CN112638502A - 用于捕获二氧化碳的方法 - Google Patents
用于捕获二氧化碳的方法 Download PDFInfo
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- CN112638502A CN112638502A CN201980056501.2A CN201980056501A CN112638502A CN 112638502 A CN112638502 A CN 112638502A CN 201980056501 A CN201980056501 A CN 201980056501A CN 112638502 A CN112638502 A CN 112638502A
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- 238000000034 method Methods 0.000 title claims abstract description 40
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims description 237
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims description 158
- 239000001569 carbon dioxide Substances 0.000 title claims description 115
- 239000007787 solid Substances 0.000 claims abstract description 184
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- 238000003795 desorption Methods 0.000 claims abstract description 121
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- 238000004064 recycling Methods 0.000 claims abstract description 6
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 230000000779 depleting effect Effects 0.000 claims description 4
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- 238000001816 cooling Methods 0.000 description 13
- 230000005484 gravity Effects 0.000 description 9
- 239000003546 flue gas Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 6
- 230000009102 absorption Effects 0.000 description 5
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
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- FEBLZLNTKCEFIT-VSXGLTOVSA-N fluocinolone acetonide Chemical compound C1([C@@H](F)C2)=CC(=O)C=C[C@]1(C)[C@]1(F)[C@@H]2[C@@H]2C[C@H]3OC(C)(C)O[C@@]3(C(=O)CO)[C@@]2(C)C[C@@H]1O FEBLZLNTKCEFIT-VSXGLTOVSA-N 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
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- Treating Waste Gases (AREA)
Abstract
