MAGNETIC REFRIGERATION MODULE, MAGNETIC REFRIGERATION SYSTEM, AND COOLING METHOD
20220268494 · 2022-08-25
Assignee
Inventors
Cpc classification
C22C28/00
CHEMISTRY; METALLURGY
F25B21/00
MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
Y02B30/00
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
F25B2321/0021
MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
F25B2321/002
MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
International classification
Abstract
This magnetic refrigeration module includes a magnetic refrigeration operation unit which has a magnetic refrigeration material, and extends in a longitudinal direction, and a fixed magnetic field excitation unit and a variable magnetic field excitation unit which are disposed apart from each other in an outer peripheral direction of the magnetic refrigeration operation unit, in which the fixed magnetic field excitation unit applies a fixed magnetic field to the magnetic refrigeration operation unit, and the variable magnetic field excitation unit applies a variable magnetic field to the magnetic refrigeration operation unit when being in an ON state and does not apply the variable magnetic field to the magnetic refrigeration operation unit when being in an OFF state.
Claims
1. A magnetic refrigeration module comprising: a magnetic refrigeration operation unit which has a magnetic refrigeration material, and extends in a longitudinal direction; and a fixed magnetic field excitation unit and a variable magnetic field excitation unit which are disposed apart from each other in an outer peripheral direction of the magnetic refrigeration operation unit, wherein the fixed magnetic field excitation unit applies a fixed magnetic field to the magnetic refrigeration operation unit, and the variable magnetic field excitation unit applies a variable magnetic field to the magnetic refrigeration operation unit when being in an ON state and does not apply the variable magnetic field to the magnetic refrigeration operation unit when being in an OFF state.
2. The magnetic refrigeration module according to claim 1, wherein the variable magnetic field excitation unit is disposed in an outer peripheral direction of the fixed magnetic field excitation unit.
3. The magnetic refrigeration module according to claim 1, wherein the magnetic refrigeration operation unit is rod-shaped, flat plate-shaped, cylindrical, or tubular.
4. The magnetic refrigeration module according to claim 1, wherein the magnetic refrigeration material is H.sub.0 (holmium), Gd.sub.5(Ge.sub.1-xSi.sub.x).sub.4 (x=0 to 1), Co (S.sub.xSe.sub.1-x).sub.2 (x=0.8 to 1.0), (Sm.sub.1-xGd.sub.x).sub.0.55Sr.sub.0.45MnO.sub.3 (x=0 to 1), Eu.sub.0.55Sr.sub.0.45MnO.sub.3, rare earth simple substances Tb (terbium), Dy (dysprosium), and Er (erbium), or an alloy obtained by a combination thereof.
5. The magnetic refrigeration module according to claim 1, wherein at least one of a superconducting magnet and a resistive magnet is used as the variable magnetic field excitation unit.
6. The magnetic refrigeration module according to claim 1, wherein when a magnetic field strength of the fixed magnetic field is 1.5 T or less, the fixed magnetic field excitation unit is a permanent magnet, and when the magnetic field strength of the fixed magnetic field is 1.5 T or more, the fixed magnetic field excitation unit is a superconducting magnet.
7. A magnetic refrigeration system comprising: at least one magnetic refrigeration module according to claim 1, wherein a magnetic field strength to be applied to the magnetic refrigeration operation unit by the fixed magnetic field excitation unit is distributed so as to become higher continuously or stepwise in the longitudinal direction.
8. The magnetic refrigeration system according to claim 7, comprising a plurality of the magnetic refrigeration modules.
9. The magnetic refrigeration system according to claim 7, wherein a magnetic field strength of a variable magnetic field to be applied to the magnetic refrigeration operation unit by the variable magnetic field excitation unit is distributed so as to become higher continuously or stepwise in the longitudinal direction.
10. The magnetic refrigeration system according to claim 7, wherein a magnetic field strength of a variable magnetic field to be applied to the magnetic refrigeration operation unit by the variable magnetic field application unit is constant in the longitudinal direction.
11. The magnetic refrigeration system according to claim 7, comprising only one magnetic refrigeration module, wherein the magnetic field strength to be applied to the magnetic refrigeration operation unit by the fixed magnetic field excitation unit is distributed so as to become higher continuously in the longitudinal direction, and a magnetic field strength of a variable magnetic field to be applied to the magnetic refrigeration operation unit by the variable magnetic field excitation unit is distributed so as to become higher continuously in the longitudinal direction.
