CN1791779A - 提供包含至少10%一氧化碳的流体混合物的方法和装置 - Google Patents

提供包含至少10%一氧化碳的流体混合物的方法和装置 Download PDF

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CN1791779A
CN1791779A CNA200480013603XA CN200480013603A CN1791779A CN 1791779 A CN1791779 A CN 1791779A CN A200480013603X A CNA200480013603X A CN A200480013603XA CN 200480013603 A CN200480013603 A CN 200480013603A CN 1791779 A CN1791779 A CN 1791779A
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carbon monoxide
gas
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methane
supply gas
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J·比利
N·艾克
J·加勒达
F·文格任
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LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
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Abstract

在通过低温分离至少包含一氧化碳、氢和甲烷的供给气体生产包含至少10％一氧化碳和可能的气态一氧化碳混合物(73)的方法中，所述供给气体(1)被分离产生富集氢的第一气体(71)，所述供给气体在甲烷洗涤塔(7)中洗涤，来自甲烷洗涤塔底部的富含一氧化碳的物流(13)被分离产生进一步富集一氧化碳的物流(23)，该进一步富集一氧化碳的物流被分离形成富含一氧化碳物流(31，49)和液体甲烷物流(27)，至少部分富含一氧化碳的物流(72)与富集氢的第一气体混合，形成包含至少10％一氧化碳的混合物作为产物流。

