CN101918104B - 用于处理包含co2的工艺气流的方法 - Google Patents

用于处理包含co2的工艺气流的方法 Download PDF

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CN101918104B
CN101918104B CN2008801174450A CN200880117445A CN101918104B CN 101918104 B CN101918104 B CN 101918104B CN 2008801174450 A CN2008801174450 A CN 2008801174450A CN 200880117445 A CN200880117445 A CN 200880117445A CN 101918104 B CN101918104 B CN 101918104B
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乌尔里希·科斯
曼弗雷德·迈尔
亚历山大·施里费尔
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Abstract

本发明涉及用于处理包含CO2的工艺气流的方法，所述包含CO2的工艺气流是在从所述工艺气流的粗气制备纯的合成气的同时，或在重油、石油焦和废料的部分氧化过程中，或在煤的气化过程中，或在处理天然气或石油伴生气过程中产生的，其中通过物理吸收或化学吸收从所述含有CO2的工艺气流中除去CO2，并且将负载有CO2的溶剂膨胀到较低压力以解吸所述CO2。为了产生尽可能纯净的CO2，将未纯化的CO2压缩到至少60巴的绝对压力或者在CO2的临界温度以下压缩到至少70巴的绝对压力，并通过使用逆流引导的气态CO2进行汽提来除去包含在所述液体CO2中的杂质。

