CN104428615A - 用于分离富含二氧化碳的气体的方法 - Google Patents

用于分离富含二氧化碳的气体的方法 Download PDF

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CN104428615A
CN104428615A CN201380037322.7A CN201380037322A CN104428615A CN 104428615 A CN104428615 A CN 104428615A CN 201380037322 A CN201380037322 A CN 201380037322A CN 104428615 A CN104428615 A CN 104428615A
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heat exchanger
carbon dioxide
liquid
tube heat
shell
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CN104428615B (zh
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A·布里格利亚
A·达德
P·泰里安
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LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
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Abstract

在一种用于分离富含二氧化碳且包含至少一种比二氧化碳轻的成分的气体的方法中,在第一热交换器(E1)冷却所述富含二氧化碳的进料气体,使所述进料气体部分地凝结并分离以形成气态部分和液体,将所述液态部分输送到蒸馏塔(K)的顶部,从所述蒸馏塔的底部取出二氧化碳含量比所述进料气体高的液流,从所述蒸馏塔的顶部取出二氧化碳含量比所述进料气体低的气态流(17)并在所述第一热交换器中将所述气态流加热,将所述气态部分输送到具有位于三相点二氧化碳浴中的管的壳管式热交换器(V3),所述气态部分在所述热交换器中至少部分地凝结而形成液态部分,将所述液态部分(35)输送到所述蒸馏塔的顶部,使来自所述蒸馏塔的底部的液流(19)在所述蒸馏塔的外部或内部气化以形成随后在所述蒸馏塔中分离的气体,使来自所述蒸馏塔的底部的液流(21)膨胀,使膨胀后的液流的至少一部分在所述壳管式热交换器中气化以形成蒸气并在所述第一热交换器中对所形成的蒸气加热。

