CN104428614B - 用于分离含有二氧化碳、水和至少一种轻质杂质的流的包括低温下的分离步骤的设备和方法 - Google Patents

用于分离含有二氧化碳、水和至少一种轻质杂质的流的包括低温下的分离步骤的设备和方法 Download PDF

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CN104428614B
CN104428614B CN201380037013.XA CN201380037013A CN104428614B CN 104428614 B CN104428614 B CN 104428614B CN 201380037013 A CN201380037013 A CN 201380037013A CN 104428614 B CN104428614 B CN 104428614B
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carbon dioxide
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CN104428614A (zh
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A·达德
R·杜贝蒂尔-格勒尼耶
D·J·哈赛
S·S·库尔卡尼
M·莱克勒克
P·泰里安
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LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
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Abstract

在用于分离含有二氧化碳、水和至少一种轻质杂质的流的方法中，包括在低温下的分离步骤，在包括至少两级的压缩机(C1,C2,C3)中压缩进料流(1,3)以形成压缩进料流(7)，在吸附床层(A1,A2)中净化压缩进料流以去除水并形成干燥的压缩流(9,11)，将所述干燥的压缩流或由其得到的流冷却至低温，并且通过在分离设备(19,31)中部分冷凝和/或蒸馏而将之分离，将富二氧化碳的液体(37,43)从所述分离设备中取出，利用再生气体(25,53)使吸附单元再生，通过分离、通过在渗透单元(21,51)中渗透所述干燥的压缩流(9)或由其得到的气体(19)形成再生气体，所述渗透单元的渗透流构成所述再生气体。

