CN102112391B - 用于生成和纯化合成气的方法和装置 - Google Patents

用于生成和纯化合成气的方法和装置 Download PDF

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CN102112391B
CN102112391B CN2009801303140A CN200980130314A CN102112391B CN 102112391 B CN102112391 B CN 102112391B CN 2009801303140 A CN2009801303140 A CN 2009801303140A CN 200980130314 A CN200980130314 A CN 200980130314A CN 102112391 B CN102112391 B CN 102112391B
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methane
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N·艾克-贝劳德
A·埃尔南德斯
P·马蒂
B·波尔斯特
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LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
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Abstract

在用于生成和纯化合成气(7)的方法中，在供入进料气体(1)和燃料(41)的生成单元(5)中生成包含氢、一氧化碳和甲烷的合成气，在分离单元(17)中纯化合成气以产生至少一个富含一氧化碳或氢的流体和至少一个富含甲烷的流体(23，55)，在此方法的进料气体或富含氢的气体(1，25，31，61，65)混合后，将富含甲烷的流体加压，并且将至少一部分混合物(59，61)送往生成单元。

Description

用于生成和纯化合成气的方法和装置
本发明涉及用于生成和纯化合成气的方法，并且涉及用于生成和纯化合成气的装置。
产生一氧化碳和氢的单元可分成两个部分：
-合成气的生成(主要包含H2、CO、CH4、CO2、Ar、H2O和N2的混合物)
-合成气的纯化。这包括：
-用于除去合成气中包含的大部分酸气(sour gas)的液体溶剂洗涤单元
-吸附床纯化单元
-用于生产CO的所谓低温箱的低温分离单元。
通常消耗燃料以预热进料，并过度加热可由所述方法消耗和/或输出的蒸汽。
所需燃料的量通常由合成气生成单元的需求限定。
由于燃料由来自分离单元(例如低温箱、CO、H2、PSA、膜等)的废气组成，通常需要外源燃料补偿以保证控制所述方法要求的燃料平衡。
在废气的量超过车间的燃料需要的情况下，剩余的废气会在锅炉中燃烧产生蒸汽，或可被输出。在产生蒸汽的情况下，通常导致专用锅炉方面的投资。
本发明建议将合成气低温分离单元产生的废甲烷作为合成气生产单元的进料再循环，以不将所述废甲烷作为燃料使用，从而减少可用燃料的量，并减少进料(烃)的消耗。这避免了辅助锅炉(将剩余燃料转化成蒸汽)的投资。此外，在辅助锅炉任选产生的蒸汽并不总是被利用。
根据本发明的一个目的，提供了用于生成和纯化合成气的方法，其中在供入进料气体和燃料的生成单元中生成包含氢、一氧化碳和甲烷的合成气，在分离单元中纯化合成气以产生至少一个富含一氧化碳或氢的流体和至少一个富含甲烷的流体，在与至少一个其他过程流体混合后，对所述富含甲烷的流体加压，并将至少部分混合物送往生成单元，其特征在于至少一个其他流体是从所述分离单元输送来的进料气体或富含氢的气体。
任选地：
-在低温分离单元中纯化合成气，通过从所述低温分离单元泵出富含甲烷的液体将所述富含甲烷的流体加压，将至少部分泵出液体蒸发并送往所述生成单元；
-将富含甲烷的流体与从所述生成单元下游单元输送来的另一流体混合以产生气体混合物，将所述气体混合物在压缩机中压缩，并将混合物送往所述生成单元；
-在供入来自低温分离单元的流体的吸附单元产生富含氢的气体；
-将富含甲烷的流体与生成单元的进料气体混合以产生气体混合物，将
所述气体混合物在压缩机中压缩，并将混合物送往所述生成单元。
根据本发明的另一个目的，提供了用于生成和纯化合成气的装置，其包括供入进料气体和燃料的生成单元，用于生产至少一个富含一氧化碳或氢的流体和至少一个富含甲烷的流体的分离单元，用于将包含氢、一氧化碳和甲烷的合成气从所述生成单元送往分离单元的设备，用于将由富含甲烷的流体和来自所述装置的至少一个其他流体组成的混合物加压的设备，和用于将至少部分混合物送往所述生成单元的设备，其特征在于所述混合物加压设备与进料气体入口或从所述分离单元输送来的富含氢的气体的入口相连。
