CN102245500B - 由重整气体生产氢并同时捕捉共产生的co2 - Google Patents

由重整气体生产氢并同时捕捉共产生的co2 Download PDF

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CN102245500B
CN102245500B CN200980149500.9A CN200980149500A CN102245500B CN 102245500 B CN102245500 B CN 102245500B CN 200980149500 A CN200980149500 A CN 200980149500A CN 102245500 B CN102245500 B CN 102245500B
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fraction
psa
rich
upstream
gaseous mixture
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CN102245500A (zh
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C·莫内罗
C·卡里尔
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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

使用CO2PSA单元、低温单元和H2PSA单元由包含氢、CO2、CO、CH4和水的气体混合物生产氢的方法，其中：a)将所述气体混合物引入CO2PSA单元，产生富CO2级分和贫CO2级分；b)将富CO2级分引入低温单元，产生富CO2级分和富H2级分；c)将该富H2级分再循环至H2PSA单元上游；和d)将来自步骤b)的贫CO2级分引入H2PSA单元，产生富氢料流和废气。

Description

由重整气体生产氢并同时捕捉共产生的CO2
本发明涉及一种生产氢并捕捉同时产生的CO2的方法。 
大多数氢由烃类，更特别是甲烷的蒸汽重整(SMR)供应。通常将该重整气体送至轮换反应器(水煤气轮换反应器)以生产更多氢。水煤气轮换反应是指一氧化碳与水反应并形成二氧化碳和水的反应。产生的气体通常具有以下特性： 
-压力为15-40巴(绝对)； 
-温度接近环境温度(冷却后)； 
-组成(以mol％计)：60-80％H2；15-25％CO2；0.5-5％CO；3-7％CH4；0-6％N2，用水饱和(saturated with)； 
-流动速度：几千至几十万Nm3/h。 
然后通常将该气体直接送至氢PSA(变压吸附)从而产生高纯度氢(99-99.9999mol％)。 
来自PSA的废弃物含有所有的CO2，极大部分的CH4和CO，大部分N2和取决于PSA单元产率的量的氢(75-90％，取决于所需效率)。 
将其中含有CO2的废弃物在蒸汽重整炉中燃烧。回收部分可利用热后，将来自该单元的废气排入大气中。 
然而，气候变化构成了最大的环境挑战之一。大气中二氧化碳浓度的增加是全球变暖的非常大的原因。就降低CO2排放而言，必须设计捕捉至少部分排放的CO2。 
已知在PSA上游通过洗涤，例如用胺洗涤而从该流体中取出CO2。 
该解决方法的缺点主要是捕捉问题的能量成本不合适。 
其他解决方法基于吸附。 
文献EP 0 341 879 B1处理来自H2PSA的废弃物从而经由PSA和制冷 而由此提取CO2。 
文献WO 2006/054008也经由PSA和低温单元处理来自H2PSA的废弃物。 
