CN102177089B - 脱硫的方法和装置 - Google Patents

脱硫的方法和装置 Download PDF

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CN102177089B
CN102177089B CN200980139510.4A CN200980139510A CN102177089B CN 102177089 B CN102177089 B CN 102177089B CN 200980139510 A CN200980139510 A CN 200980139510A CN 102177089 B CN102177089 B CN 102177089B
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J·曼泽尔
O·沃恩莫斯滕
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ThyssenKrupp Industrial Solutions AG
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Abstract

本发明涉及脱硫方法，其中气体混合物经历分离过程分离出酸性的气体成分，在该分离过程中形成含二氧化碳和硫化合物特别是硫化氢的酸性气体，为了分离单质硫，将酸性气体输送到克劳斯装置，离开克劳斯装置的残余气体经历进一步分离，其中克劳斯工艺中形成的水被至少部分除去，仅工业纯氧气作为含氧反应气体被输送到克劳斯装置，将二氧化碳以使得能够直接封存或工业利用的纯度从克劳斯装置下游排出。

Description

脱硫的方法和装置
描述
本发明涉及脱硫方法，其中气体混合物经历分离过程以分离出酸性的气体成分，在该分离过程中形成含二氧化碳和硫化合物特别是硫化氢的酸性气体。在该方法中，首先用适合的吸收剂从气流除去酸性的气体成分，并由此与有用的气体成分分离。在将输入环路中的吸收剂再生的情况下，所含有的酸性气体成分被释放，然后输送到克劳斯装置(Claus Anlage)。
克劳斯法通常通过用空气燃烧酸性气体来进行，其中硫化氢(H2S)与燃烧用空气中所包含的氧气(O2)反应生成单质硫和水(H2O)，并且其中通过随后在冷凝器中冷却分离出单质硫(S)(Ullmann′s  der technischen Chemie，第10卷，第4版，1975，第594页)。采用已知的克劳斯法，通常可以获得直至98％的收率。为了实现残余气体的额外纯化，它可经历残余气体纯化过程。虽然克劳斯法中生成的单质硫可被取出和商业利用，但经纯化的残余气体通常未被利用地排放到环境。
作为所谓的温室气体，二氧化碳促成全球温室效应，因而存在避免二氧化碳的额外释放的需要。此外，目前，还已知需要大量二氧化碳作为工艺气体的方法。例如，二氧化碳可用于在油回收 的情况下增加收率，其中将二氧化碳注入到贮油器中(“增加的油回收”，EOR)。对于封存(Sequestrierung)二氧化碳以避免排放和用于工业利用而言，必需通常将二氧化碳以相当大的耗费与其它成分例如氮气分离。
文献EP 0 059 412 A2涉及用于调节燃烧过程特别是克劳斯装置的操作中的载气量的方法，其中所形成的残余气体以常规方式被排放到环境。为了达到最佳燃烧，设计为，输入空气和工业纯氧气，其中 空气和工业纯氧气的比例适合于每种情况下存在于燃烧气中的惰性气体份额。术语“工业纯氧气”指绝大部分由氧气组成并在常规大规模工业制备方法中形成的气体。纯度通常大于90％，低温分解法中的纯度典型地是至少98％。
从H.Fischer在Chemie-Ing.-Techn.，第39卷，1967，515-520页的论文还已知，对于酸性气体的转化，当硫化氢的份额在20体积％至约5体积％之间时，向克劳斯装置提供工业纯氧气，以便获得足够高的燃烧温度。在此，残余气体也以常规方式作为废气被释放。
本发明的目的在于提供具有开篇所述的特征的方法，其使得可以低耗费地利用酸性气体中所含的二氧化碳。
该目的根据本发明通过专利权利要求1的方法实现。根据本发明，应以尽可能纯的形式分开地提取酸性气体中包含的硫成分级分和二氧化碳级分。用现有技术已知的方法，这种尽可能纯的分离只有在非常高的耗费下才是可能的，因为已知的吸收方法不能以高选择性从气体混合物一方面分开分离硫成分而另一方面分开分离二氧化碳。但是，与此相比，组合酸性气体级分中的二氧化碳和硫成分的组合分离是较简单的，为了进一步处理，将组合酸性气体级分输送到克劳斯装置，然后在本方法的范围内被成本有利地转化为单质硫和二氧化碳。对于二氧化碳和硫成分的组合分离，例如可以采用发挥化学和物理作用的洗涤法。根据本发明，只向克劳斯装置输入工业纯氧气作为含氧反应气体。由此，以尤其有利的方式实现了，在处理酸性气体时，没有输入在之后必需以高耗费与二氧化碳分离的惰性气体成分。
在本方法的优选实施方案范围内提供了当在燃烧室内超过最大允许燃烧温度时，一部分工艺自身的残余气体在克劳斯装置的下游侧排出并为了冷却而与工业纯氧气一起被输送到燃烧室。通过所述的措施，燃烧过程的精确控制是可能的，而未不利地影响二氧化碳浓缩。
在基本上由二氧化碳和硫成分尤其是H2S、COS和硫醇组成的酸性气体的情况中，由此可实现尽可能完全分离。在克劳斯工艺中通过硫成分与氧气反应生成的水和单质硫被从残余气体冷凝出来，从而实现 二氧化碳显著浓集。为了至少尽可能除去仍残留的硫化合物残余，离开克劳斯装置的残余气体可经历下游气体纯化过程。例如，可以提供氢化，其中将残余气体中所包含的除了H2S之外的硫成分氢化为H2S。然后将残余气体骤冷，并进行选择性洗涤，优选用化学吸收剂，从而尽可能除去残余气体中仍存在的H2S。在硫成分额外去除后，残余气体基本由二氧化碳、水和少量一氧化碳和氢气组成。例如， 法(壳牌尾气处理)适合作为残余气体纯化方法。
为了将氢气和/或一氧化碳转化为水和/或二氧化碳，可提供残余气体与工业纯氧气的后燃烧，优选催化地进行后燃烧。如果最初输送到克劳斯装置的酸性气体基本由硫化合物和二氧化碳组成，那么在进行残余气体纯化过程和后燃烧以除去氢和/或一氧化碳之后，残余气体几乎仅含纯二氧化碳和水蒸汽，水蒸汽在残余气体的进一步处理中被冷凝出。此外，也可采用将气体干燥的已知方法以便进一步减少含水量。通常将除去水后基本由二氧化碳组成的残余气体压缩或液化用于封存，即特别是在地质层组如石油矿层、天然气矿层、蓄水层 、煤层中或在深海中存储，或者用于工业利用，其中特别是也可以设计为临时储存或运输二氧化碳。取决于所提供的二氧化碳的进一步应用，气态中的纯度适宜为80体积％、优选90体积％、尤其优选95体积％。
除了氢和/或一氧化碳与工业纯氧气的后燃烧之外或作为替代，也可通过改变残余气体的压力和/或温度实现除去上面所列成分。例如，可以设计为，在进行残余气体纯化过程后，借助气体冷凝器和骤冷塔使残余气体脱除绝大部分水蒸汽，然后压缩以使二氧化碳液化。然后可以在适合的分离装置中将一氧化碳和氢气从液化二氧化碳除去。
如果输送到克劳斯装置的酸性气体除了二氧化碳和硫成分之外还含有惰性气体成分，那么至少可以使下游分离的耗费小，因为在本发明的脱硫方法中，没有输入额外的惰性气体成分。
根据本发明提供的工业纯氧气的应用使得以尤其有利的方式在给定量酸性气体的情况下，也能够实现克劳斯装置和任选提供的用于残 余气体纯化的装置的较小尺寸，从而可补偿提供工业纯氧气必需的附加成本。
本发明的主题还有实施权利要求11的方法的装置。除了常规部件之外，所述装置特别是还包括连接管线，其将克劳斯装置的燃烧室入口与克劳斯装置下游的气体管道或与克劳斯装置下游的残余气体储存容器连接。此外，在入口处连接管线上设置控制单元，以便控制工艺自身的残余气体的混合。