12. The magnetic refrigeration system according to claim 9, wherein a sum of the magnetic field strength of the fixed magnetic field and the magnetic field strength of the variable magnetic field is equal to or more than a magnetic field strength corresponding to a steep slope area when being in the ON state, and is equal to or less than a magnetic field strength corresponding to the steep slope area when being in the OFF state, and the steep slope area is an area in which magnetization changes with a steep slope in response to a change in the magnetic field applied to the magnetic refrigeration operation unit.
13. The magnetic refrigeration system according to claim 9, wherein a high temperature end is set to a first temperature, and a low temperature end is set to a second temperature, when a magnetic field strength to be applied to the high temperature end is higher than a magnetic field strength corresponding to the steep slope area in the first temperature, when being in the ON state, a magnetic field strength to be applied to the high temperature end is lower than a magnetic field strength corresponding to the steep slope area in the first temperature, when being in the OFF state, a magnetic field strength to be applied to the low temperature end is higher than a magnetic field strength corresponding to the steep slope area in the second temperature, when being in the ON state, and a magnetic field strength to be applied to the low temperature end is lower than a magnetic field strength corresponding to the steep slope area in the second temperature, when being in the OFF state.
14. The magnetic refrigeration system according to claim 9, wherein a temperature at the low temperature end is 10 K or higher and a temperature at the high temperature end is 150 K or lower.
15. A cooling method using the magnetic refrigeration module according to claim 1, the method comprising: an excitation step of increasing a variable magnetic field and increasing a temperature of the magnetic refrigeration operation unit; a heat removal step of flowing a gas to be cooled from the low temperature end to the high temperature end in the ON state; an adiabatic demagnetization step of demagnetizing the variable magnetic field and lowering the temperature of the magnetic refrigeration operation unit; and a cooling step of flowing the gas to be cooled from the high temperature end to the low temperature end, wherein a hydrogen gas is used inside the magnetic refrigeration operation unit as the gas to be cooled.
16. A cooling method using the magnetic refrigeration system according to claim 7, the method comprising: an excitation step of increasing a variable magnetic field and increasing a temperature of the magnetic refrigeration operation unit; a heat removal step of flowing a gas to be cooled from the low temperature end to the high temperature end in the ON state; an adiabatic demagnetization step of demagnetizing the variable magnetic field and lowering the temperature of the magnetic refrigeration operation unit; and a cooling step of flowing the gas to be cooled from the high temperature end to the low temperature end, wherein a hydrogen gas is used inside the magnetic refrigeration operation unit as the gas to be cooled.
Description
BRIEF DESCRIPTION OF DRAWINGS
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DESCRIPTION OF EMBODIMENTS
[0057] The technical terms used in the present specification will be described.
[0058] (1) Magnetocaloric effect: A temperature change is induced by changing a magnetic field applied to a magnetic material. When the magnetic field applied to the magnetic material is cut off as shown in
[0059] (2) Ferromagnet: A magnetic material showing a magnetic structure in which adjacent electron spins are oriented in the same direction. Magnetization occurs under a zero magnetic field and the ferromagnet has a property of attracting a magnet. Also, a temperature at which a ferromagnetic magnetic structure appears is called a Curie temperature.
[0060] (3) Antiferromagnet: A magnetic material showing a magnetic structure in which adjacent electron spins are oriented in opposite directions. Under a zero magnetic field, no magnetization occurs and the antiferromagnet does not have a property of attracting a magnet. Also, a temperature at which an antiferromagnetic magnetic structure appears is called a Neel temperature.
[0061] (4) Non-ferromagnetic magnetic structure: A magnetic structure in which electron spins are not aligned in the same direction as a ferromagnetic magnetic structure. For example, the antiferromagnetic magnetic structure, a spiral magnetic structure, and a magnetic structure or the like of a composite magnetic material correspond thereto.
[0062] (5) Magnetic entropy: Extensive state quantity that represents a disorder of a spin state. In a ferromagnetic structure or an antiferromagnetic structure that appears at a low temperature, the magnetic entropy becomes small because adjacent electron spins are aligned in the same direction or in opposite directions. On the other hand, in a paramagnetic structure (magnetic structure as shown on the right in
[0063] Hereinafter, the present invention will be described with reference to the drawings and examples.