文献US 5 026 406描述了使用PSA生产两种高纯度级分。实施例2部分对应于这里提出的问题。获得了富CO2(99.7mol％)级分和含有约90mol％H2的级分。实际上，该级分必须在第二单元例如H2PSA类型的PSA中处理从而获得99％纯度的H2。必须使用真空泵和/或再循环以实现预期性能。 
文献US 2007/0227353也涉及相同的技术问题。推荐的解决方法也是使用PVSA，即具有真空步骤的吸附单元。已知尽管这类步骤就性能而言是有效的，但它们就资金投入(真空泵)而言和就能量而言是昂贵的。 
此外，文献FR 2 884 304描述了一种在10巴(绝对)的最大压力下操作并产生富CO2气体的吸附单元，将该气体送至低温单元，使该气体富集高达最小80mol％。在冷却之后或不在冷却之后，将来自吸附单元的贫CO2气体膨胀从而提供低温单元的制冷功率。在膨胀之后或不在膨胀之后，将来自低温单元的至少一部分贫CO2气体再循环至PSA。将来自低温单元的至少一部分贫CO2气体用作燃料。所述吸附单元可为VSA、VPSA或PSA。 
文献FR 2 884 304中设计的方法和/或工厂仅包括单吸附单元。 
该文献基本基于在10巴(绝对)下回收流体中的CO2，并不涉及连接的氢生产。特别是，它不涉及SMR输出气体。 
当需要在高压下由气体如合成气中提取CO2时，只要还需要优先回收最小吸附性成分之一的大部分，如FR 2 884 304所述使用PSA理论上并不有效适合。具体而言，由于CO2为易吸附组分，1巴级的中等分压足以得到常用的吸附剂如沸石或活性碳的准饱和(quasi-saturation)。因此使用高压与捕获CO2无关，但当需要在压力下保持组分如氢时，这是不利的。由于后提到组分的吸附非常弱，它最特别以气相存在于吸附器中，无论是在吸附剂的孔隙体积中，在晶粒间体积(intergranular volume)中，还是在进 出死体积(in-out dead volume)中。对于给定的体积，因此氢的损失与压力成比例。在这样的应用中，通常设计处理来自H2PSA的废弃物从而分离CO2，因为已知它是富CO2和贫氢的低压料流。WO 2006/054008和EP 0341879B1均基于这些考虑。 
为部分避免这些缺点而设计的一种解决方法是如提及的使用复杂的PSA循环，该循环利用真空提取CO2。在这些条件下，可有效使用吸附剂，然后使用内部再循环使得可以限制氢损失。就资金投入和能量消耗而言这是合算的。 
由该情况产生的一个问题是如何提供能经济生产氢并捕捉CO2且无氢可测知损失的方法。 
本发明的一个解决方法是使用CO2PSA单元30、低温单元40和H2PSA单元50由包含氢(H2)、二氧化碳(CO2)、一氧化碳(CO)、甲烷(CH4)和水(H2O)的气体混合物21生产氢的方法，其中： 
a)将所述气体混合物21引入CO2PSA单元30，产生富CO2级分32和贫CO2级分31； 
b)将该富CO2级分32引入低温单元40，产生富CO2级分41和富H2级分43； 
c)将该富H2级分43再循环至H2PSA单元50上游；和 
d)将贫CO2级分31引入该H2PSA单元50，产生富氢料流51和废气52。 
根据情况，本发明方法可具有一个或多个以下特征： 
-该富H2级分43代表含在富CO2级分32中的大于90％的量的氢； 
-在步骤a)和步骤b)之间将富CO2级分32压缩至气体混合物21压力以上的压力； 
-该CO2PSA 30包含至少一个具有至少一种吸附剂的吸附器且将所述吸附器进行压力循环，该循环包括用一部分压缩的富CO2级分32冲洗吸附剂的步骤； 
-在步骤a)和步骤b)之间，将该富CO2级分32使用干燥器35至少部分 干燥； 
-在步骤a)上游，使用干燥器25将该气体混合物21至少部分干燥； 
