CN110536739A - 使用具有scr催化剂的陶瓷过滤器从烟道气中去除颗粒状物质和有害化合物的方法和系统 - Google Patents
使用具有scr催化剂的陶瓷过滤器从烟道气中去除颗粒状物质和有害化合物的方法和系统 Download PDFInfo
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Abstract
本发明涉及用于在低温下从烟道气中去除氮氧化物的方法和系统。
Description
本发明涉及一种用于减少废气和烟道气中的颗粒状物质和氮氧化物(NOx)的排放的方法和系统。特别地,本发明的方法和系统在低的气体温度下提供改善的NOx减少。
来自不同燃烧设施(例如固体或液体火力发电厂的锅炉、燃气、燃油发电机或水泥窑、以生物燃料为燃料的燃烧厂和废物焚烧厂)的烟道气都含有多种对环境有问题或甚至是有毒的化合物。这些包括颗粒状物质和NOx。
颗粒过滤器的使用和烟道气的催化清洁减少了颗粒状物质和NOx的量,因此总体上对环境有益。在大多数地区,法规要求减少烟道气中的NOx。
陶瓷过滤器,例如烛式过滤器的形式,在许多工业中用于从工艺气体中去除颗粒状物质。它们是可用的最有效的集尘器类型之一,并且对于颗粒物的收集效率可达到99%以上。过滤器可以由各种陶瓷材料制成,包括由碱金属和碱土金属硅酸盐或铝硅酸盐制成的陶瓷纤维。
WO 2016150464中公开了用活性催化剂浸渍的基于陶瓷纤维的陶瓷过滤器,用于去除NOx、NH3、二英、CO和不同的VOC以及灰尘。
特别地,在固定和汽车应用中,基于钒氧化物的催化剂是常用的催化剂,其通过用NH3选择性还原NOx来还原NOx。
通过联合氧化和用NH3的SCR反应,这些催化剂在去除烃(VOC)和NOx方面均具有活性。
在NOx的选择性催化还原(SCR)中,通过与还原剂(例如氨)在催化剂上反应,氮氧化物化合物可被选择性还原为无害的氮和水。
已知的SCR活性催化剂存在的问题是,在气体温度低于250℃时,催化剂的效率相对较低。低的烟道气温度,特别是在燃烧设备启动和关闭时,在通过SCR去除NOx中产生问题。
本发明通过在低于250℃的温度下向烟道气中注入NO2以促进“快速”SCR反应解决了该问题。
已知的是,在烟道气中NO和NO2为等摩尔量时,通过“快速”SCR反应,SCR反应可以被显著加速,并且低温活性可以被显著提高:
2NH3+NO+NO2→2N2+3H2O
因此,本发明基于:在烟道气管道外部形成NO2,并以促进“快速”SCR反应的量将所制备的NO2注入到烟道气中。通过在第一步中将NH3在含有贵金属的催化剂上氧化成NO,然后在第二步中将NO氧化成NO2,可以从NH3形成NO2。
在第一方面,本发明提供了一种用于从来自燃烧设备的烟道气中除去氮氧化物的方法,该方法包括以下步骤:
使烟道气通过一个或多个用催化剂催化的陶瓷过滤器,以使氮氧化物在氨的存在下发生选择性还原,所述氨以原样或以其前体的形式加入至烟道气中;
在低于250℃的温度下,在一个或多个陶瓷过滤器的上游,将含有二氧化氮的排出气体注入至烟道气中;
通过以下步骤提供含有二氧化氮的排出气体:
在氧化催化剂的存在下,用含氧气氛将氨或其前体催化氧化为含有一氧化氮和氧的排出气体;
将排出气体冷却至环境温度,并将经冷却的排出气体中的一氧化氮氧化为含有二氧化氮的排出气体。
优选地,陶瓷过滤器成形为烛式过滤器的形式。
在高于250℃的烟道气温度下,SCR催化剂具有足够的效率,并且当气体温度达到250℃时,可中断NO2向烟道气中的注入。
氨在烟道气管道外部氧化为NO的反应通常是在反应器中使用贵金属催化剂(通常为铂或铂与作为次要成分的其他贵金属的合金)在250至800℃的反应温度下在含氧气氛的存在下进行。
为了提供所需的反应温度,可以将氧化反应器通过例如电加热或感应加热进行加热。
在一个实施方案中,含氧气氛包括热的再循环烟道气,其然后提供了氧化反应器加热负荷的额外一部分。
优选地,含氧气氛是环境空气。
在第一步中通过与含有贵金属的催化剂接触的NH3的氧化而由NH3形成的NO随后在来自第一步的含有NO的排出气体中氧化为NO2,这是通过将气体冷却至环境温度以推动平衡反应向NO2形成的方向移动而进行的。
如本文所用,术语“环境温度”应当指采用本发明的方法和系统的燃烧设备的周围环境中普遍存在的任何温度。通常,环境温度为-20℃至+40℃。