EXAMPLE
[0064]
[0065] Here, the area is divided into five areas: a low-level side gentle slope area; a low-level side connection area; a steep slope area; a high-level side connection area; and a high-level side gentle slope area, in order from a state of low magnetization. The low-level side gentle slope area is an area in which the magnetization changes with a gentle slope in response to a change in the magnetic field, and is a spiral magnetic state in which magnetic ion spins of the magnetic refrigeration material are arranged periodically so as to draw a spiral. Focusing on the 40 K graph in
[0066] The steep slope area is an area in which the magnetization changes with a steep slope in response to a change in the magnetic field. The steep slope area corresponds to an area from the boundary points M2 to M3 in
[0067] In a case where the magnetization (M)-magnetic field (H) curves of the low-level side gentle slope area, the steep slope area, and the high-level side gentle slope area are approximated by a straight line, a deviation from an actual magnetization (M)-magnetic field (H) curve occurs in the vicinity of an intersection of these linear approximations. Therefore, the curve is approximated between the low-level side connection area and the high-level side connection area to reduce the deviation.
[0068] That is, the low-level side connection area is an area in which the low-level side gentle slope area and the steep slope area are connected in the magnetization (M)-magnetic field (H) curve. That is, the low-level side connection area corresponds to an area of the boundary points M1 to M2 in
[0069] Here, focusing on the 40 K graph, the five areas of the low-level side gentle slope area, the low-level side connection area, the steep slope area, the high-level side connection area, and the high-level side gentle slope area and boundary points thereof have been described, and the five areas and boundary points exist at any temperature. As the temperature increases, a magnitude of the magnetic field corresponding to the boundary point tends to increase.
[0070] As such a magnetic refrigeration material, holmium, Gd.sub.5(Ge.sub.1-xSi.sub.x).sub.4 (x=0 to 1), Co(S.sub.xSe.sub.1-x).sub.2 (x=0.8 to 1.0), (Sm.sub.1-xGd.sub.x).sub.0.55Sr.sub.045MnO.sub.3 (x=0 to 1), Eu.sub.0.55Sr.sub.0.45MnO.sub.3, rare earth simple substances Tb, Dy, and Er, or an alloy obtained by a combination thereof is used.
Example 1
[0071]
[0072] Table 1 shows the amount of change in magnetic entropy (−ΔS) determined using Maxwell relations and the conditions used in Maxwell relations. For example, under Condition 1, when the magnetic field to be applied to holmium simple substance to which a magnetic field H.sub.0=0.2 T has been applied is strengthened by 0.1 T, at a temperature of T.sub.M=20 K, it is shown that the amount of a change in magnetic entropy (−ΔS) changes by 2.4 J.Math.kg.sup.−1.Math.K.sup.−1. Under Condition 1, the amount of change in the magnetic field per unit driving force {−ΔS/A (μ.sub.0h)} was 24 (J.Math.kg.sup.−1.Math.K.sup.−1.Math.T.sup.−1).
[0073] In the related art, the amount of change in magnetic entropy per unit magnetic field {−ΔS/Δ (μ.sub.0h)} was about 6 K. As shown in Table 1, the amount of change in magnetic entropy per unit magnetic field {−ΔS/Δ (μ.sub.0h)} in response to varying of the magnetic field is about 5 times the maximum value of the related art at around 30 K. It is considered that this is because the effect of applying a variable magnetic field to a base magnetic field only in a portion where the change in the M-H characteristics is large is obtained.
TABLE-US-00001 TABLE 1 Amount of Amount of change in change in magnetic entropy per magnetic unit driving force -ΔS/Δ Temperature Magnetic field entropy -ΔS (μ.sub.0h) (J .Math. kg.sup.−1 .Math. K.sup.−1 .Math. Substance T.sub.M (K) H.sub.0 (T) (J .Math. kg.sup.−1 .Math. K.sup.−1) T.sup.−1) Condition 1 Holmium 20 0.2 2.4 24 Condition 2 Holmium 26 0.4 3.1 31 Condition 3 Holmium 31 0.6 3.1 31 Condition 4 Holmium 36 0.8 2.5 25 Condition 5 Holmium 41 1 1.8 18
[0074] A temperature sensor was attached to a holmium simple substance, and a temperature change of a cycle in which a magnetic field of 1.5 T was applied to no magnetic field, and then removed therefrom and a temperature change of a cycle in which a magnetic field h of 0.4 T was further applied to a base magnetic field H.sub.0=0.5 T and then removed therefrom were measured.