-在步骤a)上游，使用干燥器25将该气体混合物21至少部分干燥且在步骤c)中进行下列子步骤：将至少一部分富H2级分43在加热器44中加热；将级分43的所述加热部分用于再生干燥器35或干燥器25；和然后，在再生和分离冷凝水之后，将级分43的所述部分再循环至H2PSA单元50上游； 
-在步骤c)中，将至少一部分富H2级分43再循环至CO2PSA单元30上游； 
-将该废气52部分再循环至H2PSA 50上游； 
-使该H2PSA 50在等于或小于大气压力的压力下再生； 
-该气体混合物21为轮换重整气体； 
-该富CO2级分41包含大于90％CO2，优选大于97％CO2，甚至更优选大于99％CO2； 
-将该富CO2级分41在瓶或罐中封装或供入CO2线用于工业用途或地下储存，或以液体形式生产。 
本发明主题还为由包含氢H2、二氧化碳CO2、一氧化碳CO、甲烷CH4和水H2O的气体混合物21生产氢的装置，特征在于所述装置包括串联的CO2PSA 30和H2PSA 50，其中CO2PSA 30位于H2PSA 50上游并与低温单元40组合。 
根据情况，该装置可具有至少一个以下特征： 
-该CO2PSA 30至少包括5个吸附器，该吸附器至少包含硅胶作为吸附剂； 
-在CO2PSA 30的各吸附器中，该硅胶占总吸附剂体积的最少50％并且A型或X型沸石占总体积的最多25％； 
-该低温单元包括用于汽提至少一部分事先液化的CO2级分32从而可由其提取出溶于所述级分中的氢和通常不冷凝物的设备。 
现将借助图1和2描述本发明。 
图1显示的是对再循环由低温单元输出的料流具有各种选择的本发明装置。 
将天然气(或者更通常烃类)1和蒸汽2引入重整单元10。将包含氢(H2)、二氧化碳(CO2)、一氧化碳(CO)、甲烷(CH4)、可能的氩(Ar)和氮(N2)以及水(H2O)的重整气体在轮换反应器20中轮换，在其中至少部分一氧化碳与至少部分水反应并形成氢和二氧化碳。如此重整和轮换的气体对应于气体混合物21。 
将该气体混合物21供入CO2PSA 30中。流体32为来自CO2PSA 30的富CO2废弃物。该流体处于低压，即在3巴(绝对)以下，通常在大气压左右的压力下。由于将该流体压缩以供入低温单元40，它可稍微低于大气压(例如0.9巴(绝对))，而不背离本发明教导。 
该低温单元40一方面用于以其用途(分离、注入天然气井或油井、化学、食品加工等)所需的纯度传输CO2(41)，另一方面用于再循环43的含在料流32中的大部分氢(大于90％，优选大于95％，甚至更优选大于99％)。 
该低温单元40可产生富甲烷料流42，将该料流再循环至单元1或在别处使用。 
可将富H2级分43再循环至单元1的各位置： 
-经由通路44至重整单元上游；和/或 
-经由通路45至轮换上游；和/或 
-经由通路46至轮换下游和CO2PSA 30上游；和/或 
-经由通路47直接至CO2PSA 30；和/或 
-经由通路48至H2PSA上游；和/或 
-经由通路49直接至H2PSA 50。 
取决于氢规格，或者，如果就不纯氢而言还有要求，可将所有或部分富氢料流43在62用于另外的单元或在61与主要的氢产品51混合。可设计补充处理60，例如渗透或催化(甲烷化等)，从而根据要求调整该料流纯 度。 
可将料流46和/或48分别与主进料料流21和31混合，或构成第二进料。 
可在PSA内部使用料流47和/或49，例如将其完全或部分冲洗或加压。如果在吸附压力以下的压力下将该料流注入PSA而不是作为主进料或次级进料，则可***渗透单元从而使该料流部分富含氢。 
由CO2PSA 30产生的级分31是贫CO2的，并供入H2PSA 50。这产生富H2级分51(其为该单元的主要产品)，和包含非产生的氢级分，残留CO2以及含在至H2PSA 50的进料31中的大多数CH4、CO、N2和Ar的废弃物52。 
