CN102089411A - 从污染的气体物流中脱除气态污染物的方法 - Google Patents

从污染的气体物流中脱除气态污染物的方法 Download PDF

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CN102089411A
CN102089411A CN2009801264907A CN200980126490A CN102089411A CN 102089411 A CN102089411 A CN 102089411A CN 2009801264907 A CN2009801264907 A CN 2009801264907A CN 200980126490 A CN200980126490 A CN 200980126490A CN 102089411 A CN102089411 A CN 102089411A
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D·安德里安
R·梵德瓦尔特
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Abstract

本发明提供一种从污染的进料气体物流中脱除一种或多种气态污染物的方法，所述方法包括：1)提供污染的进料气体物流，2)使污染的进料气体物流冷却至在其下形成液体污染物以及贫含污染物的气相的温度，和3)通过将两相引入气/液分离器容器而分离它们，所述分离器容器包括位于中间位置的气/液入口、设置在气/液入口下方的液体出口和设置在气/液入口上方的气体出口，在所述容器中在气/液入口上方和整个容器横截面之上存在通常水平的聚结器，和在所述容器中在聚结器上方和整个容器横截面之上设置有离心液体分离器，所述液体分离器包括一个或多个涡流管。污染的气体物流可以是含甲烷的气体物流，特别是天然气物流，或者来自气化或燃烧过程的气体物流。本发明进一步提供用于实施所述方法的设备以及纯化的气体物流。