[0075] As shown in
[0076]
[0077] A change in entropy ΔS′ and a temperature change ΔT′ in a thermal cycle of the magnetic refrigeration using the variable magnetic field ΔH from the base magnetic field H.sub.0 (isothermal excitation step (A′.fwdarw.B′) and adiabatic demagnetization step (B′.fwdarw.C′)) have almost the same effect of the change in entropy ΔS and the temperature change ΔT in a case of using the magnetic field to a high magnetic field H1 from the zero magnetic field as the magnetic refrigeration thermal cycle (A.fwdarw.B and B.fwdarw.C).
Example 2
[0078]
[0079] A magnet that generates a base magnetic field at intervals of 0.033 T from 0.0 T to 1.5 T as a base magnetic field and at the same time generates a variable magnetic field of 0.4 T is set on an outer periphery portion of a simple substance holmium, and a magnetic field to be applied at each base magnetic field was changed.
[0080]
[0081] When using the base magnetic field as an appropriate fixed magnetic field, holmium, which also serves as a heat storage body, could be cooled by 1.2 to 1.5K from any temperature in the range of 20 to 40K.
<Magnetic Refrigeration System>
[0082]
[0083] The magnetic refrigeration system 100 has at least one magnetic refrigeration module 10. The magnetic refrigeration system 100 shown in
[0084] The magnetic refrigeration operation unit 1 has a magnetic refrigeration material. The magnetic refrigeration operation unit 1 is, for example, a cylindrical or tubular member. For the magnetic refrigeration operation unit 1, for example, a particulate, pellet-like, porous, or dense solid material is used. End portions in a longitudinal direction in which the magnetic refrigeration operation unit 1 extends are referred to as a first end 4 and a second end 5. Hereinafter, the longitudinal direction of the magnetic refrigeration operation unit 1 may be referred to as a first direction. When the magnetic refrigeration system 100 is used, one of the first end 4 and the second end 5 acts as a high temperature end and the other acts as a low temperature end.
[0085] In a case where the magnetic refrigeration operation unit 1 has a tubular or cylindrical shape, a refrigerant flow path 6 is formed inside the magnetic refrigeration operation unit 1. According to the principle to be described in detail later, a gas to be cooled moves through the refrigerant flow path 6 formed inside the magnetic refrigeration operation unit 1, and the magnetic refrigeration system 100 acts. In a case where the magnetic refrigeration operation unit 1 is in the form of particles, pellets, or a porous having low fluid resistance, the gas to be cooled also flows inside the magnetic refrigeration operation unit 1.
[0086] As the magnetic refrigeration material to be used in each magnetic refrigeration module 10, materials having different composition parts may be appropriately combined and used depending on a desired temperature.
[0087] The fixed magnetic field excitation unit 2 includes a plurality of fixed magnetic field excitation units 2a to 2f. Each of the fixed magnetic field excitation units 2a to 2f is provided in each of the magnetic refrigeration modules 10a to 10f. As the fixed magnetic field excitation unit 2, for example, a permanent magnet or a superconducting magnet is used. In a case where the magnitude of the fixed magnetic field is 1.5 T or less, it is preferable that a permanent magnet is used as the fixed magnetic field excitation unit 2. In a case where the magnitude of the fixed magnetic field is 1.5 T or more, it is preferable that the superconducting magnet is used as the fixed magnetic field excitation unit 2.
[0088] The fixed magnetic field excitation unit 2 applies a fixed magnetic field to the magnetic refrigeration operation unit 1. The fixed magnetic field is a magnetic field having a predetermined magnetic field strength, and the magnetic field strength does not vary with a passage of time. It is preferable that the magnetic field strength of the fixed magnetic field becomes higher stepwise along the first direction. For example, it is preferable that the magnetic field strength of the fixed magnetic field excitation unit 2a is the smallest among the fixed magnetic field excitation units 2a to 2f, and the magnetic field strength of the fixed magnetic field excitation unit 2f is the largest among the fixed magnetic field excitation units 2a to 2f.
[0089] As the variable magnetic field excitation unit 3, at least one selected from a resistive magnet and a superconducting magnet is used. The operation of the variable magnetic field excitation unit 3 will be described in detail later, but in an excitation step and a heat removal step, a variable magnetic field is applied to the magnetic refrigeration operation unit 1. In the present embodiment, a state in which the variable magnetic field excitation unit 3 applies the variable magnetic field to the magnetic refrigeration operation unit 1 may be referred to as an ON state, and a state of non-application may be referred to as an OFF state.