可将来自H2PSA的废弃物52完全再循环至重整装置10作为燃料和/或在压缩机70中压缩后，作为反应物71。还可将该废弃物的一部分再循环至H2PSA本身，或可将所有或部分该料流用于外部单元。这些方案不会以任何方式改变本发明精神并且没有显示在图1中。 
确实，通常而言，本发明方法使用与低温单元连接的用于通过PSA吸附而捕捉CO2的单元(也就是说不包括真空再生)，其使的可获得所需CO2纯度并将含在由CO2PSA 30输出的CO2级分32中的大部分氢再循环至重整气体线中。换句话说，将由CO2PSA提取的氢再注入从SMR进料至氢生产的高压循环，也就是说处于约15巴(绝对)至最大40巴(绝对)的压力下。因此与低温单元连接使得可以补偿PSA的中等性能(与采用真空再生的单元相比)，因为更彻底地提纯了CO2并改善了不冷凝物的再循环。术语“不冷凝物”应理解为指H2、N2、CH4、CO、Ar。对低温单元的改变，与常规CO2提纯和生产单元相比，如根据再循环调节的高操作压力，液体CO2的部分再沸以由其排出溶解的氢和液体CO2的部分膨胀以回收富含不冷凝物的蒸气级分等使得与选择真空作为再生吸附单元的推动力相比显著降低了成本。详细描述用于获得与CO2捕捉和不冷凝物(更特别是氢)的再循环有关的所需性能的、与PSA连接的低温单元不包括在所述发明上下文 中。应注意到该低温单元在氢生产以上的压力(实践中总是高于15巴(绝对))下进料并优选包括所谓的“汽提”设备，用于汽提含在CO2中的氢，更通常为不冷凝物：N2、CH4、CO和Ar，该设备包括降低压力和/或加热和/或将气体注入液化的CO2级分中。 
图2对应于本发明的优选装置。
将供入低温单元40的富CO2级分32通过压缩机34压缩至气体混合物21压力以上的压力从而能再循环富氢气体43，而不需要任何其他压缩手段。由于由CO2PSA输出的富CO2气体32含有水蒸气，将该流体在压缩和冷却之前或之后(或在离开中间压缩阶段时，冷却后)至少部分干燥。残留水含量将与低温单元的适当操作，所用材料的适当使用(腐蚀)和CO2的纯度规格相容。为了清楚起见，对于所述干燥35，在图2中仅显示在压缩机34之后的位置。所述干燥单元的再生可以流体32的干燥级分或外部流体，如氮，或来自H2PSA 50的废弃物进行，但优选用所有或部分富氢再循环级分43进行。为了再生干燥单元35(其优选为TSA(变温吸附)类型)，可将料流43在交换器44中循环加热(电加热、蒸气加热或由热流体回收热)并在交换器45中冷却并除去冷凝水。然后将该料流46再引入重整气体中。 
干燥器可为任何类型，但优选如上所示的TSA类型。吸附器可为具有垂直轴的圆柱类型，具有水平轴的圆柱类型或用于较大通量的径向类型。径向吸附器技术可用于在低温空气分离单元或O2 VSA单元之前的塔顶提纯。 
在34中压缩之前，还可将来自CO2PSA的废弃物32供入气量计33-或缓冲储存单元，然后在35中干燥。因此该储存具有两种效果，使废弃物的组成均匀或调节其流动速度。 
将轮换的重整气体21与由低温单元输出的富H2气体46混合，其包含含在富CO2级分(32)中的所有氢，CO2，取决于在低温单元中达到的热力学平衡，甲烷，一氧化碳以及可能的氮和氩。这些含量基本取决于CO2的所需纯度。 
由CO2PSA单元30输出的贫CO2级分31具有的残留CO2含量通常为0.5-7.5mol％，甚至更通常为1.5-3.5％。 
H2PSA 50提纯所述气体CO2、CH4、CO、N2等并产生纯氢51，即具有大于98％，通常99-99.9999％纯度的氢。 
通常将来自H2PSA的低压废弃物52用作燃料(SMR炉中)和/或压缩后用作SMR的原料。 
由于H2PSA的进料气体已排出CO2，它的氢含量可等于或超过85mol％。可因此经济上有利地压缩该废弃物的一部分以将其再循环至H2PSA，由此提高氢生产。 
