 is used as the ammonia storage material 18, but the measurement was also performed when SrCl 2 and MgBr 2 were used as the ammonia storage material 18. Specifically, the maximum surface pressure P acting on the container 17 was measured when SrCl 2 and MgBr 2 having a maximum particle diameter D of 210 μm were used.
　その時の測定結果を図１０に示す。図１０に示されるグラフは、図９に示されるグラフに対応している。図１０に示されるグラフから分かるように、粒子の最大粒径Ｄが２１０μｍであるＭｇＣｌ２を使用した場合に容器１７に作用する最大面圧Ｐが約１２ＭＰａ（丸印Ｘ参照）であった。これに対し、粒子の最大粒径Ｄが２１０μｍであるＳｒＣｌ２及びＭｇＢｒ２を使用した場合に容器１７に作用する最大面圧Ｐは、それぞれ約１０ＭＰａ（菱形印Ｙ参照）、約５ＭＰａ（四角印Ｚ参照）であった。つまり、ＳｒＣｌ２及びＭｇＢｒ２を使用した場合に容器１７に作用する最大面圧Ｐは、ＭｇＣｌ２を使用した場合に容器１７に作用する最大面圧Ｐよりも低くなっている。 The measurement result at that time is shown in FIG. The graph shown in FIG. 10 corresponds to the graph shown in FIG. As can be seen from the graph shown in FIG. 10, when MgCl 2 having a maximum particle diameter D of 210 μm was used, the maximum surface pressure P acting on the container 17 was about 12 MPa (see circle X). On the other hand, when SrCl 2 and MgBr 2 having a maximum particle diameter D of 210 μm are used, the maximum surface pressure P acting on the container 17 is about 10 MPa (see rhombus Y) and about 5 MPa (square mark), respectively. Z). That is, the maximum surface pressure P acting on the container 17 when using SrCl 2 and MgBr 2 is lower than the maximum surface pressure P acting on the container 17 when using MgCl 2 .
　従って、アンモニア吸蔵材１８としてＳｒＣｌ２及びＭｇＢｒ２を使用する場合にも、アンモニア吸蔵材１８としてＭｇＣｌ２を使用する場合における上記関係式（１）～（８）を適用可能である。 Therefore, even when SrCl 2 and MgBr 2 are used as the ammonia storage material 18, the above relational expressions (1) to (8) when using MgCl 2 as the ammonia storage material 18 can be applied.
　以上のように本実施形態においては、アンモニア吸蔵材１８の粒子１８ａの最大粒径をＤ（μｍ）、容器１７の許容面圧をＰａｌ（ＭＰａ）としたときに、Ｄ≦５８．４×Ｐａｌ０．５１を満たす。従って、ＮＨ３がアンモニア吸蔵材１８に吸蔵されてアンモニア吸蔵材１８が体積膨張したときに、アンモニア吸蔵材１８の粒子１８ａ間の隙間Ｋに他の粒子１８ａが入り込みやすくなる。従って、粒子１８ａが容器１７を押し付ける力が弱くなるため、容器１７に作用する面圧が低くなる。これにより、容器１７の耐圧強度を低減できるため、容器１７の厚さを小さくすることができる。その結果、容器１７の小型軽量化を図ることが可能となる。また、容器１７に作用する面圧が低くなる分だけ、ＮＨ３をアンモニア吸蔵材１８にフル吸蔵した時のかさ密度を増加させることができる。この場合には、容器１７の内容積を小さくできるため、容器１７の小型軽量化を図ることが可能となる。 As described above, in the present embodiment, when the maximum particle diameter of the particles 18a of the ammonia storage material 18 is D (μm) and the allowable surface pressure of the container 17 is Pal (MPa), D ≦ 58.4 × Pal. It satisfies 0.51 . Therefore, when NH 3 is occluded in the ammonia occlusion material 18 and the ammonia occlusion material 18 undergoes volume expansion, other particles 18a are likely to enter the gaps K between the particles 18a of the ammonia occlusion material 18. Therefore, since the force with which the particles 18a press the container 17 becomes weak, the surface pressure acting on the container 17 becomes low. Thereby, since the pressure resistance strength of the container 17 can be reduced, the thickness of the container 17 can be reduced. As a result, the container 17 can be reduced in size and weight. Further, the bulk density when NH 3 is fully occluded in the ammonia occlusion material 18 can be increased by the amount by which the surface pressure acting on the container 17 becomes lower. In this case, since the inner volume of the container 17 can be reduced, the container 17 can be reduced in size and weight.