Description

用于分离富含二氧化碳的气体的方法
技术领域
本发明涉及一种用于分离富含二氧化碳的气体的方法。
背景技术
富含二氧化碳的气体包含至少65%的二氧化碳。它还包括选自以下列表中的至少一种其它成分:氧、氮、氩、一氧化碳、氢、一氧化氮、二氧化氮、一氧化二氮、汞、甲醇、乙醇、氨或烃。
优选地,它包含5%以下的甲烷,本文献中与纯度有关的所有百分比均为摩尔百分比。
富含二氧化碳的气体可由富氧燃料燃烧、水泥厂、钢厂、蒸汽甲烷重整装置或任意其它已知的来源制得。
本发明除其它可能性外提出在壳管式交换器中执行二氧化碳净化单元进料气体的最终冷却阶段。
进料气体在由处于其三相点的二氧化碳浴包围的管中冷却。
存在许多与使系统在其三相点工作相关的优点。
首先,外壳的压力在三相点非常稳定。如果压缩来自管壳式交换器的气化的二氧化碳的压缩机移送过多气体,则液体将闪蒸,从而形成全部处于三相点压力下的固体和气体。另一方面,如果移送的气体太少,则压力由于冰冻二氧化碳的存在而不会大幅上升。当固相呈与液体混合的微晶体形式时,形成液态-固态“浆体”,其与液体中形成大块冰冻二氧化碳时的情形相比增加了固体-液体交换表面。
其次,进料气体将尽可能被冷却,以增加制得的二氧化碳的产量并由此提高设备的比能和比成本(捕集另外的数吨二氧化碳的额外开支小于每吨平均开支)。
第三,进料气体不会冻结,因为冷源稳定在三相点温度并且进料气体将必须高于该温度。
该布置结构允许储存固态二氧化碳并使其融化,从而意味着能储存能量和/或提高液化能力。
在能量被储存的情况下,当能源价格低时,另一压缩机(或产品压缩机)比通常将被气化的情况下移送更多气态二氧化碳,以形成抽吸效应。储存的液体然后闪蒸而形成气体(以稳定三相点下的压力)和与残留的液体混合的固体。
当能源成本上升时,通过向储存装置内送入另外的气态二氧化碳来使液态二氧化碳融化;通过使气态二氧化碳液化来使固态二氧化碳融化,所形成的另外的液体被泵送到冷箱外并且能在不使用产品压缩机的情况下在生产压力下制得二氧化碳。
产品压缩机被设计成利用这些流量变化,离心式压缩机的流量下降到名义流量的80%。该问题的一个解决方案可以是使用三个较小的压缩机,各具有名义流量的50%。这种情况下,在通常操作下,两个压缩机将工作。在固态CO2相的储存期间(当能源成本低时),三个压缩机将工作,而在高能源成本时段期间,一个压缩机和泵将工作。这种情况下,在使从壳管式热交换器流出的液体与(液态或超临界的)CO2产品的残留部分混合之前需要所述泵来对所述液体加压。
在通常操作下,形成固态二氧化碳并聚集在储存装置中。在生产高峰期,可获得更多要液化的二氧化碳,将它呈气态形式输送到储存装置,在该储存装置中它液化而固态二氧化碳融化,从而提高最大液化能力而不增大设备的尺寸。
WO-A-2009/007938描述了根据权利要求1的前序部分的方法。
发明内容
根据本发明的一个目的,提供了一种用于分离富含二氧化碳且包含至少一种比二氧化碳轻的成分的气体的方法,其中在第一热交换器中将所述富含二氧化碳的进料气体冷却到低温,使所述进料气体部分地凝结并分离以形成气态部分和液体,将所述液态流(液体部分)输送到蒸馏塔的顶部,从所述蒸馏塔的底部取出二氧化碳含量比所述进料气体高的液流,从所述蒸馏塔的顶部取出二氧化碳含量比所述进料气体低的气态流并在所述第一热交换器中将所述气态流加热,将所述气态部分输送到热交换器,所述气态部分在所述热交换器中至少部分地凝结而形成液态部分,将所述液态部分或自其衍生的液体输送到所述蒸馏塔的顶部,使来自所述蒸馏塔的底部的液流在所述蒸馏塔的外部或内部气化以形成随后在所述蒸馏塔中分离的气体,从所述蒸馏塔的底部取出液流,使被取出的液流的至少一部分在所述壳管式热交换器中气化以形成蒸气并在所述第一热交换器中对所形成的蒸气加热,所述方法的特征在于,在膨胀步骤之后将所述液态部分输送到所述蒸馏塔的顶部,在气化之前使来自所述蒸馏塔的底部的液流膨胀,向其输送所述气态部分的所述热交换器为壳管式热交换器,所述壳管式热交换器的管由处于其三相点的二氧化碳浴包围,并且在所述壳管式热交换器中使被取出的液流气化。
根据又一些可选方面:
-所述壳管式热交换器在二氧化碳的三相点压力和二氧化碳的三相点温度下工作。
-在至少一个压缩机中压缩在所述壳管式热交换器中形成并在所述第一热交换器中被加热的蒸气。
-使所述气态部分在所述壳管式热交换器的管中至少部分地凝结,并且使所述液流在所述管外在所述壳管式热交换器内至少部分地气化。
-在以给定二氧化碳产量工作的情况下,在所述壳管式热交换器中形成固态二氧化碳,在二氧化碳产量提高的情况下,输送到所述壳管式热交换器的所述气态部分的流量增大,并且所述壳管式热交换器中的固态二氧化碳融化且从所述壳管式热交换器取出的液态部分的流量增大。
-在以给定二氧化碳产量工作的情况下,在所述壳管式热交换器中形成固态二氧化碳,并且在二氧化碳的产量减小的情况下,在所述壳管式热交换器中形成的固态二氧化碳的量增大。
-液态二氧化碳作为最终产品从所述塔提取。
