CN105705884B - 用于在低温下分离的方法和装置 - Google Patents

用于在低温下分离的方法和装置 Download PDF

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CN105705884B
CN105705884B CN201480061009.1A CN201480061009A CN105705884B CN 105705884 B CN105705884 B CN 105705884B CN 201480061009 A CN201480061009 A CN 201480061009A CN 105705884 B CN105705884 B CN 105705884B
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heat
heat pump
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G·卡登
阿纳克莱托 A·科雷亚
B·达维迪安
C·历克斯
B·索尼耶
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LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
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Abstract

本发明涉及一种用于通过在低温下分离而分离空气的方法，其中：使用磁热效应的第一热泵(31)在低于环境温度下的冷源和低于环境温度下的热源之间交换热量，从而提供至少一些分离能；使用磁热效应的第二热泵(21)在低于环境温度下的冷源(15)和环境温度下的热源之间交换热量，从而提供至少一些维持该方法的制冷平衡所需的冷却，分离发生在单个塔(19)中，单个塔的压力低于2bara。

Description

用于在低温下分离的方法和装置
本发明涉及用于在低温(cryogenic temperature)下分离的方法和装置。分离可为通过蒸馏和/或通过分凝和/或通过吸收分离。用于这种分离的设备将被称为“塔”。因此，塔可以是例如蒸馏塔和吸收塔。缩减到其最简单的表达，其可为相分离器。或者，塔也可以是在其中发生分凝的装置。
磁制冷依赖于使用显示出磁热效应的磁性材料。可逆的，当这些材料经受施加外部磁场时，这种效应通过这些材料的温度变化表现出来。这些材料用于其内的最佳范围位于其居里温度(Tc)附近。这是因为在磁化上的变化越大，以及由此在磁熵上变化越大，在它们的温度上的变化就越大。当将材料放置在磁场中时材料的温度上升时，则认为磁热效应是直接的，当将材料放置在磁场中时材料冷却，则认为磁热效应是间接的。在说明书的其余部分将针对直接的情形给出，但对本领域技术人员而言，如何将其再应用到间接的情形是显而易见的。有许多热力循环基于该原理。常规的磁制冷循环包括ⅰ)磁化材料以增加它的温度，ⅱ)在恒定磁场冷却该材料来散热，ⅲ)将该材料去磁以将其冷却，和iv)在恒定的磁场(通常为零磁场)中加热材料以吸收热量。
磁制冷装置采用由磁热材料制成的元件，当被磁化时其产生热量且当被去磁时其吸收热量。可以采用磁热材料再生器以放大“热源”和“冷源”之间的温度差：磁制冷从而被认为是使用活性磁再生的磁制冷。
从EP-A-2551005可知如何使用磁热效应来为在低于环境温度下分离的方法提供冷却。
US-A-6502404描述了使用磁热效应(代替传统的使用膨胀涡轮)以向用于分离空气气体的低温方法提供冷却(需要来提供方法的制冷平衡)，通常通过加压空气供给的分离能允许操作双塔的蒸发器-冷凝器(在氮气发生器的情况下，能够将低压塔缩减为简单的蒸发器)。分离(蒸馏)部分地在压力下进行，通常在中压塔中5和6bara之间。
本发明解决如何完全在非常低的压力下、待分离的流体不携带用于分离和用于保持过程冷却的能量(以压力的形式)下进行分离的问题。用于分离的能量和用于保持冷却的能量通过热泵提供，不取决于待分离的流体及其压力。
人们早已知道如何使用同一个电路既为蒸馏塔的再沸器提供热又为该同一塔的冷凝器提供千卡/时(frigories)。US-A-2916888公开了烃的蒸馏的一个例子。
