CN102712469B - 运行带有集成co2分离装置的igcc发电厂过程的方法 - Google Patents
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Abstract
本发明涉及一种运行带有集成CO2分离装置的IGCC发电厂过程的方法。采用这种方法时,含H2和CO2的过程气体借助于压力交变吸附(PSA)分离为工业纯氢以及一个富含CO2的级分,其中富含CO2的级分通过压力降作为PSA废气释放。所产生的氢在至少一个用来发电的燃气轮机中燃烧,其中该燃气轮机废气在废热锅炉中用来产生水蒸气,水蒸气在一个同样用来发电的蒸汽轮机中卸压。该PSA废气在一个单独的锅炉中用工业纯氧燃烧,其中产生废气温度大于1000℃的废气。该废气用来对引入蒸汽轮机过程的蒸汽进行过热和/或用来产生蒸汽轮机过程用的压力较高的蒸汽。来自燃气轮机的废热和来自废气的废热产生一个压力大于120巴和温度超过520℃的蒸汽轮机过程用的过热的高压蒸汽。
Description
描述
本发明涉及一种运行带有集成CO2分离装置的IGCC发电厂过程的方法。IGCC代表″Integrated Gasification Combined Cycle(集成气化联合周期)″。IGCC发电厂是煤气和蒸汽轮机联合发电厂,前接一个化石燃料的气化级,特别是煤气化级。
气化是一种从化石燃料产生含CO和H2的合成气的过程。该合成气经受CO转化,此时包含在合成气中的一氧化碳与水蒸气转变为二氧化碳和氢。该合成气在转化之后主要由二氧化碳和氢组成。通过化学或物理煤气冲洗器二氧化碳可以从合成气清除。这时富含氢的合成气在燃气轮机中燃烧。在这个清除二氧化碳的概念下,与没有CO2清除装置的传统煤气和蒸汽轮机发电厂相比,总效率约降低10个百分点。
从EP 0 262 894 B1已知一种从燃料分离和制取CO2的方法,它除了碳氢化物外还含有H2和CO2,其中进料气体借助于压力交变吸附(PSA,pressure swing adsorption(压力摆动吸附)分离出工业纯氢级分以及富含CO2的级分,其中富含CO2的级分还含有可燃气体和特别是H2,而且其中来自PSA设备的富含CO2的级分在一个单独的锅炉中用工业纯氧燃烧。这时,例如该废热可以用来产生蒸汽。
从US-2007/017 8035 A1已知一种运行带有集成CO2分离装置的IGCC发电厂过程的方法。在该已知方法中从化石燃料产生一种含有CO和H2的合成气,其中至少部分合成气流在CO转化级中借助于水蒸气转化为H2和CO2。所出现的含H2和CO2的过程气体借助于压力交变吸附(PSA-设备)分离为工业纯氢级分以及富含CO2的级分,其中富含CO2的级分还含有诸如CO以及H2等可燃气体。所产生的氢在一个用来发电的燃气轮机中燃烧,其中燃气轮机的废气在废热锅炉中用来产生水蒸气,将水蒸气在一个同样用来发电的蒸汽轮机中卸压。来自压力交变吸附的富含CO2的级分,通过周期的压力降在压力交变吸附装置(PSA)中释放并被称为“PSA废气”,在一个单独的锅炉中用工业纯氧燃烧。这时,由CO2 和燃烧产物组成的废气的废热通过热交换器加以利用。在该已知方法中废气的废热用来预热在燃气轮机过程中所采用的氢气流。
WO 2006/1 12 725 A1同样描述了带有上述特征的方法。来自压力交变吸附的富含CO2的级分作为燃烧气体用来加热产生合成气用的蒸汽转化器(Steamreformers)。在燃烧时所产生的废气基本上由CO2和水蒸气组成。分离出水蒸气并把基本上由CO2组成的剩余气流输送到最终储存或者利用。