Description

用于分离含有二氧化碳、水和至少一种轻质杂质的流的包括 低温下的分离步骤的设备和方法
技术领域
本发明涉及用于分离含有二氧化碳、水和至少一种轻质杂质的流的、包括低温下的分离步骤的设备和方法。
背景技术
通常利用低温下的分离步骤净化氧燃烧烟道气，以产生纯的CO2。在分离步骤上游，通过吸附净化所述烟道气以去除水。吸附单元典型地包括按照周期操作的两个床层，调节所述周期使得所述烟道气始终可以被净化。必要的是，通过将干燥气体送经所述床层以消除积聚的湿气来使吸附单元再生。
干燥的烟道气从吸附单元被送至分离单元，以利用至少一个相分离器和/或蒸馏塔通过低温蒸馏来分离。不可冷凝的气体被从分离单元中取出，并仍含有相当部分的CO2。CO2可藉由渗透单元、吸附装置(变压吸附或真空变压吸附)而从这些不可冷凝的气体中回收。干燥的烟道气典型地含有至少65％二氧化碳或甚至至少70％二氧化碳以及至少1％氧气。二氧化碳的最大百分含量可以是95％。
从US-A-8012446中获知了利用膜式装置的渗透流在低压下使吸附单元再生并使渗透流再循环至锅炉或环境岛。这允许在环境岛或锅炉本身中有效地处理来自干燥器的再生的杂质(在锅炉内的脱硫步骤和/或燃烧，和/或锅炉内的NOx产量减缓措施)。
还从WO-A-2007/126972中获知了在相分离器中分离进料并将所形成的液体送至蒸馏塔，从而产生纯的二氧化碳。这种情形中，来自相分离器的气体与塔顶部气体混合并用于使吸附单元再生。
EP-A-0596470描述了根据权利要求1的前序部分的方法。
发明内容
本发明的一个优点是，通过使渗透流在压缩机级间处(再)循环到进料气体压缩机中来稳定渗透压力，因而提高了系统的能量效率。
这样的膜式系统的低温操作可极大地提高效率，如US-A-20120111051所示的。因为这个优点，所以尽管增大了渗透压力还是可以保持高的CO2回收率。
干燥级可以安置在第三或第四压缩级下游。膜式单元的渗透流在干燥器的前面再循环。
多个实施例是可能的：
-CPU(“冷”净化单元)+膜，渗透流在干燥器再生之后在压缩机的级间再循环
-CPU+串联的两级膜，一股渗透流使干燥器再生并且在压缩机中再循环，另一股渗透流被送至锅炉。具有最大氧浓度的渗透流将被再循环至锅炉，从而稳定氧气并降低ASU产量
-膜+CPU(在干燥器再生之后作用在残留物上和/或在渗透流上)+压缩
根据本发明的目的，提供一种用于分离含有二氧化碳、水和至少一种轻质杂质的流的方法，包括在低温下的分离步骤，其中：
i)在吸附单元中净化进料流以去除水并形成干燥的流，
ii)将所述干燥的流或由其得到的流冷却至低温，并且通过在分离设备中部分冷凝和/或蒸馏而将之分离，
iii)将富二氧化碳的液体从所述分离设备中取出，
iv)利用再生气体使吸附单元再生，通过分离、通过在渗透单元中渗透所述干燥的流或由其得到的气体来形成再生气体，所述渗透单元的渗透流构成所述再生气体，
所述方法的特征在于，在包括至少两级的压缩机中压缩所述流，以形成进料流。
根据本发明的其它可选方面：
-冷却并在相分离器中分离所述干燥的流或由其得到的气体，来自所述相分离器的气体构成由所述干燥流得到的气体并且在所述渗透单元中被分离，该渗透单元的非渗透流被加热并取出。
-所述渗透单元具有-60℃和-10℃之间的入口温度。
-在另一渗透单元中分离所述渗透单元的非渗透流，将该另一渗透单元的渗透流送至所述压缩机的级的上游。
-所述另一渗透单元具有-60℃和-10℃之间的入口温度。
-在所述渗透单元中分离所述干燥的流，所述渗透流形成所述再生气体，并且所述非渗透流形成所述步骤iii)的由所述干燥的压缩流得到的流。
-所述渗透单元具有环境温度和-10℃之间的入口温度。
-使富二氧化碳的液体气化以产生制冷并冷却所述干燥的压缩流或由其得到的非渗透流。
-将所述再生气体从所述吸附单元送至位于所述压缩机的至少一级的下游的压缩机。
-所述渗透单元的渗透流的二氧化碳的纯度比供给该渗透单元的气体低。
-所述渗透单元的渗透流的至少一种轻质组分的纯度比供给该渗透单元的气体高。
-在渗透步骤之前进一步压缩所述干燥的流。
-在冷却步骤之前进一步压缩所述干燥的流。
-所述至少一种轻质组分从包括氢气、氧气、氮气、氩气、一氧化碳、氮氧化物的组中选择。
–所述干燥的流包含至少65％摩尔浓度的二氧化碳。
根据本发明的目的，提供一种用于分离含有二氧化碳、水和至少一种轻质杂质的流的设备，该设备包括：在低温下操作的分离设备；用于净化进料流以除去水并形成干燥的流的吸附单元；用于将所述干燥流或由其得到的流冷却至低温的热交换器；用于通过部分冷凝和/或蒸馏进行分离的分离设备；用于将富含二氧化碳的液体从所述分离设备中取出的管道；用于将再生气体送至所述吸附单元的管道和用于使所述干燥的压缩流或由其得到的气体分离的渗透单元；以及用于取出所述渗透单元的作为所述再生气体的渗透流的管道，所述设备的特征在于，该设备包括用于压缩所述流以形成所述进料流的、具有至少两级的压缩机。
根据本发明的其它可选方面：
-用于分离经冷却的干燥的压缩流或由其得到的气体的相分离器和用于将来自所述相分离器的气体送至所述渗透单元的管道。
-用于将所述渗透单元的非渗透流送至所述热交换器进行加热的管道。
-所述渗透单元位于绝缘封壳内部。
-该设备包括另一渗透单元、用于将所述渗透单元的非渗透流送到所述另一渗透单元中进行分离的管道、以及用于将该另一渗透单元的渗透流送至所述压缩机的级的上游的管道。
-所述另一渗透单元位于绝缘封壳内部。
-所述干燥的压缩流在所述渗透单元中被分离，所述渗透流形成所述再生气体，所述非渗透流在所述分离设备中被分离。
-所述渗透单元位于绝缘封壳外部。
-该设备包括用于将富二氧化碳的液体送至所述热交换器以使其气化从而产生制冷并冷却所述干燥的压缩流或由其得到的非渗透流的装置。
-用于将所述再生气体从所述吸附单元送至位于所述压缩机的至少一级的下游的压缩机的管道。
-所述设备包括用于在渗透步骤之前和/或在冷却步骤之前压缩所述干燥的压缩流的压缩机。
具体实施方式
将参照图示根据本发明的方法的附图更详细地描述本发明。
图1中，含有二氧化碳摩尔浓度在65％和95％mol之间的由二氧化碳、氮气和氧气组成的混合物在过滤器F中被分离以去除颗粒，然后作为流3在压缩机级C1中被压缩，然后在冷却器R1中被冷却以形成流5。流5在压缩机级C2中被进一步压缩，在冷却器R2中被冷却，在压缩机级C3中被压缩并且在冷却器R3中被冷却，以形成流7。流7在吸附器A2中被净化以去除任何残留的湿气，并且然后在压缩机级C4中被进一步压缩并且在冷却器R4中被冷却。在冷却器R4中被冷却的干燥的流11在热交换器13中被冷却，该热交换器是钎焊板翅式热交换器。这引起流11部分冷凝，并且部分冷凝的流从热交换器13的冷端被送至相分离器15。在相分离器15中产生的液体17在阀29中膨胀后被送至塔31的顶部。然后液体17被分离，以在塔的底部形成富二氧化碳液体以及在该塔的顶部形成富轻质杂质的气体33。气体33在热交换器13中被加热并且作为进料流9的一部分在吸附床层A1、A2的下游和压缩机级C4的上游再循环。
液体35被分成两部分。一部分37在热交换器13中气化。气化的液体然后被分成两部分，一部分39被送至塔31的底部，而剩余部分41被送至压缩机级C6的入口。
来自塔31的底部的液体43在阀36中膨胀，在热交换器13中在比流37低的压力下气化，被送至压缩机级C5的入口，由冷却器R5冷却，与流41混合，在压缩机级C6中被压缩，在压缩机级C7中被压缩，在冷却器R7中冷却，在压缩机级C8中被压缩，在冷却器R8中冷却，并在冷却器R9中冷凝，之后在泵P中被加压以形成加压液体产品流。
利用在膜式分离器21中产生的气体25使吸附床层A1、A2再生。来自相分离器15的气体19在膜式分离器21中被分离，以产生渗透流25，该渗透流不在交换器13中被加热而是用于在交换器E1中冷却一股流，在交换器E2中被加热并且然后被送至吸附床层A1、A2——取决于哪个床层在运行中。用于使未运行的床层再生的气体然后被送至交换器E3，并且再循环进入位于压缩机级C1下游的进料流5。来自膜式分离器21的非渗透流23被加热并被排入大气。
图2的工艺与图1中的工艺的区别在于串联使用两个膜式分离器21、22。1.1bar压力下的来自膜式分离器21的渗透流25仍用于使吸附床层再生，而非渗透流23在另一膜式分离器22中被进一步分离以形成渗透流26，该渗透流26在2.5bar压力下在冷却器R1下游再循环。这种情形下，再生气体被送至交换器E3，然后被送至锅炉，进料流1起源于该锅炉。
在这些情形下，用于膜式分离器21、22的入口温度在-60℃和-10℃之间变化。
在图1和图2的情形中，热交换器、相分离器、膜式单元21和塔31位于绝缘(绝热)封壳(未示出)中，以将操作温度保持在低温水平。
在图3中，膜式分离器不一定是以和图1、图2中的入口温度一样的低温入口温度操作的膜式分离器，而是以-10℃或更高的入口温度操作。来自冷却器R4的进料气体11在膜式分离器51中分离，以形成渗透流53，渗透流53被送至交换器E1、E2并且然后被送至吸附床层A1。一旦再生气体被从床层取出时，其就被送至交换器E3且然后再循环进入冷却器R1下游的进料中。膜式分离器51的非渗透流57形成低温分离的进料气体，并在热交换器13中被冷却且在相分离器15中被分离。所形成的液体17如前述一样通过蒸馏被分离出，来自相分离器的气体19在热交换器13中被加热并且被排入大气。
在图3的情形中，热交换器、相分离器和塔31位于绝缘封壳(未示出)内，以将操作温度保持在低温水平。