Description

提供包含至少10％一氧化碳的流体混合物的方法和装置
本发明涉及用于提供包含至10％一氧化碳、优选40-60％一氧化碳的流体、优选气体混合物的方法和装置。该方法还可以产生包含其中含有至少90％一氧化碳的气态一氧化碳的产物。
Hausen et Linde撰写的Tieftemperaturtechnik(Springer Verlag，1985)描述了一氧化碳与氢的混合物用于供给羰基合成方法的用途。
用于分离包含一氧化碳和氢气的混合物的甲烷洗涤塔系统的实例可见于US-A-6269657、US-A-6094938、US-A-6082134、US-A-6073461、US-A-6062042、US-A-5592831、US-A-5295356、US-A-4888035、US-A-4311496、US-A-4102659、US-A-3886756和EP-A-837031。
本文所提及的所有百分比均为摩尔百分比，所有压力均为绝对压力。
根据本发明，提供一种通过在包括甲烷洗涤塔的塔系统的分离设备中低温分离至少包含一氧化碳、氢和甲烷作为基本组分的供给气体，产生包含至少10％一氧化碳和可能的气态一氧化碳混合物的方法，该方法包括下述步骤：
a)处理所述供给气体以形成富集氢的第一气体，
b)在甲烷洗涤塔中用液体甲烷物流洗涤所述供给气体或由所述供给气体衍生的气体，
c)从所述甲烷洗涤塔取出气态氢富集物流，
d)从所述甲烷洗涤塔底部分离一氧化碳富集物流以产生进一步富集一氧化碳的物流，
e)分离所述进一步富集一氧化碳的物流以形成富含一氧化碳物流和液体甲烷物流，
f)将至少部分所述液体甲烷物流送入甲烷洗涤塔，并且
g)至少将至少部分富含一氧化碳物流与富集氢的第一气体混合以形成包含至少10％一氧化碳的混合物作为产物流。
本发明方法可以包含下述步骤：利用至少两个吸附床之一进行的吸附步骤提纯所述供给气体以产生要送入分离设备的纯化的供给气体，在热交换器中冷却至少部分所述纯化的供给气体以形成冷却的纯化的供给气体，并且将所述冷却的纯化的供给气体送入甲烷洗涤塔。
根据本发明方法的附加特征：
-所述供给气体通过在热交换器中冷却处理，然后在所述热交换器的中间温度下于相分离器中或在所述热交换器的下游分离以形成富集氢的气体，并且至少部分在所述相分离器中形成的气体构成富集氢的第一气体并与至少部分富含一氧化碳的物流混合以形成包含至少10％一氧化碳的混合物作为产物流。
-部分在相分离器中形成的气体和/或至少部分在相分离器中形成的液体被送入所述甲烷洗涤塔，至少部分没有被送入所述甲烷洗涤塔的在相分离器中形成的气体构成富集氢的第一气体。
-所述供给气体在甲烷洗涤塔中处理并且在高于甲烷洗涤塔底部至多几个理论塔板处将富集氢的第一气体除去。
-所述包含至少10％一氧化碳的混合物至多包含90％一氧化碳、优选40-60％一氧化碳和优选10-90％氢。
-至少部分富集氢的第一气体在汽轮机中膨胀。
-利用一氧化碳制冷循环，其中制冷循环中的压缩机压缩至少部分富含一氧化碳的物流。
-部分富含一氧化碳的物流作为纯一氧化碳产物取出。
根据本发明的另一方面，提供一种通过低温蒸馏由至少包含一氧化碳、氢和甲烷作为基本组成的供给气体生产包含至少10％一氧化碳的混合物的装置，其中包括：
a)用于处理所述供给气体以形成富集氢的第一气体的第一分离装置，
b)甲烷洗涤塔和用于将至少部分所述供给气体或由所述供给气体衍生的气体送入甲烷洗涤塔的装置和将液体甲烷物流送到甲烷洗涤塔顶部的装置，
c)用于将液体从甲烷洗涤塔底部送到第二分离器，优选低温蒸馏塔的装置，用于将氢富集物流和一氧化碳富集物流移出第二分离器的装置，
d)用于将至少部分所述一氧化碳富集物流送入第三分离器，优选低温蒸馏塔的装置，和用于将富含一氧化碳物流和富含甲烷物流从第三分离器移出的装置，
e)用于将至少部分所述富含一氧化碳物流与富集氢的第一气体混合以形成包含至少10％一氧化碳混合物作为产物气体的装置，和可能的用于将所述富含一氧化碳物流的另一部分作为产物流移出的装置。
本发明的装置可包括：
-用于在甲烷洗涤塔中处理至少部分所述供给气体的装置，其中第一分离器是甲烷洗涤塔，在高于甲烷洗涤塔底部至多几个塔板处将富集氢的第一气体移出，
-构成第一分离器的相分离器，用于冷却所述供给气体的热交换器，用于在所述热交换器的中间点或所述热交换器下游移出所述供给气体并且将所述供给气体送入所述相分离器的装置，用于将富集氢的第一气体从相分离器移出的装置，优选，用于将来自相分离器的气体送入甲烷洗涤塔作为由所述供给气体衍生的气体的装置，
-用于将至少部分来自相分离器的液体送入甲烷洗涤塔和/或第二分离器和/或所述热交换器的装置，
-汽轮机和将至少部分富集氢的第一气体送入汽轮机的装置。
所述包含至少10％一氧化碳的混合物优选包含至少10％氢。尽管所述混合物可以包含少量其它杂质如甲烷或氮，进一步更优选所述混合物包含40-60％一氧化碳和40-60％氢。