该再循环原理描述于例如文献US 5,254,154和6,315,818中。 
如上所述，该再循环可与主进料(31)混合或可构成第二进料。 
应注意由于来自H2PSA的废弃物52为干燥的(水已在CO2PSA中除去)且贫CO2(由于相同的原因)，在压缩该废弃物中没有特别的问题。当然，在无CO2PSA存在下或料流同时含有水和CO2(腐蚀问题)的情况下不是这样。 
在将重整气体供入H2PSA之前，将CO2PSA用作干燥重整气体的方式是该方法相关的优点之一。由于来自H2PSA的废弃物52为干燥的，不仅可通过如上所述的再循环，而且还可通过降低该废弃物压力以降低成本改善所述PSA的性能。确实，在常规H2PSA的情况下，将来自PSA的废弃物送至SMR炉的燃烧器。管路和附件中的调节方式和压降意味着PSA循环的压力为约1350巴(绝对)的低压。此时该PSA性能对低再生压力非常敏感。因此做出了设计来平衡在通过使用风扇或罗茨类型的增压器(booster)至燃烧器的循环中的各种压降。CO2和水分的同时存在意味着维持或使用特定抗腐蚀材料平衡由于氢提取产率增加的收益。能使用普通碳钢的事实显著降低了该类机器的资金投入并可证明它们的使用是正确的。因此，H2PSA的再生压力可为大气压力，或甚至稍微小于该压力。 
低温单元为常规单元，其为如以工业或食品加工为目的的液体CO2生 产所用的部分冷凝的类型。第一实例由文献EP 0341 879 B1给出。更复杂的实例显示在文献FR 2 884 304的图6中。最后，文献WO 2006/054008描述了低温单元的变体。取决于所用压力和温度水平，该单元可包括用于提取溶于液体CO2中的氢从而使该损失可忽略的设备。该设备部分再沸液体CO2，此时该轻质组分优选呈气相。因此该低温单元特征在于它的操作压力等于或大于轮换气体的压力，即实际上总是高于15巴(绝对)，且循环的氢大于90％，优选大于95％，更优选还等于或大于99％，均基于含在来自CO2PSA的废弃物32中的氢。 
在将含有氢HP再循环43通过加热器44之后，将其用于再生干燥器35从而提供解吸水的能量。然后将该流体在45中冷却以除去冷凝水并注入主料流21中。当与低温单元组合时，CO2PSA 30可以以H2PSA类型的循环中操作。 
优选CO2PSA 30包括至少2个压力平衡阶段，更优选3个或4个压力平衡阶段，并能产生含有0.5-7.5％CO2，优选1.5-3.5mol％CO2，0.5-7％CO，3-10％CH4和0-10％N2的加压富氢气体。该气体基本干燥，即它平均含有小于1ppm水。 
在低压下产生的废气32富含CO2(80-95mol％)，其余由H2、CO、CH4和可能的氮构成。该气体还含有水蒸气。 
CO2的总提取度为约70-98％，优选约85-90％。 
取决于处理的通量，存在5-14个或更多个吸附器。取决于所用吸附器数，阶段时间(phase times)通常为20-120秒。应记得循环时间对应于使吸附器回到给定状态的所需时间T并且由于一个循环包括N个吸附器，阶段时间定义为等于T/N。 
对于给定的实例，描述了10-3-4循环(使用常规公认的术语)，其中一个PSA吸附循环采用10个相同吸附器，各自进行包含3个生产阶段和4个压力平衡阶段的循环。该循环可如下表所示： 
  A   A   A   A
  A   A   A   A
  A   A   A   A
  E1   I   E2   E2
  E3   E3   E4   E4
  PP   PP   PP   PP
  BD   BD   P   P
  P   P   E′4   E′4
  E′3   E′3   E′2   E′2
  E′1+R   R   R   R
