CN100339301C - 用于分离氢气和一氧化碳的混合物的方法和装置 - Google Patents

用于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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CN100339301C
CN100339301C CNB038085763A CN03808576A CN100339301C CN 100339301 C CN100339301 C CN 100339301C CN B038085763 A CNB038085763 A CN B038085763A CN 03808576 A CN03808576 A CN 03808576A CN 100339301 C CN100339301 C CN 100339301C
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hydrogen
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separation process
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E·迪蒙
A·赫尔南德兹
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LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
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Abstract

本发明涉及一种用于同时生产氢气和一氧化碳的方法，其中将合成气在脱碳单元(2)中进行脱碳并在干燥单元(5)中干燥。其余成分低温分离，并将来自脱碳单元上游和合成气生产单元(F)下游的富氢气体(7，9)循环。

Description

用于分离氢气和一氧化碳的混合物的方法和装置
本发明涉及一种用于分离氢气和一氧化碳的混合物的方法和装置。尤其涉及一种使用通过低温蒸馏的分离步骤分离所述混合物的方法。
一氧化碳和氢气的生产单元可以分为两部分：
-合成气的生产(主要含有H2、CO、CH4、CO2和N2的混合物)。在用于生产合成气的各种工业方法中，蒸汽转化是最重要的。该单元(包括加热炉)的设计是基于CO和氢气的生产要求。
-合成气的纯化，包括：
-用于除去合成气中存在的大部分CO2的胺洗涤单元；
-用于在吸附床上纯化的单元。该单元一般包括两个连续操作的瓶，一个在生产中，另一个在再生相；
-用于通过低温法(低温箱)进行低温处理，以按照用户要求的质量和纯度生产一氧化碳和氢气(可能包括所谓含氧混合气(oxogaz)的一氧化碳和氢气的混合物)的单元。最常用的方法是使用液体甲烷洗涤，以最高99％的收率获得纯一氧化碳，其中氢气和CO含量一般在几ppm-1％之间变化，而且富含甲烷的废气可用作燃料。
在Hausen等人所著的“Tieftemperaturtechnik”，Springer-Verlag1985 pp417-419、EP-A-837031、EP-A-0359629、EP-A-0790212和EP-A-1245533中描述了这类方法。
低压有利于合成气生产单元的热力学平衡，其中低压导致原料的消耗较低，而根据设备尺寸和电力的消耗，高压有利于合成气纯化单元。
这就是限制重整炉的操作压力(其在低于45巴的绝对压力下操作)的原因，并且由于这一限制，将合成气压缩机合并入合成气纯化管线中是有利的或需要的。
在大多数情况下，低温箱生产的氢气(最多含有1mol％CO)被作为再生气用于纯化，并随后在送往最终的用户之前送入吸附纯化单元(PSA)。
在低温箱产生的氢气(CO含量的规格是几ppm)被直接送往用户的情况下，该气体不再被用作再生气。
并且在生产一氧化碳和氢气的混合物(一般含50％氢气)的情况下，作为废气残留的氢气量很少，以至于不能将纯化单元再生；因此需要寻找另一种气体作为再生气。
目前的一种方法是在产生单元中生产所需额外量的氢气。存在于合成气中的该氢气在纯化单元中，尤其是在甲烷洗涤单元中处理，随后作为再生气用于纯化，并最终作为燃料使用。
本发明的目的是一种用于同时生产氢气和一氧化碳的方法，在所述类型的方法中，由合成气生产单元接收含氢气和一氧化碳的合成气，诸如来自烃重整的气体，在脱碳单元中将合成气脱碳，并在干燥单元中干燥，然后将余下的组分低温分离，其特征在于含至少60％氢气的气体被循环到脱碳单元上游和合成气生产单元下游，所述气体的组成为：
(i)来自低温分离的气体，和/或
(ii)部分合成气。
根据本发明的其它任选方面，
