CN105705217A - 通过吸附净化co2的装置和方法 - Google Patents

通过吸附净化co2的装置和方法 Download PDF

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CN105705217A
CN105705217A CN201480060593.9A CN201480060593A CN105705217A CN 105705217 A CN105705217 A CN 105705217A CN 201480060593 A CN201480060593 A CN 201480060593A CN 105705217 A CN105705217 A CN 105705217A
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gas
hydrogen
elimination
methane
carbon monoxide
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P·勒博
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LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
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Abstract

本发明涉及通过蒸馏产生的脱除二氧化碳的气体(24)，将其分离以产生脱除氢气的气体(22)，所述脱除氢气的气体用作在蒸馏上游的通过吸附进行的净化系统的再生气体，再生气体(16)在所述净化系统的入口处的组成不处于在空气中的可燃范围内。

Description

通过吸附净化CO2的装置和方法
本发明涉及CO2的净化装置和方法。
其特别涉及包含氢气和水以及任选一氧化碳和/或甲烷的富含CO2的气体混合物的净化装置。
在干燥的基础上，富含CO2的气体包含至少35摩尔％的二氧化碳，甚至至少65摩尔％的二氧化碳。
该气体混合物优选包含至少2000ppm氢气。其还可包含至少2000ppm一氧化碳和/或至少2000ppm甲烷。
本文中提到的所有纯度为摩尔纯度。
在一个实例中，CO2净化装置处理富含CO2的进料气，从中净化掉某些对食品用途不合意的成分并通过传热流体，通常氨的蒸发将其液化。
在进料气中存在的杂质中，一些成分比CO2更具挥发性并因此在最终蒸馏过程中在废气中除去。
这种废气通常用作位于最终蒸馏塔上游的通过吸附进行的净化系统(干燥器)的再生气体。
当这些挥发性成分主要是H2和CO(甚至CH4)时，已用于再生该净化系统的富集这些成分的再生气体在与空气接触时进入可燃范围。
在这种情况下，该废气不能再循环到进料气中，因为这种再循环不排出这些成分并因此累积可燃成分。
可能可以考虑排出这种废气，而不将其用于再生以避免与可燃气体的使用有关的风险和额外成本(ATEX分类)。然后使用来自液体输出物储罐并由在该液面上方天然形成的或如果没有的话，来自有意蒸发的液体的气体构成的纯CO2进行。
在这两种情况下，这种配置都损害该装置的净生产量，损害总量等于再生所需的流量，即大约5至6％。
US-A-4952223描述了在吸附单元上游和在蒸馏塔下游的分离装置以改变再生气体的组成。该进料流不含氢气，并且不排出再生流和/或不脱氢。
WO07/126972也描述了在吸附单元上游和在蒸馏塔下游的分离装置，其是相分离器，但表1中给出的组成值不符合附图，因为来自该相分离器的气体必须脱除CO2，而该表所示相反。此文献中的教导因此不清楚。
根据本发明的一个主题，提供由包含至少35摩尔％CO2、氢气和水以及至少一种，甚至两种下列杂质：一氧化碳和甲烷的富含CO2的气体为原料净化CO2的装置，其包含：
i)至少一个用于将所述富含CO2的气体压缩到第一压力P的压缩机，
