CN105378410B - 用于分离富含二氧化碳的气体的方法和设备 - Google Patents

用于分离富含二氧化碳的气体的方法和设备 Download PDF

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CN105378410B
CN105378410B CN201380036398.8A CN201380036398A CN105378410B CN 105378410 B CN105378410 B CN 105378410B CN 201380036398 A CN201380036398 A CN 201380036398A CN 105378410 B CN105378410 B CN 105378410B
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B·达维迪安
M·莱克勒克
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LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
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Abstract

在一种净化方法中，富含二氧化碳的气体在第一钎焊铝板翅式热交换器(9)中被冷却，冷却的气体或从该冷却的气体获取的至少一种流体被送至包括蒸馏步骤(23)的净化步骤，净化步骤产生富含二氧化碳的液体(33)，其被冷却，然后膨胀，然后被送至第二热交换器(35)，在那里借助于工艺流体(13)被加热，所述交换器仅在富含二氧化碳的液体与工艺流体之间进行间接热交换，富含二氧化碳的液体在第二交换器中至少部分地蒸发并且所形成的蒸发气体(37)在第一交换器中被再加热以形成富含二氧化碳的气体。

Description

用于分离富含二氧化碳的气体的方法和设备
技术领域
本发明涉及一种用于通过在低温下蒸馏而分离富含二氧化碳的气体的方法和设备。
富含二氧化碳的气体含有至少60mol％的二氧化碳，或甚至至少80mol％的二氧化碳。
该气体的其余部分可以含有以下成分中的一种或多种：氧气，氮气，氩气，氮氧化物(NO或NO2或N2O)，一氧化碳，氢气，汞。
可以通过一个或多个连续的部分冷凝步骤和/或通过蒸馏进行净化。
背景技术
在许多低温应用中，通过所述单元产生冷量是通过在足够低的压力下蒸发液体以达到足够低的温度而进行的。因为所述液体在这种压力下的方法中不是必然得到的，所以有必要使其膨胀，这可能会引起气体的产生。由此获得的气体不会产生大量的冷量，因为它将仅转移显热。因此有利的是通过使液体在膨胀前过冷而限制气体的产生。
在申请号FR-1256778下提交的专利申请为CO2捕获单元的冷箱的布置提出一种解决方案，其中交换管线分成两部分，其中一个部分在技术上较简单，使得可以降低冷箱冻结的风险。
在申请号FR-1256771下提交的专利申请提出一种用于将低温膜结合在CO2捕获单元的冷箱中的解决方案。
发明内容
本发明涉及优化冷箱的交换管线，其通过加入尤其是过冷器而分成两部分。
根据本发明的一个主题，提供了一种在低温下净化富含二氧化碳的气体以产生富含二氧化碳的流体的方法，在该方法中：
i)富含二氧化碳的气体在由通过板分隔开的波纹层构成的第一钎焊铝板式热交换器中被冷却，
ii)冷却的气体或从该冷却的气体获取的至少一种流体被送至包括蒸馏步骤和/或至少两个连续的部分冷凝步骤的净化步骤，
iii)净化步骤产生贫含二氧化碳的气体，其在第一交换器中被加热，