传统的IGCC过程燃气轮机的废气温度约为600℃。由于材料技术上的原因采用传统的燃气轮机不可能达到较高的废气温度。因此,通过燃气轮机废热利用可以为蒸汽轮机过程提供温度最大值大约只有550℃的蒸汽。生产合成气时高的气化温度也不可能用来对蒸汽进行较高的过热,因为合成气使蒸汽锅炉的材料还原,导致锅炉的持久损坏。传统的IGCC发电厂过程(只能)容忍蒸汽轮机以与现代煤发电厂水平不一致的蒸汽参数(压力和过热温度)运行。
在此背景下本发明的任务在于,改善带有集成CO2分离装置的IGCC发电厂过程的总效率。
本发明的主题和这个任务的解决方案是按照权利要求1的方法。从带有前言所描述的和权利要求1上位概念所给出的特征的方法出发,按照本发明的任务这样解决,即通过燃烧在压力交变吸附时所产生的富含CO2的级分,产生一种废气温度大于1000℃的废气,用来过热接在燃气轮机后面的废热锅炉中所产生的蒸汽,和/或用来为蒸汽轮机过程产生压力较高的蒸汽,并使得燃气轮机的废热和在燃烧富含CO2的级分时出现的废气为蒸汽轮机过程产生压力大于120巴而温度大于520℃,优选大于550℃的过热高压蒸汽。
通过PSA废气在一个单独的锅炉中的加氧燃烧产生一种温度高于1000℃的基本上由CO2和水蒸气组成的废气。通过该废气的废热利用,与传统的IGCC过程相比可能达到较高的蒸汽过热,例如达到600至700℃,以便可以与此相应地借助于按照本发明的方法大大改善IGCC设备蒸汽轮机过程的效率。优选设计为过热至大于550℃。以此至少部分地补偿由于缺少合成气的PSA废气引起的燃气轮机过程不可避免的效率损失。因此,在应用按照本发明的教导时具有集成二氧化碳分离装置的IGCC发电厂的总效率与没有二氧化碳分离装置的传统的IGCC发电厂相比只稍微低一些。
在按照本发明的方法中,采用压力交变吸附装置PSA(pressure swing adsorption)来把转化后的合成气分离为富含二氧化碳的和富含氢的馏份。这时,转化后合成气在高压下流入第一吸附器。包含于该气体中的二氧化碳被吸附。氢与吸附剂物质只有小的相互作用并在很大程度上不受障碍地流过第一吸附装置。若该吸附剂的吸收能力耗尽,则合成气流被转送到第二吸附器。在此期间该第一吸附器通过卸压而再生,其中二氧化碳从吸附剂释放出来。卸压时释放的气体称为“PSA废气”。一部分包含于引入的合成气中的氢,例如,与合成气一起引入的氢量,例如15%,不可避免地进入PSA废气,因此使生产合成气的效率恶化。因此,该PSA废气大部分由二氧化碳组成,然而它还含有一部分氢和一氧化碳。由于二氧化碳含量高,PSA废气无法用于传统的与空气进行热燃烧。
在按照本发明的方法中,该富含CO2的PSA废气用工业纯氧燃烧。因为二氧化碳克分子热容量比氮气高,形成的燃烧温度,尽管使用纯氧但仍与化石燃料用空气的燃烧的温度大致相同。因此,可以使用为化石燃料与空气燃烧设计的传统窑炉。
离开加氧PSA废气燃烧的废气差不多只由二氧化碳和水蒸气组成。这时,生产合成气时避免氮气进入合成气被证实是特别有利的。为此在排放(Schleus)和冲洗过程中优选使用二氧化碳代替氮气。
用工业纯氧进行的富含CO2的PSA废气燃烧和按照本发明的废热利用以改善蒸汽轮机过程的相关蒸汽参数之后,废气中所含的水蒸气冷却并冷凝出来,以便此后提供纯二氧化碳组分。它可以进行最终储存或用于“增强石油回收”,其时把二氧化碳压入储油容器,以此提升压力并把剩余石油压出表面。
通过按照本发明的废热利用可以毫无困难地产生压力大于200巴的高压蒸汽,蒸汽轮机过程用它可以效率良好地运行。
在蒸汽轮机过程的范围内可以使用蒸汽轮机,蒸汽轮机是多级构造的并具有至少一个高压部件和一个低压部件。这时,在一个这样的蒸汽轮机中可以设计为,借助于在富含CO2的级分燃烧时出现的废气,实现来自高压部件的卸压蒸汽中间过热达到温度大于520℃,优选大于550℃。