[0090] In each magnetic refrigeration module 10 of the magnetic refrigeration system 100 according to the present embodiment, the magnetic field strength of the fixed magnetic field and the magnetic field strength of the variable magnetic field are set based on the working temperature of the magnetic refrigeration operation unit 1 and the steep slope area. The strength of the fixed magnetic field is lower than the strength of the magnetic field corresponding to the steep slope area of the magnetic refrigeration material. Further, when a variable magnetic field is applied, the sum of the strengths of the fixed magnetic field and the variable magnetic field is higher than the strength of the magnetic field corresponding to the steep slope area of the magnetic refrigeration material. That is, the sum of the magnetic field strengths of the fixed magnetic field and the variable magnetic field is equal to or less than the magnetic field corresponding to the steep slope area when being in the OFF state, and equal to or more than the magnetic field corresponding to the steep slope area when being in the ON state. When the sum of the magnetic field strengths of the fixed magnetic field and the variable magnetic field is equal to or less than the magnetic field corresponding to the steep slope area, the magnetic field strength of the variable magnetic field in the OFF state may be a value larger than 0.
[0091] In the magnetic refrigeration system 100, it is preferable that the temperatures at both ends are set to a predetermined temperature. For example, the temperature of the high temperature end 4 is set to be a first temperature, and the temperature of the low temperature end 5 is set to be a second temperature. In this case, it is preferable that each of the magnetic field strengths applied to the high temperature end 4 and the low temperature end 5 when being in the ON state is higher than the magnetic field strength corresponding to the steep slope area at the first temperature and the magnetic field strength corresponding to the steep slope area at the second temperature. In addition, it is preferable that each of the magnetic field strengths applied to the high temperature end 4 and the low temperature end 5 when being in the OFF state is lower than the magnetic field strength corresponding to the steep slope area at the first temperature and the magnetic field strength corresponding to the steep slope area at the second temperature. The first temperature is, for example, 150 K, and the second temperature is, for example, 10 K.
Modification Example 1
[0092]
Modification Example 2
[0093]
Modification Example 3
[0094]
Modification Example 4
[0095]
<Operation of Magnetic Refrigeration System>
[0096] When using the magnetic refrigeration system according to the present embodiment, it is possible to carry out a cooling method including an excitation step, a heat removal step, an adiabatic demagnetization step, and a cooling step. In the cooling method, the gas to be cooled at the first temperature can be used, and the high temperature end 4 can be set to the first temperature and the low temperature end 5 can be set to the second temperature. Hereinafter, the operation will be described by showing an example using the magnetic refrigeration system 100 shown in
[0097] The magnetic refrigeration operation unit 1 has a simple substance holmium as a working substance. Therefore, the simple substance holmium may be formed into particles or pellets, may be porous, or may be a dense solid. If the holmium is in the form of particles or pellets, the gas to be cooled can flow inside the magnetic refrigeration operation unit 1. In the case of the dense form, the gas to be cooled becomes flows through the refrigerant flow path 6. In the case of porous, when the fluid resistance is low, the gas to be cooled can flow inside the magnetic refrigeration operation unit 1, but when the fluid resistance is extremely high, the refrigerant flow path 6 is provided and the gas to be cooled flows therethrough. An overall shape of the magnetic refrigeration operation unit 1 is preferably cylindrical, but may be rod-shaped, flat plate-shaped, or tubular.
[0098] A reciprocating magnetic field excitation unit is a reciprocating magnetic field excitation unit that generates an operation magnetic field that operates including a steep slope area in the magnetization (M)-magnetic field (H) curve of the magnetic refrigeration material, and performs reciprocating excitation of the magnetic field to be applied between a low-level side connection area side of the steep slope area in the operation magnetic field or the low-level side magnetic field corresponding to the low-level side connection area and a high-level side connection area side of the steep slope area in the operation magnetic field or the high-level side magnetic field corresponding to the high-level side connection area (see
[0099] The fixed magnetic field excitation unit 2 applies a magnetic field corresponding to the low-level side connection area of the steep slope area of the magnetic refrigeration material by a fixed magnetic field (H.sub.0; H.sub.0>0), and is thus made of, for example, a permanent magnet. The magnetic field strength of the fixed magnetic field is set to 0.2 T, 0.4 T, 0.6 T, 0.8 T, 1.0 T, and 1.2 T in the fixed magnetic field excitation units 2a, 2b, 2c, 2d, 2e, and 2f, for example.
