CN104136870B - 用于使富co2气体液化的方法和设备 - Google Patents

用于使富co2气体液化的方法和设备 Download PDF

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CN104136870B
CN104136870B CN201280028472.7A CN201280028472A CN104136870B CN 104136870 B CN104136870 B CN 104136870B CN 201280028472 A CN201280028472 A CN 201280028472A CN 104136870 B CN104136870 B CN 104136870B
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CN104136870A (zh
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B·德莫利安
H·勒比昂
X·特拉维萨
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LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
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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使包含至少60mol%的CO2的气体液化以生产至少一种液态产品的方法，其中，使气体冷却而形成流体流，在热交换器（E1）中冷却液体或超临界流的至少一部分而形成具有循环压力的循环流体，将该循环流体分成包括附属分份的至少两份分份，所述分份中的一份在阀（43）中一直膨胀到第一压力而形成两相混合物，且然后被输送到分相器（35）。使分相器的液体分份在交换器中气化而形成气化气体，该气化气体然后在膨胀装置（45）中从第一压力膨胀到第二压力，且然后在循环压缩机（C1，C2）中被压缩并与第一原料气体混合。所述附属分份包括液态产品，并且如果富二氧化碳气体中包含的比二氧化碳轻的杂质的量增加，则该第一压力升高。

Description

用于使富CO2气体液化的方法和设备
本发明涉及一种用于使富CO2气体液化的方法和设备。
富二氧化碳气体包含至少60mol%的二氧化碳，或甚至至少80mol%的二氧化碳。
该气体还包含至少一种比二氧化碳轻的杂质，例如氮、氧、一氧化碳等。
一种设想用于运输CO2的工业手段为船运，船运要求例如来自不同来源：来自燃煤动力设备、冶金设备、SMR、气体化工艺等的气体的CO2的液化。
有时需要通过管道在超临界压力下运输CO2，并且为此待运输的液体必须在高压下进行加压。
该液化可以在通过物理和/或化学分离工艺进行的一次或多次烟气（或合成气体）处理之后。
本发明提出了一种管理CO2液化单元中的来源的含量变化以防止出现CO2在系统的致冷回路中冻结的任何风险的方案。本发明还提出一种用于旋转机器的最佳调节的系统。
在图中，从一个或多个来源产生的富CO2气体经由循环压缩机被压缩或者已经处于用于在环境温度下冷凝气体所期望的压力下。使冷凝气体冷却。可以在足以通过管道运输CO2的压力下直接压缩该冷凝气体的一部分。该冷凝气体的另一部分或全部冷凝气体可用在冷箱中。送入冷箱中的冷凝气体具有两种用途：一部分被净化以生产液态CO2，另一部分通过冷凝气体在一个或多个压力下的膨胀而提供致冷平衡。然后冷凝并膨胀的气体气化并被输送到循环压缩机。
由于固体的存在能够损坏系统，冷箱中的最低液化气体膨胀压力将由冷凝气体中包含的CO2的凝固（凝华，solidification）温度决定。将温度裕度确定成防止冷箱中的冻结（最低-54.5℃）。