含有NO的排出气体的冷却和氧化可在老化反应器中进行,定制该反应器的尺寸,使得该气体的停留时间为约1分钟或更长。通常为1至2分钟。
在一个实施方案中,氧化反应在促进NO氧化为NO2的催化剂的存在下进行。那些催化剂是本领域中已知的,且包括TiO2上的Pt、SiO2和活性炭上的Pt或者氧化铝上的Pt和/或Pd。
如前文所述,所需的快速SCR反应需要等量的NO和NO2。因此,控制在低于250℃的温度下注入至烟道气中的NO2的量,使得在通向SCR催化剂单元的入口处的烟道气中的氮氧化物含量的45至55体积%为NO2。
在第二方面,本发明提供了一种用于根据本发明的方法中的系统。
该系统包括:
在烟道气管道内的过滤室,所述过滤室具有一个或多个由用于选择性还原氮氧化物的催化剂催化的陶瓷过滤器;
在一个或多个陶瓷过滤器或过滤室上游的用于将氨或尿素溶液注入至烟道气管道中的注入装置;
在一个或多个陶瓷过滤器或过滤室上游的用于注入含有二氧化氮的排出气体的注入装置;以及
在烟道气管道的外部的
氨氧化催化剂单元,和
用于冷却从氨氧化催化剂中抽取的含有一氧化氮的排出气体并将其氧化成含有二氧化氮的排出气体的装置,所述用于冷却和氧化含有一氧化氮的排出气体的装置在其出口端连接至用于注入含有二氧化氮的排出气体的注入装置。
如上文所述,NO至NO2的氧化反应需要含有NO的气体的停留时间为至少1分钟。通常为1-2分钟。
这可以通过以下来实现:在气体冷却或水冷却的热交换器中,或者当将冷却和氧化装置成形为螺旋卷绕管时,其长度使得气体通过该管时具有所需的停留时间。
在另一个实施方案中,用于冷却和氧化含有一氧化氮的排出气体的装置中设置有促进NO氧化为NO2的氧化催化剂。
在根据本发明的系统的所有实施方案中,一个或多个陶瓷过滤器为陶瓷烛式过滤器的形式。
Claims (11)
1.一种用于从来自燃烧设备的烟道气中除去氮氧化物的方法,该方法包括以下步骤:
使烟道气通过一个或多个用催化剂催化的陶瓷过滤器,以使氮氧化物在氨的存在下发生选择性还原,所述氨以原样或以其前体的形式加入至所述烟道气中;
在低于250℃的温度下,在一个或多个陶瓷过滤器的上游,将含有二氧化氮的排出气体注入至烟道气中;
通过以下步骤提供含有二氧化氮的排出气体:
在氧化催化剂的存在下,用含氧气氛将氨或其前体催化氧化为含有一氧化氮和氧的排出气体;
将排出气体冷却至环境温度,并将经冷却的排出气体中的一氧化氮氧化为含有二氧化氮的排出气体。
2.根据权利要求1所述的方法,其中所述含氧气氛包括烟道气。
3.根据权利要求1所述的方法,其中所述含氧气氛是环境空气。
4.根据权利要求1至3中任一项所述的方法,其中将含有二氧化氮的排出气体以这样的量注入至所述烟道气中:该量使得在通向用于氮氧化物的选择性还原的催化剂的入口处,氮氧化物的45至55体积%为二氧化氮。
5.根据权利要求1至4中任一项所述的方法,其中在氧化催化剂的存在下,将经冷却的排出气体中的一氧化氮氧化为含有二氧化氮的排出气体。
6.根据权利要求1至5中任一项所述的方法,其中所述一个或多个陶瓷过滤器为陶瓷烛式过滤器的形式。
7.用于权利要求1至6中任一项所述的方法中的系统,所述系统包括:
在烟道气管道内的过滤室,所述过滤室具有一个或多个由用于选择性还原氮氧化物的催化剂催化的陶瓷过滤器;
在所述一个或多个陶瓷过滤器或过滤室上游的用于将氨或尿素溶液注入至烟道气管道中的注入装置;
在所述一个或多个陶瓷过滤器或过滤室上游的用于注入含有二氧化氮的排出气体的注入装置;以及
在烟道气管道的外部的
氨氧化催化剂单元,和
用于冷却从氨氧化催化剂中抽取的含有一氧化氮的排出气体并将其氧化成含有二氧化氮的排出气体的装置,所述用于冷却和氧化含有一氧化氮的排出气体的装置在其出口端连接至用于注入含有二氧化氮的排出气体的注入装置。
8.根据权利要求7所述的系统,其中用于冷却和氧化含有一氧化氮的排出气体的装置为热交换器的形式。
9.根据权利要求7所述的系统,其中用于冷却和氧化含有一氧化氮的排出气体的装置为螺旋卷绕管的形式。
10.根据权利要求7至9中任一项所述的系统,其中用于冷却和氧化含有一氧化氮的排出气体的装置中设置有氧化催化剂。
11.根据权利要求7至10中任一项所述的系统,其中所述一个或多个陶瓷过滤器为陶瓷烛式过滤器的形式。
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