CN1950657A - 从天然气中除去污染物 - Google Patents

从天然气中除去污染物 Download PDF

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CN1950657A
CN1950657A CNA2004800036332A CN200480003633A CN1950657A CN 1950657 A CN1950657 A CN 1950657A CN A2004800036332 A CNA2004800036332 A CN A2004800036332A CN 200480003633 A CN200480003633 A CN 200480003633A CN 1950657 A CN1950657 A CN 1950657A
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R·亚明
C·K·古鲁苏伊斯
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Abstract

一种从含有水和酸性物质的天然气进料物流中除去污染物的方法，该方法包括以下步骤：在第一容器(12)中将天然气进料物流冷却至水合物形成的第一操作温度，和从第一容器(12)中移出脱水的气体物流(34)；以及在第二容器(14)中将脱水的气体冷却至固体酸性物质形成或该酸性物质溶于液体中的第二操作温度，和从第二容器(14)中移出脱水、脱硫的气体物流(62)。

Description

从天然气中除去污染物
本发明涉及一种通过形成固体污染物以及后续适当地熔化该固体污染物，以从天然气进料物流中除去污染物的方法与装置。
当污染物为水时，本发明尤其(但非排除性地)涉及一种将天然气进料物流脱水的方法和装置。
当污染物为酸性物质，例如硫化氢或二氧化碳时，本发明尤其(但非排除性地)涉及一种用于天然气进料物流脱硫(sweetening)的方法与装置。
本发明也尤其(但非排除性地)涉及一种依续将天然气进料物流脱水与脱硫的方法与装置。
不管是来自生产储槽或储存储槽的天然气，其通常都含有水，以及其它会在生产液化天然气(LNG)的液化过程中形成固体的物质。一般做法是在液化之前先让天然气经受脱水工艺。将水除去，以防止发生水合物形成于管路内和液化容器上游的热交换器内。
如果未将水除去，则固体水合物可能会在管路工件、热交换器和/或液化容器内生成。该水合物是含有水与具有冰的外观的天然气的稳定固体，且天然气储存在水合物的晶格内。
天然气水合物的形成以历史观点来看认为是应该避免的非所需的结果。然而，已经开发了一些促进天然气水合物生成的方法，如国际专利申请号01/00755以及01/12758。在这些国际专利申请的第一个中，描述了一种在适合降低天然气与水之间的界面张力以促进天然气水合物的生成的试剂的存在下混合天然气和水的方法和装置。在这些国际专利申请的第二个中，描述了一种生产装置，其包含回旋状流动路径，以在降低温度制备天然气水合物之前引起作为第一步骤的水与天然气的混合。
本领域公知的是，将天然气进料物流脱水的方法包括以乙二醇吸收水，或是使用固体(如水合氧化铝、硅凝胶、硅石-氧化铝凝胶以及分子筛)吸收水。
典型地，天然气也含有酸性物质，如硫化氢(H2S)和二氧化碳(CO2)。此种天然气被称为“酸性气体”。当H2S与CO2从天然气进料物流中被除去时，则该气体被称为“脱硫气体(sweet)”。因为在即使低浓度下从未经脱硫气体中所散发出的不良气味，术语“酸性气体”是指含有H2S的天然气。H2S是必须被除去以符合法律规定的天然气污染物，因为H2S及其二氧化硫与三氧化硫的燃烧产物也是有毒性的。此外，H2S对大部分通常与气体管路相关的金属是有腐蚀性的，使得酸性气体的加工与处理可能导致此种系统的过早损坏。
如同脱水，气体脱硫工艺是本领域公知的，该工艺典型地包括使用固体吸附方法的吸附，或是使用胺方法、分子筛等的吸收。现有的脱水和脱硫方法是极其复杂和昂贵的。
本发明是对国际专利申请公开号03/062725中所述的方法和装置的改进。
为此目的，根据本发明的从含水的天然气进料物流中除去污染物的方法包括以下步骤：在第一容器中将天然气进料物流冷却至水合物形成的第一操作温度；以及从第一容器中移出经脱水的气体物流。
本发明方法的基本特征在于故意形成水合物以除去水。一般而言，要避免水合物的形成。
当天然气进料物流进一步包含酸性物质时，根据本发明的方法适当地进一步包括在第二容器中将经脱水的气体冷却至形成固体酸性物质或该酸性物质溶于液体中的第二操作温度；以及从该第二容器中移出经脱水、脱硫的物流。
