CN1791780A - 供应气体一氧化碳和/或包含至少10%一氧化碳的气体混合物的方法和装置 - Google Patents

供应气体一氧化碳和/或包含至少10%一氧化碳的气体混合物的方法和装置 Download PDF

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CN1791780A
CN1791780A CNA200480013610XA CN200480013610A CN1791780A CN 1791780 A CN1791780 A CN 1791780A CN A200480013610X A CNA200480013610X A CN A200480013610XA CN 200480013610 A CN200480013610 A CN 200480013610A CN 1791780 A CN1791780 A CN 1791780A
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carbon monoxide
separative element
tower
methane
liquid
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J·比利
N·艾克
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LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
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Abstract

在一种用于提供气体一氧化碳和/或包含至少10%一氧化碳的气体混合物的方法中,一氧化碳以液体形式储存于储存容器(47)中,并且当需要时,从该储存容器中取出,当一氧化碳气体生产不充足时在蒸发器(53)中蒸发以产生气体一氧化碳。

Description

供应气体一氧化碳和/或包含 至少10%一氧化碳的气体混合物的方法和装置
本发明涉及用于提供气体一氧化碳和/或包含至少10%一氧化碳的混合物的方法和装置。尤其涉及当工业装置,如分离单元不能提供所有或部分气体一氧化碳时通过液体一氧化碳蒸发供应一氧化碳。
在对要送入一氧化碳分离单元的供给气体进行提纯的提纯单元周期的开始,当其中一个吸附床由再生步骤转到吸附步骤,一氧化碳大量地被吸附剂吸收,导致由分离单元生产的一氧化碳量减少。这种效应已有描述,例如在EP-A-0 748 765中。所述床可以包含吸附剂如氧化铝或沸石,例如分子筛。
为了减少这种效应,正如法国专利FR01/06041所公开,提纯周期可以调整以使在所述再生步骤之后,仅将有限量的供给气体在吸附步骤的开始被送入所述床(大约常规供给流量的5%)。
常常,甚至这些措施不足以保证所产生的一氧化碳量与要求量的偏差不超过一定的百分比。这种情况下的另一种解决方法可以是使用较大反应器生产供给气体,但是这样做当然需要额外的费用。
本文中提及的所有百分比都是摩尔百分比,并且所有压力都是绝对压力。
EP-A-0837031和EP-A-1245533介绍了一种安装在一氧化碳-甲烷分离塔顶部的液体一氧化碳储存容器,所述液体一氧化碳用于向所述塔提供回流并且向甲烷洗涤塔提供冷却并且在EP-A-0837031情况下向主热交换器提供冷却,在所述主交换器中使合成气体达到其蒸馏温度。在US-A-3886756和US-A-4102659中,独立容器收集在用于甲烷洗涤过程中的一氧化碳循环中使用的液体一氧化碳。
根据本发明,提供一种用于提供气体一氧化碳和/或包含至少10%一氧化碳的气体混合物的方法,其中:
a)在分离单元中分离包含一氧化碳作为至少一种主要组分和优选氮、甲烷和氢中至少一种作为其它主要组分的供给气体,
b)所述分离单元分离所述供给气体,产生气体一氧化碳,其中所述气体一氧化碳是最终产物和/或通过混合气体一氧化碳与至少一种来自所述分离单元的其它气体形成的包含至少10%一氧化碳的气体混合物是最终产物,