Description

用于处理包含CO2的工艺气流的方法
技术领域
本发明涉及用于处理包含CO2的工艺气流的方法，所述包含CO2的工艺气流是在由如下粗气生产纯净的合成气的过程中获得的，所述粗气是重油、石油焦或废料的部分氧化的粗气，或者在煤的气化过程中，或者在处理天然气或石油伴生气时获得的，其中通过物理吸收或化学吸收从所述包含CO2的工艺气流中除去CO2，将负载有CO2的溶剂减压至较低压力，从而解吸CO2。
背景技术
以名称
Figure GPA00001140543800011
Figure GPA00001140543800012
Figure GPA00001140543800013
Figure GPA00001140543800014
和热钾碱洗涤公知的工艺用于由如下粗气，该粗气是重油、石油焦或废料的部分氧化的粗气，或者由煤的气化，或者由处理天然气或石油伴生气来生产纯净的合成气。
在
Figure GPA00001140543800016
工艺中，将来自重油、石油焦或废料的部分氧化，或者来自煤的气化的粗气用作原料。除了需要的产物组分H2和CO之外，所述粗气还包含不需要的产物组分CO2、H2O、H2S、CS2、COS、HCN、NH3、有机硫化合物、金属羰基化合物以及烃，这些不需要的产物组分必须被分离，为此使用冷甲醇作为物理溶剂。然后，将所吸收的产物组分通过对溶剂进行减压和沸腾除去而重新解吸，并在后续设备中进行处理。由于所述不需要的产物组分在冷甲醇中的溶解度差异很大，可以选择性地分离所述产物组分，例如选择性地分离H2S和CO2。将冷却的粗气供应给H2S吸收器，所述H2S吸收器采用30至60巴的绝对压力以及用负载CO2的冷甲醇进行操作，在所述H2S吸收器的预洗涤阶段中，首先除去例如HCN和NH3的杂质。在所述H2S吸收器的第二阶段中，H2S和其它的硫化合物被吸收，从而残余的硫含量为＜0.1ppm。将离开所述H2S吸收器的经负载的甲醇膨胀至中等压力，并将由此解吸的气体H2和CO再循环到所述粗气中。然后，将甲醇加热至沸点并“沸腾除去”；在该过程中，释放出所有吸收的气体，并将富含H2S的气体进料到用于回收硫的CLAUS设备。将不含硫的合成气中所包含的CO的一部分转化为CO2，使得CO2浓度通常升高至约33％。然后将冷却的气体供给到二级CO2吸收器。将从所述CO2吸收器排出的经负载的甲醇膨胀至较低的压力并由此冷却。由此释放的CO2不含硫并且可以要么排放至大气中，要么例如用于制备尿素。将在所述CO2吸收器中获得的、CO2含量为约3％的合成气引入到甲醇合成中。在方法中使用N-甲基-2-吡咯烷酮(NMP)代替甲醇作为物理溶剂。将来自粗气的CO2以做功的方式膨胀到燃气轮机中。
在
Figure GPA00001140543800022
方法中，将待处理的粗气在具有结构化的或堆放的填料床的吸收塔的底部引入，在所述吸收塔中使用在该吸收塔顶部供应的甲基二乙醇胺(MDEA)的冷却的水性溶液以逆流洗涤所述粗气，其包含用于提高CO2收率的活化剂(a)。在所述吸收塔顶部排出净化的气体。从吸收塔底部排出的、负载有CO2和H2S的aMDEA溶液可以要么直接加热，要么在膨胀至较低压之后加热。将来自所述再生塔的热的再生的MDEA溶液用作热源。在所述再生塔中，通过再次加热使经负载的aMDEA溶液再生完全，并在冷却后将其再循环至所述吸收塔顶部。在所述再生塔的顶部排出包含CO2和H2S的气体流。将分离的富含H2S的气体要么供应到CLAUS设备，要么供应到后燃烧过程。胺对于H2S和CO2不同的反应速度形成了选择性吸收H2S和分离CO2的基础。
为了除去包含在如下粗气中的不需要的组分CO、H2O、H2S、COS、HCN、NH3、有机硫化合物、金属羰基化合物以及烃，所述粗气是来自重油、石油焦和废料的部分氧化、来自煤的气化以及来自处理天然气和石油伴生气的粗气，上述通过物理吸收和化学吸收进行的吸收方法的缺点在于：产生的CO2仍包含0.1至20体积％，特别是0.5至2.5体积％的一种或多种组分N2、CO、H2和CH4，并且因此不适用于许多应用。
发明内容
本发明的目的是发展如上所述的方法，使得借助于物理吸收或化学吸收的方式工作的吸收方法从粗气中获得的CO2具有尽可能高的纯度并可直接作为有价值产物使用；特别是所述CO2应该符合用于在石油矿床中挤压以改进油回收并且同时将CO2最终储存在所述石油矿床中所提出的质量要求。
该任务通过如下方式得以解决，将被总共0.1至20体积％，优选0.5至10体积％，特别是0.5至2.5体积％的一种或多种组分N2、CO、H2和CH4污染的CO2在室温下压缩到至少60巴的绝对压力，或者在CO2的临界温度31℃以下压缩到至少70巴的绝对压力，并将由此获得的主要具有液体状态的包含CO2的气态杂质通过使用用作汽提气的气态CO2进行汽提除去，从而获得作为液体的CO2。在汽提过程中，通过逆着所述液体CO2的流向穿过所述汽提气而将杂质从所述液体CO2中除去，并且所述杂质被转移至所述汽提气中，这是因为待从所述液体CO2中除去的杂质的蒸气压高于在所述汽提气中的蒸气压，并且因此实现了从所述液体CO2进入到所述汽提气中的转移。
根据所述方法的这个方面，将CO2压缩至10至30巴的绝对压力，并冷却至-40至-5℃的温度。
为了产生所述汽提气，连续蒸发相应量的位于所述塔底部的液体CO2。
在所述汽提塔顶部放出包含所述杂质的汽提气，并且根据本发明的另一特征将其再次进行冷却，以从所述汽提气中冷凝出至少一部分CO2并将其再循环到所述汽提塔的底部。
本发明的一个方面在于，将经负载的汽提气导入到所述方法的吸收阶段中。
具体实施方式
下文通过与附图中所示基本流程图相结合的具体实施方案对根据本发明的方法进行详细阐释。
通过
Figure GPA00001140543800041
方法，典型地通过使用甲醇，从通过部分氧化重油获得的粗气中吸收不需要的组分CO2、H2O、H2S、COS、HCN、NH3、有机硫化合物、金属羰基化合物、CnHm以及其它杂质，例如树脂形成物和硫醇。通过添加水蒸汽，通过
Figure GPA00001140543800042
方法从不需要的组分和杂质中尽可能纯化的合成气中的大部分CO被催化转化为CO2以及H2。
从经纯化的合成气中分离仍含有总共2.0体积％的作为杂质的N2、CO、H2和CH4的CO2，并且通过管路(1)将该CO2进料到压缩器(2)，在该压缩器(2)中，CO2被压缩至25巴的绝对压力，和然后通过管路(3)供应到冷却设备(4)，在冷却设备(4)中，CO2被冷却至-25℃的温度。在这些条件下，CO2几乎全部转化为液体状态，而污染了该CO2的组分几乎完全保持气态。通过管路(5)将所述液态CO2供应到汽提塔(6)的顶部并且以相对于用作汽提气的气态CO2逆流的方式穿过汽提塔(6)，在汽提塔(6)的底部，借助合适的热源(7)通过蒸发少量液体CO2来产生所述汽提气。借助于所述汽提气，将杂质从所述液体CO2中除去并转移到所述气态CO2中。在汽提塔(6)的底部，通过管路(8)排出纯净的液体CO2。在汽提塔(6)顶部排出的包含所述杂质的汽提气可以通过的管路(9)供给到冷却设备(10)，在冷却设备(10)中，一部分CO2被冷凝。通过管路(11)将负载有所述杂质的剩余汽提气供应到粗合成气中。如果剩余量的汽提气的CO2含量过高并且因此再循环所述粗合成气是不经济的，可以将所述汽提气再循环到所述方法中，例如再循环到所述
Figure GPA00001140543800043
方法中，以生产纯净的合成气，并且可以通过在合适的吸收塔中吸收以及膨胀待再循环的工艺气流，而完全去除CO2。也可以使用根据该工艺所用的冷却设备作为用于液化CO2的冷却设备。此外，也存在与所述方法的相应料流进行冷交换的可能性。
在下表中通过参照附图所示的基本流程图给出通过本发明的实际实施方式测定的关于物质流的温度、压强以及组成的数据：
Figure GPA00001140543800051
利用本发明所实现的优点特别在于，实践中，所有的CO2以纯净形式获得，并且有价值气体CO、H2和CH4的损失降低至趋近零。

