CN110121386A - 生产纯净气流的方法 - Google Patents
生产纯净气流的方法 Download PDFInfo
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Abstract
本发明涉及一种从进料气流中去除硫化氢和二氧化碳的方法。使进料气流中的H2S在克劳斯单元(Claus unit)中转化为元素硫。使所得气流的至少一部分与水性贫吸收介质在吸收区中、在0.9与2巴之间的压力下接触。所用水性贫吸收介质包含一种或多种胺,所述胺选自:‑缺乏具有足以中和氨基甲酸的pKa的叔胺官能团的多胺,所述多胺的至少一个伯胺官能团具有在25℃下小于10.0的pKa;‑缺乏具有足以中和氨基甲酸的pKa的叔胺官能团的多胺,所述多胺的至少一个仲胺官能团具有在25℃下对于每个吸附氮而言小于10.0的pKa。所述方法相较于涉及用(活化)MDEA进行克劳斯废气处理的方法得到改进。实现CO2有效去除的同时,可以使用设备更少的简化流程。
Description
技术领域
本发明涉及一种用于从进料气流中去除硫化氢和二氧化碳的方法。
背景技术
来自天然气井的气流典型地是“酸性气体”流,因为它们通常包含二氧化碳和硫化氢。此类气流能够进一步使用之前,需要去除H2S和CO2。
从“酸性气体”中去除H2S和CO2的方法是本领域熟知的。此类方法典型地包含从气态进料流中去除含硫化合物和二氧化碳的吸收步骤,这是通过使此类气态进料流与溶剂(例如胺溶剂)在吸收塔中接触来实现的。从而获得通常称为“甜气体”的纯净气流和负载有污染物的溶剂。负载的溶剂典型地在汽提器中再生,获得贫溶剂和包含相对高浓度的H2S和CO2的气流。贫溶剂可以再循环到吸收塔中。
可以在第二吸收阶段处理包含相对高浓度的H2S和CO2的气流。例如,可以对其进行克劳斯法(Claus process)而产生元素硫和克劳斯废气。克劳斯废气通常经受H2S和/或CO2去除程序。
从克劳斯废气中去除二氧化碳的常用方法是用甲基二乙醇胺(MDEA)或用活化MDEA在高压下处理。然而,MDEA在H2S存在下对降解敏感。因此,在用(活化)MDEA处理之前通常去除H2S。(活化)MDEA处理通常在高压下进行。由于克劳斯废气(也在H2S去除后)通常处于大气压下,因此这需要在(活化)MDEA处理之前对克劳斯废气加压。另外,由于所述工艺是在高压下进行,因此吸收单元的尺寸受到限制。因此在处置大规模克劳斯废气流时需要多个压缩机和多个吸收单元。
本发明的目标是一种用于从进料气流中去除硫化氢和二氧化碳的改进方法,尤其是当它涉及克劳斯尾气处理时。一个目标是实现有效的CO2去除。另一个目标是简化流程,优选减少所需的设备。另一个目标是使工艺中的能耗降低。同时,希望处理方法对H2S的存在不太敏感。
发明内容
本发明涉及一种用于从进料气流中去除硫化氢和二氧化碳的方法,所述方法包括以下步骤:
(i)使进料气流中的硫化氢在克劳斯单元中转化成元素硫,从而获得元素硫以及包含含量减少的硫化氢和二氧化碳的气流;
(ii)使步骤(i)所得气流的至少一部分与水性贫吸收介质在吸收区中接触以吸收二氧化碳,得到贫二氧化碳的处理气流和废吸收介质;
其中步骤(ii)所用吸收区中的压力在0.9与2巴之间,优选0.9与1.5巴之间的范围内;并且
其中步骤(ii)中使用的水性贫吸收介质包含一种或多种胺,所述胺选自:
-缺乏具有足以中和氨基甲酸的pKa的有效量的叔胺官能团的多胺,所述多胺的至少一个伯胺官能团具有在25℃下小于10.0的pKa,
-缺乏具有足以中和氨基甲酸的pKa的有效量的叔胺官能团的多胺,所述多胺的至少一个仲胺官能团具有在25℃下对于每个吸附氮而言小于10.0的pKa。
相较于涉及用(活化)MDEA进行克劳斯废气处理的方法,本发明是一种改进的方法。