通常也可以设想通过将压力分级来优化换热器块体处的能量并因此具有不同液化水平。可以通过将这些流导入多级一体式离心循环压缩机的级间来回收这些流。
富CO2气体中的杂质的组分强烈地影响循环压缩机的抽吸压力。当含量变化时，压缩机的不同叶轮的抽吸压力因此也必须进行调节。
本发明的创新方法涉及确保系统的致冷的环路。因此，本发明涉及使冷箱中的不纯CO2膨胀到能实现系统的致冷平衡的压力，同时防止冻结（最冷温度被限制为-54.5℃），然后使气体在热作用下再膨胀以便获得用于循环压缩机的相同的恒定抽吸压力。此外，将使气体冷却，这将实现压缩机的更低能量消耗。这样，循环压缩机不会承受由于来源的组分的可能变化而引起的可能的抽吸压力变化。
也可以设想借助涡轮-压缩机布置结构来收集额外的膨胀能量以便最大限度地减小损耗，或者借助发电机涡轮。
因此，同一液化装置将可以适应来源的内含物变化的情况和/或具有不同组分的来源随着时间的推移与液化装置连接的情况（这些情况将导致进入流的组分变化），同时确保装置的安全性。
所述单元还可以包括以下技术要素：
-通过压缩机上游的吸附来干燥气体，
-经由蒸馏塔消除或减少杂质，例如通过吸附获得的Hg、NOx，
-经由蒸馏塔净化CO2，
-经由冷箱中的中间压缩提高CO2产量。
该布置结构因此即使在损失一个CO2来源的情况下也能实现液化装置的可靠使用。
如果至少一个不纯CO2来源处于用于CO2的液化的适当压力下，优先选择来自该来源的气体用于液态CO2的生产。
可选地，可能需要来自一个来源的气体的压缩以至少均衡所生成的液态CO2的压力。
根据JP-A-58208117、EP-A-0646756和SU-A-1479802，已知通过压缩CO2流和通过冷却CO2流来使CO2流液化。
US-A-4699642描述了一种根据权利要求1的前序部分的、用于使包含至少60mol%的CO2的气体液化的方法。
根据本发明的一个目的，提供了一种使包含至少60mol%的CO2和至少一种轻杂质的气体液化以生产至少一种液态产品的方法，其中，使处于供给压力下的、包含至少60mol%的CO2和至少一种轻杂质的第一原料气体可能地在已在循环压缩机中被压缩之后冷却而形成液体或超临界流，在热交换器中冷却所述液体或超临界流的至少一部分以形成具有循环压力的循环流体，将该循环流体分成包括附属分份的至少两份分份，所述分份中的一份在阀中膨胀而下降到第一压力以形成两相混合物并被输送到分相器，使分相器的液体分份在交换器中气化而形成气化气体，所述气化气体然后在膨胀装置中从所述第一压力膨胀到第二压力且然后在循环压缩机中被压缩并与所述第一原料气体混合，所述附属分份包括所述液态产品或一种液态产品，或者在至少一个分离装置中在低于环境的温度下通过分离而被处理以形成液态产品或一种液态产品，其中所述第一压力根据富二氧化碳气体中包含的比二氧化碳轻的杂质的量变化，所述方法的特征在于，所述第一压力变化，使得轻杂质的浓度越高，所述第一压力就越高。
根据其它可选特征：
-所述第二压力大致恒定并且独立于富二氧化碳气体的组分，
-所述第二压力等于循环压缩机的入口压力并且将在膨胀装置中膨胀的气体从膨胀装置直接输送到循环压缩机的入口，
-将所述第一压力选择成低于富二氧化碳气体将在分相器或阀中凝固的压力，
-根据待在膨胀装置中膨胀的气体的组分和/或根据在膨胀阀中膨胀的流体的组分来调节膨胀装置中的膨胀率，
-根据待在膨胀装置中膨胀的气体中的轻杂质的量和/或根据在膨胀阀中膨胀的流体的组分来调节膨胀装置中的膨胀率，
本发明还涉及一种使包含至少60mol%的CO2和至少一种轻杂质的气体液化以生产至少一种液态产品的设备，该设备包括：热交换器；循环压缩机；冷却装置；用于将包含至少60mol%的CO2和至少一种轻杂质的原料气体输送到冷却装置以形成液体或超临界流体的导管；用于将所述液体或超临界流体输送到交换器以形成经冷却流体的导管；用于将所述经冷却流体的一部分作为附属分份输送到客户或处理设施的导管；膨胀阀；用于将所述经冷却流体的一部分输送到膨胀阀的导管；分相器；用于将在膨胀阀中膨胀的流体输送到分相器的导管；用于将液体从分相器输送到交换器的导管；膨胀装置；用于将在交换器中气化的液体输送到膨胀装置以形成膨胀气体的导管；用于将所述膨胀气体输送到循环压缩机的导管；用于使所述膨胀气体在循环压缩机的上游、下游或其中与包含至少60mol%的CO2的气体混合的装置；以及用于根据原料气体的组分而改变膨胀阀的出口压力的装置，所述设备的特征在于，所述膨胀装置为涡轮。