按照本发明的方法出现一种基本上由CO2组成的剩余气流。这时,存在这样的可能性,即提取所产生的CO2部分,并例如在从化石燃料产生合成气时用来输送燃料和/或用于冲洗和惰性化目的。
按照本发明在富含CO2级分燃烧时出现的废气,用来过热在接在燃气轮机后面的废热锅炉中产生的蒸汽,和/或用来为蒸汽轮机过程产生压力较高的蒸汽。为了达到进一步提高效率,此后还可以利用富含CO2级分内包含的残余热量,在富含CO2的级分燃烧之前将其预热和/或用来预热引入燃烧中的工业纯氧。
富含CO2的PSA废气与纯氧燃烧时释放的热量的热利用优选在锅炉中进行,用来产生蒸汽。若PSA废气燃烧时的燃烧温度不符合所需要的锅炉温度,则可以通过专利权利要求6至13中描述的多个措施修正,,而且现将加以阐述。
通过引入CO转化的合成气的比例来调整燃烧温度,被证实是特别有利的。若锅炉温度太低,则缩小引入转化的合成气比例,以便使较大比例的合成气通过部分绕行,绕过(vorbeigeschleust)CO转化。若锅炉温度太高,则提高引入转化的合成气比例,并使较小比例的合成气通过部分绕行,绕过CO转化。在锅炉温度太高时也可能的是全部合成气都进行转化。
此外,燃烧温度可以用CO转化的转化率调节,其中设计为一级、二级或三级CO转化。还可能的是通过改变转化反应器中的温度影响转化率。一氧化碳转化为二氧化碳的转化率越高,在PSA废气加氧燃烧时形成的燃烧温度就越低。
影响燃烧温度的另一种可能性是,把部分离开PSA废气加氧燃烧的燃烧气体送回。送回燃烧的燃烧气体的比例越大,燃烧温度降低越严重。
按照本发明的方法的另一个方法方案设计为,通过输入合成气或者输入来自其他燃烧气体源的燃烧气体提高PSA废气燃烧的废气温度。通过把一部分富含氢的级分引入燃烧而可能的是,提高富含CO2的级分与氧的转化温度。另外,可以把在IGCC生产过程中产生的低热量气体引入PSA废气加氧燃烧的燃烧过程。
宜在合成气加工过程中就已经进行脱硫。这时,脱硫可以在CO转化之前进行,或者在此之后进行。这时PSA废气加氧燃烧的废气差不多只由二氧化碳和水蒸气组成,因为脱硫已经在合成气加工时进行。
以此在含有CO2的级分燃烧时出现的废气,基本上只含有二氧化碳和水,优选产生无氮粗合成气。已经证实,它最好采用没有氮气参与的蒸气分解反应来制造粗合成气,或者在制造粗合成气的部分氧化时使用纯氧。此外,在排放(Schleus)和冲洗过程中优选用二氧化碳来代替氮气。制造合成气时借助于煤气化来输送煤和用于冲洗目的,使用二氧化碳被证明是特别有利的。
不在合成气路径上脱硫和在PSA废气燃烧时出现的废气借助于传统的废气脱硫方法脱硫也在本发明的范围内。
因为不在这种方法方案下使合成气脱硫,故所有硫组分都会和其他PSA废气组分一起进入PSA废气。在PSA废气燃烧中硫组分转化为SOx。SOx组分借助于传统的废气脱硫方法,例如,石灰冲洗产生石膏,从含有CO2的废气分离。作为替代方案,还有这样的可能性,即包含在PSA废气中的硫组分在用工业纯氧燃烧之前清除。
Claims (13)
1.运行带有集成CO2分离装置的IGCC发电厂过程的方法,
其中从化石燃料产生含有CO和H2的合成气,
其中该合成气的至少一个支流在CO转化级中借助于蒸气转化为H2和CO2,
其中所出现的含H2和CO2的过程气体,借助于压力交变吸附(PSA)分离出工业纯氢以及富含CO2的级分,富含CO2的级分还含有CO和H2,
其中所产生的氢在至少一个用来发电的燃气轮机中燃烧,
其中燃气轮机的废气在废热锅炉中用来产生水蒸气,水蒸气在同样用来发电的蒸汽轮机过程中卸压,
其中使来自压力交变吸附的富含CO2的级分在单独的锅炉中用工业纯氧燃烧,由CO2和燃烧产物组成的废气的废热通过热交换器利用,
其中从在富含CO2级分燃烧时所产生的废气分离水蒸气和将基本上由CO2组成的剩余气流输送到最终储存或者利用,