[0100] The variable magnetic field excitation unit 3 applies a variable magnetic field corresponding to a variable magnetic field amplitude from the low-level side connection area to the high-level side connection area of the steep slope area of the magnetic refrigeration material by the variable magnetic field (h; h>0) having a constant width, and is thus made of, for example, a normal conducting or superconducting magnet. The magnetic field strength of the variable magnetic field when the variable magnetic field excitation unit 3 acts is set to, for example, 0.4 T.
[0101] In this example, the variable magnetic field excitation unit 3 is provided in a tubular shape on the outer peripheral side of the magnetic refrigeration operation unit 1, and the fixed magnetic field excitation unit 2 is provided in a tubular shape on the outer peripheral side of the variable magnetic field excitation unit 3. The fixed magnetic field excitation unit 2 and the variable magnetic field excitation unit 3 may be disposed concentrically in the order shown in
[0102] Hereinafter, an example will be described in which the first end 4 acts as a high temperature end and the second end acts as a low temperature end 5. The high temperature end 4 is a high temperature end of the magnetic refrigeration operation unit 1, and is located on the high magnetic field side in a case where the magnetic field generated by the fixed magnetic field excitation unit 2 is provided with a high or low slope. The high temperature end 4 may have a structure in which heat is exchanged with the gas to be cooled by the flow of a refrigerant, or the gas to be cooled is used as a refrigerant gas.
[0103] The low temperature end 5 is a high temperature end of the magnetic refrigeration operation unit 1, and is located on the low magnetic field side in a case where the magnetic field generated by the fixed magnetic field excitation unit 2 is provided with a high or low slope. The low temperature end 5 may have a structure in which heat is exchanged with the gas to be cooled by the flow of a refrigerant, or the gas to be cooled is used as a refrigerant gas.
[0104] The refrigerant flow path 6 is provided along the longitudinal direction of the magnetic refrigeration operation unit 1, and the refrigerant can move between the high temperature end 4 and the low temperature end 5, and the refrigerant existing in the refrigerant flow path 6 is configured to exchange heat with the magnetic refrigeration material.
[0105] Next, the magnetic refrigeration module forming the magnetic refrigeration system will be described. In the magnetic refrigeration module, ring-shaped permanent magnets are concentrically arranged outside the simple substance holmium forming the magnetic refrigeration operation unit 1 as the fixed magnetic field excitation unit 2, and a ring-shaped resistive magnets that generate a variable magnetic field of 0.4 T are arranged outside the fixed magnetic field excitation unit 2, as the variable magnetic field excitation unit 3.
[0106] The magnetic refrigeration system shown in
[0107] As the variable magnetic field excitation unit 3, a resistive magnets that generate a variable magnetic field of 0.4 T are arranged outside the fixed magnetic field excitation unit 2. The resistive magnet may be provided independently for each magnetic refrigeration module, or may be provided in common with magnetic refrigeration modules.
[0108] In the simple substance holmium as a working substance in the magnetic refrigeration operation unit 1, a refrigerant flow path 6 through which hydrogen or helium gas to be cooled can pass and exchange heat is provided. In a case of hydrogen, since the hydrogen reacts with holmium, it is necessary to set a flow path structure that can indirectly exchange heat. The refrigerant flow path 6 may be provided independently for each magnetic refrigeration module, or may be provided in common with magnetic refrigeration modules. In a case where the refrigerant flow path 6 is provided independently for each magnetic refrigeration module, it is necessary to provide a connection pipe for connecting refrigerant flow paths 6 to each other.
[0109]
[0110] First, in the excitation step shown in
[0111] Next, in the heat removal step of the working substance shown in
[0112] Next, in the adiabatic demagnetization step shown in
[0113] Further, as shown in
[0114] In the magnetic refrigeration system 100, by repeating the four steps shown in
[0115] The variable magnetic field excitation unit 3 can also be a superconducting magnet, and the energy efficiency is improved by using an oxide superconducting wire and operating at a liquid nitrogen temperature (77 K).