　このとき、アンモニア吸蔵材１８の粒子１８ａの最大粒径Ｄを１０２μｍ以下とすることにより、アンモニア吸蔵材１８の体積膨張時に容器１７に作用する最大面圧Ｐを３ＭＰａ以下に抑えることができる。 At this time, by setting the maximum particle diameter D of the particles 18a of the ammonia storage material 18 to 102 μm or less, the maximum surface pressure P acting on the container 17 during the volume expansion of the ammonia storage material 18 can be suppressed to 3 MPa or less.
　また、アンモニア吸蔵材１８はＭｇＣｌ２、ＳｒＣｌ２及びＭｇＢｒ２のいずれかを含むので、アンモニア吸蔵材１８の粒子１８ａの最大粒径Ｄを５８．４×Ｐａｌ０．５１以下としたときに、容器１７に作用する面圧を確実に低くすることができる。 Further, since the ammonia storage material 18 contains any of MgCl 2 , SrCl 2 and MgBr 2 , when the maximum particle diameter D of the particles 18a of the ammonia storage material 18 is 58.4 × Pal 0.51 or less, the container The surface pressure acting on 17 can be reliably reduced.
　さらに、本実施形態においては、容器１７の厚さをＴ（ｍｍ）、容器１７の安全率をα、容器１７の材料の許容応力をσ（ＭＰａ）、容器１７の側壁部１７ａの対向する内壁面間の距離をＬ（ｍｍ）、アンモニア吸蔵材１８の粒子１８ａの最大粒径をＤ（μｍ）としたときに、Ｔ≧α×Ｌ×（Ｄ／５８．４）（１／０．５１）／２／σを満たすので、アンモニア吸蔵材１８の粒子１８ａの最大粒径Ｄを小さくすることで、容器１７の厚さＴの下限値が小さくなる。アンモニア吸蔵材１８の粒子１８ａの最大粒径Ｄを小さくすると、アンモニア吸蔵材１８の粒子１８ａ間の隙間Ｋに他の粒子１８ａが入り込みやすくなり、粒子１８ａが容器１７を押し付ける力が弱くなるため、容器１７に作用する面圧が低くなる。これにより、容器１７の厚さを小さくすることができる。また、Ｔ≧α×Ｌ×（Ｄ／５８．４）（１／０．５１）／２／σを満たしているため、容器１７の強度を確保することができる。 Furthermore, in the present embodiment, the thickness of the container 17 is T (mm), the safety factor of the container 17 is α, the allowable stress of the material of the container 17 is σ (MPa), and the inner side of the side wall portion 17a of the container 17 is opposed. T ≧ α × L × (D / 58.4) (1 / 0.51 ) where L (mm) is the distance between the wall surfaces, and D (μm) is the maximum particle size of the particles 18a of the ammonia storage material 18. Since / 2 / σ is satisfied, the lower limit value of the thickness T of the container 17 is reduced by reducing the maximum particle diameter D of the particles 18a of the ammonia storage material 18. When the maximum particle diameter D of the particles 18a of the ammonia storage material 18 is reduced, other particles 18a are likely to enter the gap K between the particles 18a of the ammonia storage material 18, and the force with which the particles 18a press the container 17 is weakened. The surface pressure acting on the container 17 is reduced. Thereby, the thickness of the container 17 can be made small. Moreover, since T ≧ α × L × (D / 58.4) (1 / 0.51) / 2 / σ is satisfied, the strength of the container 17 can be ensured.
　このとき、Ｔ≧１．８×Ｌ／σを満たすことにより、容器１７の安全率αを１．２以上に確保しつつ、容器１７に作用する最大面圧を３ＭＰａ以下に抑えるために、アンモニア吸蔵材１８の粒子１８ａの最大粒径Ｄを１０２μｍ以下としても、容器１７の強度を確実に確保することができる。 At this time, by satisfying T ≧ 1.8 × L / σ, in order to suppress the maximum surface pressure acting on the container 17 to 3 MPa or less while ensuring the safety factor α of the container 17 to 1.2 or more, ammonia Even if the maximum particle diameter D of the particles 18a of the occlusion material 18 is set to 102 μm or less, the strength of the container 17 can be reliably ensured.