为了获得一氧化碳与氢的混合物，常规步骤是将纯一氧化碳的提纯物流与纯氢混合以在所述混合物中提供期望的一氧化碳/氢比。
所述第二分离器可以是汽提塔或相分离器。
本发明通过仅提纯部分所述供给气体，使其转变为纯产物，由此降低了分离设备，特别是塔的尺寸。这样也降低了能源的消耗。用于形成所述混合物的富含氢的气体不处在所述分离设备的任何塔中。
本发明将通过参考附图更加详细描述，所述附图是高度简化的，但包含了本发明装置的主要元素。
图1示出了用于分离主要包含甲烷、一氧化碳和氢的混合物的装置。所述混合物可以包含少量的氮、二氧化碳、湿气、高级烃等。该混合物通常是部分氧化单元、蒸汽甲烷重整器或自热重整器产生的合成气。
图2示出了图1方法的另一种可选择的供给气体的布局。
在图1中，包含一氧化碳、氢、甲烷和可能的其它杂质的混合物1在大约环境温度下在提纯单元3前端提纯以除去水和二氧化碳。然后所述混合物在热交换器5中冷却到低温并送入在10-60巴压力下操作的甲烷洗涤塔7的底部。甲烷洗涤物流9被送入塔7的顶部，并且从该塔的顶部移出氢富集物流11。从该塔的底部移出富集一氧化碳的液体物流13。
富集氢的气态物流71在进入甲烷洗涤塔之前或在甲烷洗涤塔的底部(该塔的底部用作相分离器)或在比该塔底部高几个塔板处移出并在所述热交换器5中加热。所述气体71将被称作粗气体。
部分或所有气态物流71可以在汽轮机89中膨胀以为该方法提供制冷。
物流13被进一步处理后进入于4-17巴压力下操作的汽提塔19，至少一种由物流13形成的物流应被送入汽提塔19的顶部。作为选择，如果甲烷物流也被送入汽提塔19的顶部，该供给物流以较低点送入。来自汽提塔顶部的气体21在交换器5中加热并用作燃料或燃烧。来自汽提塔19底部的液体物流23被进一步处理后进入塔27。特别是，几种不同的物流(液态、双相、气态)可被提供给塔27。塔27在1-10巴、通常为约2.5巴的压力下操作。在此被分离形成所述塔底部的富含甲烷的液体29和所述塔顶部的富含一氧化碳的气体。部分富含甲烷的液体被取出送到甲烷洗涤塔的顶部，其余的作为洗涤物流。两部分富含甲烷的液体可单独从所述塔排出。在该实施例中，富含甲烷的液体通过泵33抽出并部分送入甲烷洗涤塔7的顶部，剩余的洗涤物流与物流21混合。与(或不与)物流21混合的部分不需要泵压。
所述富含一氧化碳物流31可以在压缩机35中压缩并且其中部分可作为压缩CO产物气体37移出。但是，纯一氧化碳的生产不是本发明的主要特征，且所生产的所有一氧化碳都可用于形成包含至少10％一氧化碳的混合物。
所述富含一氧化碳物流的另一部分可以在压缩机35中压缩并作为物流72与加热的物流71(和/或来自汽轮机89的加热的膨胀物流91)混合以形成包含至少10％一氧化碳和至少10％氢的混合物73(称为羰基合成气体)。如果必要的话，可以存在羰基合成气体压缩机。
所述体系的冷却通过一氧化碳循环提供，其中压缩机35构成其一部分。所述一氧化碳在压缩机35中压缩到10-60巴的压力。如果需要，部分被压缩的一氧化碳39在交换器5中被冷却到该交换器的中间温度并且然后在汽轮机41中膨胀。该膨胀的一氧化碳气体在交换器5中加热并在其入口或中间压力下再循环到压缩机35。未膨胀的一氧化碳43用于使塔19和27再沸腾，并且由此冷却的一氧化碳优选是低温冷却的，在阀45中膨胀并送入储存容器47。
在该特定情况下，储存容器47与塔27构成一整体，并且额外用于向塔27顶部提供回流，提供液体一氧化碳以冷却甲烷洗涤塔7，并且将液体一氧化碳直接提供到主热交换器5中，在其中蒸发以在所述热交换器5冷端平衡热交换曲线。
通过所述热膨胀产生的闪蒸气体49在压缩前与富含一氧化碳的气体31混合。
液体一氧化碳物流57在交换器59中与甲烷洗涤塔7的气体物流换热蒸发，并构成气态一氧化碳循环中的部分。
从容器47中提取的另一股一氧化碳物流61在交换器5中蒸发。
这两种液体物流的取出是本发明方法的普通功能部分的体现。
储存的、要在蒸发器53中蒸发的液体一氧化碳不是本发明的基本特性。
本发明方法用于生产包含至少10％一氧化碳的混合物，例如用于生产羰基合成醇的羰基合成气体。
图2示出了不同于图1的本发明方法中向所述甲烷洗涤塔供料的可选择方法。其中，所述供给气体1被冷却到交换器5的中间温度(加热气体没有显示)并送入相分离器75。在其中分离形成气体77和液体81。所述气体被分为两部分，一部分71被加热，在与图1的一氧化碳物流72混合后，形成至少10％一氧化碳混合物、优选40-60％一氧化碳混合物的一部分，剩余部分79在所述热交换器5的下游冷却并送入甲烷洗涤塔7的底部。所述液体81可被送入甲烷洗涤塔7，或者闪蒸塔或鼓19，或者送入热交换器5被加热。作为选择，所述液体物流81A与气体物流79混合以形成如虚线所示的双相物流，并且混合物83然后被进一步冷却并送入甲烷洗涤塔7。

