CN1325010A - 具有多组分制冷剂流体预冷的磁制冷*** - Google Patents

具有多组分制冷剂流体预冷的磁制冷*** Download PDF

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CN1325010A
CN1325010A CN01119713A CN01119713A CN1325010A CN 1325010 A CN1325010 A CN 1325010A CN 01119713 A CN01119713 A CN 01119713A CN 01119713 A CN01119713 A CN 01119713A CN 1325010 A CN1325010 A CN 1325010A
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heat exchanger
multicomponent refrigerant
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A·阿查亚
B·阿曼
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Praxair Technology Inc
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    • F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
    • F25J1/003—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production
    • F25J1/0047—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production using an "external" refrigerant stream in a closed vapor compression cycle
    • F25J1/0052—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the kind of cold generation within the liquefaction unit for compensating heat leaks and liquid production using an "external" refrigerant stream in a closed vapor compression cycle by vaporising a liquid refrigerant stream
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    • F25J1/00—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures
    • F25J1/006—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures characterised by the refrigerant fluid used
    • F25J1/0097—Others, e.g. F-, Cl-, HF-, HClF-, HCl-hydrocarbons etc. or mixtures thereof
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    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25J—LIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
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    • F25J1/02—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures requiring the use of refrigeration, e.g. of helium or hydrogen ; Details and kind of the refrigeration system used; Integration with other units or processes; Controlling aspects of the process
    • F25J1/0225—Processes or apparatus for liquefying or solidifying gases or gaseous mixtures requiring the use of refrigeration, e.g. of helium or hydrogen ; Details and kind of the refrigeration system used; Integration with other units or processes; Controlling aspects of the process using other external refrigeration means not provided before, e.g. heat driven absorption chillers
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    • F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
    • F25B2321/00—Details of machines, plants or systems, using electric or magnetic effects
    • F25B2321/002—Details of machines, plants or systems, using electric or magnetic effects by using magneto-caloric effects
    • F25B2321/0022—Details of machines, plants or systems, using electric or magnetic effects by using magneto-caloric effects with a rotating or otherwise moving magnet
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    • F25J2270/00—Refrigeration techniques used
    • F25J2270/90—External refrigeration, e.g. conventional closed-loop mechanical refrigeration unit using Freon or NH3, unspecified external refrigeration
    • F25J2270/908—External refrigeration, e.g. conventional closed-loop mechanical refrigeration unit using Freon or NH3, unspecified external refrigeration by regenerative chillers, i.e. oscillating or dynamic systems, e.g. Stirling refrigerator, thermoelectric ("Peltier") or magnetic refrigeration
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Abstract

本发明涉及一种在很冷的温度下产生致冷和向热负荷提供致冷的***,该***包括利用多组分致冷剂流体的预冷回路和磁致冷回路,后一回路向热负荷提供致冷,并将热排入预冷回路。

