CN115289782A - 用于在低温下分离氢气和一氧化碳的混合物的方法和装置 - Google Patents

用于在低温下分离氢气和一氧化碳的混合物的方法和装置 Download PDF

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CN115289782A
CN115289782A CN202210469207.8A CN202210469207A CN115289782A CN 115289782 A CN115289782 A CN 115289782A CN 202210469207 A CN202210469207 A CN 202210469207A CN 115289782 A CN115289782 A CN 115289782A
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heat exchanger
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B·德蒙莱恩斯
A·埃尔南德斯
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LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
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Abstract

本发明涉及用于分离含有氢气和一氧化碳的混合物(1)以获得气态氢气的方法，其中将所述混合物在换热器(E1)中冷却到低于‑180℃的温度，然后通过部分冷凝和/或蒸馏和/或涤气的至少一个阶段在低于‑100℃的温度下分离以得到富含氢气的气体(7)和富含一氧化碳的流体(17)；将至少一部分的所述富含氢气的气体送到在高于0℃的温度下操作的变压吸附分离装置(PSA)以得到处于至少20巴压力的富含氢气的气体(13)，并将此气体的至少一部分(13A,13)在换热器中冷却到低于‑100℃的温度，在汽轮机(T)中将其压力降低到至少8巴，并在换热器中再加热以形成处于至少8巴的富含氢气的产物(15,15A)。