本发明提供了一种用于从气流中捕获CO2的方法,所述方法至少包含以下步骤:(a)提供含CO2的气流;(b)在吸附区中使步骤(a)中提供的所述气流与固体吸附剂颗粒接触,从而获得富CO2固体吸附剂颗粒(c)将步骤(b)中获得的富CO2固体吸附剂颗粒从所述吸附区的底部传递到第一解吸区的底部;(d)在所述第一解吸区中,从所述富CO2固体吸附剂颗粒中除去一部分所述CO2,从而获得部分贫CO2固体吸附剂颗粒和第一富CO2气流;(e)将步骤(d)中获得的所述部分贫CO2固体吸附剂颗粒经由立管传递到第二解吸区;(f)在所述第二解吸区中,从所述部分贫CO2固体吸附剂颗粒中除去另一部分所述CO2,从而获得再生的固体吸附剂颗粒和第二富CO2气流;和(g)将步骤(f)中获得的再生的固体吸附剂颗粒再循环到步骤(b)的所述吸附区;其中所述第二解吸区位于所述吸附区上方。
Description
本发明涉及一种使用固体吸附剂颗粒从气流中,具体地说从CO2含量相对低(小于25摩尔%CO2)的气流(如烟道气)中捕获二氧化碳(CO2)的方法。
使用固体吸附剂颗粒从气流中除去二氧化碳的方法是本领域已知的。
在WO2016074980中描述了在使用固体吸附剂颗粒的同时从气流中捕获CO2的方法的实例,其公开内容通过引用并入本文中。根据WO2016074980,可以通过使气流与可再生的固体吸附剂在逆流多级流化床中接触来从气流中除去二氧化碳。尽管WO2016074980已经公开了一种用于捕获CO2的简单、有效和节能的方法,但是人们一直希望改进该方法。
如WO2016074980中所述的方法的问题在于,为了使固体吸收剂颗粒循环,使用了相对大量的立管。这可能导致固体循环和分配停滞的风险增加,并导致固体运输气体需求增加。
如WO2016074980中所述的方法的另一个问题在于,其要求(参见WO2016074980的权利要求1的步骤(e))在解吸区和吸附区的每一个流化的固体吸附剂颗粒床中存在至少一个内部加热装置(如加热盘管)。
本发明的目的是解决、最小化或至少减少一个或多个以上问题。
本发明的另一个目的是提供一种使用固体吸附剂颗粒从气流中捕获CO2的替代方法,具体地说需要较少的内部加热装置(如加热盘管)。
根据本发明,可以通过提供一种从气流中捕获二氧化碳(CO2)的方法来实现以上或其它目的中的一个或多个,所述方法至少包含以下步骤:
(a)提供含CO2的气流;
(b)在吸附区中使步骤(a)中提供的气流与固体吸附剂颗粒接触,从而获得富CO2固体吸附剂颗粒,其中吸附区具有至少两个流化的固体吸附剂颗粒床,并且其中固体吸附剂颗粒从一个床向下流到另一个床,并且其中气流向上流动;
(c)将步骤(b)中获得的富CO2固体吸附剂颗粒从吸附区的底部传递到第一解吸区(或‘预再生器’)的底部;
(d)在第一解吸区中,从富CO2固体吸附剂颗粒中除去一部分CO2,从而获得部分贫CO2固体吸附剂颗粒和第一富CO2气流;
(e)将步骤(d)中获得的部分贫CO2固体吸附剂颗粒经由立管传递到第二解吸区(或‘再生器’);
(f)在第二解吸区中,从部分贫CO2固体吸附剂颗粒中除去另一部分CO2,从而获得再生的固体吸附剂颗粒和第二富CO2气流,其中第二解吸区具有至少两个流化的固体吸附剂颗粒床,并且其中固体吸附剂颗粒从一个床向下流到另一个床,并且汽提气向上流动;和
(g)将步骤(f)中获得的再生的固体吸附剂颗粒再循环到步骤(b)的吸附区;
其中第二解吸区(‘再生器’)位于吸附区上方。
根据本发明令人惊讶地发现,通过第二解吸区(‘再生器’)相对于吸附区的竖直堆叠,通过增加重力流的使用来改善固体吸附剂颗粒在吸附容器(的一个或多个吸附容器)上的循环和分布。由于在该方法中运输固体吸附剂颗粒所需的机械旋转装置和/或立管较少,这导致精细生产较少和固体吸附剂颗粒损失较少,并降低了固体运输气体的需求。
根据本发明的方法的另一个优点是,需要较少的内部加热和冷却装置(如加热或冷却盘管),具体地说在(一个或多个)(组合的第一和第二)解吸区和吸附区中。可以通过增加(一个或多个)解吸区中水的吸收(通过固体吸附剂颗粒)来减少在(一个或多个)解吸区中的加热盘管的需求。可以通过增加吸附区中水的释放来减少吸附区中冷却盘管的需求。可以通过控制(一个或多个)解吸区和吸附区中的相对湿度来控制水的释放和吸收。
由于本领域技术人员熟悉吸附区、解吸区、固体吸附剂颗粒(及其流化)、立管等,因此这里将不对这些术语进行详细讨论。有关固体流化的更多信息,请参考“流化工程(Fluidization Engineering)”,Butterworth-Heinemann Ltd,1991年10月(ISBN 0-409-90233-0)和“流化、固体处理和加工、工业应用(Fluidization,Solids Handling andProcessing,Industrial Applications)”,Wen-Ching Yang,1998(ISBN 978-0-8155-1427-5)。