[0116] In the device shown in
Modification Example A
[0117]
[0118] In the magnetic refrigeration system 105, superconducting magnets having a magnetic field with a slope of 0.2 to 2.5 T as the fixed magnetic field excitation unit 7 are arranged outside the simple substance holmium configuring the magnetic refrigeration operation unit 1. As the variable magnetic field excitation unit 3, a superconducting or resistive magnet that generates a variable magnetic field of 0.4 T is arranged outside the fixed magnetic field excitation unit 2. In the simple substance holmium, a refrigerant flow path 6 through which hydrogen or helium gas to be cooled can exchange heat (directly or indirectly).
[0119] In the magnetic refrigeration system shown in
[0120] First, in a step corresponding to the excitation step shown in
[0121] Next, in a step corresponding to the heat removal step of the working substance shown in
[0122] Next, in a step corresponding to the adiabatic demagnetization step shown in
[0123] Further, in a step corresponding to the cooling step shown in
[0124] In the magnetic refrigeration system shown in
[0125] In the example, a magnetic refrigeration system having a temperature gradient of 57 K (100 K) of 77 K (or 120 K) at the high temperature end and 20 K (17 K in the case of helium) at the low temperature end was realized by using a gradient magnetic field superconducting magnet to generate a fixed magnetic field and using a normal conducting (or superconducting) magnet to generate a variable magnetic field.
Modification Example B
[0126] Similar to the simple substance holmium, a phenomenon that the magnetization (M)-magnetic field (H) characteristics vary depending on the temperature and the magnetization (M) changes rapidly from a certain magnetic field (H) occurs on Gd.sub.5(Ge.sub.1-xSi.sub.x).sub.4 (x=0 to 1), Co (S.sub.xSe.sub.1-x).sub.2 (x=0.8 to 1.0), (Sm.sub.1-xGd.sub.x).sub.0.55Sr.sub.0.45MnO.sub.3 (x=0 to 1), Eu.sub.0.55Sr.sub.0.45MnO.sub.3, rare earth simple substances Tb, Dy, and Er, or an alloy obtained by a combination thereof.
[0127] As an example,
[0128]
[0129] Similar to the simple substance holmium, Gd.sub.5Ge.sub.4, Co (S.sub.xSe.sub.1-x).sub.2, and (Gd.sub.0.5Sm.sub.0.5).sub.0.55Sr.sub.0.45MnO.sub.3 also have different M-H characteristics depending on the temperature, and the M-H characteristics change rapidly from a certain magnetic field. Therefore, the same magnetic refrigeration effect as that of the simple substance holmium can be expected.
[0130] However, since the magnetic field strength corresponding to the steep slope area varies for each magnetic refrigeration material, the optimum magnetic field for the fixed magnetic field varies depending on each substance. For example, in the case of Co(S.sub.xSe.sub.1-x).sub.2, the steep slope area is located in the area in which the magnetic field strength is 2 to 7 T, and the width thereof is approximately 1 T or less, although the magnetic field strength varies depending on the temperature. Therefore, a continuous gradient magnetic field superconducting magnet from 2 to 7 T is required as a fixed magnetic field, and a superconducting magnet having a variation width of 1 T is required as a variable magnetic field. The total magnetic field change of the fixed magnetic field and the variable magnetic field is 2 T to 8 T. Other configurations are the same as those of the magnetic refrigeration system 100. In Modification Example B, for example, a magnetic refrigeration system having a 60 K at the high temperature end and 20 K (10 K for helium) at a low temperature end can be realized.
Comparative Example
[0131] Table 2 shows examples of typical magnetic refrigeration materials for low temperatures suitable for hydrogen liquefaction. Table 2 shows the change in entropy and the entropy change efficiency when only a predetermined variable magnetic field (magnetic field) is applied to the magnetic refrigeration material in a temperature T.sub.M without applying a magnetic field as a fixed magnetic field. In Table 2, the numerical values after “@” in the column of Entropy change efficiency indicate the magnetic field strength given as the variable magnetic field. For example, in sample A, it is shown that when a variable magnetic field of 5 T is applied, a change by 14.9 (J.Math.kg.sup.−1.Math.K.sup.−1) occurs. The entropy change efficiency is the change in entropy when a variable magnetic field of 1 T is applied.