-使来自所述塔的底部的两股液态二氧化碳流膨胀并输送到所述壳管式热交换器。
-使来自所述壳管式热交换器的部分地凝结的给料分离并且使所形成的液流膨胀并输送到所述蒸馏塔的顶部。
-清洗所述液体在所述管外的部分以使所述液体的至少一种杂质稀释。
-所述至少一种杂质选自SOx、NOx、汞、烃、甲醇、乙醇、氨。
-所述第一热交换器是板翅式热交换器。
所述方法可以在一种用于分离富含二氧化碳并且包含至少一种比二氧化碳轻的成分的气体的装置中执行,所述装置包括:用于将所述富含二氧化碳的进料气体冷却至低温的第一热交换器;壳管式热交换器;第一分相器;塔;用于将部分地凝结的进料从所述第一热交换器输送到所述第一分相器的管道;用于将液态部分从所述第一分相器经由膨胀阀输送到蒸馏塔的顶部的管道;用于从所述蒸馏塔的底部取出二氧化碳含量比所述进料气体高的液流的管道;用于从所述蒸馏塔的顶部取出二氧化碳含量比所述进料气体低的气态流并且用于输送所述气态流以在所述第一热交换器中被加热的管道;将所述第一分相器与所述壳管式热交换器连接的管道;用于将来自所述壳管式热交换器的液体部分或自其衍生的液体输送到所述蒸馏塔的顶部的管道;用于输送来自所述蒸馏塔的底部的液流以在所述蒸馏塔的外部或内部气化而形成随后在所述蒸馏塔中分离的气体的管道;使来自所述蒸馏塔的底部的液流膨胀的膨胀阀;用于将膨胀后的液流输送到所述壳管式热交换器以至少部分地气化而形成蒸气的管道;和用于将所形成的蒸气输送到所述第一热交换器的管道。
所述装置可包括用于压缩在所述壳管式热交换器中形成的蒸气的压缩机。
-存在用于输送所述气态部分以使其在所述壳管式热交换器的管中至少部分地凝结的装置和用于输送所述液流以使其在所述壳管式热交换器中在所述管外至少部分地气化的装置。
优选地,存在用于使来自所述塔的底部的两股液态二氧化碳流膨胀的装置和用于将所述两股膨胀的流输送到所述壳管式热交换器的装置。
又一分相器可分离来自所述壳管式热交换器的部分地凝结的给料并且可设置膨胀装置以使所形成的液流膨胀以及用于将膨胀的液体输送到所述蒸馏塔的顶部的装置。
可设置清洗装置以取出位于所述壳管式热交换器的管外的液体。
附图说明
将参考附图更详细地描述本发明,
图1示出根据本发明的用于分离富含二氧化碳的气体的方法,且
图2更详细地示出图1的构件。
具体实施方式
在图1中,气体1包含至少65%的二氧化碳和选自从以下列表中选择的至少一种其它成分的至少一种其它成分:氧、氮、氩、一氧化碳、氢、一氧化氮、二氧化氮、一氧化二氮、汞。所述气体可源自富氧燃料燃烧,这种情况下它至少包含氧、氮和氩。
气体1在压缩机C1中被压缩至介于6与20bar abs之间的压力,利用冷却器3冷却,然后在一对吸附器A之一中净化以除去水分。净化后的进料流5然后在板翅式热交换器E1中冷却至约-50℃的温度并由此部分地冷凝。部分地凝结的进料被输送到第一分相器V1,进料在第一分相器中分离成气态部分11和液态部分9。二氧化碳含量比进料5低的气态部分11被输送到壳管式热交换器V3。液态部分9在阀13中膨胀并被输送到塔K的顶部。塔K的底部利用热交换器E3加热以使底部液体19沸腾并将所形成的气体送回塔。从塔K取出的另一液态部分21被分为三部分。两个部分23、37在阀25、29中膨胀并输送到热交换器V3。其余部分33在阀33中膨胀并在热交换器E1中气化而形成气态流35。流23、27在热交换器V3中气化而形成气态流41,该气态流在热交换器E1中被加热以形成加温流43,该加温流43在压缩机C2中被压缩。气体35被输送到压缩机35的中间级并且全部气态流45作为气态产品被取出。液态产物15也作为来自塔K的底部的液体被取出,在交换器E1中加温,膨胀,并作为液态产物被取出。
来自第一分相器V1的气体11在热交换器V3中冷凝而形成液体35并且该液体被输送到第二分相器V2。在第二分相器中形成的液体37在阀39中膨胀并被输送到塔K的底部。来自第二分相器V2的气体47在热交换器E1中被加热。来自塔顶部的气体17在热交换器E1中被加热并被输送到压缩机C1。
热交换器E1,E3、分相器V1,V2、热交换器V3和塔K容纳在冷箱7内。
壳管式热交换器V3的更多细节在图2中示出,图2示出更真实的气体和液体的进出口布局。来自第一分相器V1的气体11进入热交换器的顶部并向下流经管53以形成液体35。两股底部液体23、27在外壳51内进入热交换器V3的底部并形成液态二氧化碳浴49。在液体的表面上方,二氧化碳浓度比进料5低的气化气体41被取出并输送到热交换器E1。
壳管式热交换器49在二氧化碳的三相点压力和二氧化碳的三相点温度下工作。
该方法被设计成在给定的二氧化碳产量下操作。在该设计情形中,在液流23、27进入外壳51的部位在壳管式热交换器49中形成固态二氧化碳。在二氧化碳的产量增大的情况下,输送到壳管式热交换器的气态部分11的流量增大并且壳管式热交换器中的固态二氧化碳融化且从壳管式热交换器取出的液态部分35的流量增大。
在二氧化碳的产量减小的情况下,在壳管式热交换器49中形成的固态二氧化碳的量增大。