根据其它可选特征：
-所述设备包括连接到用于将所述经冷却流体的一部分作为附属分份输送到处理设施的导管的处理单元，该处理单元是处于低于环境的温度的液化单元或分离单元，
-所述设备包括用于检测待膨胀的流体的温度和/或在膨胀阀中膨胀的流体的温度的装置和用于根据该温度或这些温度改变膨胀阀中的膨胀率的装置，
-所述设备包括用于检测输送到膨胀装置的气体和/或输送到膨胀阀的流体的浓度的装置和用于根据该浓度而改变膨胀装置的膨胀率的装置，
-所述设备包括用于检测输送到膨胀装置的气体的压力的装置和用于根据该压力而改变膨胀装置中的膨胀率的装置，
-所述涡轮联接到循环压缩机或所述处理单元包括压缩机并且所述涡轮联接到所述处理单元的压缩机，
-所述交换器配置成使得来自分相器的液体的气化的潜热被传递到经交换器冷却的液体或超临界流体。
将参照示出了根据本发明的方法的附图更详细地描述本发明。
在图1中，所述设备包括热交换器E1、泵42、具有四个级C1、C2、C3、C4的压缩机和一系列分相器P1、P2、P3。
所述分相器、热交换器和膨胀阀位于冷箱中。
来自三个不同来源的气体的混合物被液化而形成超临界CO2流并被净化以形成纯液态CO2流。
使处于热电联产产生的第一压力下的、包括至少60mol%的CO2和至少一种轻杂质——这种情况下为氮气——的气体1与气体1A、1B混合，所形成的混合物被输送到四级压缩机的第三级C3。气体通过冷却器R3冷却，在第四级C4中被压缩到超过临界压力的第二压力，例如83barabs，且然后在交换器E3、E4中被冷却而形成超临界流体。如果压力低于临界压力，则明显将形成液体。
可以通过交换器E4上游或压缩机上游的吸附来使原料气体干燥。
可选地，流体的一部分40未被输送到热交换器E1，而是通过泵42加压到150barabs的压力而形成例如要在管道中输送的产品。使处于级C4的出口压力下的流体或流体的剩余部分在交换器E1中冷却并液化而形成超临界流体或循环液体。对于本发明的情况而言，其被认为是超临界流体。将处于83barabs下的超临界流体分成至少五分份。分份4在阀6中一直膨胀到很高的压力，在交换器E1中冷却并被输送到压缩机的第四级C4。分份5在阀15中一直膨胀到高压力，在交换器中冷却并被输送到压缩机的第三级C3。分份7在阀16中一直膨胀到平均压力，在交换器E1中冷却并被输送到压缩机的第二级C2的入口。低压分份34在阀43中膨胀。由气体1、1A和1B形成的混合物包含CO2和仅作为轻杂质的氮，但含量可变化。为了确保超临界流体3的分份34当在阀43中从83barabs膨胀时不会冻结，如下表所示计算膨胀压力：
流34中的mol%N2 最低气化压力
abs bar
0.035 5.85
1 7.9
2 8.9
这意味着，在阀43中，流体膨胀到最低压力的有效膨胀根据进入的流体中的氮含量将分别为从83barabs至5.85、7.9或8.9barabs。将阀出口43处的两相混合物输送到分相器35。所形成的液体39和所形成的气体37在交换器E1中冷却并混合。混合物41在热阀45中一直膨胀到5.85barabs的压力，以便保持循环压缩机的恒定抽吸压力。热阀45的入口压力因此是可变的，因为在热阀45与阀43之间既不存在膨胀，也不存在加压。
通过检测在阀43的出口处膨胀的流的温度以验证其是否不低于-54.5℃以及通过检测交换器E1中的过冷液体3的温度来控制该阀出口43的压力。流34中的不可冷凝物的水平越高，流34就将通过膨胀越快地冷却。不可冷凝物实际上明显更易挥发：因此如果流34由纯CO2组成，则它们不会膨胀到这么低的压力。