根据本发明的方法实现了有效的CO2去除,同时可以使用简化流程。由于不需要对克劳斯废气加压,因此可以用较少的设备进行所述方法。这也使得能耗降低。此外,上列胺类的处理方法对克劳斯单元下游存在的H2S不太敏感。
具体实施方式
本发明涉及一种用于从根据权利要求1的进料气流中去除硫化氢和二氧化碳的方法。进料气流包含硫化氢并且包含二氧化碳并且任选地包含其它污染物,例如COS。
在步骤(i)中,使进料气流中的硫化氢在克劳斯单元中转化为元素硫。获得包含含量减少的硫化氢的气流。克劳斯法不能或几乎不能去除二氧化碳,且因此二氧化碳仍然存在于气流中。
优选地,步骤(i)中使用的进料气流包含至多25vol%的二氧化碳。
步骤(i)优选具有两个步骤。在步骤(ia)中,进料气流中的硫化氢在克劳斯单元中转化为元素硫,从而获得元素硫以及包含含量减少的硫化氢且包含二氧化碳的气流。在步骤(ib)中,借助于溶剂从(ia)所得气流中去除甚至更多的硫化氢。
在步骤(ib)中,使用包含胺的溶剂来去除硫化氢,优选选择性地去除硫化氢而不去除或几乎不去除二氧化碳。获得包含含量进一步减少的硫化氢并且仍还包含CO2的物流。在步骤(ib)中,优选借助于壳牌克劳斯废气处理(SCOT)方法去除硫化氢。在步骤(ib)中去除硫化氢的另一种合适方法是使用溶剂,如Flexsorb(ExxonMobil)。
在步骤(ii)中,使步骤(i)所得气流的至少一部分与水性贫吸收介质在吸收区中接触。二氧化碳被吸收。获得贫二氧化碳的处理气流。获得废吸收介质。
步骤(ii)所用吸收区中的压力是在0.9与2巴之间,优选在0.9与1.5巴之间的范围内。
步骤(ii)中使用的水性贫吸收介质包含一种或多种胺,所述胺选自:
-缺乏具有足以中和氨基甲酸的pKa的有效量的叔胺官能团的多胺,所述多胺的至少一个伯胺官能团具有在25℃下小于10.0的pKa,
-缺乏具有足以中和氨基甲酸的pKa的有效量的叔胺官能团的多胺,所述多胺的至少一个仲胺官能团具有在25℃下对于每个吸附氮而言小于10.0的pKa。
“缺乏具有足以中和氨基甲酸的pKa的有效量的叔胺官能团的多胺、所述多胺的至少一个伯胺官能团具有在25℃下小于10.0的pKa”的优选实例是二亚乙基三胺(DETA)、三亚乙基四胺(TETA)、四亚乙基五胺(TEPA)和其混合物。
“缺乏具有足以中和氨基甲酸的pKa的有效量的叔胺官能团的多胺、所述多胺的至少一个仲胺官能团具有在25℃下对于每个吸附氮而言小于10.0的pKa”的优选实例是N-(2-羟乙基)哌嗪。
由于步骤(ii)不需要在高压下进行,因此在吸收单元的设计和尺寸方面存在自由度。处置大规模克劳斯废气流时,在大多数情况下,不需要使用多个压缩机和多个吸收单元。相反,在大多数情况下,避免在步骤(i)和步骤(ii)之间使用压缩机就足够了。另外或可替代地,在大多数情况下,使用单个吸收单元就足够了。因此,在大多数情况下,简单的单个序列就足够了。
优选地,步骤(ii)中在吸收区中与水性贫吸收介质接触的气流,在步骤(i)和步骤(ii)之间不被加压到2巴以上。优选地,步骤(ii)中在吸收区中与水性贫吸收介质接触的气流,在步骤(i)和步骤(ii)之间、在压缩机中不加压。由于需要气流,因此气流的压力可以略高于大气压。步骤(ii)中使用的气流的压力是在0.9与2巴之间,优选0.9与1.5巴之间的范围内。
优选地,步骤(i)所得的至少70%、优选至少85%、更优选至少95%、更优选整个气流在步骤(ii)中、在单个吸收单元中被处理。
本发明的方法对H2S或其它硫组分不太敏感。因此,在步骤(ii)中,吸收区中的贫吸收介质可包含硫化氢和任选存在COS。
因此,步骤(ii)中仍存在于待处理的气流中的含量减少的H2S无需加以去除。因此,例如,步骤(i)所得的气体在步骤(ii)之前无需焚烧。优选地,步骤(ii)中在吸收区中与水性贫吸收介质接触的气流,在步骤(i)和步骤(ii)之间不焚烧。这节省了复杂性和设备。