iv)净化步骤产生富含二氧化碳的液体，其被冷却，然后膨胀，然后被送至第二热交换器，在那里借助于工艺流体(其为从在第一交换器中冷却的气体获取的气体)被加热，该交换器仅在富含二氧化碳的液体与工艺流体之间进行间接热交换，以及
v)富含二氧化碳的液体在第二热交换器中至少部分地蒸发并且所形成的蒸发气体在第一交换器中被加热以形成富含二氧化碳的气体，该气体是所述方法的最终产物，
其特征在于，冷却的气体在第一交换器中至少部分地冷凝并被送至第一相分离器，来自第一相分离器的气体被送至第二交换器，在那里冷凝以形成冷凝液体。
根据其它可选的方面：
-富含二氧化碳的气体被压缩和冷凝以形成富含二氧化碳的液体，其是该方法的最终产物。
-来自第一相分离器的液体膨胀并被送至第二相分离器或送至蒸馏塔。
-冷凝的液体被送至第二相分离器，来自所述第二相分离器的液体被送至蒸馏塔的顶部以供给蒸馏塔。
-来自所述第二相分离器的气体在第一交换器中被加热。
-第二交换器是管壳式交换器，富含二氧化碳的液体被送至壳内以加热，工艺流体被送至管内以冷却。
-富含二氧化碳的液体在膨胀前在热交换器中通过与在第一交换器中被加热的贫二氧化碳气体间接热交换而被冷却。
-富含二氧化碳的液体在膨胀装置的上游在第三交换器中或第一交换器中被冷却。
-来自第二相分离器的气体通过渗透被分离。
根据本发明的另一个主题，提供了一种用于在低温下净化含有二氧化碳的气体以产生富含二氧化碳的流体的设备，该设备包括：由通过板隔开的波纹层构成的第一钎焊铝板式热交换器；与前述类型不同的能够容许仅在两种流体之间进行间接热交换的第二热交换器；第三热交换器；包括至少一个蒸馏塔和/或至少两个串联联接的相分离器的净化单元；用于传送富含二氧化碳的气体以在第一交换器中冷却的管道；用于将冷却的气体或从该冷却的气体中获取的至少一种流体送至净化单元的管道；用于从净化单元提取贫含二氧化碳的气体并连接至第一交换器的管道；用于从净化单元提取富含二氧化碳的液体并连接至第三交换器用于冷却富含二氧化碳的液体的管道；用于膨胀所述冷却的液体的阀，所述阀连接至第二热交换器；和用于将工艺流体从第一交换器送至第二交换器以便使所述富含二氧化碳的液体在壳中蒸发的管道，所述工艺流体是从在第一交换器中冷却的气体获取的气体；和用于将通过富含二氧化碳的液体在第二交换器中的蒸发产生的气体送至第一交换器以便升温的管道，其特征在于，所述设备包括：第一相分离器；用于将至少部分冷凝的冷却气体从第一交换器送至第一相分离器的装置；和用于将气体从第一相分离器送至第二交换器的装置。
所述设备可以包括用于将蒸馏塔的塔顶气体和/或在第二交换器中蒸发的气体和/或从工艺流体中获取的气体送至第三交换器以在第一交换器的上游被加热的装置。
根据其它可选的方面，所述设备包括：
-用于将膨胀的液体从第一相分离器送至第二相分离器或送至蒸馏塔的装置。
-用于从第二交换器送至第二相分离器的装置和用于将液体从第二相分离器送入蒸馏塔的塔顶以供给蒸馏塔的装置。
-用于传送来自第二相分离器的气体以在第一交换器中升温的装置。
第二交换器可以是管壳式交换器，可能包括用于传送富含二氧化碳的液体以在壳中加热的装置。
在以FR-1256778提交的专利申请提出的解决方案中，CO2在最低温度(接近三相点)下的冷凝通过技术上较简单的第二交换器进行。因此，选择只有两个通道的交换器(尤其是使用管壳技术)。因此CO2与来自蒸馏塔的CO2(其已经膨胀以达到接近CO2的三相点的温度)换热而冷凝。现在，如果专门用于此目的的交换器只包含两个通道，其它流体(来自蒸馏塔顶部、例如最终分离容器的顶部)也可在接近CO2的三相点的温度下可用并且因此无法在最冷部分中交换其冷量以冷凝CO2。如果要利用这些流体来冷凝CO2并进而利用这些流体中的冷量，必须使用多通道的主交换器，其温度高得多(在最冷位置介于大约-30℃和-40℃之间)。