Claims (14)

1.一种通过在包括甲烷洗涤塔(7)的塔系统的分离设备中低温分离至少包含一氧化碳、氢和甲烷作为基本组分的供给气体(1)产生包含至少10％一氧化碳，和可能的气态一氧化碳的混合物(73)的方法，该方法包括下述步骤：
a)处理所述供给气体以形成富集氢的第一气体(71，77)，
b)在甲烷洗涤塔中用液体甲烷物流(9)洗涤所述供给气体或由所述供给气体衍生的气体，
c)从所述甲烷洗涤塔移出气态氢富集物流(11)，
d)从所述甲烷洗涤塔塔底分离一氧化碳富集物流(13)，产生富集一氧化碳的物流，
e)分离所述富集一氧化碳的物流以形成富含一氧化碳物流(31，49，55)和液体甲烷物流(27)，
f)将至少部分所述液体甲烷物流送入甲烷洗涤塔，并且
g)至少将至少部分富含一氧化碳物流(72)与富集氢的第一气体混合以形成包含至少10％一氧化碳的混合物作为产物流。
2.如权利要求1所述的方法，其中包括利用至少两个吸附床(3)之一进行的吸附步骤提纯所述供给气体的步骤，产生送入分离单元的纯化的供给气体，在热交换器(5)中冷却至少部分所述纯化的供给气体以形成冷却的纯化的供给气体，并且将所述冷却的纯化的供给气体送入甲烷洗涤塔(7)。
3.如权利要求1或2所述的方法，其中所述供给气体通过在热交换器(5)中冷却处理，然后在所述热交换器的中间温度下于相分离器(75)或在所述热交换器的下游分离以形成富集氢的气体(77)，并且至少部分在所述相分离器中形成的气体构成富集氢的第一气体(71)并与至少部分富含一氧化碳的物流(72)混合，形成包含至少10％一氧化碳的混合物(73)作为产物流。
4.如权利要求3所述的方法，其中部分(79)在相分离器中形成的气体和/或至少部分在相分离器中形成的液体(81，81A)被送入所述甲烷洗涤塔，至少部分(71)没有被送入所述甲烷洗涤塔的在相分离器中形成的气体构成富集氢的第一气体。
5.如权利要求1或2所述的方法，其中所述供给气体(1)在甲烷洗涤塔(7)中处理，在高于甲烷洗涤塔底部至多几个理论塔板处将富集氢的第一气体(71)移出。
6.如前述任一权利要求所述的方法，其中所述包含至少10％一氧化碳的混合物(73)至多包含90％一氧化碳、优选40-60％一氧化碳和优选10-90％氢。
7.如前述任一权利要求所述的方法，其中至少部分富集氢的第一气体(87)在汽轮机(89)中膨胀。
8.如前述任一权利要求所述的方法，该方法利用一氧化碳制冷循环，其中所述制冷循环中的压缩机(35)压缩至少部分富含一氧化碳的物流。
9.如前述任一权利要求所述的方法，其中部分富含一氧化碳的物流(37)作为纯一氧化碳产物移出。
10.一种通过低温蒸馏至少包含一氧化碳、氢和甲烷作为基本组成的供给气体生产至少包含10％一氧化碳的混合物(73)的装置，包括：
a)用于处理所述供给气体以形成富集氢的第一气体的第一分离装置(7，75)，
b)甲烷洗涤塔(7)和用于将至少部分所述供给气体(1)或由所述供给气体衍生的气体(79)送入甲烷洗涤塔的装置和将液体甲烷物流(9)送到甲烷洗涤塔顶部的装置，
c)用于将液体从甲烷洗涤塔底部送到第二分离器(19)，优选低温蒸馏塔的装置，用于将氢富集物流(21)和一氧化碳富集物流(23)移出第二分离器的装置，
d)用于将至少部分所述一氧化碳富集物流(23)送入第三分离器(27)，优选低温蒸馏塔的装置，和用于将富含一氧化碳物流(31，47，51)和富含甲烷物流(27)从第三分离器移出的装置，
e)用于将至少部分(72)所述富含一氧化碳物流与富集氢的第一气体(71)混合以形成包含至少10％一氧化碳混合物作为产物气体(73)的装置，和可能的用于将所述富含一氧化碳物流的另一部分(37)作为产物流移出的装置。
11.如权利要求10所述的装置，其中包括在甲烷洗涤塔中处理至少部分所述供给气体的装置，其中第一分离器是甲烷洗涤塔(7)，在高于甲烷洗涤塔底部至多几个塔板处将富集氢的第一气体(71)移出。
12.如权利要求10所述的装置，其中包括构成第一分离器的相分离器(75)，冷却所述供给气体的热交换器(5)，在所述热交换器的中间点或所述热交换器下游移出所述供给气体并且将所述供给气体送入所述相分离器的装置，将富集氢的第一气体(71)从相分离器移出的装置，以及优选，将来自相分离器的气体(79)送入甲烷洗涤塔作为由所述供给气体衍生的气体的装置。
13.如权利要求12所述的装置，其中包括将至少部分来自相分离器的液体(81，81A)送入甲烷洗涤塔(7)和/或第二分离器(19)和/或所述热交换器(5)的装置。
14.如权利要求10-13任一项所述的装置，其中包括汽轮机(89)和将至少部分(87)富集氢的第一气体送入汽轮机的装置。
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EP1479990A1 (en) 2004-11-24
JP2007502398A (ja) 2007-02-08
WO2004102093A1 (en) 2004-11-25

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