Description

用于在低温下分离氢气和一氧化碳的混合物的方法和装置
技术领域
本发明涉及用于在低温下分离氢气和一氧化碳的混合物的方法和装置。具体而言，本发明涉及在低于-100℃的温度下通过蒸馏和/或涤气和/或部分冷凝进行分离。
背景技术
待分离的混合物优选含有至少10摩尔％的氢气，甚至含有至少30摩尔％的氢气。
混合物可以是合成气，且可以除了氢气和一氧化碳之外还含有至少一种以下组分：二氧化碳、氮气、甲烷或水。
混合物可以含有至少一种以下组分作为额外杂质：硫化物，氰化物，氨，或比甲烷更重的至少一种烃。
部分冷凝工艺和涤气工艺是在高压下特别有效的；所以如果要在高压力下分离混合物，则有利地通过在高压下的部分冷凝或涤气进行分离，且不需要降低混合物的压力。这可以获得处于比混合物压力略低的压力下的氢气。
例如，在煤粉气化器的情况下，获得处于60巴压力的氢气和一氧化碳的混合物，从而可以在约56巴下通过部分冷凝和/或涤气获得氢气。
从DE4210638和FR 3 021 044已经知晓通过在变压吸附装置PSA中在低温下分离所制得的氢气。
考虑这样的情况：其中在管道中需要处于28巴压力的氢气，而用户需要处于8巴压力的氢气。在这种情况下将在最高压力下制备氢气以避免使用两个PSA装置。
变压吸附装置PSA优选在约30巴下操作，这出于两个原因：
-30巴的压力代表用于此技术的最佳值：如果在更高的压力下操作，则氢气产率将降低；而如果在更低的压力下操作，将无法达到产物的压力。
-PSA的阀门必须在约35巴的压力下操作以使阀门保持在最大300psi的范围内，更高的压力则需要更昂贵的阀门。
变压吸附装置(PSA)是按照用于分离气体混合物的工艺操作，在此期间使用固体或液体在给定压力下吸附气体，然后在更低的压力下解吸，这两者交替进行。
此操作包括利用化学亲合性以及针对固体材料的特定特性而从气体混合物取出气体，其中吸附剂暴露于严格受控的压力波动下。通过不同的平衡能力(平衡吸附剂)或通过吸附速率的差异(动态吸附剂)来进行选择性吸附。
如果在56巴下获得氢气，则除了将所需产物的压力降低到8巴之外，还需要在吸附操作的下游降低氢气压力。
发明内容
本发明的目的是将变压吸附装置与低温分离装置一体化，由此使用降低压力的氢气以向冷温分离操作提供冷却作用。
US 3 691 779描述了用于通过部分冷凝进行分离的装置和在-195℃至-162℃下操作的吸附装置的一体化。由吸附得到的一部分氢气通过在汽轮机中使压力降低到2.4巴，用于向分离装置提供冷却作用，并随后用于再生所述吸附装置。
根据本发明的一个主题，提供用于分离含有氢气和一氧化碳的混合物以获得气态氢气的方法，其中：
i)将所述混合物在换热器中冷却到低于-180℃的温度，然后通过部分冷凝和/或蒸馏和/或涤气的至少一个阶段在低于-100℃的温度下进行分离，由此得到富含氢气的气体和富含一氧化碳的流体，
ii)将至少一部分的所述富含氢气的气体送到在高于0℃的温度下操作的变压吸附分离装置，由此得到处于至少20巴压力的富含氢气的气体，和
iii)将至少一部分的所述富含氢气的气体在换热器中冷却到低于-100℃的温度，在汽轮机中将压力降低到至少8巴的压力，并在换热器中再加热以形成处于至少8巴压力的富含氢气的产物。
根据其它可选的方面：
-将至少一部分的所述富含氢气的气体在位于吸附分离装置上游的换热器中进行再加热；
-所述阶段ii)的富含氢气的气体是处于至少51巴的压力；通过吸附分离装置在至少50巴的压力下获得富含氢气的气体，并且通过汽轮机将其压力降低到至少20巴的压力；
-将压力已降低到至少20巴的所述富含氢气的气体分成两部分，其中将仅仅一部分的此气体在换热器中再加热操作的下游降低到至多12巴的压力；
-所述阶段ii)的富含氢气的气体是处于28-32巴的压力；通过吸附分离装置在27-31巴的压力下获得富含氢气的气体，并且通过汽轮机将其压力至少部分地降低到至多12巴的压力；
-所述压力已降低到至多12巴的气体构成此工艺的富含氢气的产物；
-在换热器中冷却的混合物(1)是处于至少50巴的压力；
-将混合物在第一个部分冷凝阶段中分离，将来自第一个部分冷凝阶段的气体进行冷却并送到第二个部分冷凝阶段，并将已在汽轮机中降低压力的富含氢气的气体通过与来自第一个部分冷凝阶段的已冷却的气体进行热交换而再加热；
-在第二个部分冷凝阶段的入口处的温度比-200℃更低，甚至比-203℃更低；
-来自外部来源的富含氢气的料流也在变压吸附分离装置中进行分离，这任选地使得在汽轮机中降低压力的气体的量大于在低于-100℃的温度下分离的富含氢气的气体的量；
-在汽轮机出口处的气体的温度比-200℃更低，甚至比-203℃更低；