这个解决方案具有显著缺点：
-很难在低温下通过与热得多的流体交换而使用冷量，因此有显著的辐射本能损失，表现为能量损失(必要的是，使更低压的液态CO2蒸发以便达到CO2的相同的冷凝)。
-多通道交换器中热流体和冷流体之间的温度差将变得很大：如果热侧的冷点是-30℃和冷侧上为-52.5℃，那么温差是22.5℃。这种差异因引起的机械应力而非常有问题，特别是对钎焊，如果所选择的技术是钎焊交换器(该技术在低温应用及多通道交换器中很典型)。
因此有必要寻求使这个低温冷流体与将被冷却至相似温度的热流体换热。
因此，本发明涉及将这些流体的冷量传递到CO2，该CO2将在低压下蒸发(在交换器的冷端)并将随后与待液化的CO2换热。低温冷量因此在冷箱的低温部分中传送，因而降低了放射本能的损失。此外，如果“低压”CO2在膨胀之前被冷却，那么它将过冷，因此限制了由其膨胀引起的气体的产生。因此更多冷量可用，进而优化了系统的能量消耗。
所有低温冷流体升温至接近“低压”(过冷器附近)的温度。然后这些流体能够将其冷量在较高温度下在主交换器中传递。
该过冷器还适用于例如在冷箱中使用低温膜的情况(见以编号FR-1256771提交的专利申请)。具体地，在进入所述膜之前容器的顶部的加热并利用渗透物的和残留物的冷量可以在过冷器中实现，因为它们处于与CO2的三相点之间比主交换器的温度接近得多的温度。总体布局如下：
在此提出的本发明寻求能够尽可能接近三相点地操作，或甚至在液态CO2处于三相点的情况下操作。
本发明涉及一种使富含二氧化碳的液体在容许在仅两种流体之间进行间接热交换的交换器中蒸发的方法。该交换器可以是例如“管壳式”交换器，其中CO2在壳中蒸发，待部分冷凝的流处于管中。由于壳中存在沸腾液体，不需再担心出现固体相而堵塞通道和当一些固体在两个冰的堵塞物之间升华时导致局部过压。
因此，能够在沸腾液体的三相点压力下运行所述容器，周期性出现的固态CO2会在压力回升到三相点以上时或在供给交换器的液体略微过热时融化。
可能存在于蒸发的液态CO2中的杂质会从交换器排放：
·对于最轻的杂质以气相清除；
·对于最重的杂质以清洗液清除。
这种清洗液会从交换器排出。
附图说明
下面将通过参考示出根据本发明的方法的图1至3对本发明进行更详细的说明。
具体实施方式
在图1中，气体1含有至少60mol％的二氧化碳，或甚至至少80mol％的二氧化碳。
该气体1的其余部分可以含有以下成分中的一种或多种：氧气，氮气，氩气，氮氧化物(NO或NO2或N2O)，一氧化碳，氢气，汞。
该气体在过滤器F中被过滤以去除灰尘，然后在第一压缩级C1中被压缩以形成压缩流3。压缩流3在第二压缩级C2中被压缩、在冷却器R2中被冷却、在第三压缩级C3中被压缩、在冷却器R3中被冷却、在第四压缩级C4中被压缩、在冷却器R4中被冷却、在第五压缩级C5中被压缩并在冷却器R5中被冷却以形成处于6和20bar abs(绝对压力)之间的流5。该气体流5在吸附剂床层A2中被净化除去水以形成净化流7。净化流7在第一交换器9中部分地冷凝，该交换器是由一叠被板分隔开的波纹层构成的铝交换器。部分冷凝流被送至第一相分离器11。所形成的气体13被送至允许在仅两种流体之间进行间接热交换的管壳式类型的第二交换器35的管中。附图示出从所述气体获得的气体13冷凝所在的多个管。所形成的液体43被送至第二相分离器17。
来自第二相分离器17的气体24在第三热交换器109中被加热，该第三热交换器是板翅式交换器。来自第二相分离器17的液体19与来自第一相分离器的在阀16中膨胀的液体19混合，然后在阀22中膨胀并被送至蒸馏塔23的顶部。