该表意味着，给定的吸附器一方面将以时间顺序进行从最左上框向下至最右下框的所有步骤，另一方面，在给定的时刻，10个吸附器处于对应于塔的状态。行对应于如上所定义的阶段。可以看出每一阶段包含对应于控制和指挥***中的特定时间的几个步骤(从一个步骤移动到另一个对于PSA通常意味着至少一个阀移动)。更具体地，本文所述的10-3-4循环因此包含： 
-3个顺序的吸附阶段(A)； 
-顺序包含压力平衡步骤(E1)，死时间(I：例如分离的吸附器)和第二压力平衡步骤(E2)的阶段； 
-与第三和第四压力平衡步骤(E3和E4)相关的阶段； 
-冲洗提供阶段(PP)，即产生富氢级分和轻质组分(CO、CH4、N2)，其然后在低压下用作吸附器的洗脱气体； 
-包含最终逆流减压(放空)，降至低压，然后是冲洗步骤(P)的阶段； 
-包含冲洗结束(P)和经由第四压力平衡步骤(E′4)开始再加压的阶段； 
-具有第三(E′3)和第二(E′2)压力平衡步骤的阶段；和 
-包含第一压力平衡步骤(E′1)和最终再加压的第十阶段。 
应注意再加压缩废弃物32时，潜在地可添加高压或中压冲洗步骤以冲洗吸附剂。该步骤-通常称为漂洗，例如由Ruthven等描述于“变压吸附”， 1994，第69页，表3.1中的。 
该步骤似的吸附器能够被部分冲洗出含有的氢，能够得到更富含CO2的废弃物。将该步骤在再加压过程中和放空步骤之前加入循环。由此获得的性能改善将与CO2PSA的较大复杂性相对比。 
在CO2PSA 30中，必须使用兼顾吸附容量和容易解吸的吸附剂，因为不使用真空来结束解吸。更准确地，广泛推荐用于该应用的X型或A型沸石的使用必须被禁止或至少非常受到限制，优选作为位于CO2含量降低的点的吸附器出口处的最终层。优选地，该沸石A或X层占吸附剂总体积的小于25％。对该应用测试的最佳吸附剂之一为硅胶，例如由BASF以名称LE 32生产的产品。它尤其可与优选置于上游的活性氧化铝(吸附剂总体积的5-25％)，与活性碳(5-20％)组合使用。可使用对CO2具有有限亲和性的特定分子筛(NaY等)，以优化根据所用CO2提取目标的性能。最近合成的吸附剂如MOF(金属有机骨架)吸附剂也对应于选择标准。 
用于CO2PSA 30的吸附器的几何形状可具有各种类型。优选将具有垂直轴的圆柱吸附器用于小通量，即进料流动速度至多为数千或数万Nm3/h，而具有水平轴的圆柱吸附器或径向吸附器用于最大通量。径向吸附器技术可用于在低温空气分离单元或O2 VSA单元之前的塔顶提纯。 
H2PSA 50为具有根据进料组成而调整吸附剂分布的常规H2PSA。在组成变化的情况下它可包括特定预先安排的循环，例如由于停止使用CO2PSA。该另外循环的原理描述于文献US 7 255 727。至于理论上与CO2捕捉组合的大容量H2PSA，将使用包含几个吸附器、通常8个或更多个吸附器的循环。氢提取产率可为约90％，具有将废弃物送至燃烧器的增压器时为约92％，具有再循环时为约92-95％。 
图3所示的变体包括在轮换单元20之后和CO2PSA 30之前在单元25中干燥合成气。该安排避免了干燥器35。该单元25的优点为它允许标准材料在下游使用，特别是在CO2PSA和压缩机34(参见图2)中使用。 
该干燥器25还防止任何水/CO2干扰CO2PSA吸附剂，因此更容易捕 获CO2。然而，单元25必须处理整个合成气流。基础解决方法或所述变体的选择取决于操作条件，当地经济条件等。该选择构成本领域熟练技术人员所进行的优化工作的一部分。图3显示了这样的变体，其中干燥25为TSA类型，并且再生这样进行，即在压力下，使用在交换器44中循环加热(高至约100-250℃的温度)的料流43，然后，在解吸保留在25中的水之后，在交换器45中冷却，其中除去冷凝水。然后将所得料流46再注入干燥25的上游。 