-在低温分离单元的甲烷洗涤塔顶部抽出含至少60％氢气的气体，其中余下组分被分离；
-含至少60％氢气的气体是产生的氢气纯度最高的部分气体；
-含至少60％氢气的气体被用于在送往脱碳单元的上游之前再生干燥单元；
-将脱碳单元中的纯化合成气在送往干燥单元之前在压缩机中压缩；
-另一股富氢气体由低温分离单元送往压缩机上游和脱碳单元下游。
本发明的另一方面提供了一种用于同时生产氢气和一氧化碳的装置，包括合成气生产单元、脱碳单元、干燥单元和低温分离单元，以及将合成气生产单元与脱碳单元、脱碳单元与干燥单元，和干燥单元与低温分离单元连接的设备，以及用于将氢气和一氧化碳作为产物抽出的设备，其特征在于其包括用于循环含至少60％氢气的气体到脱碳单元上游和合成气生产单元下游的设备，所述气体的组成为：
(i)来自低温分离单元的富氢气体，和/或
(ii)部分合成气。
用于循环气体的设备优选连接至脱碳单元上游区和合成气生产单元下游，并且位于低温分离单元或低温分离单元的上游区。
根据本发明的其它任选方面，装置包括：
-脱碳设备下游的压缩设备。
-用于将富氢气体送往干燥单元的设备。
-用于将来自汽提塔的富氢气体送往脱碳单元下游的设备。
低温分离单元可包括甲烷洗涤塔、汽提塔、精馏塔和用于从甲烷洗涤塔抽出富氢气体的设备。可以考虑其它类型的单元，诸如部分冷凝单元。
在存在合成气压缩器的情况下，提供的改进之处在于在低温箱和胺洗涤单元上游之间安装富氢气体循环回路。
在低温箱的出口通过液体甲烷洗涤塔生产的该富氢气体被用作纯化再生气，膨胀并送往胺洗涤单元的上游，与来自再生单元的合成气混合。
不必生产过量的氢气。
这使得合成气生产单元的尺寸减少约5％-15％。
另一个优点是恢复了在纯化单元中被共同吸附的CO量，所述CO返回了合成回路。这使得一氧化碳的回收率增加了约0.5％。
来自低温箱的闪蒸气体还可以循环至合成器压缩机的上游，以改善CO的单位收率。
此处给出的所有百分比均为摩尔百分比，压力是绝对压力。
以下参照附图，更详细地描述本发明，其中图1是通过若干步骤，包括低温分离，分离合成气的示意图，图2显示了适合合并入图1的低温分离设备。
在图1中，在胺洗涤单元2中将来自蒸汽重整炉F的约16bar的合成气流1分离，以除去二氧化碳。随后在压缩机3中将该产物压缩至18-43bar的绝对压力。压缩后的气流4在纯化单元5中汽提水，以55500Sm3/h的流速产生含62％氢气、少于1％的氮气、35％一氧化碳和3％甲烷的气体。
随后在低温分离设备中分离该气流，以生产25400Sm3/h的构成一氧化碳和氢气的混合物(一般50％氢气和略多于49％的一氧化碳)的气态产物8、18700Sm3/h的富氢(一般99％氢)气态产物9、6500Sm3/h的富一氧化碳(一般99％一氧化碳)的气态产物11、甲烷吹扫气13、富氢气体7和1300Sm3/h的富氢气体15(一般含95％氢气、1％一氧化碳和4％甲烷)。含超过98％氢气的1700Sm3/h的阶段气流(stage gas)14被送往膨胀汽轮机。
6800Sm3/h的气流7被送往纯化单元5，并用于再生其一个吸附床，并随后用水饱和，其与胺洗涤单元2上游的合成气混合。
废气15的一部分17任选可以循环至压缩机3上游以及胺洗涤单元2的上游或下游。
纯氢气产物9可以无需经PSA单元纯化而作为纯产品直接出售。闪蒸气15和甲烷吹扫气13的气流非常小，以致于不能再生纯化单元5。甲烷吹扫气13优选被送往蒸汽重整炉F的入口。
该富氢循环气7将蒸汽重整炉的尺寸减少约10％，并将CO收率增加约0.5％。
作为可变或额外的方案，合成气GS的一部分19可以在干燥单元5下游分离，并送往脱碳单元2上游。该气流19还可以在与未处理合成气1混合之前用于再生干燥单元5。
这样的优点是减少了低温分离单元6的低温箱的尺寸。
图2显示了用于通过低温蒸馏分离合成气的设备6。与图1中符号相同的气流对应于图1中设计的气流。设备包括甲烷洗涤塔K1、汽提塔K2和精馏塔K3。冷却和纯化后的合成气GS被送往甲烷洗涤塔K1的底部。从塔中抽出两股富氢气流，包括气流9和从气流9下方若干塔板处抽出的气流7。
富含甲烷和一氧化碳的液流20被分离为液流22和两相物流23，并送往塔K2。物流23被直接送往塔K2，而液流22在送往塔K2之前被部分蒸发(未示出)。
富氢气体15在汽提塔K2的顶部抽出。在汽提塔K2的底部，主要含一氧化碳和甲烷的物流24被抽出、低温冷却(未示出)并分离为两股物流25和26。物流25被直接送往塔K3，物流26被蒸发(未示出)并送往塔K3。富含一氧化碳的产物11在塔K3的顶部被抽出。甲烷液流27在塔K3的底部被抽出并随后在泵P中加压，分成两股，一部分送往汽提塔K2的顶部，其余的送往甲烷洗涤塔K1的顶部，物流13构成甲烷吹扫气。
按照已知方式，通过一氧化碳循环(未示出)在塔K2底部提供再沸，并在塔K3顶部提供冷凝。