术语“操作温度”用以指低于污染物在操作第一或第二容器的给定压力下的固体/液体转变温度的温度。
在本说明书中，“温热”液体物流可为任何相容的液体物流，其具有高于污染物在操作第一或第二容器的给定压力下固体/液体转变温度的温度。因此温热液体物流具有高至足以引起污染物固体熔化的温度。温热液体可能使或可能不会使污染物全部形成溶液。
现将参照附图更详细地描述本发明，其中
图1为本发明第一实施方案的示意性流程图；以及
图2为本发明另一实施方案的示意性流程图。
现请参照图1。图1显示进行本发明的方法的装置10。装置10包括第一容器12。在第一容器12中除去的污染物是水，因此离开第一容器12的气体是干燥的。移出重质烃也是本方法的结果，且因此离开第一容器12的气体物流为由第一容器12中的条件决定的烃的露滴。然而，离开第一容器12的气体的水露点，由于水合物的形成，所以较其平衡露点低。
如图1所述的具体实施方案，来自水源的湿进料气体由导管15进料到第一闪蒸罐16，其中冷凝液从进料气体中分离。第一闪蒸罐16内的压力和温度条件典型地为约75-130巴和25-40℃(约高于水合物形成温度5-10℃)。经由导管17离开第一闪蒸罐16的冷凝液物流为如前所定义的“温热液体”。该冷凝液由与天然气一起生成的液态烃组成。在第一闪蒸罐16中与酸性湿进料气体分离的气体物流经由湿酸性气体进料物流入口20进入第一容器12。中间热交换器22可用来冷却介于第一闪蒸罐16与第一容器12间的湿酸性气体。中间热交换器22使湿酸性气体的温度降低到正好高于在进料物流的特定压力下水合物的形成温度。在进料物流的特定压力下水合物的形成温度为第一操作温度的最大值，该第一操作温度为第一容器12内的操作温度。
可使用Joule-Thompson阀24或其它适当的膨胀装置(如涡轮膨胀机)来膨胀进料到第一容器12的湿气体进料物流，以在该物流进入第一容器12时进一步冷却。Joule-Thompson阀24另可限定进入第一容器12的入口20。在膨胀进入第一容器12的湿酸性气体进料物流之后，容器12内的气体压力-温度条件使得形成水合物。必要的冷却程度可通过流经Joule-Thompson阀24的湿酸性气体进料物流的膨胀度来达到。
将第一容器12内的第一操作温度与压力维持在水合物可借以形成的水平。进入Joule-Thompson阀24下游而至第一容器12的天然气进料物流处于第一操作温度。
如果天然气进料物流也含有酸性物质，第一容器12内的进料气体被冷却到的第一操作温度为低于水合物形成的温度，但高于固体酸性物质(如H2S与CO2)的形成温度。这是用来产生水合物及避免在第一容器12内形成固体酸性物质。
干燥的酸性气体经由干燥酸性气体出口34离开第一容器12。典型地，离开第一容器12的干燥酸性气体具有10-30巴、且低于膨胀装置24上游压力的标称压力，以及10-25℃、且低于膨胀装置24上游温度的温度。术语“干燥气体”是指不含水的气体。
含有水合物的液体物流经由水冷凝液出口28从第一容器12中移出，并经导管29流至分离器30。水在水冷凝液分离器30中从冷凝液中分离出来。此分离器例如可以是带有挡板的重力分离单元。由于水比冷凝液重，故任何适当的重力分离技术都可使用。所分离出的冷凝液经由导管31移出，而分离出的水经由导管33移出。
将进入第一容器12的天然气进料物流冷却至第一操作温度。或者，可使用经由过冷却液体入口26导入的一或多个过冷却液体喷射液来冷却天然气进料物流。于另一替代具体实施方案中，天然气进料物流是用Joule-Thompson阀24与经由入口26提供的过冷却液体两者来冷却的。在喷射液冷却的例子中，天然气进料物流可于水合物形成温度或高于水合物形成温度进入第一容器12。
过冷却液体入口26应设置于第一容器12内、湿酸性气体进料物流的入口20之上。在所述具体实施方案中，过冷却液体入口26为多个喷嘴。特别的过冷却液体为从本方法循环和喷洒入第一容器12的冷凝液。使用喷射液以使过冷却液体与气体的接触面积最大化，并因此使过冷却液体与湿酸性气体接触的冷却效果最大化。
将在10-30巴的压力(低于膨胀装置24的上游压力)以及第一容器12的操作温度下的干燥酸性气体，经由导管35中的第二交换器36导入第二闪蒸罐40。其于第二热交换器36中冷却而形成高于-56℃的温度的气体与冷凝液的两相混合物。未显示可通过与经外部冷冻循环(如丙烷冷冻循环)循环的冷冻剂间接热交换提供的额外冷却。在第二闪蒸罐40中，将冷凝液从干燥酸性气体物流分离。液体物流经由液体出口42离开第二闪蒸罐40，且被充分冷却以满足可能被送入第一容器12内的过冷却液体入口26的过冷却液体所需的标准。过冷却液体经由设置有泵44的导管43供应至过冷却液体入口26。