ii)至少一个净化系统，其能运行在基本等于P的压力下的吸附阶段和在低于P的压力下的再生，以在源自所述至少一个压缩机的第一压力下净化所述气体以产生至少净化掉水的气体，
iii)用于经净化气体的塔系统，包含至少一个蒸馏塔，能在基本等于P的压力下运行，以产生富集CO2并脱除氢气和任选脱除一氧化碳和/或脱除甲烷的液体和富集氢气和任选富集一氧化碳和/或富集甲烷并脱除二氧化碳的气体，
iv)分离设备，
其特征在于所述装置包含用于将所述富集氢气和任选富集一氧化碳和/或富集甲烷并脱除二氧化碳的气体从所述塔系统传送到所述分离设备的第一管道和连接到所述分离设备上以送回脱除氢气和任选脱除一氧化碳和/或脱除甲烷的气体的第二管道，第二管道连向所述通过吸附进行的净化系统以向其传送仅由至少一部分所述脱除氢气和任选脱除一氧化碳和/或脱除甲烷的气体构成或由与另一气体混合的至少一部分所述脱除氢气和任选脱除一氧化碳和/或脱除甲烷的气体构成的再生气体，且所述净化系统包含用于排出已用于再生的再生气体的工具。
根据其它任选主题：
-该分离设备是渗透设备，
-由所述分离设备生成的脱除氢气并任选脱除CO的气体的组成不处于在空气中的可燃范围内，
-所述塔系统位于隔离室内且所述分离设备位于任何隔离室外，
-所述装置包含在所述分离设备上游的用于加热脱除二氧化碳的气体的工具，
-所述加热气体的工具能够实现所述气体和氨和/或在第一压力下的富含CO2的气体之间的热交换，
-所述装置包含用于检测送往所述分离设备的所述富集氢气和任选富集一氧化碳和/或富集甲烷并脱除二氧化碳的气体的内含物的工具，
-所述装置包含用于检测所述脱除氢气并任选脱除一氧化碳的气体的内含物的工具，
-将上述检测工具连向用于关闭所述脱除氢气并任选脱除一氧化碳的气体的管道的工具，
-将上述检测工具连向用于打开另一气体的管道的工具。
根据本发明的另一主题，提供由包含至少35摩尔％CO2、氢气和水和任选至少一种，甚至两种下列杂质：一氧化碳和甲烷的富含CO2的气体为原料净化CO2的方法，其包含至少下列阶段：
i)将所述富含CO2的气体压缩到第一压力P以产生富含CO2的压缩气体，
ii)在至少一个净化系统中通过在基本等于P的压力下的吸附和在低于P的压力下的再生净化所述富含CO2的压缩气体以产生净化掉水的富含CO2的气体，
iii)所述净化气体在包含至少一个蒸馏塔的塔系统中在基本等于P的压力下蒸馏以产生富集CO2并脱除氢气和/或脱除一氧化碳和/或脱除甲烷的液体和富集氢气和/或富集一氧化碳和/或富集甲烷并脱除二氧化碳的气体，
iv)在分离设备中的分离阶段，
其特征在于将所述脱除二氧化碳的气体从所述塔系统送往分离设备，所述分离设备产生脱除氢气和任选脱除一氧化碳和/或脱除甲烷的气体，将任选与另一气体混合的所述脱除氢气和任选脱除一氧化碳和/或脱除甲烷的气体送往所述通过吸附进行的净化系统以充当再生气体，并至少不时地排出已用于再生的再生气体。
根据本发明的其它任选方面：
-所述再生气体在所述净化系统的入口处的氢气含量低于对应于在空气中的可燃范围的阈值，
-可源于由所述塔系统产生的液体的二氧化碳气流用于构成所述再生气体的一部分，
-将所述二氧化碳流与所述分离设备产生的脱除氢气和任选脱除一氧化碳和/或脱除甲烷的气体混合以产生再生气体，
-检测下列气体的氢气和任选一氧化碳和/或甲烷的含量：
i)来自所述塔系统的富集氢气和任选富集一氧化碳和/或富集甲烷并脱除二氧化碳的气体或
ii)所述分离设备产生的脱除氢气和任选脱除一氧化碳和/或脱除甲烷的气体，
如果所述含量超过给定阈值，例如在空气中的可燃性极限，则不使用所述分离设备产生的脱除氢气和任选脱除一氧化碳和/或脱除甲烷的气体或将二氧化碳气体与所述分离设备产生的脱除氢气和任选脱除一氧化碳和/或脱除甲烷的气体混合以充当再生气体，
-送往所述分离设备的富集氢气和任选富集一氧化碳和/或富集甲烷并脱除二氧化碳的气体在空气中可燃，
-送往所述分离设备的富集氢气和任选富集一氧化碳和/或富集甲烷并脱除二氧化碳的气体包含至少5％的氢气，甚至至少10％的氢气，
-来自所述分离设备的脱除氢气和任选脱除一氧化碳和/或脱除甲烷的气体在空气中可燃，
-检测所述脱除氢气并任选脱除一氧化碳的气体的内含物，