　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、粉末状のアンモニア吸蔵材１８が容器１７内に収容されているが、特にそれには限られず、粉末状のアンモニア吸蔵材１８を圧縮成形してペレット化し、そのペレット化されたアンモニア吸蔵材１８を容器１７内に収容してもよい。 Note that the present invention is not limited to the above embodiment. For example, in the above embodiment, the powdery ammonia storage material 18 is accommodated in the container 17, but is not particularly limited thereto, and the powdery ammonia storage material 18 is compression-molded and pelletized. The ammonia storage material 18 may be accommodated in the container 17.
　また、本発明のアンモニア吸放出装置を化学蓄熱装置の反応部に適用してもよい。アンモニア吸放出装置を化学蓄熱装置の反応部に適用した一例を図１１に示す。 Further, the ammonia absorption / release device of the present invention may be applied to a reaction part of a chemical heat storage device. An example in which the ammonia absorption / release device is applied to the reaction section of a chemical heat storage device is shown in FIG.
　図１１は、図１に示された排気浄化システム１の変形例を示す概略構成図である。図１１において、排気浄化システム１は、化学蓄熱装置４０を備えている。化学蓄熱装置４０は、排気通路８におけるエンジン２とＤＯＣ４との間に配設された反応部付き熱交換器３と、ＮＨ３の物理吸着による保持及びＮＨ３の脱離が可能な活性炭等の吸着材４１を有する吸着器４２と、反応部付き熱交換器３と吸着器４２とを接続すると共に、ＮＨ３が流通するＮＨ３供給管４３と、このＮＨ３供給管４３に配設され、ＮＨ３の流路を開閉させるバルブ４４と、を備えている。 FIG. 11 is a schematic configuration diagram showing a modification of the exhaust purification system 1 shown in FIG. In FIG. 11, the exhaust purification system 1 includes a chemical heat storage device 40. Chemical heat storage device 40 includes a reaction section with the heat exchanger 3 disposed between the engine 2 and the DOC4 in the exhaust passage 8, the holding and NH 3 by physical adsorption of NH 3 desorption of activated carbon can be the adsorber 42 having an adsorbent 41, a reaction part with the heat exchanger 3 with connecting the adsorber 42, the NH 3 supply pipe 43 is NH 3 flows, is disposed in the NH 3 supply pipe 43, And a valve 44 for opening and closing the NH 3 flow path.
　反応部付き熱交換器３は、図１２に示されるように、複数の熱交換部４５と複数の反応部４６とが交互に積層されてなる積層体４７と、この積層体４７を取り囲むように配置された円筒状の配管４８とを有している。配管４８の両端部には、各熱交換部４５を露出させると共に各反応部４６を覆う円形状の蓋部材（図示せず）が固定されている。 As shown in FIG. 12, the heat exchanger 3 with a reaction unit surrounds a laminate 47 in which a plurality of heat exchange units 45 and a plurality of reaction units 46 are alternately laminated, and surrounds the laminate 47. It has a cylindrical pipe 48 arranged. A circular lid member (not shown) is fixed to both ends of the pipe 48 so as to expose the heat exchange units 45 and cover the reaction units 46.
　熱交換部４５は、排気ガスを流通させる流路を形成すると共に、排気ガスと反応部４６との間で熱交換を行う。熱交換部４５は、断面矩形状のチューブ４９と、このチューブ４９内に配置された波状のフィン５０とを有している。チューブ４９は、上流側及び下流側に開口されている。 The heat exchanging unit 45 forms a flow path through which the exhaust gas flows, and performs heat exchange between the exhaust gas and the reaction unit 46. The heat exchanging part 45 includes a tube 49 having a rectangular cross section and a wave-like fin 50 disposed in the tube 49. The tube 49 is opened on the upstream side and the downstream side.
　反応部４６は、ＮＨ３を吸蔵すると共に排気ガスの排熱によりＮＨ３を放出するアンモニア吸蔵材５１を有している。アンモニア吸蔵材５１がＮＨ３を吸蔵していない状態では、反応部４６内に自由空間が形成される。アンモニア吸蔵材５１は、微粒化された材料がペレット成型されることで構成されている。アンモニア吸蔵材５１と配管４８との間には、断熱材５２が配置されている。上記の配管４８、チューブ４９、断熱材５２及び蓋部材（図示せず）は、アンモニア吸蔵材５１を収容する容器を構成している。 The reaction unit 46 includes ammonia storage material 51 that emits NH 3 by exhaust heat of exhaust gas while occluding and NH 3. In a state where the ammonia storage material 51 does not store NH 3 , a free space is formed in the reaction unit 46. The ammonia storage material 51 is configured by pelletizing the atomized material. A heat insulating material 52 is disposed between the ammonia storage material 51 and the pipe 48. The pipe 48, the tube 49, the heat insulating material 52, and the lid member (not shown) constitute a container that accommodates the ammonia storage material 51.