Claims (6)

1.用于处理包含CO2的工艺气流的方法，所述包含CO2的工艺气流是在由如下粗气来制备纯净的合成气的过程中生成的，所述粗气是在重油、石油焦和废料的部分氧化过程中，或者在煤的气化过程中、或者在处理天然气或石油伴生气时得到的，其中通过物理吸收或化学吸收从所述包含CO2的工艺气流中除去CO2，将负载有CO2的溶剂膨胀到较低的压力，从而解吸CO2，其特征在于，将被总计0.1至20体积％的一种或多种组分N2、CO、H2和CH4污染的CO2在室温下压缩到至少60巴的绝对压力，或者在CO2的临界温度31℃以下压缩到至少70巴的绝对压力，并且通过使用逆流引导的气态CO2进行汽提来除去由此获得的、具有液体状态的、包含CO2的杂质。
2.根据权利要求1所述的方法，其特征在于，将所述CO2压缩到10至30巴的绝对压力，并冷却到-40至-5℃的温度。
3.根据权利要求1或2所述的方法，其特征在于，使用的是被总计0.5至10体积％，特别是0.5至2.5体积％的一种或多种组分N2、CO、H2和CH4污染的CO2。
4.根据权利要求1或2所述的方法，其特征在于，将负载有一种或多种组分N2、CO、H2和CH4的汽提气添加进所述粗气中。
5.根据权利要求1或2所述的方法，其特征在于，将一部分负载有一种或多种组分N2、CO、H2和CH4的汽提气进行冷凝，将冷凝物再循环至吸收塔的底部，并将剩余的汽提气添加进所述粗气中。
6.根据权利要求1或2所述的方法，其特征在于，将负载有一种或多种组分N2、CO、H2和CH4的汽提气导入到所述方法的吸收阶段中。
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