-如果所述脱除氢气的气体的氢气含量在阈值以上，则关闭所述脱除氢气并任选脱除一氧化碳的气体的管道，
-如果所述脱除氢气的气体的氢气含量在阈值以上，则打开另一气体的管道。
参照附图更详细描述本发明。
包含至少35％CO2、水、10000ppmH2、2000ppmCO和2000ppmCH4的富含CO2的气体1必须分离以产生富集二氧化碳的液体。该气体在压缩机3中压缩到20巴(绝对)以产生压缩气体3。压缩气体3在通过吸附运行的净化装置5中在20巴(绝对)下净化。将净化掉水的气体6冷却(未显示)并送往包含至少一个蒸馏塔的塔系统7中蒸馏。该系统产生富集二氧化碳并脱除一氧化碳、脱除氢气和脱除甲烷、包含至少55％二氧化碳的液体8，将其储存在储罐11中并作为产品10送交客户。
所述塔系统7还产生富集氢气、一氧化碳和甲烷并脱除二氧化碳的气体24。气体24包含15％氢气、3％甲烷和3％一氧化碳。气体24包含至少5％氢气，优选至少10％氢气。
本发明的目标是以下列方式使与可燃化合物相关的损失最小化：
将CO2与H2、CO和甲烷分离的分离设备13，例如HF膜，分离废气24。在废气24的压力(大约20巴(绝对))与大气压之间的压力差的作用下，一部分可燃化合物发生渗透且该膜能够获得：
-脱除H2和CO的加压气流22，其已变得不可燃并因此适用于再生，
-富集H2和CO的低压气流14，其可燃并排出或烧掉。
剩余再生气体12取自产物储罐11。
分离设备13(其可以是渗透设备)可以在低温(在所述塔系统的出口)下处理废气24：效率低但该系统容易安装并使可燃气体的运输最小化。分离设备13和塔系统7优选在同一个隔离室内。实际上，塔系统7可位于隔离室内，而分离设备13位于任何隔离室外。
分离设备13(其可以是渗透设备)可以在借助传热流体(NH3、气体1或4等)再加热后在环境温度或更高温度下处理废气24。渗透效率良好。在40℃的渗透温度下，当气体1包含少于5％的氢气时，在产物中获得75％的CO2回收率。实际上，这假设了会带来花费的可燃气体24的运输。
可以测量气体6、24、22或16的一氧化碳和/或氢气和/或甲烷的含量并根据观察到的含量改变与气体22混合的二氧化碳12的量。该气体越富含一氧化碳和/或富含氢气和/或富含甲烷，越有必要将二氧化碳再添加到再生气体中以避免将爆炸性气体排放到大气中。
气体20,16充当净化设备5的再生气体并随后作为气体18排放到大气中。
在这一实例中，气体22不可燃。要认识到，重点在于气体16,20不可燃。因此气体22可以可燃并由于将其与气体12混合的事实而使其不可燃。
根据本发明的另一形式，检测下列气体的氢气和任选一氧化碳和/或甲烷的含量
i)来自所述塔系统的富集氢气和任选富集一氧化碳和/或富集甲烷并脱除二氧化碳的气体24或
ii)所述分离设备产生的脱除氢气和任选脱除一氧化碳和/或脱除甲烷的气体22。
如果气体22,24或这些气体之一的内含物超过在空气中的可燃性极限，则在一些情况下，分离设备产生的脱除氢气和任选脱除一氧化碳和/或脱除甲烷的气体不用作再生气体。
在这种情况下，根据含量，未与气体22混合的气体12可用作再生气体16。在另一些情况下，根据含量，将二氧化碳气体12与分离设备13产生的脱除氢气和/或脱除一氧化碳和/或脱除甲烷的气体22混合以充当再生气体16。
二氧化碳在这两种情况下都不必源自储罐11而是可源自外部来源。另一气体也可替代气体16。
该装置可包含至少一个用于检测气体22和/或24的内含物的工具，其连向用于关闭气体22的管道的工具和/或连向用于打开气体12的管道的工具。
实施例:
气体6(在该净化系统中干燥后的进料气)包含：98.5％CO2、1％(10000ppm)甲烷、0.2％(2000ppm)H2、0.2％(2000ppm)CO和0.1％惰性材料(N2+O2)
气体24包含78％CO2、15％H2、3％CO、3％CH4和1％惰性材料(N2+O2)
气体22包含93％CO2、5％H2和1.5％CH4。
在用纯CO212稀释后，气体20,16包含96.7％CO2、2.5％H2和0.8％CH4。