优选地,步骤(ii)中在吸收区中与水性贫吸收介质接触的气流包含硫化氢、二氧化碳和任选存在的COS。
在一个优选的实施例中,所述方法在步骤(ii)之后包含以下步骤:
(iii)使步骤(ii)所得的废吸收介质在再生区中再生,产生已再生的水性吸收介质和二氧化碳;和
(iv)将步骤(iii)获得的再生水性吸收介质的至少一部分再循环至步骤(ii)。
在一个优选实施例中,使步骤(iii)所得的再生水性吸收介质的一部分循环至步骤(ii)并且所述方法在步骤(iv)之后包含以下步骤:
(v)从步骤(iii)所得的再生水性吸收介质的第二部分中去除热稳定盐,优选借助于离子交换树脂、电渗析、结晶或热回收;和
(ⅵ)将步骤(v)获得的热稳定盐含量减少的所得再生水性吸收介质的至少一部分再循环至步骤(ii)。
优选地,步骤(iii)是在再沸器中进行,
优选在釜式再沸器、强制循环再沸器、燃烧再沸器、降膜再沸器、直接蒸汽再沸器或热虹吸器中,优选在热虹吸器中进行。
Claims (9)
1.一种从进料气流中去除硫化氢和二氧化碳的方法,所述方法包含以下步骤:
(i)使所述进料气体流中的硫化氢在克劳斯单元转化成元素硫,从而获得元素硫以及包含含量减少的硫化氢且包含二氧化碳的气流;
(ii)使步骤(i)所得的所述气流的至少一部分与水性贫吸收介质在吸收区中接触,以吸收二氧化碳,得到贫二氧化碳的处理气流和废吸收介质;
其中步骤(ii)使用的所述吸收区中的压力是在0.9与2巴之间,优选0.9与1.5巴之间的范围内;并且
其中步骤(ii)使用的水性贫吸收介质包含一种或多种胺,所述胺选自:
二亚乙基三胺(DETA)、三亚乙基四胺(TETA)、四亚乙基五胺(TEPA)及其混合物,
N-(2-羟乙基)哌嗪。
2.根据权利要求1所述的方法,其中步骤(i)所得的所述气流的至少70%、优选至少85%、更优选至少95%在步骤(ii)中、在单个吸收单元被处理。
3.根据权利要求1或2所述的方法,其中步骤(ii)中与水性贫吸收介质在吸收区中接触的所述气流在步骤(i)和步骤(ii)之间不焚烧。
4.根据上述权利要求中任一项所述的方法,其中步骤(ii)中与水性贫吸收介质在吸收区中接触的所述气流包含硫化氢、二氧化碳和任选存在的COS。
5.根据上述权利要求中任一项所述的方法,其中步骤(i)包含:
(ia)将所述进料气流中的硫化氢在克劳斯单元中转化为元素硫,从而获得元素硫以及包含含量减少的硫化氢和二氧化碳的气流;
(ib)借助于包含胺的溶剂从(ia)所得的所述气流中去除甚至更多的硫化氢,从而获得包含含量进一步减少的硫化氢的物流。
6.根据上述权利要求中任一项所述的方法,所述方法具有以下额外步骤:
(iii)使步骤(ii)所得的废吸收介质在再生区中再生,以产生再生的水性吸收介质和二氧化碳;和
(iv)将步骤(iii)获得的所述再生水性吸收介质的至少一部分再循环至步骤(ii)。
7.根据权利要求6所述的方法,其中在步骤(iv)中,使步骤(iii)所得的所述再生水性吸收介质的一部分再循环到步骤(ii),和所述方法具有以下额外步骤:
从步骤(iii)所得的所述再生水性吸收介质的第二部分中去除热稳定盐,优选借助于离子交换树脂、电渗析、结晶或热回收来进行;和
(vi)使如步骤(v)所得具有减少的热稳定盐含量的所得再生水性吸收介质的至少一部分再循环至步骤(ii)。
8.根据权利要求6或7所述的方法,其中步骤(iii)是在再沸器中进行,
优选在釜式再沸器、强制循环再沸器、燃烧再沸器、降膜再沸器、直接蒸汽再沸器或热虹吸器中,优选在热虹吸器中进行。
9.根据上述权利要求中任一项所述的方法,其中步骤(i)中使用的所述进料气流包含至多25vol%的二氧化碳。
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