Description

具有多组分致冷剂流体预冷的磁致冷***
本发明，一般说来，涉及致冷，更具体而言，涉及在液化气体如氢的非常冷的温度下产生和提供的致冷。
某些气体如氖、氢和氦的液化要求产生很低温的致冷。例如，在大气压下，氖在27.1K液化，氢在20.39K液化，氦在4.21K液化。这种产生很低温致冷的费用甚高。由于诸如氖、氢和氦等流体的应用日显重要，例如在能量产生、能量传输、和电子学等等领域，因此液化这类流体的***的任何改进都会受到很大的欢迎。产生很低温度的致冷冻***是已知的，但这些***只在较小的规模内才是有效的。
因此，本发明的目的是提供一种在很低温度下能有效产生和提供致冷的***。
本发明的另一目的是提供一种改进性***，该***产生足以使难于液化的流体如氖、氢和氦液化和致冷。
本发明的再一目的是提供一种用于使难于液化的流体如氖、氢或氦液化的***，该***能在较高的生产水平下运行。
在阅读本发明说明书时，对本领域专业人员是显而易见的。上述目的和另一些目的可通过本发明能达到，本发明的一个方面为：
一种在很冷温度下提供致冷的方法，它包括：
(A)压缩多组分致冷剂流体，冷却压缩的多组分致冷剂流体以产生冷却的多组分致冷剂流体，和膨胀冷却的多组分致冷剂流体；
(B)磁化磁致冷机***的回热器床，使回热器床升温，使工作流体通过磁致冷机***而升温，然后使从磁致冷机***流出的工作流体与冷却的膨胀的多组分致冷剂流体进行间接热交换，以产生冷却的工作流体；
(C)去磁回热器床，以冷却回热器床，并使冷却的工作流体通过磁致冷机***，以在很低的温度下进一步冷却工作流体；和
(D)将很冷温度的工作流体的致冷送往热负荷。
本发明的另一方面是：
一种在很冷温度下提供致冷的设备，它包括：
(A)压缩机，多组分致冷剂流体热交换器，使流体从压缩机通到多组分致冷剂流体热交换器的装置，膨胀部件，和使流体从多组分致冷剂流体热交换器通到膨胀部件的装置；
(B)中温换热器和将流体从多组分致冷剂流体换热器通到中温换热器的装置；
(C)磁致冷机***，包括可磁化床物料的床，磁化可磁化床物料的装置，将流体从磁致冷机***通到中温换热器的装置，和将流体从中温换热器通到磁致冷机***的装置；和
(D)热负荷和使来自磁致冷机***的流体与热负荷进行热交换的装置。
本文所用的术语“多组分致冷剂流体”系指包括两种或多种物质并能产生致冷的流体。
本文所用的术语“可变负荷致冷剂”系指两组分或多组分的混合物，其比例要使这些组分的液相在混合物的始沸点和露点之间经受连续的温升变化。混合物的始沸点是这样的温度，即在给定压力下整个混合物处于液相，但添加热即会引发与液相平衡的汽相形成的温度。混合物的露点是这样的温度，即在给定压力下整个混合物处于汽相，但引出热即会引发与汽相平衡的液相形成的温度。因此，混合物始沸点和露点之间的温度区间是液相和汽相两者平衡共存的区间。在本发明的实践中，可变负荷致冷剂的始沸点和露点之间的温差一般至少为10℃，优选至少20℃，最优选至少50℃。
本文所用之术语“很冷温度”系指90K或更低的温度。
本文所用之术语“间接热交换”系指流体发生热交换关系，但流体相互之间不发生实体接触或相互混合。
本文所用的术语“直接热交换”系指通过冷体和热体接触进行的致冷冻传递。
本文所用的术语“膨胀”系指实施减压。
本文所用的术语“大气气体”系指下列之一种：氮(N2)、氩(Ar)、氪(Kr)、氙(Xe)、氖(Ne)、二氧化碳(CO2)、一氧化碳(CO)、氧(O2)，氘(D2)，氢(H2)和氦(He)。
本文所用的术语“磁化”系指利用外部施加电场使物质感应磁性质。
本文所用的术语“热负荷”系指将一定量的热施加到具体的物体或物质上。
图1是本发明一个优选实施方案的简化图示。
图2是能用于本发明实践的活性磁回热器致冷***图的一个实施方案的剖面图。
图3是本发明的对液化工艺气体特别有效的另一优选实施方案的简图。
一般说来，本发明利用多组分致冷剂流体致冷***和活性磁回热器致冷***产生很冷温度的致冷。多组分致冷剂流体***与磁回热器***按一种确定的方式整体化，从而将磁回热器***的热排入多组分致冷剂流体***，能对热负荷产生很冷温度的致冷，例如能将较大量的产品流体带入很冷的状态。
将参照附图对本发明作较详细的叙述。参看图1，物流310中的多组分致冷剂流体在压缩机311中一般压缩至50-1000磅/平方英寸(绝对)(Psia)的压力。对本发明的实践有效的分组分致冷剂流体一般包含至少一种大气气体，优选氮、氩和/或氖，并宜包括至少一种其碳原子数可达6的含氟的化合物。如碳氟化合物，氢碳氟化合物，氢氯碳氟化合物，氟代醚和氢氟代醚，和/或至少一种碳原子数达5的烃。
能有效地实施本发明的多组分致冷剂流体的一个优选实施方案包含选自碳氟化物、氢碳氟化物，氟代醚和氢氟代醚的至少两种组分。
能有效地实施本发明的多组分致冷剂流体的另一优选实施方案包含选自碳氟化物、氢碳氟化物、氟代醚和氢氟代醚的至少一种组分和至少一种大气气体。
能有效地实施本发明的多组分致冷剂流体的另一优选实施方案包含选自碳氟化物、氢碳氟化物、氟代醚和氢氟代醚的至少两种组分和至少两种大气气体。
能有效地实施本发明的多组分致冷剂流体的另一优选实施方案包含至少一种氟代醚和选自碳氟化物、氢碳氟化物，氟代醚和大气气体的至少一种组分。
在一个优选的实施方案中，多组分致冷剂流体只由碳氟化物组成。在另一优选实施方案中，多组分致冷剂流体仅由碳氟化物和氢碳氟化物组成。在另一优选实施方案中，多组分致冷剂流体仅由碳氟化物和大气气体组成。在另一优选实施方案中，多组分致冷剂流体仅由碳氟化物、氢碳氟化物、氟代醚和氢氟代醚组成。在另一优选实施方案中，多组分致冷剂流体仅由碳氟化物、氟代醚、氢氟代醚和大气气体组成。