根据其他任选的目标：
-所述分离单元是低温分离单元，所述加压设备由泵组成，并且包含用于蒸发部分泵出液体并用于将其送往所述生成单元的设备，并且任选地包含用于将另一部分泵出液体送往所述低温分离单元的塔的设备。
-所述装置包含压缩机，用于将所述气体混合物送往所述压缩机以形成压缩气体混合物的设备，和用于将所述压缩气体送往所述生成单元的设备；
-所述装置包含压缩机，用于将至少部分进料气体与所述富含甲烷的流体混合以形成气体混合物的设备，用于将所述气体混合物送往所述压缩机的设备，和用于将所述压缩气体混合物送往所述生成单元的设备；
-所述混合物加压设备与从所述分离单元输送来的富含氢的气体的入口相连；
-所述装置包含用于作为富含氢的气体从所述分离单元的气提塔抽出的富含氢的气体的设备；
-所述装置包含用于纯化来自所述分离单元的气体以提供富含氢的气体的设备；
-所述装置包含用于抽出富含氢的气体的设备；
-所述分离单元是低温蒸馏单元。
各种方案均可用于将废甲烷作为进料再循环到合成气生成单元：
a)通过低温泵再循环。将从低温箱的CO/CH4塔抽出的废甲烷泵出，随后蒸发并在将其作为进料再循环到合成气生成单元前在热交换管线中加热。这些泵可以是专用的再循环泵，或者共用用于洗涤甲烷的泵。
b)通过CH4压缩机再循环。将从低温箱的CO/CH4塔底抽出的废甲烷蒸发，并在将其在热交换管线中加热，随后通过专用压缩机压缩以作为进料再循环。
c)通过与闪蒸气体共用的压缩机一起再循环。
d)通过与低温箱出口的富含氢的气体共用的压缩机再循环，其中所述富含氢的气体充当用于氢化天然气进料的氢。在这种情况下，将所述混合物再循环到加氢脱硫单元的上游。
e)通过与纯氢共用的压缩机再循环，离开充当用于氢化天然气进料的氢的PSA。在这种情况下，将所述混合物再循环到加氢脱硫单元的上游。
f)通过与酸气洗涤单元产生的CO2共用的压缩机再循环。
g)通过与进料气体共用的压缩机再循环(可任选地在压缩前泵压CH4再循环物)。
h)各种方案的组合(例如3和6，7和3等)。
以下将参考图1更详细地描述本发明。为了简要起见，图1显示了本发明涵盖的一系列不同的方案。应用这些方案中的单独一个可能已经足够。
任选地在压缩机3中压缩后，将进料气流1送往合成气7生成单元5，例如SMR、ATR型等。向此单元供入燃料41，燃料41中的部分38可来自外部源，而另一部分37可来自生成单元5下游的合成气处理。
任选地，将合成气7送往可产生富含一氧化碳的气体45的酸气气提单元9。将任选地气提去酸气的合成气11送往吸附器13以将其干燥并纯化，并将所形成的气体15供入低温蒸馏分离单元17。分离单元17的显示高度示意性，但其可以是包含甲烷洗涤塔67、气提塔和CO/CH4分离塔19的甲烷洗涤单元。F.Kerry的“Industrial Gas Handbook”第238页描述了此类单元的实例，但仅使用了两个塔。可从塔19的底部抽出富含甲烷的液体，在泵21(其可以是用于将甲烷65送往甲烷洗涤塔67的泵)中加压，蒸发以形成气流23，并从分离单元17的低温箱排出。
可通过多种方式将此料流23再循环到生成单元5。可将其直接送往单元5而不进行压缩。否则，如料流49，可将其与进料气体1混合，并在向生成单元5供料的压缩机3中与所述气体压缩。
也可从塔19的底部去除富含甲烷的液体，并将其蒸发而不对其加压，并将其作为料流55取出。可将此料流与另一个流体混合形成混合物，将此混合物在压缩机中压缩，并作为进料气体送往生成单元5。例如，压缩机63压缩富含甲烷的气体55和至少一种以下气体的混合物：来自分离单元，特别是甲烷洗涤塔67和/或气提塔的富含氢的气体25、27和31，吸附单元35生产的富含氢的气体，其中将来自分离单元17的富含氢的气体29供入吸附单元35。将压缩机63中产生的混合物59在生成单元的上游再循环。
另一个选择是使用压缩机53压缩富含甲烷的气体43和至少一种以下气体的混合物：来自酸气气提单元的富含一氧化碳的气体。可将由此形成的混合物61作为进料送往生成单元5。
向吸附单元35，优选PSA单元，供入来自分离单元17的气体29，并产生富氢产物39，任选地，再循环气体61，和，任选地，燃料气37(任选地与来自分离单元17的气体部分33混合)。
应理解，在使用泵之外的方式压缩富含甲烷的流体的情况下，分离单元17可以是通过低温蒸馏以外的方式操作的单元，例如通过渗透或通过吸附操作的单元。
综上所述，富含甲烷的流体的压缩可以是：
i)任选地在泵中泵出，所述泵还泵出预期不送往生成单元，但预期送往，例如低温单元的甲烷洗涤塔的富含甲烷的流体；
ii)或与将再循环到生成单元和来自生成单元下游的处理单元的气体和/或与生成单元的进料气体一起压缩。