Claims (8)

1.脱硫方法，
其中，气体混合物经历分离过程以分离出酸性的气体成分，在该分离过程中形成了含二氧化碳和硫化合物的酸性气体，
其中，为了分离单质硫，将酸性气体输送到克劳斯装置，仅工业纯氧气作为含氧反应气体被输送到克劳斯装置，和
其中，将二氧化碳以使得能够直接封存或工业利用的纯度从克劳斯装置下游排出，
其中，在燃烧室中超过最大允许燃烧温度的情况下，向克劳斯装置输送关于克劳斯装置下游侧排出的一部分工艺自身的残余气体的混合物，和其中为了除去氢和一氧化碳，将残余气体经历与工业纯氧气的后燃烧，并且水蒸汽从残余气体中冷凝出来。
2.权利要求1的方法，其特征在于，进行残余气体的催化后燃烧。
3.权利要求1的方法，其特征在于，在所述分离过程中所有的酸性气体成分一起被从气体混合物分离出来并以组合级分形式作为酸性气体提取。
4.权利要求1的方法，其特征在于，所述分离过程包括用物理和/或化学吸收剂洗涤气体混合物和使吸收剂再生。
5.权利要求1的方法，其特征在于，离开克劳斯装置的残余气体经历残余气体纯化过程，以便至少尽可能地除去硫化合物残余。
6.权利要求1的方法，其特征在于，将残余气体压缩以进一步利用。
7.权利要求1的方法，其中，所述硫化合物包括硫化氢。
8.权利要求5的方法，其中，所述残余气体纯化过程是SCOT过程。
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