热泵是热力学装置，其允许将一定量的热量从被认为是“发射器”并被称为“冷源”的介质(从其中取出热量)传送至被认为是“接收器”并被称为“热源”的介质(向其供给热量)，冷源处于比热源更冷的温度。
对于这类应用，在现有技术中使用的常规循环为将制冷流体压缩-冷却(冷凝)-膨胀-再加热(蒸发)的热力学循环。
标题为“TECHNIQUES DE L’INGENIEUR-Réfrigération magnétique[Engineeringtechniques-Magnetic refrigeration]2005”的文件的图12显示，与常规循环相比，用磁循环的制冷系统的性能系数提高了2倍。
由于待分离的组分之间的更大的挥发性，在低压下或几乎在接近大气压下分离是更容易的。通过组合该效果和应用磁热效应的热泵的非常良好的性能，能够得到具有非常好的分离能的方法。
此外，在低温下或甚至在接近大气压的压力下分离，使得在设计和分离装置的设备的机械完整性上简化，从而降低其成本。
环境温度为所述方法所处于的环境空气的温度，或可选地，为与空气温度相连接的冷却水回路的温度。
“低于环境温度”是指比环境温度低至少10℃。
低温为低于-50℃。
本发明的第一主题提供一种用于通过在低温下分离而分离空气的方法，其中：
a.至少一个被称为分离热泵的第一热泵，在低温下的第一冷源和低温下的第一热源之间直接或间接地交换热量，从而提供至少一些分离能，和
b.至少一个被称为制冷平衡热泵的第二热泵，在第一低温下的第二冷源和比第一温度更高的温度下(例如环境温度下)的第二热源之间直接或间接地交换热量，从而提供至少一些维持该方法的制冷平衡所需的冷却，分离发生在单个塔或塔组中，单个塔的压力或塔组塔的压力低于2bara，优选低于1.5bara，优选至少在与大气压的差别仅在于连接一个或多个塔与大气的元件的压头损失的压力下，第一冷源和第一热源直接或间接地热连接至单个塔或塔组中的一个塔，其特征在于，第一和第二热泵使用磁热效应，以及第二冷源由待在单个塔或塔组中分离的空气(7)或包括来自单个塔(19)或塔组塔的流体组成。
根据其他任选的特征：
-被称为分离热泵的第一热泵直接或间接地将热量从塔的顶部，优选通过将塔的气体冷凝，传递至塔的底部，优选通过蒸发单个塔的液体；
-被称为分离热泵的第一热泵直接或间接地在塔组塔中将热量，优选通过将塔组塔中的气体冷凝，传递至塔组塔，优选通过在塔组塔中蒸发；
-第一和第二热泵经由单个塔彼此热连接；
-其中在将空气引入单个塔或塔组塔中之前，第二热泵至少部分直接或间接地冷凝空气；
-在将空气的完全冷凝的部分引入单个塔或塔组塔中之前，第二热泵直接或间接地完全冷凝部分空气，优选在其余部分的空气的供给之上；
-通过最终产物的方式，所述方法生产至少一种富含混合物的某个组分的气体；
-通过最终产物的方式，所述方法生产至少一种富含混合物的某个组分的液体；
-被称为制冷平衡热泵的第二热泵在热交换器中，通过与第二热泵的传热流体之间的热交换，直接或间接地冷却或冷凝来自单个塔或塔组塔的流体；
-第一热泵和第二热泵没有共同的热交换器
-至少使得待分离的流体和/或来自单个塔或塔组塔的分离的流体与第一和第二热泵之一的磁热材料直接接触；
-热交换至少部分地在待分离的流体和/或来自所述塔或塔组塔的分离的流体与传热流体之间通过交换器进行，所述传热流体已与第一和第二热泵之一的磁热材料接触；
-热交换至少部分地在待分离的流体和/或来自所述塔或塔组塔的分离的流体与传热流体之间通过中间传热回路进行，所述传热流体已与第一和第二热泵的磁热材料接触。
本发明的另一主题提供一种用于使用在低于环境温度下或甚至在低温下分离的方法分离混合物(例如空气气体)的装置，所述装置包括在其中发生低于环境温度或甚至低温分离的单个塔或塔组，用于将混合物(例如空气气体)输送至所述塔或塔组塔的设施，用于从所述塔或塔组的一个塔中取出至少一种富含混合物的某个组分的流体的设施，至少被称为分离热泵的使用磁热效应的第一热泵，所述第一热泵用于在低于环境温度下或甚至低温下的第一冷源和低于环境温度下或甚至低温下的第二热源之间直接或间接地交换热量从而提供至少部分分离能，和至少被称为制冷平衡热泵的使用磁热效应的第二热泵，所述第二热泵用于在第一低于环境温度下或甚至低温下的第二冷源和比第一温度更高的温度下(例如环境温度下)的第二热源之间直接或间接地交换热量，从而提供至少一些维持该方法的制冷平衡所需的冷却，单个塔的压力或塔组塔的压力低于2bara，优选低于1.5bara，以使得该单个塔或塔组塔通过不包括膨胀设施的至少一个管连接至大气，第一冷源和第一热源直接或间接地热连接至单个塔或塔组塔。