能有效地实施本发明的多组分致冷剂流体可含其它组分如氢氯碳氟化物和/或烃。多组分致冷剂流体宜不含氢氯碳氟化物。在本发明的另一优选实施方案中，多组分致冷剂流体不含烃。最优选的多组分致冷剂流体既不含氢氯碳氟化物又不含烃。最优选的多组分致冷剂流体是无毒的、不可燃的和不引起臭氧贫化的，多组分致冷剂流体最优选的每一组分或者是碳氟化物、氢碳氟化物、氟代醚或大气气体。
压缩的多组分致冷剂流体312在冷却器313中经过与合适的冷却流体如冷却水进行热交换而冷却去除压缩热，所得多组分致冷剂流体314流经多组分致冷剂流体换热器301，其中314与将在下面叙述的加温的多组分致冷剂流体进行间接热交换而冷却。冷却的多组分致冷剂流体315从换热器301通入膨胀部件316，后者宜为一膨胀阀，它在其中减压到较低的压力，从而使其温度降低。多组分致冷剂因在膨胀部件316中膨胀而产生温度的降低有助于冷却，一般有助于部分冷凝，优选有助于全部冷凝多组分致冷剂流体。所得该多组分致冷剂流体然后经管线317进入中温换热器303。一般物流317中冷却的膨胀流体的温度在50-250K范围内。
磁致冷机***302包括包容可磁化床物料的壳体。一个或多个可磁化床物料的床可用作本发明磁致冷机***。在可用于本发明实践的适宜的可磁化床物料中可举出GdNi2、GdZn2、GdTiO3、Gd2Ni17、GdAl2、GdMg、GdCd、Gd4Co3、GdGa、Gd5Si4和GdZn。
可磁化物料的床被磁化，有助于床的温度升高。工作流体如氦、氖、氮、氩、甲烷、四氟化碳、碳氟化物、氢碳氟化物、氟代醚和氢氟代醚用于与床进行传热。
工作流体327流经体系302，并作为温的工作流体320流出。温的工作流体320经泵321，然后作为物流322通入中温换热器303，其中它与加温的多组分致冷剂流体进行间接热交换被冷却，该加温的多组分致冷剂流体是以物料317进入中温换热器303的。所得加温过的多组分致冷冻流体以物流318离开中温换热器313，并通入多组分致冷剂流体换热器301。在多组分致冷剂流体换热器301中，多组分致冷剂流体与如前所述的物流314进入换热器301的冷却的多组分致冷剂流体进行间接热交换而被进一步加温，所得进一步加温的多组分致冷剂流体从换热器301经管线310通到压缩机311，重新开始多组分致冷剂流体预冷致冷循环。
由于工作流体经过中温换热器303，它被冷却至中温，并作为中温工作流体324从换热器流出，其温度一般在50-250K范围内。
磁致冷机***302的床被去磁，从而使床物料冷却。中温工作流体324通过***302，并在过程中进一步冷却。所得的经进一步冷却的工作流体以很冷温度工作的流体326从体系302排出，物流325可处于气态、液态或混合态。
很冷温度的工作流体325与热负荷发生热交换关系，从而将很冷温度工作流体的致冷传给热负荷。热交换可是间接或直接热交换。图1中，热负荷用箭头Q标记，热交换用换热器326表示。本发明实践中的热负荷例子包括用于家庭、办公室、建筑物和汽车冷却的空调机；家用或工业用冷却食物的冰箱；冷冻食品的食品冷冻机；工业气体如天然气、氧、氮、氩和氖的液化；热泵；水冷凝器；和如用于废物分离和处理***的冷却器。换热器326中的热交换同样可有产生更低温致冷的致冷回路中的多组分致冷剂流体。与热负荷的热交换使工作流体升温，所得的工作流体327通入磁致冷机***302按前面所述的方式加温，并使很冷温度的致冷循环重新开始。
磁致冷靠磁致热效应运行。磁颗粒床的温度用施加的电场加载。向磁颗粒施加磁场的温度效果特别快。氦气是典型的用作传热流体将磁颗粒子产生的致冷或热传到工作流体。
能有效地实践本发明的一个活性磁回热器致冷***的例子示于图2。参见图2，该***包括多孔颗粒磁床1、可移动的强电磁铁或超导磁铁2、两活塞3和4、冷换热器5和热换热器6。围绕床1中磁床颗粒的空隙空间和活塞缸7和8的体积充满带压力的氦气。磁床1可由一系列不同的磁物质组成；钆镍(GdNi2)是一个例子。在磁致冷***的另一实施例子中可采用1个以上的可移动磁铁，或者可磁化物料的床和多个床本身是可移动的。
循环开始时，冷换热器5最先处在低温下，例如40K，而热换热器6处于较温温度下，例如70K。磁铁2向右移动，从而使回绕磁回热器床1的磁场增大。磁热效应使床1中的每个磁颗粒稍微升温。活塞3和4移到其最右位置，使封闭的氦气从左气缸7流出，经冷换热器5、磁致冷机床1和热换热器6以充满气缸8的容积。床1中的颗粒被流动的气体冷却，而气体则被升温。当气体流经热换热器6时热从气体传到工作流体。当活塞达到其最右的位置时，气流停止，借助于磁铁2位移至左端使磁场去除，由磁致热效应使床1冷却。活塞3和4回到其极左位置，使氦气流出气缸8，经热换热器6、磁致冷床1和冷换热器5流入气缸容积7。氦气流经床1而冷却，而在冷换热器5中因它通过间接热交换使流过那里的工作流体冷却而升温。
虽然参照某一优选实施方案对本发明进行了阐述，专业技术人员应该理解，在权利要求的实质和范围内，存在本发明的其它实施方案。
一种其它实施方案中示于图3。图3与图共同部件的编号相同，这些部件不再详述。图3所示的实施方案具体用于液化工艺气体如氧、氮、氩或天然气。参看图3，工艺气体物流400在换热器301中与多组分致冷剂流体发生热交换而被预冷，然后作为物流401在换热器303中与多组分致冷剂流体和从磁致冷机***来的工作流体两者发生间接热交换而被进一步冷却。所得工艺气体402至少部分在***302中冷凝，然后作为物流403流入作为热负荷的换热器326，其中借助冷凝的工艺流体的可能过冷完成工艺气体的液化。得到的液化工艺气体物流404然后送去贮存或用其它方式回收。