c)液体一氧化碳储存在储存容器内,
d)从所述储存容器内取出液体一氧化碳并且蒸发至少部分所述液体以产生气体一氧化碳,该气体一氧化碳形成至少部分气体一氧化碳产物和/或至少部分包含至少10%一氧化碳的气体混合物,
该方法的特征在于液体一氧化碳的取出和蒸发在下述条件下发生:
i)在送入分离单元的供给气体的量减少时,和/或
ii)在供给气体利用至少两个吸附床之一进行吸附步骤提纯,产生被送入所述分离单元的提纯的供给气体时,在所述吸附步骤开启至吸附床被一氧化碳饱和前的至少部分时间段,和/或
iii)在所述产物的需求超过了所述分离单元的最大生产能力时。
根据本发明的可选择特征:
-在所述装置中分离的气体一氧化碳以气体形式从塔或所述单元的塔顶冷凝器或所述单元的渗透器或所述单元的提纯床移出;
-所述分离单元通过低温蒸馏、渗透或吸附操作;
-所述分离单元通过低温蒸馏操作并且包括下述步骤:利用至少两个吸附床之一进行吸附步骤提纯供给气体,产生提纯的被送入所述分离单元的供给气体,在热交换器中冷却至少部分提纯的供给气体,形成冷却的提纯供给气体,用至少部分冷却的提纯供给气体供给所述分离单元并通过在塔系统内低温蒸馏提纯的供给气体以产生气体一氧化碳和/或与另一种气体混合形成包含至少10%一氧化碳的气体混合物作为最终产物;
-低温分离单元包括用于分离主要包含一氧化碳和甲烷的混合物的CO/CH4塔,储存容器优选构成该塔的一部分;
-至少部分气体一氧化碳产物从CO/CH4塔提取,被送入储存容器的液体一氧化碳或者通过液化来自构成所述分离单元组成部分的一氧化碳制冷循环的一氧化碳和/或通过从CO/CH4塔移出液体一氧化碳和/或通过气体一氧化碳与源自外部来源的冷流体如液氮之间的热交换在热交换器内液化气体一氧化碳形成;
-所述分离单元包括甲烷洗涤塔,其中,第一液体一氧化碳流被蒸发以冷却甲烷洗涤塔,第二液体一氧化碳流在热交换器内蒸发,第三液体一氧化碳流仅在权利要求1的条件i)-iii)中的一个被满足时才蒸发;
-取出的液体在蒸发之前使用至少一个泵加压或被蒸发的液体在压缩机内压缩;
-所述储存容器在1-60巴压力,优选在气体一氧化碳和/或包含至少10%一氧化碳的气体混合物的供给压力下储存液体一氧化碳;
-由蒸发器蒸发的液体一氧化碳使用一氧化碳制冷循环压缩机和/或一氧化碳产物压缩机压缩。
根据本发明的另一方面,提供了一种通过蒸发液体一氧化碳供给气体一氧化碳和/或包含至少10%一氧化碳的气体混合物的装置,包括:
a)分离单元,
b)储存容器,
c)蒸发器,
d)将液体一氧化碳送入储存容器的管路,
e)将液体一氧化碳从储存容器取出和将液体一氧化碳送入蒸发器蒸发的管路,
f)将蒸发的一氧化碳从蒸发器移出的管路,
g)将包含一氧化碳作为主要组分和优选氮、甲烷和氢至少一种作为其它主要组分的供给气体送入分离单元的管路和将气体一氧化碳从所述分离单元移出的管路,所述装置的特征在于包括:
h)在下述条件下将液体一氧化碳送入蒸发器的装置:
i)在送入分离单元的供给气体的量减少时,和/或
ii)在所述分离单元上游存在吸附单元提纯供给气体时,在所述吸附步骤开启至吸附床用一氧化碳饱和前的至少部分时间段,和/或
iii)在所述产物的需求超过了所述分离单元的最大生产能力时。
该装置适合根据权利要求1的方法操作。
根据本发明的可选择特征:
-所述分离单元是低温蒸馏单元、吸附单元或渗透单元;
-所述分离单元包括冷箱,包括至少一个低温蒸馏塔的塔系统,用于将冷却提纯的包含一氧化碳作为主要组分和优选氮、甲烷和氢至少一种作为其它主要组分的供给气体送入所述塔系统的装置,并且进一步包括热交换器和吸附单元;
-所述低温分离塔包括甲烷洗涤塔以及与其相连的通过蒸发一氧化碳的热交换对塔进行冷却的热交换器,蒸发器是与甲烷洗涤塔的热交换器不同的热交换器;
-所述低温分离塔包括甲烷洗涤塔、甲烷/一氧化碳分离塔和汽提塔或相分离器,所述冷箱包括用于从所述甲烷洗涤塔向所述汽提塔或所述相分离器供给底部液体的管路,用于从所述汽提塔或所述相分离器向所述甲烷/一氧化碳分离塔供给底部液体的管路,用于从所述甲烷/一氧化碳分离塔移出一氧化碳的管路,用于从所述甲烷/一氧化碳分离塔移出甲烷的管路和用于将甲烷从所述甲烷/一氧化碳分离塔送入甲烷洗涤塔顶部的管路;