根据本发明的一个主题，提供一种用于分离含有氢气和一氧化碳的混合物以获得气态氢气的装置，其包括：分离单元，在这里进行部分冷凝和/或蒸馏和/或涤气的至少一个阶段；换热器；变压吸附分离装置(PSA)；汽轮机；用于将所述混合物送到换热器的装置，其中在换热器中将所述混合物冷却到低于-180℃的温度；用于将已冷却的混合物送到分离单元的装置，其中在分离单元中通过部分冷凝和/或蒸馏和/或涤气的至少一个阶段在低于-100℃的温度下进行分离，由此得到富含氢气的气体和富含一氧化碳的流体；用于将至少一部分的所述富含氢气的气体送到变压吸附分离装置的装置，所述变压吸附分离装置在高于0℃的温度下操作以得到处于至少20巴压力的富含氢气的气体；用于将至少一部分的所述富含氢气的气体送到换热器的装置，此部分的气体在换热器中被冷却到低于-100℃的温度，随后在汽轮机中将其压力降低到至少8巴的压力；以及用于将已降低压力的气体送到换热器中进行再加热操作的装置，其中所述再加热操作获得处于至少8巴压力的富含氢气的产物。
附图说明
下面参考两个附图更详细地描述本发明。
[图1]显示根据本发明的方法。
[图2]显示根据本发明的方法。
具体实施方式
[图1]显示这样的方法：变压吸附装置PSA接收处于约55巴压力的富含氢气的料流11。经过吸附提纯的氢气13是处于约54巴的，并可以降低其压力以向低温分离工艺提供冷却作用。将此氢气送回初始的隔绝室，并在这里降低氢气的压力以帮助产生冷却作用和降低能耗。假定气体是非常纯的氢气，则可以降低其压力以达到非常低的温度，例如-204℃。这使得可以在该室中在较低温度下分离氢气，并改善一氧化碳和任选甲烷的产率。
所述室包含换热器E1,E2和相分离器S1,S2。
处于56巴压力的合成气1的料流含有一氧化碳和氢气，优选含有至少10摩尔％的氢气，甚至至少30摩尔％的氢气。
除了氢气和一氧化碳之外，混合物1还可以含有至少一种以下组分：二氧化碳、氮气、甲烷或水。
混合物可以含有至少一种以下组分作为额外杂质：硫化物，氰化物，氨，或比甲烷更重的至少一种烃。
在低温处理之前必须除去水和二氧化碳。
料流1在换热器E1中进行冷却，并在这里部分地冷凝，然后在-180℃下送到相分离器S1。可以将所得的液体5送到低温处理操作，例如通过蒸馏和/或涤气和/或部分冷凝在低于-100℃的温度下进行处理。低温处理可以尤其包括甲烷的涤气、一氧化碳的涤气或蒸馏，从而分离一氧化碳和甲烷，如果料流1包含它们的话。
来自分离器S1的气体3在换热器E2中进行冷却，从而将其在更低的温度下部分冷凝，并送到相分离器S2。可以将所得的液体17送到低温处理操作，例如通过蒸馏和/或涤气和/或部分冷凝在低于-100℃的温度下进行处理。低温处理可以尤其包括甲烷的涤气、一氧化碳的涤气或蒸馏，从而分离一氧化碳和甲烷，如果若料流1包含它们的话。
来自分离器S2的气体7富含氢气，气体7在换热器E2,E1中进行再加热，任选地在低于0℃的温度下与来自转换单元的富含氢气的气体料流9混合。
将处于55巴的气体7加入变压吸附分离单元，在这里分离得到处于54巴的富含氢气的气体13。使气体13返回包含换热器E1,E2和分离器S1,S2的室，且不需要提纯除去二氧化碳和水。
气体13在换热器E1中进行冷却，然后在汽轮机T中降低压力，由此降低到-204℃的温度以实现冷却。已降低压力的料流15处于29巴的压力，在换热器E2,E1中进行再加热，随后用作产物。可以在阀门中将产物的一部分15A的压力降低到至多12巴，例如至多8巴，从而形成低压产物。
如果提供来自另一个来源的氢气料流9，则料流13,15的量可以比料流7更大。如果料流9含有水和/或二氧化碳，则必须将它们在低温冷却操作的上游从料流13除去。
除了在阀门中的焦耳-汤姆孙(Joule-Thomson)降低压力效应之外，在汽轮机T中降低压力的操作是唯一向低温分离工艺提供冷却作用的贡献。
[图2]显示这样的方法：变压吸附装置PSA接收处于比[图1]更低压力的料流11，这是因为已经在吸附装置的上游将料流7的压力降低到28-32巴，在这种情况下是29巴，以使料流7可以在接近最佳压力的压力下操作。吸附装置获得处于27-31巴的富含氢气的气体，在这种情况下是28巴。产物的一部分13B处于28巴的压力，其被直接输送给用户；其余部分13A在换热器E1中进行冷却，然后在汽轮机T中将其压力从28巴降低到8巴，由此降低到-204℃的温度以实现冷却。已降低压力的料流15处于8巴的压力，该料流在换热器E2,E1中进行再加热，随后用作产物。
所以，本发明方法获得处于两个压力的两个氢气料流，其中一个料流处于用于吸附的最佳压力，另一个料流处于比最佳压力更低的压力。这两个压力之差对应于在汽轮机T中的压力降低。
此方法的其余部分参见上文关于[图1]在56巴下处理合成气1的操作的描述。