Claims (15)

1.由包含至少35摩尔％CO2、氢气和水以及至少一种，甚至两种下列杂质：一氧化碳和甲烷的富含CO2的气体为原料净化CO2的装置，其包含：
i)任选至少一个用于将所述富含CO2的气体(1)压缩到第一压力P的压缩机(3)，
ii)至少一个净化系统，其能运行在基本等于P的压力下的吸附阶段(5)和在低于P的压力下的再生，以在源自所述至少一个压缩机的第一压力(4)下净化所述气体以产生至少净化掉水的气体(6)，
iii)用于经净化气体的塔系统(7)，包含至少一个蒸馏塔，能在基本等于P的压力下运行，以产生富集CO2并脱除氢气和任选脱除一氧化碳和/或脱除甲烷的液体(8)和富集氢气和任选富集一氧化碳和/或富集甲烷并脱除二氧化碳的气体(24),
iv)分离设备(13)，
其特征在于所述装置包含用于将所述富集氢气和任选富集一氧化碳和/或富集甲烷并脱除二氧化碳的气体从所述塔系统传送到所述分离设备的第一管道和连接到所述分离设备上以送回脱除氢气和任选脱除一氧化碳和/或脱除甲烷的气体(22)的第二管道，第二管道连向所述通过吸附进行的净化系统以向其传送仅由至少一部分所述脱除氢气和任选脱除一氧化碳和/或脱除甲烷的气体(22)构成或由与另一气体(12)混合的至少一部分所述脱除氢气和任选脱除一氧化碳和/或脱除甲烷的气体构成的再生气体(16)，所述净化系统包含用于排出已用于再生的再生气体(18)的工具。
2.如权利要求1中所述的装置，其中所述分离设备是渗透设备(13)。
3.如权利要求1或2中所述的装置，其中由分离设备(13)生成的脱除氢气并任选脱除CO和/或脱除甲烷的气体(22)的组成不处于在空气中的可燃范围内。
4.如前述权利要求之一中所述的装置，其中塔系统(7)位于隔离室内且分离设备(13)位于任何隔离室外。
5.如前述权利要求之一中所述的装置，其包含在分离设备(13)上游的用于加热脱除二氧化碳的气体(24)的工具。
6.如权利要求5中所述的装置，其中用于加热气体(24)的工具能够实现所述气体和氨和/或在第一压力(4)下的富含CO2的气体之间的热交换。
7.由包含至少35摩尔％CO2、氢气和水和任选至少一种，甚至两种下列杂质：一氧化碳和甲烷的富含CO2的气体为原料净化CO2的方法，其包含至少下列阶段：
i)将所述富含CO2的气体(1)压缩到第一压力P以产生富含CO2的压缩气体(4)，
ii)在至少一个净化系统中通过在基本等于P的压力下的吸附(5)和在低于P的压力下的再生净化所述富含CO2的压缩气体以产生净化掉水的富含CO2的气体(6)，
iii)经净化气体在包含至少一个蒸馏塔的塔系统(7)中在基本等于P的压力下蒸馏以产生富集CO2并脱除氢气和/或脱除一氧化碳和/或脱除甲烷的液体(8)和富集氢气和/或富集一氧化碳和/或富集甲烷并脱除二氧化碳的气体，
iv)在分离设备(13)中的分离阶段，
其特征在于将所述脱除二氧化碳的气体(24)从所述塔系统送往分离设备，所述分离设备产生脱除氢气和任选脱除一氧化碳和/或脱除甲烷的气体(22)，将任选与另一气体(12)混合的所述脱除氢气和任选脱除一氧化碳和/或脱除甲烷的气体送往所述通过吸附进行的净化系统以充当再生气体，并至少不时地排出已用于再生的再生气体(18)。
8.如权利要求7中所述的方法，其中再生气体(16)在所述净化系统的入口处的氢气含量低于对应于在空气中的可燃范围的阈值。
9.如权利要求7或8中所述的方法，其中可源于由所述塔系统产生的液体(8)的二氧化碳气流(12)用于构成所述再生气体(16)的一部分。
10.如权利要求7、8和9中所述的方法，其中将所述二氧化碳流(12)与所述分离设备产生的脱除氢气和任选脱除一氧化碳和/或脱除甲烷的气体(22)混合以产生再生气体(16,20)。
11.如权利要求7、8、9或10中所述的方法，其中检测下列气体的氢气和任选一氧化碳和/或甲烷的含量：
i)来自所述塔系统的富集氢气和任选富集一氧化碳和/或富集甲烷并脱除二氧化碳的气体(24)或
ii)所述分离设备产生的脱除氢气和任选脱除一氧化碳和/或脱除甲烷的气体(22)，
如果所述含量超过对应于在空气中的可燃性极限的阈值，则不使用所述分离设备产生的脱除氢气和任选脱除一氧化碳和/或脱除甲烷的气体作为再生气体或将二氧化碳气体(12)与所述分离设备产生的脱除氢气和任选脱除一氧化碳和/或脱除甲烷的气体混合以充当再生气体。
12.如权利要求7至11之一中所述的方法，其中送往分离设备(13)的富集氢气和任选富集一氧化碳和/或富集甲烷并脱除二氧化碳的气体(24)包含至少5％的氢气，甚至至少10％的氢气。
13.如权利要求7至12之一中所述的方法，其中检测所述脱除氢气并任选脱除一氧化碳的气体的内含物。
14.如权利要求7至13之一中所述的方法，其中如果所述脱除氢气的气体的氢气含量在阈值以上，则关闭所述脱除氢气并任选脱除一氧化碳的气体(22)的管道。
15.如权利要求7至14之一中所述的方法，其中如果所述脱除氢气的气体(22)的氢气含量在阈值以上，则打开另一气体(12)的管道。
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