TABLE-US-00002 TABLE 2 Change in Temperature entropy ΔS.sub.M Entropy change Magnetic refrigeration material T.sub.M (K) (J .Math. kg.sup.−1 .Math. K.sup.−1) efficiency Sample A Er.sub.5Pd.sub.2 20 14.9@5T 2.98 Sample B Ho.sub.5.4Pd.sub.2 28.1 15.9@5T 3.18 Sample C Ce.sub.0.5Nd.sub.0.5Si 31 4.8@3T 1.6 Sample D ErCo.sub.2 35 33@5T 6.6 Sample E Gd.sub.5Ge.sub.4 42 24.5@5T 4.9 Sample F La.sub.0.65Ce.sub.0.35(Fe.sub.0.860Mn.sub.0.025Si.sub.0.115).sub.13 43 8@2T 16 Sample G high-entropy glass 45 8.53@5T 1.71
[0132] The temperature, change in entropy, and entropy change efficiency of Sample A, Sample B, and Sample D are based on Japanese Unexamined Patent Application, First Publication No. 2017-39993. The temperature, the change in entropy, and entropy change efficiency of Sample C, Sample E, Sample F, and Sample G are based on PCT International Publication No. 2018/129476, J. J. Appl. Phys Appl. Phys. 105, 07A934 (2019) and Chinese Patent Application Publication No. 1017012408.
[0133] Since it is necessary to have a refrigerating capacity in a temperature range of about 40-50K, which reduces the efficiency of gas refrigerating, to a boiling point of liquid hydrogen of 20K, which is equal to or more than twice the temperature range, parallel use of a plurality of types of substances is also being considered.
[0134] Although the present invention has been described in detail above, the present invention is not limited to the above-described examples, and can be appropriately carried out within a range obvious to those skilled in the art without departing from the spirit of the present invention. For example, it is possible to omit, add, or change numbers, numerical values, quantities, ratios, characteristics, and the like without departing from the gist of the present invention. In addition, the configurations described in a plurality of embodiments and modification examples may be combined as appropriate.
[0135] Further, for example, in the above examples, the magnetic refrigeration operation unit, the fixed magnetic field excitation unit, and the variable magnetic field excitation unit are not provided with a mechanism for changing the mutual positional relationship. However, the magnetic refrigeration module and the magnetic refrigeration system using the same of the present invention may be provided with a substance that causes a magnetic refrigeration material substance to generate heat or absorb heat or a mechanism for reciprocating or rotating a variable magnetic field excitation unit.
[0136] In the above examples, the case where the entire shape of the magnetic refrigeration operation unit is cylindrical is shown, but the magnetic refrigeration operation unit may be rod-shaped or flat plate-shaped. In this case, the fixed magnetic field excitation unit and the variable magnetic field excitation unit may have a sandwich shape in which the magnetic refrigeration operation unit is sandwiched between the upper and lower parts.
[0137] The fixed magnetic field excitation unit includes an upper fixed magnetic field excitation unit and a lower fixed magnetic field excitation unit provided so as to sandwich the magnetic refrigeration operation unit in at least one of the thickness direction and the width direction of the magnetic refrigeration operation unit, and for example, a flat plate-shaped permanent magnet is used. The variable magnetic field excitation unit is a flat plate-shaped electromagnet that generates a variable magnetic field in addition to the fixed magnetic field generated by the upper fixed magnetic field excitation unit and the lower fixed magnetic field excitation unit, and may be, for example, a resistive magnet or a superconducting magnet.
INDUSTRIAL APPLICABILITY
[0138] According to the magnetic refrigeration module of the present invention, when changing the magnetic field only in the range where the M-H characteristics change significantly, a highly efficient magnetic refrigeration system can be constructed even when a substance having a single composition is used.
[0139] Further, according to the magnetic refrigeration system of the present invention, when adopting a magnetic field application structure in which a variable magnetic field is superimposed on the base magnetic field, it is possible to apply only the magnetic field range having the largest magnetic refrigeration effect, and the efficiency can be improved.
REFERENCE SIGNS LIST
[0140] 1: Magnetic refrigeration operation unit [0141] 2: Fixed magnetic field excitation unit [0142] 3: Variable magnetic field excitation unit [0143] 4: First end (high temperature end) [0144] 5: Second end (low temperature end) [0145] 6: Refrigerant flow path [0146] 7: Fixed magnetic field excitation unit [0147] 10: Magnetic refrigeration module [0148] 100, 101, 102, 103, 104, 105: Magnetic refrigeration system