Claims (8)

1.一种用于分离含有二氧化碳、水和至少一种轻质杂质的流的方法，包括在低温下的分离步骤，其中：
i)在包括至少两级的压缩机(C1，C2，C3)中压缩流(1，3)以形成进料流(7)，并且所述进料流包含至少65％摩尔浓度的二氧化碳，和所述进料流包含氮氧化物，
ii)在吸附单元(A1,A2)中净化进料流(7)以去除水并形成干燥的压缩流(9,11)，
iii)将所述干燥的压缩流冷却至低温，并且通过在相分离器(15)中部分冷凝和在分离设备(31)中蒸馏而将之分离，
iv)将富二氧化碳的液体(37,43)从所述分离设备中取出，
v)利用再生气体(25,53)使吸附单元再生，
所述方法的特征在于，通过分离、通过在渗透单元中渗透来自相分离器的气体(19)来形成再生气体，所述渗透单元的渗透流构成所述再生气体，在吸附单元再生之后渗透流再循环到压缩机级间。
2.根据权利要求1所述的方法，其特征在于，该渗透单元的非渗透流(23)被加热并取出。
3.根据权利要求1所述的方法，其特征在于，所述渗透单元(21)具有-60℃和-10℃之间的入口温度。
4.根据权利要求2所述的方法，其特征在于，在另一渗透单元(22)中分离所述渗透单元的非渗透流(23)，将该另一渗透单元的渗透流送至所述压缩机的级的上游。
5.根据权利要求4所述的方法，其特征在于，所述另一渗透单元(22)具有-60℃和-10℃之间的入口温度。
6.根据权利要求1-5中任一项所述的方法，其特征在于，使富二氧化碳的液体气化以产生制冷并冷却所述干燥的压缩流(9,11)或由其得到的非渗透流。
7.根据权利要求1-5中任一项所述的方法，其特征在于，将所述再生气体从所述吸附单元送至位于所述压缩机的至少一级的下游的压缩机。
8.根据权利要求1-5中任一项所述的方法，其特征在于，所述渗透单元的渗透流的二氧化碳纯度比供给该渗透单元的气体低。
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CN104428614A (zh) 2015-03-18
CA2875795A1 (en) 2014-01-16
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EP2872841B1 (en) 2018-10-03
US9895653B2 (en) 2018-02-20
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EP2685190A1 (en) 2014-01-15
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