贫含二氧化碳但富含至少一种杂质(氧气，氮气，氩气，氮氧化物(NO或NO2或N2O)，一氧化碳，氢气)的来自蒸馏塔23的塔顶气体26在第三热交换器109中被加热，然后在第一热交换器9被加热。
塔底液体从塔的壳部被抽取并在第三交换器109中被冷却。该液体含有至少80mol％的二氧化碳。该液体在阀31中膨胀，然后被送至第二交换器35的壳，在那里部分地蒸发。所形成的气体37在第三交换器109中被加热，然后在第一交换器9中被加热。从那里被压缩级C6压缩和在冷却器R6中被冷却，然后与蒸发的液体32混合。由此形成的气体通过压缩级C7，C8，C9压缩并通过冷却器R7，R8，R9，R10冷却以形成冷凝的气体。该冷凝的气体与来自第二交换器的清洗液41混合并通过泵P1部分地加压以形成处于至少50bar压力下的加压液态产品51。所述清洗液41先前已在泵P2中被加压。
来自第二相分离器17的气体24在第三热交换器109中被部分加热，然后通过膜25分离以形成渗透物29和非渗透物27。非渗透物27在第三和第一交换器中被加热然后排放到大气。渗透物29在第三和第一交换器中被加热，然后用于再生处于再生阶段的吸附剂床A1。用于再生的流55与压缩级C1下游的流3混合。
很明显，可以通过与另一工艺流体例如蒸发的塔底液体的一部分进行间接热交换从而在第二交换器35中蒸发液体33。
可以在使液体41在室温下与液态CO2混合之前加热在泵P2中加压的液体41，从而回收清洗液的显热的冷量。
在图2的变型中，气体24仅在第三交换器中被加热然后在第一交换器中被加热而不通过渗透分离。
在图3的变型中，所述方法对应于图2的方法，不同之处在于过冷器109结合在交换器9中。因此可以看出，液体33在被送至阀31之前部分地穿过交换器9时被冷却。

Claims (12)

1.一种用于在低温下净化富含二氧化碳的气体以生产富含二氧化碳的流体的方法，在该方法中：
i)富含二氧化碳的气体在第一交换器(9)中被冷却，该第一交换器是由通过板分隔开的波纹层构成的钎焊铝板式热交换器，
ii)冷却的气体或从该冷却的气体获取的至少一种流体被送至包括蒸馏步骤和/或至少两个连续的部分冷凝步骤的净化步骤，
iii)净化步骤产生贫含二氧化碳的气体，其在第一交换器中被加热，
iv)净化步骤产生富含二氧化碳的液体(33)，其被冷却，然后膨胀，然后被送至第二交换器(35)，在第二交换器中借助于工艺流体被加热，所述工艺流体是从在第一交换器中冷却的气体(7)获取的气体，所述第二交换器仅在富含二氧化碳的液体与工艺流体之间进行间接热交换，以及
v)富含二氧化碳的液体在第二交换器中至少部分地蒸发并且所形成的蒸发气体在第一交换器中被加热以形成富含二氧化碳的气体，该富含二氧化碳的气体是所述方法的最终产物，
其特征在于，冷却的气体在第一交换器(9)中至少部分地冷凝并被送至第一相分离器(11)，来自第一相分离器的气体被送至第二交换器(35)，在第二交换器中冷凝以形成冷凝液体(43)，所述第二交换器(35)是管壳式交换器，富含二氧化碳的液体被传送以在壳中加热，工艺流体被传送以在管中冷却，所述富含二氧化碳的液体(33)在膨胀之前在热交换器中通过与贫含二氧化碳的气体的间接热交换而被冷却，所述贫含二氧化碳的气体在第一交换器中被加热，并且在第二交换器(35)中蒸发的气体被送至第三交换器(109)以在第一交换器的上游被加热。
2.根据权利要求1所述的方法，其中，富含二氧化碳的气体被压缩和冷凝以形成富含二氧化碳的液体，该富含二氧化碳的液体是所述方法的最终产物。
3.根据权利要求1或2所述的方法，其中，来自第一相分离器的液体膨胀并被送至第二相分离器(17)或被送至蒸馏塔(23)。