Description

从污染的气体物流中脱除气态污染物的方法
本发明涉及从包含甲烷的污染气体物流、特别是天然气物流中脱除一种或多种气态污染物例如二氧化碳或硫化氢的方法。本发明进一步涉及用于实施所述方法的设备和可通过所述方法获得的纯化气体物流。
从含甲烷的气体物流中脱除酸性气态污染物、特别是二氧化碳和/或硫化氢已经描述于几篇出版物中。
在WO2004/070297中描述了一种从天然气物流中脱除气态污染物的方法。在这种方法中，通过冷却从进料气体物流中脱除水，冷却导致形成甲烷水合物。这一步骤之后是分离水合物和进一步冷却剩余的气体物流，导致形成固体酸性污染物。在分离固体酸性污染物之后获得清洁的天然气物流。使用加热将固体污染物转化成浆液或液体。从分离区脱除所述浆液或液体。通常还需要特殊措施从气体物流中脱除最小的固体颗粒。
在WO2003/062725中描述了一种从天然气物流中脱除可冻结物质的方法，其中通过将天然气物流冷却形成固体酸性污染物在压缩液化天然气中的浆液。通过旋风使固体与液体分离。很清楚不容易实现液体与固体完全分离。
在WO2007/030888中描述的方法与WO2004/070297中所述方法类似，其中之后用甲醇洗涤清洁的天然气物流。
在US4,533,372中描述了从天然气中脱除二氧化碳和/或硫化氢的低温方法，其中通过在蒸馏区和受控冷冻区中处理进料物流进行。
仍然需要从天然气物流中脱除二氧化碳和/或硫化氢的进一步改进方法。特别希望设计一种相对简单的方法，所述方法不需要任何旋转装置、不需要低温蒸馏过程、不需要处理固体颗粒或液/固浆液和仅有最小的结构空间要求(底座)。
本发明的方法包括不多于两个只需要相对简单的装置的步骤。在第一步骤中，使包含甲烷的污染气体物流冷却直到液体污染物冷凝，随后是简单的气/液分离器，不需要任何旋转装置和不需要任何用于蒸馏段的能量。
因此，所述方法提供一种从污染的进料气体物流中脱除一种或多种气态污染物的方法，所述方法包括：1)提供污染的进料气体物流，2)使污染的进料气体物流冷却至在其下形成液体污染物以及贫含污染物的气相的温度，和3)通过将两相引入气/液分离器容器而分离它们，所述分离器容器包括位于中间位置的气/液入口、设置在气/液入口下方的液体出口和设置在气/液入口上方的气体出口，在所述容器中在气/液入口上方和整个容器横截面之上存在通常水平的聚结器，和在所述容器中在聚结器上方和整个容器横截面之上设置有离心液体分离器，所述液体分离器包括一个或多个涡流管。
该方法是相当容易和简单的方法。该方法实际上仅包括冷却步骤，随后是简单的气/液分离步骤，所述分离步骤不包括任何移动装置和不包括任何能量消耗步骤。当使用垂直的气/液分离器容器时，所述方法可以在仅需要相对小的结构空间的设备中进行。
根据优选实施方案，气/液入口包括带有在分离器容器中水平延伸的供给和分配组件的输入端。在最简单形式中，所述入口是一根简单的管子，该管子具有封闭端和均匀分布在管子长度上的多个孔。任选地，所述管子可以具有截锥形或圆锥形。可以存在一个或多个十字管以形成格栅系统，使气-液混合物在容器横截面上更均匀地分布。优选地，所述组件包括与气体入口相连和具有至少一个带有在流动方向上看彼此前后设置的导流叶片格栅的开放垂直侧的隔室，例如纵向盒状结构。通过所述供给和分配组件，气体通过导流叶片在塔横截面上均匀分布，这进一步改进聚结器/离心分离器组合中的液体分离。另一个优点是所述供给和分配组件从气体中分离出可能突然出现在气体物流中的任何液体波，所述分离通过液体与导流叶片碰撞和落在塔内实现。合适地，所述盒状结构沿流动方向向下变窄。在已经通过叶片在塔横截面上分布之后，气体向上流入聚结器。在优选实施方案中，纵向隔室具有两个带有导流叶片格栅的开放垂直侧。合适的气/液入口描述于例如GB 1,119,699、US 6,942,720、EP 195,464、US 6,386,520和US 6,537,458中。合适的可商购气/液入口是Schoepentoeter入口设备。
可获得许多水平聚结器，特别是用于垂直塔的水平聚结器。聚结器的公知例子是金属丝网。所有这些相对纤细(渗透性较大)和具有相对大的特定(内部)结构空间。它们的操作基于液滴捕集进行，其中通过液滴与内表面碰撞，随后液滴在这些表面上生长，和最后通过气体或通过重力脱除长大的液滴。
水平聚结器可以具有多种本身已知的形式，和可以例如由多层丝网、特别是金属或非金属丝网如有机聚合物丝网的床层组成，或者由叶片层或规整填料层组成。也可以使用非规整填料和也可以存在一块或多块塔板。所有这些类型的聚结器的优点是可商购获得和在本发明的塔中有效操作。还参见Perry的Chemical Engineers’Handbook，第6版，特别是18章。还参见EP195464。
在一种最简单的形式中，离心液体分离器可以包括水平塔板和一个或多个从所述塔板向下延伸的垂直涡流管，每一涡流管具有一个或多个在水平塔板下方在所述涡流管上端的液体出口。在另一种形式中，离心液体分离器包括一个或多个从所述塔板向上延伸的垂直涡流管，每一涡流管具有一个或多个在其上端的液体出口。所述塔板配有降液管，优选延伸至分离器容器下端的降液管。
在优选实施方案中，离心液体分离器包括：两块水平塔板，垂直的端部开放涡流管在所述塔板之间延伸，每一个从下部塔板的开口延伸至上部塔板的同轴开口下方一定的距离，用于将次要气体和液体从涡流管外部的塔板间空间排出的装置，和配在涡流管下部以赋予气/液围绕垂直轴旋转运动的装置。