Claims (12)

1.一种用于分离含有氢气和一氧化碳的混合物(1)以获得气态氢气的方法，其中：
i)将所述混合物在换热器(E1)中冷却到低于-180℃的温度，然后通过部分冷凝和/或蒸馏和/或涤气的至少一个阶段在低于-100℃的温度下进行分离，由此得到富含氢气的气体(7)和富含一氧化碳的流体(17)，
ii)将至少一部分的所述富含氢气的气体送到在高于0℃的温度下操作的变压吸附分离装置(PSA)，由此得到处于至少20巴压力的富含氢气的气体(13)，和
iii)将所述富含氢气的气体的至少一部分(13A,13)在换热器中冷却到低于-100℃的温度，在汽轮机(T)中将其压力降低到至少8巴的压力，并在换热器中进行再加热以形成处于至少8巴压力的富含氢气的产物(15,15A)。
2.根据权利要求1所述的方法，其中将至少一部分的所述富含氢气的气体(7)在位于吸附分离装置(PSA)上游的换热器(E1)中进行再加热。
3.根据权利要求1或2所述的方法，其中所述阶段ii)的富含氢气的气体(7)是处于至少51巴的压力；通过吸附分离装置(PSA)在至少50巴的压力下获得富含氢气的气体(13)，并且通过汽轮机将其压力降低到至少20巴的压力。
4.根据权利要求3所述的方法，其中将压力已降低到至少20巴的富含氢气的气体分成两部分，其中将仅仅一部分此气体(13A)在换热器中再加热操作的下游降低到至多12巴的压力。
5.根据权利要求1或2所述的方法，其中所述阶段ii)的富含氢气的气体(7)是处于28-32巴的压力；通过吸附分离装置(PSA)在27-31巴的压力下获得富含氢气的气体(13)，并且通过汽轮机(T)将其压力至少部分地降低到至多12巴的压力。
6.根据权利要求5所述的方法，其中所述压力已降低到至多12巴的气体构成此工艺的富含氢气的产物(15)。
7.根据前述权利要求中任一项所述的方法，其中在换热器(E1)中冷却的混合物(1)是处于至少50巴的压力。
8.根据前述权利要求中任一项所述的方法，其中将混合物(1)在第一个部分冷凝阶段中分离，将来自第一个部分冷凝阶段的气体(3)进行冷却并送到第二个部分冷凝阶段，并使已在汽轮机(T)中降低压力的富含氢气的气体(15)通过与来自第一个部分冷凝阶段的已冷却的气体进行热交换而再加热。
9.根据权利要求8所述的方法，其中在第二个部分冷凝阶段的入口处的温度比-200℃更低，甚至比-203℃更低。
10.根据前述权利要求中任一项所述的方法，其中来自外部来源的富含氢气的料流(9)也在变压吸附分离装置(PSA)中进行分离，这任选地使得已在汽轮机(T)中降低压力的气体(15)的量大于在低于-100℃的温度下分离的富含氢气的气体(7)的量。
11.根据前述权利要求中任一项所述的方法，其中在汽轮机(T)出口处的气体(15)的温度比-200℃更低，甚至比-203℃更低。
12.一种用于分离含有氢气和一氧化碳的混合物(1)以获得气态氢气的装置，其包括：分离单元，在这里进行部分冷凝和/或蒸馏和/或涤气(S1,S2)的至少一个阶段；换热器(E1)；变压吸附分离装置(PSA)；汽轮机(T)；用于将所述混合物送到换热器(E1)的装置，其中在换热器(E1)中将所述混合物冷却到低于-180℃的温度；用于将已冷却的混合物送到分离单元的装置，其中在分离单元中通过部分冷凝和/或蒸馏和/或涤气的至少一个阶段在低于-100℃的温度下进行分离，由此得到富含氢气的气体(7)和富含一氧化碳的流体(17)；用于将至少一部分的所述富含氢气的气体送到变压吸附分离装置(PSA)的装置，所述变压吸附分离装置在高于0℃的温度下操作以得到处于至少20巴压力的富含氢气的气体(13)；用于将所述富含氢气的气体的至少一部分(13A,13)送到换热器的装置，所述部分(13A,13)在换热器中被冷却到低于-100℃的温度，随后在汽轮机(T)中将其压力降低到至少8巴的压力；以及用于将已降低压力的气体送到换热器以进行再加热操作的装置，其中所述再加热操作获得处于至少8巴压力的富含氢气的产物(15,15A)。
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