干燥酸性气体经由气体出口44离开第二闪蒸罐40，并经由导管45进入中间热交换器22，并由此至终端使用者(未显示)。
如同较早所观察到的，本发明涉及通过形成水合物来将天然气脱水。为防止水合物堵塞出口28和导管29，优选将存在于第一容器12底部的冷凝液加热。这可适当地借助使温热液体导入低于进料物流被导入的高度来导入第一容器12中。
在第一闪蒸罐16中分离的一部份温热冷凝液物流经由导管17和入口18供入到第一容器12。该温热冷凝液足够热，以至于可液化在第一容器12的第一区域内形成的水合物。当水合物熔化时，在水合物晶格内捕捉的气体被释放出来，而水进入含有冷凝液的溶液中。此外，至少一部分在水/冷凝液分离器30中分离的冷凝液可(于加热后，未显示)经由导管37被循环，而当作用以加热第一容器12内的固体可冷冻物质的温热液体来使用。
任何存在于水冷凝液分离器内的气体皆可被循环至第一容器12中。或者或另外地，在水/冷凝液分离器30中分离的一部份气体可被循环至经由入口20进入第一容器12的湿酸性气体进料物流中。
适当地，经由入口26喷洒入第一容器的液体为天然气液体，此天然气液体是C2，液化石油气组分，C3和C4以及C5+烃组分的混合物。
适当地，经由入口18导入第一容器的温热液体也为天然气液体。
现请参照图2，其显示本发明的另一实施方案。于此另一实施方案中，处理已脱水的酸性气体以从其除去酸性组分。脱水工艺已参照图1进行了讨论，故于此将不再重复。与图1所示部件具有相同功能的部件使用相同的参考符号。
干燥酸性气体经由气体出口44离开第二闪蒸罐40，并经由干燥酸性气体入口46进入第二容器14。就如同第一容器12一样，供应到第二容器14的干燥酸性气体可通过Joule-Thompson阀48或其它适当的膨胀装置(如涡轮膨胀机)膨胀，以进一步冷却该气体。如同先前的第一容器12，Joule-Thompson阀可限定干燥酸性气体入口46。进入第二容器14的干燥气体温度处于第二操作温度。第二操作温度是固体酸性物质形成的最高温度，或是酸性物质溶于液体中的温度。
对经由出口62离开第二容器14的气体进行脱水和脱硫。干燥经脱硫的气体通常的压力为20-50巴以及温度不低于-85℃。此经脱硫的干燥气体的产物流典型地于室温下送至终端使用者。
可通过使干燥经脱硫的气体于膨胀装置63中膨胀而进一步冷却该气体的产物流，且该进一步冷却的干燥经脱硫的气体被用于一或多个热交换器38、36或22，以影响装置10内的一或多个其它工艺物流的冷却。请注意，干燥气体在热交换器36内被冷却到的温度高于在给定管线压力下固体酸性物质形成的温度。
从出口52移出的液体含有酸性物质。
通过使干燥酸性气体于Joule-Thompson阀48中膨胀而将干燥酸性气体冷却至第二操作温度。或者，可使用经由入口49提供的一或多个过冷却液体喷射液来冷却干燥酸性气体。在另一实施方案中，天然气进料物流同时被Joule-Thompson阀48和经由入口49提供的过冷却液体所冷却。在喷洒冷却的例子中，干燥气体可以处于或高于固体酸性物质形成的温度或酸性物质溶于液体中的温度进入第二容器14。
过冷却液体入口49应该位于第二容器14中且在干燥酸性气体入口46之上。在举例说明的实施方案中，过冷却液体入口49为多个喷雾喷嘴。可调节第二容器14内的温度和压力条件，以形成固体可冷冻物质。对于气体的脱硫，只需调节温度-压力条件以形成固体硫化氢(H2S)和二氧化碳(CO2)。然而，第二容器内的工艺条件足以导致其它烃(如苯、甲苯、乙基苯和二甲苯)的固体可冷冻物质的形成。
适当地，过冷却液体为流经导管43的一部份液体。为了降低温度，该液体流经导管50而后到达热交换器38，在此处，可通过与干燥的脱硫气体进行间接热交换而冷却。然后，干燥的脱硫气体流经导管65而至热交换器36，以冷却来自第一容器12的干燥酸性气体。
申请人已发现，特别的是C2-C4烃组分于液体中的浓度为进料气体中的每摩尔CO2具有0.5-1.5摩尔。第二容器14中的液体是从入口49喷洒入容器的液体。因此，C2-C4烃组分于过冷却液体中的浓度应该在指定范围内。应当理解，如果在导管50中C2-C4烃组分于液体物流中的浓度太低，则可将额外的C2-C4烃组分加入到此物流中。
为防止酸性物质堵塞出口52，优选对存在于第二容器14底部的冷凝液进行加热。这可通过将温热液体经由低于进料物流导入的高度的温热冷凝液入口56导入第二容器14中而适当地进行。适当的液体为流经导管50的液体。或者也可使用流经导管31的液体。
进一步优化上述流程图以改善热整合是有可能的。例如，部分经由出口52离开第二容器14的烃液体物流可被循环至第一容器12的入口26。为了这样做，于是使用分离容器(未显示)来将富含酸性物质的液体物流从循环的烃物流中分离出来。