根据其他任选的主题：
-所述装置包括用于在单个塔或塔组塔的顶部或底部取出液态产物的设施
-所述装置包括用于在单个塔或塔组塔的顶部或底部取出气态产物的设施。
参照解释说明根据本发明的方法的所附附图更详细地描述本发明。
在图1中，将气态空气流1在压缩机3中压缩并在冷却器5中冷却以形成经压缩和经冷却的空气7。在纯化单元9中纯化该经冷却的空气7以除去水和二氧化碳及其他杂质。然后在板翅式热交换器11中冷却经纯化的空气。将在热交换器11中冷却的空气分成两部分13、15。将部分13输送至单个蒸馏塔的中部，在其中所述部分13分离以在塔19的顶部形成富含氮的气体，在塔19的底部形成富含氧的液体。
空气的部分15(第二热泵的间接冷源)在热交换器17中通过与流体流23热交换而至少部分地被冷凝，所述流体流23通过使用磁热效应的第二热泵21而变冷。将通常为环境空气或冷却水的冷却流体51(第二热泵的热源)输送至使用磁热效应的第二热泵21。塔包括底部再沸器33和顶端冷凝器35。通过与使用磁热效应的第一热泵31连接的流体回路37加热再沸器(在再沸器煮沸的液体是第一热泵的间接热源)。使用磁热效应的第一热泵31也用于冷却流体39，所述流体39冷却顶端冷凝器35(在冷凝器中冷凝的气体是第一热泵的间接冷源)。流体37和39可以是相同的或不同的。将富含氧的液体29从塔19的底部取出，富含氮的气体41在热交换器11中加热并至少部分地用于再生纯化单元9。将富含氧的气体25从塔19的底部取出，在热交换器11中加热并通过压缩机27压缩。
在图2中，与在图1中不同的是，流体37，39被来自塔19的流体流代替。塔19既不具有顶端冷凝器也不具有底部再沸器。底部液体的部分29A(第一热泵的热源)在使用磁热效应的第一热泵31中蒸发并以气态形式返回至塔。将头部气体的部分41A(第一热泵的冷源)输送至使用磁热效应的第一热泵31，在此将其冷凝。形成的液体返回至塔的顶部。类似地，将流体15(第二热泵的冷源)直接输送至使用磁热效应的第二热泵21，在此将其至少部分地冷凝。
在图3中，与在图1中不同，不将空气一分为二。利用使用磁热效应的第二热泵21冷却整个流7，通过热交换器17和在使用磁热效应的第二热泵21中冷却的流体23移除热能。结果是，空气在热交换器17中部分地冷凝，并被输送至塔19。
在图4中，在底部再沸器33顶端冷凝器35之间的热传递如在图1中一样通过使用磁热效应的第一热泵31发生。与之相反，塔头气态氮的部分43通过使用磁热效应的第二热泵21在热交换器17中冷凝。经冷凝的氮返回至塔，从而使得一些在塔顶部的冷凝通过使用磁热效应的第二热泵21发生。
类似地，如在图5中可以看出，可在热交换器17中使用流体回路53冷却并至少部分地冷凝部分富含氧的气体26。流体53传递热量至使用磁热效应的第二热泵21，所述第二热泵21本身通过冷却流体51冷却，所述冷却流体51通常为环境空气或冷却水。
在图6中，塔19具有顶端冷凝器35但没有底部再沸器。所有用于塔的空气通过热交换器11、然后通过热交换器17(在其中其至少部分地被冷凝)、通过流体23和使用磁热效应的第二热泵21来冷却。如在图1中所示，只有一部分空气可以通入热交换器17中。将氮41加热并通过压缩机42压缩。将在塔的底部的液体29首先在热交换器53中加热，在其中将其至少部分地蒸发，然后将其在热交换器11中加热。流体回路55在热交换器53中冷却，并在使用磁热效应的第一热泵31中收集热。如在图1中所示冷却顶端冷凝器。
在图7中，塔既不具有冷凝器也不具有再沸器。所有的空气7在热交换器11中、然后在热交换器17中(在其中其至少部分地通过使用磁热效应的第二热泵21被冷凝)冷却，如在图3中所示。如在图1中所示，只有一部分空气可以进入热交换器17中。可选地，可将全部或部分空气直接输送至使用磁热效应的第二热泵21。将底部液体37全部输送至使用磁热效应的第一热泵31，在该处将其至少部分地蒸发。然后将经蒸发的流37A在热交换器11中加热，并至少部分地用于再生纯化单元9。将头部气体一分为二，将部分41加热并压缩，将剩余的41A输送至使用磁热效应的第一热泵31，在该处将其至少部分地冷凝，形成被输送至塔顶部的流41B。
在本文中描述本发明应用于在低温下分离空气。显然，本发明也适用于在低于环境温度下的其他的分离，例如应用于分离含有一氧化碳和/或氢和/或氮和/或甲烷的混合物。