在步骤(a)中,提供含CO2的气流。含CO2的气流只要含有CO2就没有任何限制(就组成、温度、压力等而言)。含CO2的气流可以有多种来源;仅作为实例,含CO2的气流可以是天然气、伴生气、合成气、源自煤气化的气体、焦炉气、炼厂气或烟道气。
通常,含CO2的气流包含0.1至70摩尔%的CO2,优选2.0至45摩尔%的CO2,更优选3.0至30摩尔%的CO2。假使该方法用于具有相对低的CO2含量的流(例如烟道气),则含CO2的气流优选包含至多25摩尔%的CO2。
优选地,步骤(a)中提供的含CO2的气流的氧(O2)浓度至多为15摩尔%(并且优选更低)。假使含CO2的气流是烟道气,然后将其通常含有在0.25至15摩尔%O2的范围内的O2。
通常,步骤(a)中提供的含CO2气流的温度在0至90℃、优选15至80℃的范围内,更优选低于35℃。此外,步骤(a)中提供的含CO2的气流的压力通常在0.5至5.0巴的范围内,优选高于1.0巴和优选低于3.0巴。如果合适,可以对流进行预处理以获得所需的组成和条件。
通常,步骤(a)中提供的含CO2气流的水含量为5至20摩尔%。优选地,如步骤(a)中提供的含CO2气流的水露点温度比吸附区底部的操作温度低至少20℃。
在步骤(b)中,在吸附区中使步骤(a)中提供的气流与固体吸附剂颗粒(逆流地)接触,从而获得富CO2固体吸附剂颗粒(和贫CO2气流),其中吸附区具有至少两个流化的固体吸附剂颗粒床,并且其中固体吸附剂颗粒从一个床向下流到另一个床,并且其中气流向上流动。
吸附区具有至少两个流化的固体吸附剂颗粒床。床排列在彼此上方。固体吸附剂颗粒从一个床层向下流到另一个床,而气流向上流动。吸附区优选包含在2至30、更优选3至15个范围内的流化的固体吸附剂颗粒床。固体吸附剂颗粒作为再生的固体吸附剂颗粒进入吸附区的顶部。如果需要,可以不时添加新鲜的固体吸附剂颗粒。
优选地,在吸附区中的流化的固体吸附剂颗粒床存在于筛板和/或喷嘴板上方。优选地,这些筛板和/或喷嘴板包含溢流堰。优选地,这些筛板和/或喷嘴板包含降液管。最优选地,筛板和/或喷嘴板包含降液管和溢流堰。
一旦固体吸附剂颗粒到达吸附区的底部,它们就会富含CO2。
进入吸附区(在其底部附近)的含CO2的气流的温度通常低于离开吸附区(在其顶部处)的贫CO2气流。优选地,进入吸附区的含CO2气流的温度在0至90℃的范围内,优选低于60℃,更优选低于55℃。优选地,吸附区顶部的温度为50℃至140℃,优选低于120℃,更优选低于80℃。通常,从吸附区的底部到顶部的温度梯度在3至30℃的范围内,优选高于5℃并且优选低于25℃。温度梯度允许增加吸附区顶部中的蒸发,同时在较低温度下在吸附区底部维持相对可忽略的水吸收能力。可以通过使待处理的进入气流的露点至少比吸附区底部的操作温度低20℃,进一步控制水的吸收和冷凝。另外,通过保持吸附区中的温度在顶部高于在底部,水往往会从固体吸附剂颗粒中蒸发,从而产生冷却效果(从而减少了对如吸附区中的冷却盘管的冷却装置的需要)。
气流中的水将开始从气相中凝结的气流温度是气流的露点。露点取决于压力。
吸附区中气流的压力在吸附区的底部高于在吸附区的顶部。优选地,步骤(b)在0.8至8巴,更优选0.8至4巴,甚至更优选0.8至1.5巴的范围内的压力下进行。
当气流作为贫CO2气流离开吸附区的顶部时,其压力可以等于或接近大气压。当气流进入吸附区时,压力可以高于大气压,例如1.05巴。吸附区(例如吸附塔)上的总压降可以相对小,例如其可以为50毫巴。
可以通过调节气流的湿度来调节进入步骤(a)中的吸附区的气流的露点。
根据本发明的特别优选的实施例,吸附区包含两个或更多个吸附容器,每个吸附容器含有至少两个流化的固体吸附剂颗粒床,并且每个吸附容器限定了用于一部分固体吸附剂颗粒和一部分气流的单独的流动路径。优选地,两个或更多个吸附容器并置(即,彼此相邻放置)。在该实施例中,步骤(a)中提供的气流在吸附区之前被分开,然后流过两个或更多个吸附容器并且在其进入第一解吸区之前合并或在第一解吸区中合并。其中吸附包含两个或更多个吸附容器的该实施例特别适合于大于35m3/s的气体流速的较大容量。