　このような化学蓄熱装置４０において、排気ガスの温度が低いときは、吸着器４２から各反応部４６にＮＨ３が供給され、各反応部４６のアンモニア吸蔵材５１とＮＨ３とが化学反応して化学吸着し、アンモニア吸蔵材５１から熱が発生する。そして、アンモニア吸蔵材５１から発生した熱が熱交換部４５に伝わり、熱交換部４５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。一方、排気ガスの温度が高くなると、排気ガスの排熱が熱交換部４５からアンモニア吸蔵材５１に与えられることで、アンモニア吸蔵材５１とＮＨ３とが分離する。そして、アンモニア吸蔵材５１から放出されたＮＨ３は、吸着器４２に戻り回収される。 In such a chemical heat storage device 40, when the temperature of the exhaust gas is low, NH 3 is supplied from the adsorber 42 to each reaction section 46, and the ammonia storage material 51 and NH 3 in each reaction section 46 chemically react. Thus, heat is generated from the ammonia storage material 51. Then, the heat generated from the ammonia storage material 51 is transmitted to the heat exchange unit 45, and the exhaust gas flowing through the heat exchange unit 45 is heated. Then, the heated exhaust gas raises the DOC 4 to an activation temperature suitable for purification of pollutants. On the other hand, when the temperature of the exhaust gas increases, exhaust heat of the exhaust gas is given from the heat exchange unit 45 to the ammonia storage material 51, whereby the ammonia storage material 51 and NH 3 are separated. Then, NH 3 released from the ammonia storage material 51 returns to the adsorber 42 and is recovered.
　以上のような化学蓄熱装置４０では、本発明のアンモニア吸放出装置が適用されるため、アンモニア吸蔵材５１を収容する容器の一部を構成するチューブ４９及び蓋部材（図示せず）の厚さを小さくして、当該部品の小型軽量化を図ることができる。 In the chemical heat storage device 40 as described above, since the ammonia storage / release device of the present invention is applied, the thickness of the tube 49 and the lid member (not shown) constituting a part of the container for storing the ammonia storage material 51 is used. The size of the component can be reduced and the weight can be reduced.
　また、上記実施形態では、アンモニア吸放出装置１０がディーゼルエンジンの排気系に配設されているが、本発明のアンモニア吸放出装置は、ガソリンエンジンの排気系に配設されていてもよいし、或いはエンジンの排気系以外に配設されていてもよい。 Moreover, in the said embodiment, although the ammonia absorption / release apparatus 10 is arrange | positioned in the exhaust system of a diesel engine, the ammonia absorption / release apparatus of this invention may be arrange | positioned in the exhaust system of a gasoline engine, Alternatively, it may be disposed other than the exhaust system of the engine.
　上述の実施形態では、アンモニア吸放出装置を、排気ガスを加熱する化学蓄熱装置の反応部に適用しているが、本発明はエンジンの排気系以外の加熱対象を加熱する化学蓄熱装置の反応部にも適用可能である。そのような加熱対象としては、例えばエンジンオイル、変速機オイル、冷却水、又は空気等の種々の熱媒体であってもよい。このとき、化学蓄熱装置の反応部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、反応部でその熱交換器を介して熱媒体を加熱するとしてもよい。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加熱器を構成し、その熱交換部一体型の加熱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、エンジン以外に配設される化学蓄熱装置にも適用可能である。 In the above-described embodiment, the ammonia adsorption / desorption device is applied to the reaction unit of the chemical heat storage device that heats the exhaust gas, but the present invention is a reaction unit of the chemical heat storage device that heats a heating target other than the exhaust system of the engine. It is also applicable to. Such heating object may be various heat media such as engine oil, transmission oil, cooling water, or air. At this time, the reaction part of the chemical heat storage device may be disposed on the outer peripheral part (a part of the outer peripheral part or the entire outer periphery 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. . 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 through the heat exchanger in the reaction unit. In addition, a heat exchange unit integrated heater 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 exchanger integrated heater 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, the present invention can also be applied to a chemical heat storage device arranged other than the engine.