-所述储存容器在所述冷箱内并且用源自所述低温分离塔之一、优选源自一氧化碳/甲烷分离塔的液体一氧化碳供给;
-所述蒸发器位于所述低温分离单元的冷箱的外部并且优选允许与空气或比要蒸发的一氧化碳温度高的流体进行热交换。
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,但是包括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、较高级烃等。该混合物通常是通过部分氧化装置、蒸汽甲烷重整器或自生热重整器产生的合成气。
混合物1在大约环境温度下在提纯单元3的前端提纯以脱出水和二氧化碳。然后所述混合物在热交换器5中冷却到低温温度并送入在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的塔顶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。
物流13经处理进入于4-17巴压力下操作的汽提塔19,至少一种由物流13形成的物流被送入汽提塔19的塔顶。作为选择,如果甲烷物流被送入汽提塔19的塔顶,该供给物流以较低点送入其中。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经处理进入塔27。特别是,不同的几种物流(液态、双相、气态)可被提供到塔27。塔27在1-10巴、通常为约2.5巴的压力下操作。经分离后形成塔底部的富含甲烷的液体29和塔顶部的富含一氧化碳的气体31。部分富含甲烷的液体被泵送到甲烷洗涤塔的顶部,其余的作为洗涤物流移出。该两部分富含甲烷的液体可单独从所述塔移出。在该实例中,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。与物流21混合的部分不需要泵压。
所述富含一氧化碳物流31在压缩机35中压缩并且作为压缩气体37移出。
所述体系的冷却通过其中压缩机35为一部分的一氧化碳循环提供。所述一氧化碳在压缩机35中压缩到10-60巴的压力。部分被压缩的一氧化碳39在交换器5中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用于塔19和27的再沸腾,并且由此冷却的一氧化碳在阀45中膨胀并送入储存容器47。
在该特定情况下,储存容器47构成塔27的一部分并且额外用于向塔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的冷端平衡热交换曲线。但是,其中可以存在两个储存容器,其中之一向塔27顶部提供回流,而其中的另一个独立于该塔或任何塔。该独立的储存容器可以处于所述冷箱的内部或外部(没有显示),所述冷箱内包括塔7、19、27,交换器5和汽轮机41,以及任选的用于膨胀气体71的部分87的汽轮机89。
所述储存容器可以加压以使一氧化碳储存于高于1巴但低于60巴的压力下。理想的是,所述储存容器应处于基本为一氧化碳气体37或所述一氧化碳混合物73的产物压力下,其应允许在所述管路和蒸发器53中压力下降。作为选择,所述一氧化碳可以在大气压力下储存,如果需要的话,然后以液体形式抽取和/或以气体形式压缩至其最终压力。
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中气体物流换热蒸发,构成气态一氧化碳循环中的部分。
从容器47中取出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一般功能的体现。
另外,在必要时,自所述储存容器47取出液体51并在蒸发器53中蒸发。所述蒸发器如果在所述冷箱的外部可以与环境空气、水或蒸汽热交换,或者可以在所述冷箱的内部并且可以由热交换器5或另一个热交换器构成。
所产生的蒸发一氧化碳55被送入压缩机35以形成所有或部分产物气体。
如果被蒸发的所述液体51可以以高压获得,例如在蒸发器53的上游的泵压过程之后或在所述液体以高压储存的条件下,所产生的气体可直接与产物气体37混合。