Claims (10)

1．一种在很冷温度下提供致冷的方法，它包括：
(A)压缩多组分致冷剂流体，冷却压缩的多组分致冷剂流体以产生冷却的多组分致冷剂流体，和膨胀冷却的多组分致冷剂流体；
(B)磁化磁致冷机***的回热器床，使回热器床升温，使工作流体通过磁致冷机***而升温，然后使从磁致冷机***流出的工作流体与冷却的膨胀的多组分致冷剂流体进行间接热交换，以产生冷却的工作流体；
(C)去磁回热器床，以冷却回热器床，并使冷却的工作流体通过磁致冷机***，以在很低的温度下进一步冷却工作流体；和
(D)将很冷温度的工作流体的致冷送往热负荷。
2．权利要求1的方法，其中膨胀的多组分致冷剂流体至少部分冷凝。
3．权利要求1的方法，其中膨胀的多组分致冷流体完全冷凝。
4．权利要求1的方法，其中多组分致冷流体至少包括一种大气气体。
5．权利要求1的方法，其中多组分致冷流体是一种可变负荷的致冷剂。
6．权利要求1的方法，还包括工艺气流经与多组分致冷剂流体发生间接热交换而被冷却，以及之后经与工作流体发生间接热交换而被冷凝。
7．一种在很冷温度下提供致冷的设备，它包括：
(A)压缩机，多组分致冷剂流体热交换器，使流体从压缩机通到多组分致冷剂流体热交换器的装置，膨胀部件，和使流体从多组分致冷剂流体热交换器通到膨胀部件的装置；
(B)中温换热器和将流体从多组分致冷剂流体换热器通到中温换热器的装置；
(C)磁致冷机***，包括可磁化床物料的床，磁化可磁化床物料的装置，将流体从磁致冷机***通到中温换热器的装置，和将流体从中温换热器通到磁致冷机***的装置；和
(D)热负荷和使来自磁致冷机***的流体与热负荷进行热交换的装置。
8．权利要求7的设备，还包括使工艺气体通入多组分致冷剂流体换热器、从多组分致冷剂流体换热器通入中温换热器、并从中温换热器通入磁致冷机***的装置。
9．权利要求7的设备，其中磁致冷机***包括两个活塞气缸，它们位于可磁化床物料床的相对的两侧，使气体从一活塞气缸通过床进入另一活塞气缸。
10．权利要求7的设备，其中磁化可磁化床物料的装置包括至少一可移动磁铁。
CN01119713A 2000-05-18 2001-05-16 具有多组分制冷剂流体预冷的磁制冷*** Pending CN1325010A (zh)

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