应注意到通过将干燥器置于该位置(25)，显然可保留描述于上文中的在进行干燥的同时捕获CO2的优点。 

Claims (42)

1.一种使用CO2PSA单元(30)，低温单元(40)和H2PSA单元(50)的、由包含氢(H2)、二氧化碳(CO2)、一氧化碳(CO)、甲烷(CH4)和水(H2O)的气体混合物(21)生产氢的方法，其中：
a)将所述气体混合物(21)引入CO2PSA单元(30)，产生富CO2级分(32)和贫CO2级分(31)，其中CO2PSA单元(30)的操作不包括真空再生；
b)将所述富CO2级分(32)引入低温单元(40)，产生富CO2级分(41)和富H2级分(43)；
c)将所述富H2级分(43)再循环至H2PSA单元(50)上游；和
d)将所述贫CO2级分(31)引入所述H2PSA单元(50)，产生富氢料流(51)和废气(52)。
2.如权利要求1的方法，其特征在于所述富H2级分(43)占含在所述富CO2级分(32)中的氢的大于90％。
3.如权利要求1的方法，其特征在于在步骤a)和步骤b)之间，将所述富CO2级分(32)压缩至气体混合物(21)的压力以上的压力。
4.如权利要求2的方法，其特征在于在步骤a)和步骤b)之间，将所述富CO2级分(32)压缩至气体混合物(21)的压力以上的压力。
5.如权利要求3的方法，其特征在于所述CO2PSA(30)包含至少一个具有至少一种吸附剂的吸附器且将所述吸附器进行压力循环，所述循环包括用一部分压缩的富CO2级分(32)冲洗所述吸附剂的步骤。
6.如权利要求4的方法，其特征在于所述CO2PSA(30)包含至少一个具有至少一种吸附剂的吸附器且将所述吸附器进行压力循环，所述循环包括用一部分压缩的富CO2级分(32)冲洗所述吸附剂的步骤。
7.如权利要求1的方法，其特征在于在步骤a)和步骤b)之间，使用干燥器(35)将所述富CO2级分(32)至少部分干燥。
8.如权利要求2的方法，其特征在于在步骤a)和步骤b)之间，使用干燥器(35)将所述富CO2级分(32)至少部分干燥。
9.如权利要求3的方法，其特征在于在步骤a)和步骤b)之间，使用干燥器(35)将所述富CO2级分(32)至少部分干燥。
10.如权利要求5的方法，其特征在于在步骤a)和步骤b)之间，使用干燥器(35)将所述富CO2级分(32)至少部分干燥。
11.如权利要求1的方法，其特征在于在步骤a)上游，使用干燥器(25)将所述气体混合物21至少部分干燥。
12.如权利要求2的方法，其特征在于在步骤a)上游，使用干燥器(25)将所述气体混合物21至少部分干燥。
13.如权利要求3的方法，其特征在于在步骤a)上游，使用干燥器(25)将所述气体混合物21至少部分干燥。
14.如权利要求5的方法，其特征在于在步骤a)上游，使用干燥器(25)将所述气体混合物21至少部分干燥。
15.如权利要求7的方法，其特征在于在步骤a)上游，使用干燥器(25)将所述气体混合物21至少部分干燥且在步骤c)中进行下列子步骤：
-将至少一部分富H2级分(43)在加热器(44)中加热；
-将所述级分(43)的加热部分用于再生干燥器(35)或干燥器(25)；和然后
-将级分(43)的所述部分再循环至H2PSA单元(50)上游。
16.如权利要求8的方法，其特征在于在步骤a)上游，使用干燥器(25)将所述气体混合物21至少部分干燥且在步骤c)中进行下列子步骤：
-将至少一部分富H2级分(43)在加热器(44)中加热；
-将所述级分(43)的加热部分用于再生干燥器(35)或干燥器(25)；和然后
-将级分(43)的所述部分再循环至H2PSA单元(50)上游。
17.如权利要求9的方法，其特征在于在步骤a)上游，使用干燥器(25)将所述气体混合物21至少部分干燥且在步骤c)中进行下列子步骤：