Claims (12)

1.一种用于分离富含二氧化碳且包含至少一种比二氧化碳轻的成分的气体的方法,其中在第一热交换器(E1)中将所述富含二氧化碳的进料气体冷却到低温,使所述进料气体部分地凝结并分离以形成气态部分和液体,将所述液态部分输送到蒸馏塔(K)的顶部,从所述蒸馏塔的底部取出二氧化碳含量比所述进料气体高的液流,从所述蒸馏塔的顶部取出二氧化碳含量比所述进料气体低的气态流(17)并在所述第一热交换器中将所述气态流加热,将所述气态部分输送到热交换器(V3),所述气态部分在所述热交换器中至少部分地凝结而形成液态部分,将所述液态部分(35)或自其衍生的液体(37)输送到所述蒸馏塔的顶部,使来自所述蒸馏塔的底部的液流(19)在所述蒸馏塔的外部或内部气化以形成随后在所述蒸馏塔中分离的气体,从所述蒸馏塔的底部取出液流(21),使被取出的液流的至少一部分在热交换器中气化以形成蒸气并在所述第一热交换器中对所形成的蒸气加热,所述方法的特征在于,在膨胀步骤之后将所述液态部分输送到所述蒸馏塔(K)的顶部,在气化之前使来自所述蒸馏塔的底部的液流膨胀,向其输送所述气态部分的所述热交换器为壳管式热交换器(V3),所述壳管式热交换器的管由处于其三相点的二氧化碳浴包围,并且在所述壳管式热交换器中使被取出的液流气化。
2.根据权利要求1所述的方法,其中,所述壳管式热交换器(V3)在二氧化碳的三相点压力和二氧化碳的三相点温度下工作。
3.根据权利要求1或2所述的方法,其中,在至少一个压缩机(C2)中压缩在所述壳管式热交换器(V3)中形成并在所述第一热交换器(E1)中被加热的蒸气。
4.根据任一项前述权利要求所述的方法,其中,使所述气态部分(11)在所述壳管式热交换器(V3)的管中至少部分地凝结,并且使所述液流(23,27)在所述管外在所述壳管式热交换器内至少部分地气化。
5.根据任一项前述权利要求所述的方法,其中,在以给定二氧化碳产量工作的情况下,在所述壳管式热交换器(V3)中形成固态二氧化碳,在提高二氧化碳产量的情况下,输送到所述壳管式热交换器的所述气态部分(11)的流量增大,并且所述壳管式热交换器中的固态二氧化碳融化且从所述壳管式热交换器取出的液态部分(35)的流量增大。
6.根据任一项前述权利要求所述的方法,其中,在以给定二氧化碳产量工作的情况下,在所述壳管式热交换器(V3)中形成固态二氧化碳,并且在二氧化碳的产量减小的情况下,在所述壳管式热交换器中形成的固态二氧化碳的量增大。
7.根据任一项前述权利要求所述的方法,其中,将液态二氧化碳(15)作为最终产品从所述塔(K)提取。
8.根据任一项前述权利要求所述的方法,其中,使来自所述塔的底部的两股液态二氧化碳流(23,27)膨胀并输送到所述壳管式热交换器(V3)。
9.根据任一项前述权利要求所述的方法,其中,使来自所述壳管式热交换器(V3)的部分地凝结的给料分离,并且使所形成的液流(37)膨胀并输送到所述蒸馏塔(K)的顶部。
10.根据权利要求4所述的方法,其中,清洗所述液体在所述管外的部分以使所述液体的至少一种杂质被稀释。
11.根据权利要求10所述的方法,其中,所述至少一种杂质选自SOx、NOx、汞、烃、甲醇、乙醇、氨。
12.根据任一项前述权利要求所述的方法,其中,所述第一热交换器(E1)是板翅式热交换器。
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