液体分离器还优选配有从上部塔板的同轴开口向下伸入涡流管和直径比这些涡流管更小的垂直管段。这种设置强化了主要气体一方面与次要气体的分离和另一方面与液体的分离，这是因为这些液体不能从涡流管进入用于主要气体的上部塔板的开口中。
根据优选实施方案，用于将次要气体从塔板间空间排出的装置由穿过上部塔板的垂直管组成，和用于将液体从塔板间空间排出的装置由一个或多个从所述空间延伸至塔底部的垂直排放管组成。这种设置具有如下优点：次要气体在已经在所述塔板间空间中与液体分离后立即返回到主要气体中，和将所述液体在经过聚结器后加入塔底部的液体中，使得在离心分离器中脱除的次要气体和液体不需要单独处理。
为了更进一步改进离心分离器中的液体分离，根据本发明，优选在涡流管的顶部提供开口，用于将液体排到涡流管外部的塔板间空间内。这种设置的优点在于更少的次要气体被带入塔板间空间内。合适的可商购的离心分离器是Shell Swirltube deck。
在优选实施方案中，分离容器包括在离心液体分离器上方和容器整个横截面之上的第二个通常水平的液体聚结器。设置第二聚结器以从次要气体中脱除液体。这种设置的优点是如上文所述脱除仍然存在于次要气体中的任何液滴。优选地，第二个聚结器是一层或多层丝网、特别是金属或非金属丝网如有机聚合物丝网的床层。在另一个优选实施方案中，第二个通常水平的液体聚结器位于次要气体出口的上方，例如为EP83811中所述的方式，特别如其中图4所述。
污染的气体物流可以是包含酸性污染物的任何气体物流。
合适地，污染的气体物流是含甲烷的气体物流，例如作为天然气、伴生气或煤床甲烷来自天然来源，或者作为炼厂物流来自工业来源或作为费-托物流来自合成来源或作为厌氧废物或肥料发酵来自生物来源。甲烷的存在量可以在宽范围内变化，例如为3-90vol％，优选为5-80vol％甲烷，更优选为10-75vol％。
污染的气体物流也可以是包含二氧化碳的合成气物流、烟道气物流或煤燃烧后得到的气体物流。合成气是一氧化碳和氢气的混合物。包含二氧化碳的合成气物流通常在所谓的水煤气变换反应中将部分或大部分一氧化碳转化成二氧化碳之后得到。
进料物流中的酸性污染物特别为二氧化碳和硫化氢，尽管也可能存在羰基硫化物(COS)、二硫化碳(CS2)、硫醇、硫化物和芳族硫化合物。除了酸性污染物，还可能存在惰性物质例如氮气和稀有气体如氩气和氦气。进料气体中酸性污染物的存在量可以在宽范围内变化。进料气体中二氧化碳的量合适地为15-90vol％，优选20-75vol％。进料气体中硫化氢的量合适地为5-55vol％，优选10-45vol％。
进料气体的冷却可以通过本领域已知的方法进行。例如，冷却可以利用外部冷却流体进行。在进料气体的压力足够高的情况下，可以通过使进料气体物流膨胀实现冷却。组合也是可能的。使进料气体物流冷却的合适方法是通过近似等熵膨胀进行，特别是通过膨胀器、优选涡轮膨胀器或收缩扩散喷嘴进行。另一种合适方法是通过等焓膨胀使进料气体物流冷却，优选经孔或阀、特别是经一个或多个Joule-Thomson阀的等焓膨胀。优选使用一个以上膨胀器，因为这能够影响液滴尺寸和/或液滴尺寸分布。
在优选实施方案中，在膨胀前使进料气体物流预先冷却。这可以利用外部冷却回路或冷工艺物流例如液体酸性污染物进行。优选地，在膨胀前使气体物流预先冷却至15至-35℃、优选-10℃至-20℃的温度。预先冷却可以利用内部工艺物流进行。特别当进料气体物流已经压缩时，进料气体物流的温度可以为100-150℃。在该情况下可以使用空气冷却首先降低温度，任选随后进一步冷却。
另一种合适的冷却方法是与冷流体介质换热，所述冷流体介质特别是外部致冷剂例如丙烷循环、乙烷/丙烷级联或混合的致冷剂循环，任选与内部过程回路、合适地为二氧化碳物流(液体或浆液)、冷的贫含污染物的物流或者洗涤液体组合，或者其中冷却通过压缩、冷却和膨胀进行。
合适地，将进料气体物流冷却到-30至-80℃、特别为-40至-60℃的温度。在这些温度下形成液体。
可以预处理原始进料气体物流以部分或全部脱除水和任选的一些重质烃。这可以例如通过预冷循环利用外部冷却回路或冷的内部工艺物流进行。也可以通过用分子筛例如沸石或硅胶或氧化铝或者其它干燥剂的预处理脱除水。也可以通过用乙二醇、MEG、DEG或TEG或者甘油洗涤脱除水。气体进料物流中的水含量合适地少于1vol％，优选少于0.1vol％，更优选少于0.01vol％。
任选如上所述预处理的用于本发明方法的进料物流的压力合适地为10-120bara，或者甚至直到160bara。特别地，进料物流的压力为15-70bara，优选20-50bara。优选预处理的进料物流的温度合适地为-30至150℃，合适地为-20至70℃，优选0至50℃。
在本发明的优选实施方案中，例如通过用化学溶剂例如含水胺溶液、特别是含水乙醇胺例如DIPA、DMA、MDEA等或者用物理溶剂例如冷甲醇、DEPG、NMP等萃取剩余的酸性组分，进一步纯化贫含污染物的气相。
连续提供、连续冷却和连续分离污染的气体物流。
进一步通过图1解释本发明。在图1中给出了用于实施本发明方法的设备。干燥进料物流(水含量20ppm，60bara)通过管1流入涡轮膨胀器2。在膨胀器中，温度降至-45℃。进料气体包含40vol％二氧化碳、2vol％乙烷和58vol％甲烷。将所得的气/液混合物通过供给和分配组件4引入垂直的气/液分离器3。大部分液体将向下流到分离器的下端和通过液体出口5离开分离器。包含较大和较小液滴的气体物流将向上流过液体聚结器6、离心分离器7和第二液体聚结器8到达分离器容器的顶部，和通过气体出口9离开分离器容器。