-将至少一部分富H2级分(43)在加热器(44)中加热；
-将所述级分(43)的加热部分用于再生干燥器(35)或干燥器(25)；和然后
-将级分(43)的所述部分再循环至H2PSA单元(50)上游。
18.如权利要求10的方法，其特征在于在步骤a)上游，使用干燥器(25)将所述气体混合物21至少部分干燥且在步骤c)中进行下列子步骤：
-将至少一部分富H2级分(43)在加热器(44)中加热；
-将所述级分(43)的加热部分用于再生干燥器(35)或干燥器(25)；和然后
-将级分(43)的所述部分再循环至H2PSA单元(50)上游。
19.如权利要求1-18中任一项的方法，其特征在于在步骤c)中，将至少一部分富H2级分(43)再循环至CO2PSA单元(30)上游。
20.如权利要求1-18中任一项的方法，其特征在于将所述废气(52)部分再循环至H2PSA上游。
21.如权利要求19的方法，其特征在于将所述废气(52)部分再循环至H2PSA上游。
22.如权利要求1-18中任一项的方法，其特征在于使所述H2PSA(50)在等于或小于大气压的压力下再生。
23.如权利要求19的方法，其特征在于使所述H2PSA(50)在等于或小于大气压的压力下再生。
24.如权利要求20的方法，其特征在于使所述H2PSA(50)在等于或小于大气压的压力下再生。
25.如权利要求1-18中任一项的方法，其特征在于所述气体混合物(21)为轮换重整气体。
26.如权利要求19的方法，其特征在于所述气体混合物(21)为轮换重整气体。
27.如权利要求20的方法，其特征在于所述气体混合物(21)为轮换重整气体。
28.如权利要求22的方法，其特征在于所述气体混合物(21)为轮换重整气体。
29.如权利要求1-18中任一项的方法，其特征在于所述富CO2级分(41)包含大于90％CO2。
30.如权利要求29的方法，其特征在于所述富CO2级分(41)包含大于97％CO2。
31.如权利要求29的方法，其特征在于所述富CO2级分(41)包含大于99％CO2。
32.如权利要求19的方法，其特征在于所述富CO2级分(41)包含大于90％CO2。
33.如权利要求20的方法，其特征在于所述富CO2级分(41)包含大于90％CO2。
34.如权利要求22的方法，其特征在于所述富CO2级分(41)包含大于90％CO2。
35.如权利要求25的方法，其特征在于所述富CO2级分(41)包含大于90％CO2。
36.如权利要求29的方法，其特征在于所述富CO2级分(41)在瓶或移动式罐中封装或供入CO2线用于工业用途或地下储存，或以液体形式生产。
37.一种由包含氢(H2)、二氧化碳(CO2)、一氧化碳(CO)、甲烷(CH4)和水(H2O)的气体混合物(21)生产氢的装置，特征在于所述装置包括串联的CO2PSA(30)和H2PSA(50)，其中CO2PSA(30)位于H2PSA(50)上游并与低温单元(40)组合。
38.如权利要求37的装置，其特征在于所述CO2PSA(30)包含至少5个至少包含硅胶作为吸附剂的吸附器。
39.如权利要求38的装置，其特征在于在CO2PSA(30)的各吸附器中，所述硅胶占总吸附剂体积的至少50％并且A型或X型沸石占总体积的至多25％。
40.如权利要求37-39中任一项的装置，特征在于所述低温单元包括用于汽提至少一部分事先液化的CO2级分(32)、从而由其提取出溶于所述级分中的氢和不冷凝物的设备。
41.如权利要求37-39中任一项的装置，特征在于所述装置在CO2PSA(30)上游包括干燥器(25)。
42.如权利要求40的装置，特征在于所述装置在CO2PSA(30)上游包括干燥器(25)。
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