所述一氧化碳的提取和蒸发可在下述条件下发生:
i)在送入分离单元的供给气体1的量减少时,和/或
ii)在吸附步骤开启至吸附床用一氧化碳饱和前的至少部分时间段,和/或
iii)在所述产物的需求超过了所述分离单元的最大生产能力。
应该理解的是,当这些条件中没有一项存在时,所述储存容器的水平将保持恒定或将提高。无论满足所述条件中的那一项时,所述水平将下降并且所述容器将需要补充,例如当供给气体量增加时和/或当所述吸附剂被一氧化碳饱和时和/或当所述产物需求低于所述分离单元的最大生产能力时。为了达到此目的,或者所述一氧化碳汽轮机需要大尺寸以补充所述容器或者可以加入来自外部来源的低温液体。这种低温液体可以是外部来源的液体一氧化碳或液氮,后者用于通过在热交换器中的热交换液化气体一氧化碳。
在所述吸附步骤开启时,吸附剂的操作如FR01/06041(作为参考引入本文)所述,送入到吸附剂的进料量直到其所送入的吸附床被一氧化碳饱和后才达到足量。在FR01/06041的实施例中,料流以标准流量的5摩尔%开始送入,然后提高到50摩尔%,最后到100摩尔%。例如,当所述料流处于其最小流量时,可开始将液体一氧化碳送入所述蒸发器,或,作为选择,可在所述料流处于其最小流量前几分钟开始将液体一氧化碳送入所述蒸发器。优选地,一旦所述料流的流量被提高到50%,不再送入所述液体一氧化碳。
另外,还可以这样操作所述分离单元,使得在晚上将所述储存容器充满,然后在白天的高峰需求时使用储存的一氧化碳。
气体和液体一氧化碳分别定义为包含至少85%一氧化碳、优选至少95%一氧化碳的气体和液体。
本发明方法还用于生产包含至少10%一氧化碳的混合物73,例如用于生产羰基合成醇的羰基合成气体。该混合物通过下述过程产生:从该塔系统的一个塔中提取气体混合物71、在交换器5中加热并通过加入气体一氧化碳72增浓至期望的一氧化碳浓度。在一氧化碳不充足时,可通过蒸发部分来自储存器47的液体一氧化碳满足部分需求。
应该理解的是,本发明适用于包含一氧化碳和氢、氮和甲烷中的至少一种作为主要组分的混合物的其它低温分离方法,例如分离氢,一氧化碳和甲烷混合物的方法,如部分冷凝方法,或分离仅包含一氧化碳和氮作为主要组分的混合物的方法。
这里以低温蒸馏单元示例的分离单元当然可以通过采用膜系统的渗透方式或通过吸附方式操作。这种情况下液体一氧化碳可以由外部来源输入或在低需求情况下可以通过液化气体一氧化碳产物产生。

Claims (16)

1.一种用于提供气体一氧化碳和/或包含至少10%一氧化碳的气体混合物的方法,其中:
a)在分离单元中分离包含一氧化碳作为至少一种主要组分和优选氮、甲烷和氢中至少一种作为其它主要组分的供给气体(1),
b)所述分离单元分离所述供给气体,产生气体一氧化碳,其中所述气体一氧化碳是最终产物(37)和/或通过混合气体一氧化碳(72)与至少一种来自所述分离单元的其它气体(71)形成的包含至少10%一氧化碳的气体混合物(73)是最终产物,
c)液体一氧化碳储存在储存容器(47)内,
d)从所述储存容器内取出液体一氧化碳并且蒸发至少部分(61)所述液体以产生气体一氧化碳,该气体一氧化碳形成至少部分气体一氧化碳产物和/或至少部分包含至少10%一氧化碳的气体混合物,
该方法的特征在于液体一氧化碳的取出和蒸发在下述条件下发生:
i)在送入分离单元的供给气体的量减少时,和/或
ii)在供给气体利用至少两个吸附床(3)之一进行吸附步骤提纯,产生被送入所述分离单元的提纯的供给气体时,在所述吸附步骤开启至吸附床被一氧化碳饱和前的至少部分时间段,和/或
iii)在所述产物的需求超过了所述分离单元的最大生产能力时。
2.如权利要求1所述的方法,其中所述分离单元通过低温蒸馏、渗透或吸附操作。
3.如权利要求2所述的方法,其中所述分离单元通过低温蒸馏操作并且包括下述步骤:利用在至少两个吸附床(3)的吸附步骤提纯供给气体的步骤,产生被送入所述分离单元的提纯的供给气体,在热交换器(5)中冷却至少部分提纯的供给气体,形成冷却的提纯供给气体,用至少部分冷却的提纯供给气体供给所述分离单元并通过在塔系统(7、19、27)内低温蒸馏提纯的供给气体,产生气体一氧化碳和/或包含至少10%一氧化碳的气体混合物作为最终产物。