根据本发明使用的固体吸附剂颗粒没有特别限制。通常,这些颗粒完全由吸附剂材料制成或包含涂覆有吸附涂层的载体材料。而且,固体吸附剂颗粒可以具有各种形状。由于本领域技术人员熟悉这种固体吸附剂颗粒,因此这里不对这进行详细讨论。吸附剂材料已在以下中进行了描述,例如:“用于从大量人为点源捕获二氧化碳的吸附剂材料(Adsorbent material for carbon dioxide capture from large anthropogenic pointsources)”,Choi等人,2009(https://doi.org/10.1002/cssc.200900036);“固体吸附剂捕获CO2及其应用:现状和新趋势(CO2capture by solid adsorbents and theirapplications:current status and new trends)”,Wang等人,《能源与环境科学(Energy&Environmental Science)》,第1期,2011;和“通过CO2吸附处理烟道气(Flue gastreatment via CO2 adsorption)”,Sayari等人,《化学工程杂志(Chemical EngineeringJournal)》,第171卷,第3期,第760-774页,2011年7月15日。
通常,固体吸附剂颗粒的平均粒径(d50)在100至800微米、优选300至700微米的范围内,并且平均孔隙率在10%至70%、优选20%至50%的范围内。此外,优选的是,按固体吸附剂颗粒的干重计,固体吸附剂颗粒的氮含量为5至15重量%。
通常,固体吸附剂颗粒包含有机胺材料,如一种或多种伯胺化合物、仲胺化合物和/或叔胺化合物,优选伯胺化合物和仲胺化合物。已发现苄胺特别有用。
假使使用载体材料,则本领域技术人员将容易理解,可以使用多种载体材料,包括但不限于碳、二氧化硅、氧化铝、二氧化钛、氧化锆、氧化镁、交联聚合物(例如与二乙烯基苯交联的聚苯乙烯)等。
优选地,固体吸附剂颗粒确实包含用有机胺材料如上述胺化合物中的一种或多种官能化的多孔载体。
特别合适的吸附剂材料的实例是官能化到聚苯乙烯载体上的苄胺或浸渍有聚乙烯亚胺或接枝有氨基烷基烷氧基硅烷的二氧化硅。
在步骤(b)中,获得了富CO2固体吸附剂颗粒和贫CO2气流。以在步骤(b)中与固体吸附剂颗粒接触的气流中CO2的总量计算,优选除去大于70%,更优选大于80%,甚至更优选大于90%,还更优选大于95%的CO2。
在步骤(c)中,优选经由重力流将步骤(b)中获得的富CO2固体吸附剂颗粒从吸附区的底部传递到第一解吸区(‘预再生器’)的底部。如果需要的话,可以在进入第一解吸区之前,例如使用外部热交换器,加热富CO2固体吸附剂颗粒。
尽管第一解吸区不受特别限制,并且可以具有不同的形式,但是其通常具有容器或管道的形式,其直径比立管的直径宽。与第二解吸区不同的是,第一解吸区没有竖直地排列在彼此上方的床;而且,固体吸附剂颗粒沿与气体相同的方向,即并流地,行进。
在第一解吸区中,通过使用加压的汽提气,固体吸附剂颗粒从底部移动到顶部。汽提气通常包含至少40摩尔%的蒸汽,优选至少50摩尔%,更优选至少99摩尔%。
优选地,第一解吸区(‘预再生器’)位于吸附区下方。这是为了允许在吸附区和第一解吸区之间的重力流动。
此外,优选的是,将第一解吸区域的顶部附近的固体吸附剂颗粒加热。这可以例如通过热交换来实现。同样,优选的是,第一解吸区(‘预再生器’)含有内部加热装置(如加热盘管),优选在其顶部附近。这导致在第二解吸区中需要较少的加热。同样,由于优选将第一解吸区放置成低于第二解吸区,从而保持负载更靠近地面(与在重放高的第二解吸区施加相同的热量相比)。
在步骤(d)中,在第一解吸区中,从富CO2固体吸附剂颗粒中除去一部分CO2,从而获得部分贫CO2固体吸附剂颗粒和第一富CO2气流。
第一CO2富气流和部分贫CO2固体吸附剂颗粒在其顶部处离开解吸区,并且在步骤(e)中将通常共同行进通过立管,因为立管优选连接到第一解吸区的顶部。
通常,在步骤(d)中,基于进入第一解吸区的富CO2固体吸附剂颗粒计算,在第一解吸区中,从富CO2固体吸附剂颗粒中除去至少20%的CO2。
优选地,步骤(d)在100至140℃、优选110至130℃的范围内的温度下进行。此外,优选的是,步骤(d)在0.8至8巴、更优选0.8至4巴、甚至更优选0.8至1.5巴的压力下进行。
在步骤(e)中,使步骤(d)中获得的部分贫CO2固体吸附剂颗粒(以及通常还有第一富CO2气流)经由立管传递到第二解吸区(‘再生器’),通常到第二解吸区的顶部附近。
尽管立管没有特别限制,但通常为管道。假使第一解吸区具有管道的形式,则立管的直径通常小于第一解吸区。
通常,使用立管气体将部分贫CO2固体吸附剂颗粒向上移动通过立管。优选地,立管气体包含至少40摩尔%的CO2,优选至少60摩尔%的CO2。通常,立管气体至少部分包含在过程中的其它地方产生的再循环气流,优选实施例将在下面进一步描述。
在步骤(f)中,在第二解吸区中,从部分贫CO2固体吸附剂颗粒中除去另一部分CO2,从而获得再生的固体吸附剂颗粒和第二富CO2气流,其中第二解吸区具有至少两个流化的固体吸附剂颗粒床,并且其中固体吸附剂颗粒从一个床向下流到另一个床,并且汽提气向上流动。因此,类似于吸附区,气体和固体在第二解吸区中逆流流动。