可以注意到测量过冷液体3的温度的温度检测装置TIC和测量在阀43中膨胀的流体的温度的温度检测装置TSLL。设定不应该被超过的低温极限，并且在温度低于比该极限高1℃和比该极限高0.5℃的温度的情况下启动警报，以便使得能根据这些温度来调节阀的膨胀。因而，如果在阀43的出口处的流体中观察到温度下降，这表明流体3的纯度降低，则将升高该阀的出口压力。类似地，如果膨胀后的流体的温度升高，则将降低阀43的出口压力。
热阀45接收处于不同压力下的气体。因此根据通过PIC分析仪测得的流41的压力来调节该阀的膨胀率。如果液体3足够纯，则不需要使液体34膨胀到高于压缩机C1的入口压力的压力，因此，在这种情况下，将气化液体输送到基本上或完全不会使其膨胀的旁通阀46。
其余液体13在阀19（或液体涡轮）中膨胀而不经过交换器E1，并被输送到分相器P1。在分相器中，其形成液体23和气体21。液体23在交换器中被加热然后被输送到第三分相器P3。该分离器的液体为设备的处于-50℃和7barabs下的富二氧化碳产品25。分配器P1和P3的气体被混合，在交换器E1中冷却，通过压缩机C5压缩，在冷却器31中冷却，然后在交换器E1中加热并被输送到第二分相器P2。该分离器的气体33包含30%的氢、50%的二氧化碳和15%的氮并在交换器E1中被加热。该液体作为流36在交换器中被加热，然后与分份13混合并被输送到分离器P1。
显然，该过程不必包括分份13的处理。在这种情况下，液体20构成该过程的一种液态产品。
还可以通过蒸馏来处理分份13以便产生富二氧化碳的液态产品或很简单地处理分份13以便去除气态部分，部分22包括液态产品。例如，代替脱氮塔或脱氧塔或除脱氮塔或脱氧塔以外，可以设置脱汞和/或脱NOx塔。
可设想该工艺利用单个源供给并且给料气体的组分随时间变化。在这种情况下，将有必要将压力调整到阀43使液体34膨胀达到的压力。因而，还将修改阀45的入口压力，但阀45的出口压力将保持恒定。
也可能的是，原料气体的来源随时间变化，因为具有不同组分的原料气体在操作期间开始供给该工艺。在这种情况下，有必要能够考虑在工艺的操作期间具有增加的轻杂质含量的可能的组合物。
应该理解的是，更简单而言，该工艺仅需使流34在最低压力下气化。较高压力下的其它气化使得可以改善交换图（交换关系，diagrammed’échange），但不是必不可少的。
根据图2，如果流3中的轻杂质比例高，则图1的用于处理流体13的系统中的所谓的输出压缩机C5的存在变得特别有利。在这种情况下，图1的阀45可以由联接到压缩机C5的涡轮替换。
在该图中，原料气体的一部分1已经处于足够高的压力以在交换器E1中液化。处于第一压力下的两股流1A、1B因此通过如上所述的被输送到压缩机的第三级而被一直压缩到第二压力，并且处于第二压力下的另一股流1被直接输送到交换器E1，在此其在被输送到分相器之前至少部分地液化。应该指出的是，流1可以是在分相器中被处理的唯一流，或者其可以与分份13混合。该过程还使得可以管理流1和流1A、1B具有截然不同的杂质的情况。例如，流1可以根据其组分被输送到分离器P1或分离器P2或分离器P3。
与图1相比，分相器P1、P2的顶部气体通过压缩机C5压缩，在冷却器31中冷却，然后通过压缩机C6压缩且然后在于位于分离器P2上游的交换器E1中冷却之前在冷却器32中冷却。涡轮45联接到压缩机C5或压缩机C6。
除了根据流41的压力调节涡轮46的膨胀率之外，如图1那样执行调节。
可以将涡轮45与压缩机C1联接。

Claims (14)