Claims (18)

1.一种用于通过在低温下分离而分离空气的方法，其中：
a)至少一个被称为分离热泵的使用磁热效应的第一热泵(31)在低温下的第一冷源(39，41A)和低温下的第一热源(37，29A，55)之间直接或间接地交换热量，从而提供至少一些分离能，和
b)被称为制冷平衡热泵的使用磁热效应的至少第二热泵(21)在第一低温下的第二冷源(15，23，53)和比第一低温更高的温度下的第二热源(51)之间直接或间接地交换热量，从而提供至少一些维持该方法的制冷平衡所需的冷却，分离发生在单个塔(19)或塔组中，单个塔的压力或塔组塔的压力至少在与大气压的差别仅在于连接一个或多个塔与大气的元件的压头损失的压力下，第一冷源和第一热源直接或间接地热连接至该单个塔或塔组中的一个塔，其特征在于，第一和第二热泵使用磁热效应，以及第二冷源由待在该单个塔或塔组中分离的空气组成、或由来自该单个塔(19)或来自塔组塔的流体组成。
2.根据权利要求1所述的方法，其中比第一低温更高的温度是环境温度。
3.根据权利要求1所述的方法，其中被称为分离热泵的第一热泵(31)直接或间接地将热量从单个塔(19)或塔组塔的顶部，传送至该塔或塔组塔的底部。
4.根据权利要求3所述的方法，其中被称为分离热泵的第一热泵(31)直接或间接地将热量从单个塔(19)或塔组塔的顶部，通过将该塔或塔组塔的气体冷凝，传送至该塔或塔组塔的底部。
5.根据权利要求3所述的方法，其中被称为分离热泵的第一热泵(31)直接或间接地将热量从单个塔(19)或塔组塔的顶部，传送至该塔或塔组塔的底部，通过蒸发该单个塔或塔组塔的液体。
6.根据权利要求1至5中任一项所述的方法，其中第一和第二热泵经由该单个塔彼此热连接。
7.根据权利要求1至5中任一项所述的方法，其中在将空气引入单个塔(19)或塔组塔中之前，第二热泵(21)直接或间接地至少部分冷凝空气。
8.根据权利要求1至5中任一项所述的方法，其中在将空气的完全冷凝的部分引入单个塔(19)或塔组塔中之前，第二热泵(21)直接或间接地完全冷凝部分空气。
9.根据权利要求1至5中任一项所述的方法，其中在将空气的完全冷凝的部分引入单个塔(19)或塔组塔中之前，在其余部分的空气的供给之上，第二热泵(21)直接或间接地完全冷凝部分空气。
10.根据权利要求1至5中任一项所述的方法，其中被称为制冷平衡热泵的第二热泵(21)在热交换器(17)中直接或间接地冷却或冷凝来自单个塔(19)或来自塔组塔的流体，允许在流体和第二热泵的传热流体之间的热交换。
11.根据权利要求1至5中任一项所述的方法，其中至少使得待分离的流体和/或来自所述塔(19)或塔组塔的分离的流体与第一和第二热泵(31，21)之一的磁热材料直接接触。
12.根据权利要求1至5中任一项所述的方法，其中热交换至少部分地在待分离的流体和/或来自所述塔(19)或塔组塔的分离的流体与传热流体之间通过热交换器(17)进行，所述传热流体已与第一和第二热泵(31，21)之一的磁热材料接触。
13.根据权利要求1至5中任一项所述的方法，其中热交换至少部分地在待分离的流体和/或来自所述塔(19)或塔组塔的分离的流体与传热流体之间通过中间传热回路进行，所述传热流体已与第一和第二热泵(31，21)的磁热材料接触。
14.根据权利要求1至5中任一项所述的方法，其中第二热泵包括热交换器(17)，其允许在待蒸馏的空气与热泵的传热流体(23)之间的热交换。
15.根据权利要求14所述的方法，其中热交换器(17)仅仅在空气和传热流体之间交换热量。
16.根据权利要求14所述的方法，其中，热交换器(17)被用于冷却待用于蒸馏的所有空气。
17.根据权利要求15所述的方法，其中，热交换器(17)被用于冷却待用于蒸馏的所有空气。
18.根据权利要求1至5中任一项或权利要求15-17中任一项所述的方法，其中第一和第二热泵没有共同的热交换器。
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EP3071910A2 (fr) 2016-09-28
CN105705893A (zh) 2016-06-22
CN105705884A (zh) 2016-06-22
US20160216013A1 (en) 2016-07-28

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