通常,在步骤(f)中,基于进入第二解吸区的部分贫CO2固体吸附剂颗粒计算,在第二解吸区中从部分贫CO2固体吸附剂颗粒中除去至少70%的CO2。第二富CO2气流通常含有比第一富CO2气流少的CO2,因为蒸汽通常用作汽提气第二解吸区。
如上所述,第二解吸区具有至少两个流化的固体吸附剂颗粒床。床排列在彼此上方。固体吸附剂颗粒从一个床向下流到另一个床,而汽提气向上流动。
第二解吸区优选包含在3至10个、更优选4至8个范围内的流化的固体吸附剂颗粒床。
优选地,第二解吸区中的流化的固体吸附剂颗粒床存在于筛板和/或喷嘴板上方。优选地,这些筛板和/或喷嘴板包含溢流堰。优选地,这些筛板和/或喷嘴板包含降液管。最优选地,筛板和/或喷嘴板包含降液管和溢流堰。
通常,在第二解吸区中,使用汽提气。通常,汽提气包含至少50摩尔%的蒸汽,优选至少90摩尔%,更优选至少99摩尔%的蒸汽。
优选地,步骤(f)在100至140℃,优选110至130℃的范围内的温度下进行。此外,优选的是,步骤(f)在0.8至8巴,更优选0.8至4巴,甚至更优选0.8至1.5巴的压力下进行。
第二解吸区(‘再生器’)可以包括或可以不包含内部加热装置,如加热盘管。优选地,少于一半的床设置有加热盘管。然而,优选的是,第二解吸区在没有这类内部加热装置的情况下运行。
优选地,在进入第二解吸区之前,在步骤(e)中经由立管传递的部分贫CO2固体吸附剂颗粒在气/固分离器中分离,从而获得富固体流和富气体流,其中富固体流被传递到第二解吸区。合适的气/固分离器是旋风分离器。优选地,气/固分离器位于第二解吸区上方。
根据本发明的特别优选的实施例,在气/固分离器中获得的富气体流的至少一部分在步骤(e)的立管中用作立管气体。
作为如上所述在气/固分离器中分离步骤(e)中经由立管传递的部分贫CO2固体吸附剂颗粒的替代方案或除其以外,优选地,在第二解吸区的顶部中分离步骤(e)中经由立管传递并馈送到第二解吸区中的至少部分贫CO2固体吸附剂颗粒的至少一部分,从而获得富固体流和富气体流,其中富固体流在第二解吸区中传递,并且其中至少一部分富气体流在步骤(e)的立管中用作立管气体。
根据本发明的优选实施例,第二解吸区(‘再生器’)不含有内部加热装置(如加热盘管)。还如上所述,根据本发明,这可以通过在第一解吸区施加加热来实现。这导致在第二解吸区域中需要更少或不需要加热装置,如加热盘管(但当然可以通过使过程中其它地方的热流再循环来增加热量)。由于优选将第一解吸区放置成低于第二解吸区,从而保持加热盘管的负载更靠近地面(与在重放较高的第二解吸区施加相同的热量相比),这带来了结构优势。
在步骤(g)中,将步骤(f)中获得的再生的固体吸附剂颗粒再循环到步骤(b)的吸附区,通常至其顶部附近。由于第二解吸区(‘再生器’)位于吸附区上方,因此在步骤(g)中,经由重力流将再生的固体吸附剂颗粒再循环。
优选地,在进入吸附区之前,使步骤(f)中获得的再生的固体吸附剂颗粒冷却。这种冷却例如可以通过使用热交换器、喷湿器、干燥的惰性气体(如氮气)或干燥的大气中的一种或多种来实现。
按照根据本发明的特别优选的实施例,在再生的固体吸附剂颗粒进入吸附区之前,将水添加到在步骤(g)中再循环到步骤(b)的吸附区的再生的固体吸附剂颗粒中。
水的添加可以通过多种方式来实现,例如通过使用喷水器。水的添加导致在吸附区中固体吸附剂颗粒的水含量增加,这提供了在吸附区中更多的水蒸发和相关的冷却。这种冷却减少了对间接冷却装置如热交换器等的需求。优选地,进入吸附区的再生的固体吸附剂颗粒的水含量在4至16重量%的范围内。
在另一方面,本发明提供了一种适合于执行根据本发明的从气流中捕获二氧化碳(CO2)的方法的设备,所述设备至少包含:
-吸附区,用于使含CO2的气流与固体吸附剂颗粒接触,从而获得富CO2固体吸附剂颗粒,其中吸附区具有至少两个流化的固体吸附剂颗粒床,并且其中在使用期间,固体吸附剂颗粒可以从一个床向下流到另一个床,并且其中含CO2的气流可以向上流动;
-第一解吸区(‘预再生器’),用于接收在吸附区中获得的富CO2固体吸附剂颗粒,并且从富CO2固体吸附剂颗粒中除去一部分CO2,从而获得部分贫CO2固体吸附剂颗粒和第一富CO2气流;
-立管,用于将在所述第一解吸区中获得的部分贫CO2化固体吸附剂颗粒传递到第二解吸区(‘再生器’);
-第二解吸区,用于在第二解吸区中从部分贫CO2固体吸附剂颗粒中除去另一部分CO2,从而获得再生的固体吸附剂颗粒和第二富CO2气流,其中第二解吸区具有至少两个流化的固体吸附剂颗粒床,并且其中固体吸附剂颗粒可以从一个床向下流到另一个床,并且汽提气可以向上流动;和
-再循环管线,用于将在第二解吸区中获得的再生的固体吸附剂颗粒再循环到吸附区;