4.根据权利要求3所述的方法，其中，所述冷凝液体被送至第二相分离器(17)，来自所述第二相分离器的液体被送至蒸馏塔(23)的顶部以供给该蒸馏塔。
5.根据权利要求4所述的方法，其中，来自所述第二相分离器(17)的气体(24)在第一交换器中被加热。
6.根据权利要求1或2所述的方法，其中，所述富含二氧化碳的液体(33)在膨胀装置的上游在第三交换器(109)或第一交换器(9)中被冷却。
7.一种用于在低温下净化含有二氧化碳的气体以产生富含二氧化碳的流体的设备，所述设备包括：第一交换器(9)，该第一交换器是由通过板隔开的波纹层构成的钎焊铝板式热交换器；管壳式的能够容许仅在两种流体之间进行间接热交换的第二交换器(35)；第三交换器(109)；包括至少一个蒸馏塔(23)和/或至少两个串联联接的相分离器的净化单元；用于传送富含二氧化碳的气体(5)以在第一交换器中冷却的管道；用于将冷却的气体或从该冷却的气体中获取的至少一种流体送至净化单元的管道；用于从净化单元提取贫含二氧化碳的气体并连接至第一交换器的管道；用于从净化单元提取富含二氧化碳的液体(33)并连接至第三交换器(109)用于冷却该富含二氧化碳的液体的管道；用于膨胀所述冷却的液体的阀(31)，所述阀连接至第二交换器；和用于将工艺流体从第一交换器送至第二交换器以便使所述富含二氧化碳的液体在壳中蒸发的管道，所述工艺流体是从在第一交换器中冷却的气体(7)获取的气体；和用于将通过富含二氧化碳的液体在第二交换器中的蒸发产生的气体送至第一交换器以便加热的管道，其特征在于，所述设备包括第一相分离器(11)，用于将至少部分冷凝的冷却气体从第一交换器(9)送至第一相分离器(11)的装置，用于将气体从第一相分离器(11)送至第二交换器(35)的装置，和用于将蒸馏塔(23)的塔顶气体(26)和在第二交换器(35)中蒸发的气体送至第三交换器(109)以在第一交换器的上游加热的装置。
8.根据权利要求7所述的设备，包括用于将从工艺流体中获取的气体送至第三交换器(109)以在第一交换器的上游加热的装置。
9.根据权利要求7或8所述的设备，包括用于将膨胀的液体从第一相分离器送至第二相分离器(17)或送至蒸馏塔(23)的装置。
10.根据权利要求7或8所述的设备，包括用于从第二交换器送至第二相分离器(17)的装置和用于将液体从第二相分离器送入蒸馏塔(23)的塔顶以供给该蒸馏塔的装置。
11.根据权利要求10所述的设备，包括用于将气体从第二相分离器(17)送至第一交换器以加热的装置。
12.根据权利要求7所述的设备，包括用于传送富含二氧化碳的液体以在壳中加热的装置。
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CA2876620A1 (fr) 2014-01-16
AU2013288516B2 (en) 2017-12-21
FR2993352A1 (fr) 2014-01-17
CA2876620C (fr) 2019-11-12
EP2938414A2 (fr) 2015-11-04
WO2014009664A3 (fr) 2015-11-12
FR2993352B1 (fr) 2018-07-13
US10281208B2 (en) 2019-05-07
AU2013288516A1 (en) 2015-02-05
US20150168054A1 (en) 2015-06-18
WO2014009664A2 (fr) 2014-01-16
CN105378410A (zh) 2016-03-02

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