Claims (11)

1.一种用于同时生产氢气和一氧化碳的方法，其中，接收来自合成气生产单元(F)的含氢气和一氧化碳的合成气，在脱碳单元(2)中将合成气脱碳，并在干燥单元(5)中干燥，然后在低温分离单元(6)将余下的组分低温分离，其特征在于含至少60mol％氢气的气体被循环到脱碳单元上游和合成气生产单元下游，所述气体组成为：
(i)来自低温分离的气体(7)，和/或
(ii)部分合成气(19)。
2.权利要求1的方法，其中含至少60mol％氢气的气体(7)在低温分离单元(6)的甲烷洗涤塔(K1)的顶部被抽出，其中余下的组分被分离。
3.权利要求1的方法，其中含至少60mol％氢气的气体是产生的氢气纯度最高的气体(7)的一部分。
4.权利要求1或2的方法，其中含至少60mol％氢气的气体(7)在送往脱碳单元上游之前用于再生干燥单元(5)。
5.上述权利要求1-3任一项的方法，其中在脱碳单元(2)中纯化的合成气在被送往干燥单元(5)之前在压缩机(3)中压缩。
6.权利要求5的方法，其中另一股富氢气体(17)由低温分离送往压缩机上游和脱碳单元下游。
7.一种用于同时生产氢气和一氧化碳的装置，包括用于接收来自合成气生产单元(F)的合成气的设备、脱碳单元(2)、干燥单元(5)和低温分离单元(6)，以及将合成气生产单元与脱碳单元、脱碳单元与干燥单元，和干燥单元与低温分离单元连接的设备，以及用于将氢气和一氧化碳作为产物抽出的设备，其特征在于其包括用于循环含至少60mol％氢气的气体到脱碳单元(2)上游和合成气生产单元(F)下游的设备，所述气体的组成为：
(i)来自低温分离单元的、与合成气相比富含氢气的气体，和/或
(ii)部分合成气(19)。
8.权利要求7的装置，包括脱碳单元(2)下游的压缩机(3)。
9.权利要求7或8的装置，包括用于将富氢气体送往干燥单元(5)的设备。
10.权利要求7或8的装置，其中低温分离单元(6)包括甲烷洗涤塔(K1)、汽提塔(K2)、精馏塔(K3)和用于从甲烷洗涤塔抽出富氢气体的设备。
11.权利要求10的装置，包括用于将富氢气体(17)由汽提塔(K2)送往脱碳单元(2)下游的设备。
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