其中第二解吸区(‘再生器’)位于吸附区上方。
在下文中将通过以下非限制性附图进一步说明本发明。本文中示出:
图1示意性地示出了根据本发明的用于从气流中捕获CO2的方法的流程图。
为了该描述的目的,相同的附图标记指代相同或相似的组件。
图1的流程图大体上用附图标记1表示,示出了骤冷器2、吸附区3、第一解吸区4、立管5、第二解吸区6、塔顶冷凝器7和气/液分离器8。此外,图1示出了热交换循环9,其含有热交换器10(冷却器)和11(加热器)。
在使用期间,提供含CO2的烟道气流作为流F3。如图1的实施例所示,流F3在增压器中加压(作为流F1),并在骤冷器2的水淬中进行预处理(作为流F2)(用于水清除和温度调节)。在进入其底部附近的吸附区3之前,流F3可以分成数个流,这些流在两个或多个单独的吸附容器中平行处理,其中每个吸附容器限定用于一部分固体吸附剂颗粒和一部分气流流动路径。
尽管在(示意图)图1中没有明确反映,但第二解吸区6位于吸附区3上方,从而在第二吸附区6和吸附区3之间允许针对固体吸附剂颗粒的重力流。
使气流F3在吸附区3中与固体吸附剂颗粒接触,从而获得富CO2固体吸附剂颗粒和贫CO2流。贫CO2流作为流F4离开吸附区3,并且例如被输送到烟道气烟囱(假使进料流F1为烟道气)。
在图1的实施例中,吸附区3具有五个流化的固体吸附剂颗粒床。固体吸附剂颗粒从一个床向下流到另一个床,而气流向上流动,因此逆流。如图1的实施例所示,吸附区3中的每个床都设置有冷却装置(呈冷却盘管形式)。然而,并且作为根据本发明的优选的,在没有这种冷却盘管的情况下,吸附区3中的至少两个最低的床可以做,以节省CAPEX成本。
在吸附区3中获得的富CO2固体吸附剂颗粒经由重力流(在图1中未完全反映)作为流M10从吸附区3的底部传递到第一解吸区(‘预再生器’)4的底部,其中固体吸附剂颗粒被部分再生。在图1的实施例中,流M10在热交换器11中被加热并且作为流M12进入第一解吸区4。
在第一解吸区4(在图1的实施例中,位于吸附区3下方以允许针对M10和M12的重力流)中,从富CO2固体吸附剂颗粒中除去一部分CO2,从而获得部分贫CO2固体吸附剂颗粒(流M13)和第一富CO2气流(F13)。如图所示,第一解吸区4含有加热盘管,所述加热盘管使用加热流体(例如低压蒸汽)来加热固体吸附剂颗粒。
为了帮助以M12形式馈送的固体吸附剂颗粒流传递通过第一解吸区4(并随后通过立管5),将流F12(如下所逃论)用作立管气体。
部分贫CO2固体吸附剂颗粒M13和第一富CO2气流F13经由立管5一起传递到第二解吸区(‘再生器’)6。
如图1的实施例所示,将合并的流M13+F13馈送到第二解吸区6(在其顶部)中并在其顶部中分离,从而获得富固体流和富气体流。富固体流在第二解吸区6中从一个床向下(通过重力流)流到另一个床。富气体流作为流F7在其顶部附近离开第二解吸区6。在图1的实施例中,流F7是在向上传递通过第二解吸区6之后同时吸收一些CO2的(蒸汽)流F5和传递通过立管5并馈送到第二解吸区6的顶部中的气流F13的组合。
如图1的实施例所示,富气体流F7被分成两个流F14和F18。流F14在增压器中加压并馈送到第一解吸区4的底部以帮助固体吸附剂颗粒沿向上方向传递通过其并穿过通过立管5。
流F18被发送到塔顶冷凝器7并在气/液分离器8中分离。富CO2塔顶流F8可以被发送到压缩队列以用于随后的压缩和存储(未示出);冷凝物流F9可以被发送到例如废水处理厂。
如图1所示,在这个实施例中,第二解吸区6包含七个床,而仅在第二解吸区6的上部和七个床中的三个中(经由蒸汽加热的盘管)提供加热(即少于一半)。此外,经由流F5在第二解吸区6的底部附近添加蒸汽。在本发明的优选实施例中,第二解吸区6根本不含有任何加热盘管(或其它间接加热装置)。
在第二解吸区6中,从部分贫CO2固体吸附剂颗粒中除去另一部分CO2,从而获得再生的固体吸附剂颗粒和第二富CO2气流。第二富CO2气流(也含有蒸汽)向上移动通过第二解吸区6,并作为流F7离开第二解吸区6,而再生的固体吸附剂颗粒作为流M11(经由重力流)再循环到吸附区3。如图1的实施例所示,流M11中的再生的固体吸附剂颗粒在热交换器10中冷却,并作为流M14进入吸附区3的顶部。
实例
图1的流程图用于说明从气流中捕获CO2。下表1中提供了各种流线中的流体(即气体和液体)流的组成和条件,并且表2中列出了固体流的组成和条件。
作为固体吸附剂颗粒,使用球形的Lewatit VP OC 1065颗粒(弱碱阴离子交换树脂,可从郎盛(Lanxess)(德国科隆(Cologne,Germany))商购获得),其粒度为315至1250微米,平均总表面积50m2/g并且孔体积为0.3ml/g。