4.如权利要求2或3所述的方法,其中所述低温分离单元包括用于分离主要包含一氧化碳和甲烷的混合物的CO/CH4塔(27),储存容器(47)优选构成该塔的一部分。
5.如权利要求4所述的方法,其中至少部分气体一氧化碳产物从CO/CH4塔(27)取出,被送入储存容器的液体一氧化碳或者通过液化来自构成所述分离单元组成部分的一氧化碳制冷循环的一氧化碳和/或通过从CO/CH4塔移出的液体一氧化碳和/或通过气体一氧化碳与源自外部来源的冷流体如液氮之间的热交换在热交换器内液化的气体一氧化碳形成。
6.如权利要求2-5任一项所述的方法,其中所述分离单元包括甲烷洗涤塔(7),其中,第一液体一氧化碳流(57)被蒸发以冷却甲烷洗涤塔,第二液体一氧化碳流(61)在热交换器内蒸发,第三液体一氧化碳流(51)仅在权利要求1的条件i)-iii)中的一个被满足时才蒸发。
7.如前述权利要求任一项所述的方法,其中被取出的液体(51)在蒸发之前使用至少一个泵加压或被蒸发的液体在压缩机(35)内压缩。
8.如前述权利要求任一项所述的方法,其中所述所述储存容器(47)在1-60巴压力,优选在气体一氧化碳和/或包含至少10%一氧化碳的气体混合物的供给压力下储存液体一氧化碳。
9.如前述权利要求中任意一项所述的方法,其中由蒸发器蒸发的液体一氧化碳使用一氧化碳制冷循环压缩机(35)和/或一氧化碳产物压缩机(35)压缩。
10.一种通过蒸发液体一氧化碳供给气体一氧化碳和/或包含至少10%一氧化碳的气体混合物的装置,包括:
a)分离单元,
b)储存容器(47),
c)蒸发器(53),
d)将液体一氧化碳送入储存容器的管路(43),
e)将液体一氧化碳从储存容器取出和将液体一氧化碳送入蒸发器蒸发的管路,
f)将蒸发的一氧化碳从蒸发器移出的管路(55),
g)将包含一氧化碳作为主要组分和优选氮、甲烷和氢至少一种作为其它主要组分的供给气体(1)送入分离单元的管路和将气体一氧化碳从所述分离单元移出的管路,所述装置的特征在于包括:
h)在下述条件下将液体一氧化碳送入蒸发器的装置:
i)在送入分离单元的供给气体的量减少时,和/或
ii)在所述分离单元上游存在吸附单元提纯供给气体时,在所述吸附步骤开启至吸附床用一氧化碳饱和前的至少部分时间段,和/或
iii)在所述产物的需求超过了所述分离单元的最大生产能力时。
11.如权利要求10所述装置,其中所述分离单元是低温蒸馏单元、吸附单元或渗透单元。
12.如权利要求10所述装置,其中所述分离单元包括冷箱、包括至少一个低温蒸馏塔(7、18、27)的塔系统,用于将冷却提纯的包含一氧化碳作为主要组分和优选氮、甲烷和氢中至少一种作为其它主要组分的供给气体(1)送入所述塔系统的装置,还包括热交换器(5)和吸附单元(3)。
13.如权利要求12所述装置,其中所述低温分离塔包括甲烷洗涤塔(7)以及与其相连的通过蒸发一氧化碳(57)进行热交换来冷却塔的热交换器(59),蒸发器(53)是与该甲烷洗涤塔的热交换器不同的热交换器。
14.如权利要求12或13所述的装置,其中所述低温分离塔包括甲烷洗涤塔(7)、甲烷/一氧化碳分离塔(27)和汽提塔(19)或相分离器,所述冷箱包括用于从所述甲烷洗涤塔向所述汽提塔或所述相分离器供给底部液体的管路(13),用于从所述汽提塔或所述相分离器向所述甲烷/一氧化碳分离塔供给底部液体的管路(23),用于从所述甲烷/一氧化碳分离塔移出一氧化碳的管路(49),用于从所述甲烷/一氧化碳分离塔移出甲烷的管路(27)和用于将甲烷从所述甲烷/一氧化碳分离塔送入甲烷洗涤塔顶部的管路(9)。
15.如权利要求11-14任一项所述的装置,其中所述储存容器在所述冷箱内并且用源自所述低温分离塔之一的液体一氧化碳、优选源自一氧化碳/甲烷分离塔的液体一氧化碳供给。
16.如权利要求11-15任一项所述的装置,其中所述蒸发器(53)位于所述低温分离单元的冷箱的外部。
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