1.一种用于使包含至少60mol％的CO2和至少一种比二氧化碳轻的杂质的气体液化以生产至少一种液态产品的方法，其中，使处于供给压力下的、包含至少60mol％的CO2和至少一种轻杂质的第一原料气体冷却而形成液体或超临界流，在热交换器(E1)中冷却所述液体或超临界流的至少一部分以形成具有循环压力的循环流体，将所述循环流体分成包括附属分份的至少两份分份，所述分份中的一份在阀(43)中膨胀而下降到第一压力以形成两相混合物并被输送到分相器(35)，使所述分相器的液体分份在所述交换器中气化而形成气化气体，所述气化气体然后在膨胀装置(45)中从所述第一压力膨胀到第二压力且然后在一循环压缩机(C1)中被压缩并与所述第一原料气体混合，所述附属分份包括所述至少一种液态产品中的一者，或者在至少一个分离装置中在低于环境温度下通过分离而被处理以形成所述至少一种液态产品中的一者，其中所述第一压力根据富二氧化碳气体中包含的比二氧化碳轻的杂质的量变化，所述方法的特征在于，所述第一压力变化，使得轻杂质的浓度越高，所述第一压力就越高。
2.根据权利要求1所述的方法，其中，使所述第一原料气体在已在循环压缩机(C3，C4)中被压缩之后冷却而形成液体或超临界流。
3.根据权利要求1或2所述的方法，其中，所述第二压力大致恒定并且独立于所述富二氧化碳气体的组分。
4.根据权利要求1或2所述的方法，其中，所述第二压力等于所述循环压缩机(C1)的入口压力并且将在所述膨胀装置中膨胀的气体从所述膨胀装置(45)直接输送到所述循环压缩机的入口。
5.根据权利要求1或2所述的方法，其中，将所述第一压力选择成低于所述富二氧化碳气体能够在所述分相器(35)或所述阀(43)中凝固的压力。
6.根据权利要求1或2所述的方法，其中，根据待在所述膨胀装置中膨胀的气体的组分和/或根据在所述膨胀阀(43)中膨胀的流体的组分来调节所述膨胀装置(45，46)中的膨胀率。
7.根据权利要求6所述的方法，其中，根据待在所述膨胀装置中膨胀的气体中的轻杂质的量和/或根据在所述膨胀阀(43)中膨胀的流体的组分来调节所述膨胀装置(45)中的膨胀率。
8.一种使包含至少60mol％的CO2和至少一种比二氧化碳轻的杂质的气体液化以生产至少一种液态产品的设备，所述设备包括：热交换器(E1)，循环压缩机(C1)，冷却装置(E4)，用于将包含至少60mol％的CO2和至少一种轻杂质的原料气体输送到所述冷却装置以形成液体或超临界流体的导管，用于将所述液体或超临界流体输送到所述交换器以形成经冷却流体的导管，用于将所述经冷却流体的一部分作为附属分份输送到客户或处理设施的导管，膨胀阀(43)，用于将所述经冷却流体的一部分输送到所述膨胀阀的导管，分相器(35)，用于将在所述膨胀阀中膨胀的流体输送到所述分相器的导管，用于将来自所述分相器的液体输送到所述交换器的导管，膨胀装置(45)，用于将在所述交换器中气化的液体输送到所述膨胀装置以形成膨胀气体的导管，用于将所述膨胀气体输送到循环压缩机的导管，用于使所述膨胀气体在所述循环压缩机的上游、下游或其中与包含至少60mol％的CO2的气体混合的装置，以及用于根据所述原料气体的组分而改变所述膨胀阀的出口压力的装置(TIC，TSLL)，所述设备的特征在于，所述膨胀装置为涡轮(45)。
9.根据权利要求8所述的设备，所述设备包括处理单元(P1，P2，P3)，所述处理单元连接到用于将所述经冷却流体的一部分作为附属分份输送到处理设施的导管，所述处理单元是处于低于环境的温度的液化单元或分离单元。
10.根据权利要求8或9所述的设备，其中，所述涡轮(45)联接到所述循环压缩机(C1)。
11.根据权利要求8或9所述的设备，其中，所述处理单元包括压缩机(C5，C6)，所述涡轮联接到所述处理单元的所述压缩机。
12.根据权利要求8或9所述的设备，所述设备包括用于检测输送到所述膨胀装置的气体和/或输送到所述膨胀阀的流体的浓度的装置和用于根据该浓度而改变所述膨胀装置的膨胀率的装置。
13.根据权利要求12所述的设备，所述设备包括用于检测输送到所述膨胀装置的气体的压力的装置和用于根据该压力而改变所述膨胀装置中的膨胀率的装置。
14.根据权利要求8或9所述的设备，其中，所述交换器配置成使得来自所述分相器的液体的气化的潜热被传递到经所述交换器冷却的所述液体或超临界流体。
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