表1
流体流 | F1 | F2 | F3 | F4 | F5 | F6 | F7 | F8 | F9 |
相 | V | V | V | V | V | V | V | V | L |
温度[℃] | 92 | 100 | 30 | 57 | 120 | 119 | 118 | 30 | 30 |
压力[巴] | 1.00 | 1.07 | 1.07 | 1.00 | 1.70 | 1.00 | 1.00 | 1.00 | 1.00 |
CO<sub>2</sub>[kg/s] | 41.45 | 41.45 | 41.45 | 4.15 | - | 15.61 | 43.59 | 37.30 | - |
H<sub>2</sub>O[kg/s] | 35.53 | 35.53 | 16.22 | 23.52 | 23.42 | 8.84 | 18.85 | 0.67 | 15.44 |
N<sub>2</sub>[kg/s] | 466.01 | 466.01 | 466.01 | 466.01 | - | - | - | - | - |
O<sub>2</sub>[kg/s] | 86.13 | 86.13 | 86.13 | 86.13 | - | - | - | - | - |
Ar[kg/s] | 7.18 | 7.18 | 7.18 | 7.18 | - | - | - | - | - |
CO<sub>2</sub>[摩尔%] | 4.2 | 4.2 | 4.4 | 0.5 | - | 41.9 | 48.6 | 95.8 | - |
H<sub>2</sub>O[摩尔%] | 8.8 | 8.8 | 4.2 | 6.2 | 100 | 58.1 | 51.4 | 4.2 | 100 |
N<sub>2</sub>[摩尔%] | 74.2 | 74.2 | 77.9 | 79.6 | - | - | - | - | - |
O<sub>2</sub>[摩尔%] | 12.0 | 12.0 | 12.6 | 12.9 | - | - | - | - | - |
Ar[摩尔%] | 0.8 | 0.8 | 0.8 | 0.9 | - | - | - | - | - |
表1(续)
流体流 | F10 | F11 | F12 | F13 | F14 | F17 | F18 |
相 | L | L | V | V | V | L | V |
温度[℃] | 104 | 75 | 137 | 118 | 118 | 30 | 118 |
压力[巴] | 3 | 8 | 1.20 | 1.00 | 1.00 | 1.00 | 1.00 |
CO<sub>2</sub>[kg/s] | - | - | 6.29 | 27.98 | 6.29 | - | 37.30 |
H<sub>2</sub>O[kg/s] | 172.04 | 172.04 | 2.73 | 10.00 | 2.73 | 19.31 | 16.12 |
N<sub>2</sub>[kg/s] | - | - | - | - | - | - | - |
O<sub>2</sub>[kg/s] | - | - | - | - | - | - | - |
Ar[kg/s] | - | - | - | - | - | - | - |
CO<sub>2</sub>[摩尔%] | - | - | 48.6 | 53.4 | 48.6 | - | 48.6 |
H<sub>2</sub>O[摩尔%] | 100 | 100 | 51.4 | 46.6 | 51.4 | 100 | 51.4 |
N<sub>2</sub>[摩尔%] | - | - | - | - | - | - | - |
O<sub>2</sub>[摩尔%] | - | - | - | - | - | - | - |
Ar[摩尔%] | - | - | - | - | - | - | - |
表2
固体流 | M10 | M11 | M12 | M13 | M14 |
温度[℃] | 50 | 120 | 88 | 118 | 100 |
从表1可以看出,根据本发明的方法允许了一种从含CO2的流中捕获二氧化碳的有效方法:通过传递通过吸附区3,使含CO2的烟气流F3(4.4摩尔%CO2)在作为流F4(0.5摩尔%CO2)离开吸附区后,使CO2含量降低了90%。
此外,离开气/液分离器8的含CO2的气流F8具有高纯度(并且除CO2以外主要包含水分)。该流F8适合在标准压缩机中压缩,并且适合用于各种工业过程中以生产各种产品、用于CO2储存、在温室中加速植物生长等。