　１０…アンモニア吸放出装置、１７…容器、１７ａ…側壁部、１８…アンモニア吸蔵材、１８ａ…粒子。 10 ... Ammonia absorption / release device, 17 ... container, 17a ... side wall, 18 ... ammonia storage material, 18a ... particles.

Claims (5)

  1. 　アンモニアを吸蔵すると共に熱により前記アンモニアを放出するアンモニア吸蔵材と、前記アンモニア吸蔵材を収容する容器と、を備えたアンモニア吸放出装置において、
    　前記アンモニア吸蔵材の粒子の最大粒径をＤ（μｍ）、前記容器に許容される面圧をＰａｌ（ＭＰａ）としたときに、Ｄ≦５８．４×Ｐａｌ０．５１を満たすことを特徴とするアンモニア吸放出装置。     In an ammonia storage / release apparatus comprising: an ammonia storage material that stores ammonia and releases the ammonia by heat; and a container that stores the ammonia storage material.
    When the maximum particle diameter of the ammonia storage material particles is D (μm) and the surface pressure allowed for the container is Pal (MPa), D ≦ 58.4 × Pal 0.51 is satisfied. Ammonia absorption / release device.
  2. 　前記アンモニア吸蔵材の粒子の最大粒径Ｄは、１０２μｍ以下であることを特徴とする請求項１記載のアンモニア吸放出装置。 The ammonia storage / release device according to claim 1, wherein the maximum particle diameter D of the ammonia storage material particles is 102 µm or less.
  3. 　前記アンモニア吸蔵材は、ＭｇＣｌ２、ＳｒＣｌ２及びＭｇＢｒ２のいずれかを含むことを特徴とする請求項１または２記載のアンモニア吸放出装置。 The ammonia absorber is, MgCl 2, SrCl 2 and ammonia absorbing and releasing device according to claim 1 or 2, characterized in that it comprises one of MgBr 2.
  4. 　アンモニアを吸蔵すると共に熱により前記アンモニアを放出するアンモニア吸蔵材と、前記アンモニア吸蔵材を収容する容器と、を備えたアンモニア吸放出装置において、
    　前記容器は、筒状の側壁部を有し、
    　前記容器の厚さをＴ（ｍｍ）、前記容器の安全率をα、前記容器の材料の許容応力をσ（ＭＰａ）、前記側壁部の対向する内壁面間の距離をＬ（ｍｍ）、前記アンモニア吸蔵材の粒子の最大粒径をＤ（μｍ）としたときに、Ｔ≧α×Ｌ×（Ｄ／５８．４）（１／０．５１）／２／σを満たすことを特徴とするアンモニア吸放出装置。     In an ammonia storage / release apparatus comprising: an ammonia storage material that stores ammonia and releases the ammonia by heat; and a container that stores the ammonia storage material.
    The container has a cylindrical side wall,
    The thickness of the container is T (mm), the safety factor of the container is α, the allowable stress of the material of the container is σ (MPa), the distance between the inner wall surfaces facing the side walls is L (mm), When the maximum particle diameter of the ammonia storage material particle is D (μm), T ≧ α × L × (D / 58.4) (1 / 0.51) / 2 / σ is satisfied. Ammonia absorption / release device.
  5. 　Ｔ≧１．８×Ｌ／σを満たすことを特徴とする請求項４記載のアンモニア吸放出装置。 The ammonia absorption / release device according to claim 4, wherein T ≧ 1.8 × L / σ is satisfied.
PCT/JP2015/078097 2014-11-19 2015-10-02 Ammonia absorption/desorption apparatus WO2016080090A1 (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002154801A (en) * 2000-11-15 2002-05-28 Japan Steel Works Ltd:The Air permeable material for hydrogen storage vessel
JP2013072558A (en) * 2011-09-26 2013-04-22 Toyota Central R&D Labs Inc Heat recovery type heating device
JP2014015360A (en) * 2012-07-10 2014-01-30 Toyota Industries Corp Ammonia storage tank

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002154801A (en) * 2000-11-15 2002-05-28 Japan Steel Works Ltd:The Air permeable material for hydrogen storage vessel
JP2013072558A (en) * 2011-09-26 2013-04-22 Toyota Central R&D Labs Inc Heat recovery type heating device
JP2014015360A (en) * 2012-07-10 2014-01-30 Toyota Industries Corp Ammonia storage tank

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