Claims (15)

1.一种用于生成和纯化合成气的方法，其中在供入进料气体(1)和燃料(41)的生成单元(5)中生成包含氢、一氧化碳和甲烷的合成气，在分离单元中纯化合成气以产生至少一个富含一氧化碳或氢的流体和至少一个富含甲烷的流体，将所述富含甲烷的流体在与至少一个其他过程流体混合后加压，并将至少部分混合物送往生成单元，其特征在于至少一个其他流体是从所述分离单元(25,27,31,61,65)输送来的进料气体或富含氢的气体。 
2.如权利要求1所述的方法，其中在低温分离单元中纯化合成气，通过从所述低温分离单元泵出富含甲烷的液体将所述富含甲烷的流体加压，将至少部分泵出液体蒸发并送往生成单元，其中富含甲烷的流体即富含甲烷的液体。 
3.如权利要求1所述的方法，其中将富含甲烷的流体与从所述生成单元的下游单元(9,13)输送来的另一个流体混合以产生气体混合物，将所述气体混合物在压缩机(53,63)中压缩，并将混合物送往生成单元。 
4.如权利要求3所述的方法，其中在供入来自低温分离单元的流体的吸附单元(35)产生富含氢的气体。 
5.如权利要求1-4中任一项所述的方法，其中将富含甲烷的流体与所述生成单元的进料气体(1)混合以产生气体混合物，将所述气体混合物在压缩机(3)中压缩，并将混合物送往生成单元。 
6.一种用于生成和纯化合成气的装置，其包括供入进料气体和燃料的生成单元(5)，用于生产至少一个富含一氧化碳或氢的流体和至少一个富含甲烷的流体的分离单元，用于将包含氢、一氧化碳和甲烷的合成气从所述生成单元送往分离单元的设备，用于将由富含甲烷的流体和来自所述装置的至少一个其他流体组成的混合物加压的设备(3,21,53,63)，和用于将至少部分混合物送往所述生成单元的设备，其特征在于所述混合物 加压设备与进料气体入口或从所述分离单元输送来的富含氢的气体的入口相连。 
7.如权利要求6所述的装置，其中所述分离单元是低温分离单元，所述加压设备包含泵(21)并且包含用于蒸发部分泵出的富含甲烷的流体并用于将其送往所述生成单元的设备，其中所述流体为液体。 
8.如权利要求7所述的装置，其中所述加压设备进一步包含用于将另一部分泵出的富含甲烷的流体送往所述低温分离单元的塔的设备。 
9.如权利要求6所述的装置，其包含压缩机(63)，用于将所述气体混合物送往所述压缩机以形成压缩气体混合物的设备，和用于将所述压缩气体送往所述生成单元的设备。 
10.如权利要求6-9中任一项所述的装置，其包含压缩机(3)，用于将至少部分进料气体与所述富含甲烷的流体混合以形成气体混合物的设备，用于将所述气体混合物送往所述压缩机的设备，和用于将所述压缩气体混合物送往所述生成单元的设备。 
11.如权利要求6-9中任一项所述的装置，其中所述混合物加压设备与从所述分离单元输送来的富含氢的气体的入口相连。 
12.如权利要求11所述的装置，其包含用于作为富含氢的气体从所述分离单元的气提塔抽出富含氢的气体的设备。 
13.如权利要求11所述的装置，其包含用于纯化来自所述分离单元的气体以提供富含氢的气体的设备。 
14.如权利要求11所述的装置，其包含用于抽出富含氢的气体的设备。 
15.如权利要求6-9中任一项所述的装置，其中所述分离单元是低温蒸馏单元。 
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