其特征在于,通过在压力交变吸附时产生的富含CO2级分的燃烧,产生废气温度大于1000℃的废气,其用来过热接在燃气轮机后面的废热锅炉中所产生的蒸汽,和/或用来产生压力较高的蒸汽,用于蒸汽轮机过程,
还在于,由燃气轮机的废热和在富含CO2级分燃烧时出现的废气的废热,来产生压力大于120巴且温度大于520℃的蒸汽轮机过程用的过热高压蒸汽。
2.按照权利要求1的方法,其特征在于,产生压力大于200巴的蒸汽轮机过程用的过热高压蒸汽。
3.按照权利要求1或2方法,其特征在于,蒸汽轮机过程使用蒸汽轮机,它具有至少一个高压部件和一个低压部件,并借助于在富含CO2级分燃烧时出现的废气将来自高压部件的卸压蒸汽中间过热至大于520℃的温度。
4.按照权利要求1的方法,其特征在于,在由化石燃料产生合成气时,将CO2用于燃料输送和/或冲洗和惰性化目的,以便产生无氮合成气。
5.按照权利要求1的方法,其特征在于,使在富含CO2级分燃烧时出现的废气在过热接在燃气轮机之后的废热锅炉中产生的蒸汽之后,或在产生蒸汽轮机过程用的压力较高的蒸汽之后,在富含CO2的级分燃烧之前用来对其进行预热,和/或用来预热引入的工业纯氧。
6.按照权利要求1的方法,其特征在于,富含CO2级分燃烧的燃烧温度通过富含CO2级分中可燃气体的含量进行调节。
7.按照权利要求1的方法,其特征在于,合成气的支流在旁路中绕过CO转化级,并通过控制引入旁路的流量,调节富含CO2级分燃烧时产生的燃烧温度。
8.按照权利要求1的方法,其特征在于,为了降低废气温度,将来自富含CO2级分的废气支流回输到用于燃烧富含CO2级分的锅炉。
9.按照权利要求1的方法,其特征在于,富含CO2级分燃烧时产生的废气温度通过输入合成气或者输入来自其他燃烧气体源的燃烧气体而提高。
10.按照权利要求1的方法,其特征在于,使该合成气在CO转化之前脱硫。
11.按照权利要求1的方法,其特征在于,使该合成气在CO转化之后脱硫。
12.按照权利要求1的方法,其特征在于,包含于合成气中的硫组分通过压力降进入在压力交变吸附时产生的富含CO2级分,其中使该富含CO2的级分在与工业纯氧燃烧之前脱硫。
13.按照权利要求1的方法,其特征在于,包含于合成气中的硫组分通过压力降进入在压力交变吸附时产生的富含CO2的级分,并在富含CO2级分燃烧时转化为SOx,并且,SOx组分借助于废气脱硫从含有CO2的废气分离。
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PCT/EP2010/063670 WO2011039059A1 (de) | 2009-09-30 | 2010-09-17 | Verfahren zum betrieb eines igcc-kraftwerkprozesses mit integrierter co2-abtrennung |
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DE102017005627A1 (de) | 2016-10-07 | 2018-04-12 | Lennart Feldmann | Verfahren und System zur Verbesserung der Treibhausgas-Emissionsminderungsleistung biogener Kraft-, Heiz- und Brennstoffe und/oder zur Anreicherung landwirtschaftlich genutzter Flächen mit Humus-C |
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