Claims (15)

1.一种从含有水的天然气进料物流中除去污染物的方法，该方法包括以下步骤：在第一容器中将该天然气进料物流冷却至形成水合物的第一操作温度；以及从该第一容器中移出脱水的气体物流。
2.如权利要求1的方法，其中该天然气进料物流进一步包括酸性物质，该方法进一步包括以下步骤：在第二容器中将该脱水的气体冷却至固体酸性物质形成或该酸性物质溶于液体中的第二操作温度；以及从该第二容器中移出脱水、脱硫的气体物流。
3.如权利要求1的方法，其中在第一容器中将该天然气进料物流冷却至第一操作温度的步骤包括于低于该第一操作温度的温度下将天然气进料物流导入第一容器。
4.如权利要求2的方法，其中在第二容器中将该脱水的气体冷却至第二操作温度的步骤包括于低于该第二操作温度的温度下将脱水的气体导入第二容器。
5.如权利要求2的方法，其中在第一容器中将该天然气进料物流冷却至第一操作温度的步骤包括于低于该第一操作温度的温度下将天然气进料物流导入第一容器，以及其中在第二容器中将该脱水的气体冷却至第二操作温度的步骤包含于低于该第二操作温度的温度下将脱水的气体导入第二容器。
6.如权利要求1的方法，其中在第一容器中将该天然气进料物流冷却至第一操作温度的步骤包括将天然气进料物流导入第一容器，以及于低于该第一操作温度的温度下将液体物流导入第一容器，以与水合物形成浆液。
7.如权利要求2-5中任一项的方法，其中在第二容器中将该脱水的气体冷却至第二操作温度的步骤包括将脱水的气体导入第二容器，以及于低于该第二操作温度的温度下将液体物流导入第二容器，以与酸性污染物形成浆液或混合物。
8.如权利要求2-5中任一项的方法，其中在第一容器中将该天然气进料物流冷却至第一操作温度的步骤包括将天然气进料物流导入第一容器，以及于低于该第一操作温度的温度下将液体物流导入第一容器，以与水合物形成浆液，且其中在第二容器中将该脱水的气体冷却至第二操作温度的步骤包括将脱水的气体导入第二容器，以及于低于该第二操作温度的温度下将液体物流导入第二容器，以与酸性污染物形成浆液或混合物。
9.如权利要求5-8中任一项的方法，其中该液体为天然气液体。
10.如权利要求1的方法，其进一步包括于该第一容器中加热水合物至高于该第一操作温度的温度以获得含水液体的步骤。
11.如权利要求2-9中任一项的方法，其进一步包括在该第二容器中加热酸性物质至高于该第二操作温度的温度以获得含酸性物质的液体的步骤。
12.如权利要求2-9中任一项的方法，其进一步包括在该第一容器中加热水合物以获得含水液体以及在该第二容器中加热酸性物质以获得含酸性物质的液体的步骤。
13.如权利要求10或12的方法，其中在该第一容器中加热水合物包括向水合物中加入温热液体。
14.如权利要求11或12的方法，其中在该第二容器中加热酸性物质包括向酸性物质中加入温热液体。
15.如权利要求13或14的方法，其中该温热液体为天然气液体。
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