而且,根据本发明的方法适合于含有低或高CO2浓度的大规模气流(以作为气流F3馈送到吸附区)。
本领域技术人员将容易理解,在不脱离本发明的范围的情况下可以进行许多修改。此外,本领域技术人员将容易理解,虽然在一些情况下已经参考特征和量度的特定组合来说明本发明,但是这些特征和量度中的许多在功能上独立于在各个实施例中给出的其它特征和量度,使得可以将它们等同地或类似地独立地应用在其它实施例中。
Claims (10)
1.一种用于从气流中捕获二氧化碳(CO2)的方法,所述方法至少包含以下步骤:
(a)提供含CO2的气流;
(b)在吸附区中使步骤(a)中提供的所述气流与固体吸附剂颗粒接触,从而获得富CO2固体吸附剂颗粒,其中所述吸附区具有至少两个流化的固体吸附剂颗粒床,并且其中所述固体吸附剂颗粒从一个床向下流到另一个床,并且其中所述气流向上流动;
(c)将步骤(b)中获得的富CO2固体吸附剂颗粒从所述吸附区的底部传递到第一解吸区的底部;
(d)在所述第一解吸区中,从所述富CO2固体吸附剂颗粒中除去一部分所述CO2,从而获得部分贫CO2固体吸附剂颗粒和第一富CO2气流;
(e)将步骤(d)中获得的部分贫CO2固体吸附剂颗粒经由立管传递到第二解吸区;
(f)在所述第二解吸区中,从所述部分贫CO2固体吸附剂颗粒中除去另一部分所述CO2,从而获得再生的固体吸附剂颗粒和第二富CO2气流,其中所述第二解吸区具有至少两个流化的固体吸附剂颗粒床,并且其中所述固体吸附剂颗粒从一个床向下流到另一个床,并且汽提气向上流动;和
(g)将步骤(f)中获得的再生的固体吸附剂颗粒再循环到步骤(b)的所述吸附区;
其中所述第二解吸区位于所述吸附区上方。
2.根据权利要求1所述的方法,其中所述吸附区包含两个或更多个吸附容器,每个吸附容器含有至少两个流化的固体吸附剂颗粒床,并且每个吸附容器限定用于一部分所述固体吸附剂颗粒和一部分所述气流的单独的流动路径。
3.根据权利要求1或2所述的方法,其中所述第一解吸区位于所述吸附区下方。
4.根据权利要求1至3中任一项所述的方法,其中加热在所述第一解吸区的顶部附近的所述固体吸附剂颗粒。
5.根据权利要求1至4中任一项所述的方法,其中所述第一解吸区含有内部加热装置,
并且其中优选地,所述第二解吸区不含有内部加热装置。
6.根据权利要求1至5中任一项所述的方法,其中在进入所述第二解吸区之前,在气/固分离器中分离在步骤(e)中经由立管传递的所述部分贫CO2固体吸附剂颗粒,从而获得富固体流和富气体流,其中将所述富固体流传递到所述第二解吸区,
并且其中优选地,将在所述气/固分离器中获得的所述富气体流的至少一部分用作步骤(e)的所述立管中的立管气体。
7.根据权利要求1至5中任一项所述的方法,其中在所述第二解吸区的顶部中分离在步骤(e)中经由所述立管传递并馈送到所述第二解吸区中的所述部分贫CO2固体吸附剂颗粒的至少一部分,从而获得富固体流和富气体流,其中所述富固体流在所述第二解吸区中传递,并且其中所述富气体流的至少一部分用作步骤(e)的所述立管中的立管气体。
8.根据权利要求1至7中任一项所述的方法,其中在进入所述吸附区之前,使在步骤(f)中获得的所述再生的固体吸附剂颗粒冷却。
9.根据权利要求1至8中任一项所述的方法,其中在所述再生的固体吸附剂颗粒进入所述吸附区之前,将水添加到在步骤(g)中再循环到步骤(b)的所述吸附区的所述再生的固体吸附剂颗粒中。
10.一种适合于执行根据前述权利要求1至9中任一项所述的从气流中捕获二氧化碳(CO2)的方法的设备,所述设备至少包含:
-吸附区,用于使含CO2的气流与固体吸附剂颗粒接触,从而获得富CO2固体吸附剂颗粒,其中所述吸附区具有至少两个流化的固体吸附剂颗粒床,并且其中在使用期间,所述固体吸附剂颗粒能够从一个床向下流到另一个床,并且其中所述含CO2的气流能够向上流动;
-第一解吸区,用于接收在所述吸附区中获得的所述富CO2固体吸附剂颗粒并且从所述富CO2固体吸附剂颗粒中除去一部分所述CO2,从而获得部分贫CO2固体吸附剂颗粒和第一富CO2气流;
-立管,用于将在所述第一解吸区中获得的所述部分贫CO2固体吸附剂颗粒传递到第二解吸区;
-所述第二解吸区,用于在所述第二解吸区中从所述部分贫CO2固体吸附剂颗粒中除去另一部分所述CO2,从而获得再生的固体吸附剂颗粒和第二富CO2气流,其中所述第二解吸区具有至少两个流化的固体吸附剂颗粒床,并且其中所述固体吸附剂颗粒能够从一个床向下流到另一个床,并且汽提气能够向上流动;和
-再循环管线,用于将在所述第二解吸区中获得的再生的固体吸附剂颗粒再循环到所述吸附区;
其中所述第二解吸区位于所述吸附区上方。
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