Claims (15)

1.一种从污染的进料气体物流中脱除一种或多种气态污染物的方法，所述方法包括：1)提供污染的进料气体物流，2)使污染的进料气体物流冷却至在其下形成液体污染物以及贫含污染物的气相的温度，和3)通过将两相引入气/液分离器容器而分离它们，所述分离器容器包括位于中间位置的气/液入口、设置在气/液入口下方的液体出口和设置在气/液入口上方的气体出口，在所述容器中在气/液入口上方和整个容器横截面之上存在通常水平的聚结器，和在所述容器中在聚结器上方和整个容器横截面之上设置有离心液体分离器，所述液体分离器包括一个或多个涡流管。
2.权利要求1的方法，其中气体入口包括带有在分离器容器中水平延伸的供给和分配组件的输入端，所述组件由纵向盒状结构组成，所述纵向盒状结构与气体入口相连和具有至少一个带有在流动方向上看彼此前后设置的导流叶片格栅的开放垂直侧。
3.权利要求1或2的方法，其中水平凝结器由一层或多层丝网、特别是金属或非金属丝网或它们的组合组成。
4.权利要求1或2的方法，其中水平凝结器由叶片层组成。
5.权利要求1或2的方法，其中水平凝结器由规整填料层组成。
6.权利要求1-5任一项的方法，其中离心液体分离器包括：两块水平塔板，垂直的端部开放涡流管在所述塔板之间延伸，每一个从下部塔板的开口延伸至上部塔板的同轴开口下方一定的距离，用于将次要气体和液体从涡流管外部的塔板间空间排出的装置，和配在涡流管下部以赋予气/液围绕垂直轴旋转运动的装置，所述液体分离器还优选配有从上部塔板的同轴开口向下伸入涡流管和直径比这些涡流管更小的垂直管段，或者其中用于将次要气体从塔板间空间排出的装置由穿过上部塔板的垂直管组成，和其中用于将液体从塔板间空间排出的装置由一个或多个从所述空间延伸至塔底部的垂直排放管组成。
7.权利要求6的方法，其中在分离容器中在离心液体分离器上方和整个容器横截面之上存在第二个通常水平的液体聚结器，其中设置第二聚结器以从次要气体中脱除液体。
8.权利要求7的方法，其中第二个聚结器是一层或多层丝网、特别是金属或非金属丝网或它们的组合的床层。
9.前述权利要求任一项的方法，其中气态污染物是酸性气态污染物，特别是二氧化碳或硫化氢，优选其中天然气物流包含5-80vol％的甲烷，优选10-75vol％，或者其中污染的气体物流包含5-55vol％的硫化氢，优选10-45vol％。
10.前述权利要求任一项的方法，其中污染的气体物流的温度为-20至150℃，优选-10至70℃，和压力为10-150bara，优选15-70bara。
11.权利要求1-10任一项的方法，其中冷却通过等焓膨胀进行，优选经孔或阀、特别是Joule-Thomson阀的等焓膨胀进行，或者其中冷却通过近似等熵膨胀进行，特别是通过一个或多个膨胀器、优选涡轮膨胀器或收缩扩散喷嘴进行。
12.权利要求11的方法，其中在膨胀前使进料气体物流预先冷却至15至-35℃、优选5至-20℃的温度。
13.权利要求1-10任一项的方法，其中冷却通过与冷流体介质换热进行，所述冷流体介质特别是外部致冷剂如丙烷循环、乙烷/丙烷级联或混合的致冷剂循环，或者为内部工艺回路、合适地为二氧化碳或硫化氢物流或者冷甲烷物流，或者其中冷却通过压缩、冷却和膨胀进行。
14.前述权利要求任一项的方法，其中使污染的气体物流冷却到-30至-80℃、优选-40至-60℃的温度。
15.用于实施权利要求1-14任一项的方法的设备。
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