CN102173417A - 从可燃物氧化产生的废气或烟中分离和回收二氧化碳的方法 - Google Patents
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Abstract
本发明描述了一种从可燃物氧化产生的废气中分离和回收二氧化碳的方法,该方法包括如下步骤:将废气流输送到气体半透性材料,通过该气体半透性材料从废气流中分离出含高浓度二氧化碳的气流,并至少使用部分含高浓度二氧化碳的气流作为工业生产装置中供给的原材料和/或将至少部分含二氧化碳的气流储存起来。
Description
本申请是PCT国际申请日为2002年3月22日,PCT国际申请号为PCT/EP02/03243,中国国家申请号为02808003.3并且发明名称为“从可燃物氧化产生的废气或烟中分离和回收二氧化碳的方法”的申请的分案申请。
发明领域
从最广义的方面讲,本发明涉及从可燃物氧化产生的废气或烟中分离和回收二氧化碳的方法。
具体而言,本发明涉及从空气氧化矿物燃料或馏份及其衍生物而产生的废气或烟中分离和回收二氧化碳的方法。
术语“氧化”的含义既包括燃料,特别是矿物燃料,在家用或工业规模上和空气进行的正常燃烧,又包括其电化学氧化,例如在燃料电池中所发生的。
现有技术
众所周知工业或家用设备中矿物燃料(易燃的)的燃烧或其他氧化过程产生的排(废)气或烟被分散到大气中,造成多种环境问题。其中最严重的问题涉及对行星的整体加热效应,即已知的“温室效应”,而废气或烟中所含的二氧化碳对此负有责任。
而且,已知二氧化碳在若干工业工序中是供给的原材料;为了完成这种工序,通常采用矿物燃料燃烧产生的热能。因此,对于这些工序而言,为了提高产量和/或降低购买这种原材料的成本,是希望能够从燃烧废气中便利地分离和回收至少部分二氧化碳。
例如,在生产氨和尿素或甲醇的工序中,已知供给的原材料,例如氢、一氧化碳和二氧化碳,一般是通过沼气或诸如天然气、LPG(液化石油气)、石脑油的其他轻质烃的重整,以气体混合物形式获得的。
沼气的转化是在重整装置的专用炉中进行的,通常和氨和尿素或甲醇的生产有关,所利用的是供给的沼气部分和空气燃烧产生的热能。
在氨和尿素的生产过程中,为了使氢转化为氨,随后向重整获得的气体混合物中按照化学计量加入氮气。
但是,按照这种方式,上述气体混合物所含的二氧化碳量小于将产生的氨全部转化为尿素所需的化学计量,以致尿素生产装置能力被不利地降低了。
而在甲醇生产过程中,重整所得气体混合物中的氢超过将一氧化碳和二氧化碳全部转化为甲醇所必须的数量,因此部分氢气从合成反应器被清除,并经常用作燃料。
因此,在上述的两种方法中,这一点很清楚:只要能够回收甚至只是部分沼气重整装置地燃烧气体中所含的二氧化碳,尿素和甲醇各自的产量都可以有较大的提高。
所以,关于从燃烧气体或烟中分离和回收二氧化碳的问题是非常敏感的,在过去的几十年中一直是若干研究的课题。
这些研究大部分针对的是所谓的二氧化碳的“湿”分离和回收方法。即,基于用能够选择性吸附二氧化碳的合适溶液或溶剂洗涤燃烧气体,并通过加热吸附溶液或溶剂来回收所吸附的二氧化碳的方法。
在现有技术中已经开发出了多种上述类型的方法;但是,它们都有限制其工业应用的各种缺点。
其中经常遇到的一个缺点在于洗涤溶液受到其组分氧化现象的影响,该现象是由燃烧气体中存在的氧气造成的,因此需要频繁替换。
而且,应当注意到燃烧气体通常还包含硫和氮氧化物(SOx和NOx),它们和洗涤溶液中的某些组分反应,产生稳定的盐和难以清除和处理的其他有害化合物。
因此,需要经常替换洗涤溶液,并清除和处理其降解产生的有害化合物,这就意味着相应地增加上述已知气体二氧化碳分离和回收方法的生产费用。
此外,用现有技术进行二氧化碳分离和回收所需的设备复杂、昂贵、难以操作,而且体积庞大,因而还意味着高的投资和维护费用。
本发明根本的技术难题是提供一种从可燃物氧化产生的废气中分离和回收二氧化碳的方法,该方法简单、有成本效益,且没有先前所述的与现有技术的二氧化碳分离和回收方法有关的缺点。
发明概述
这个技术难题是通过从可燃物氧化产生的废气中分离和回收二氧化碳方法解决的,该方法包括如下步骤:
-将废气流输送到气体半透性材料,
-通过所述气体半透性材料从废气流中分离含高浓度二氧化碳的气流,以及
-至少用部分含高浓度二氧化碳的气流作为工业生产装置中供给的原材料和/或将至少部分所述的含二氧化碳的气流储存起来。
气体半透性材料可以从中空纤维膜和诸如分子筛的能够优先吸附二氧化碳的材料中选择。
中空纤维膜可以是二氧化碳优先渗透类型或者基本不渗透该气体的类型。
术语“分子筛”的含义包括所有具有适合优先吸附气体混合物所含二氧化碳的微孔的常规材料,包括活性碳。按照二氧化碳被吸附和释放的具体方式,将这些材料分为PSA(压力摆动吸附)或TSA(温度摆动吸附)型分子筛或者活性碳。
在PSA吸附法中,施压使含二氧化碳的混合气体通过分子筛,以促进二氧化碳在微孔中的优先吸附。然后,减少压力以获得解吸的二氧化碳和其他可能保留在微孔中的气体组分,因而使分子筛再生。
与之不同,在TSA法中,是让待分离的含二氧化碳的气体混合物在不高于80℃的温度下通过上述分子筛,将二氧化碳优先吸附到微孔中。然后升高温度,例如借助于蒸汽流,以这种方式使二氧化碳和其他可能保留在微孔中的气体组分一起被解吸出来,从而再生分子筛。
在本发明的方法中,优选使用至少使用一种TSA型分子筛。
在本发明的方法中使用TSA型分子筛不需要压缩大量待分离的气体,因而由于其低能耗而具有优势。
而且为了再生TSA型分子筛,让蒸汽流或者,作为选择,部分含高浓度二氧化碳的气流通过这些分子筛就足够了,其中这一部分气流在这种分子筛的再生温度下被适当地加热。
另外,在本发明的方法中使用中空纤维膜或PSA型分子筛,如果和使用TSA型分子筛相比,则不太有利,因为它们需要对待处理的废气进行压缩,与之相联系的是相关的能耗。
再者,中空纤维膜非常昂贵,即使它们保证有更高的效率和将二氧化碳从燃烧废气所含其他气体组分中分离出来的更高的产率。
按照本发明的优选实施方案,气体半透性材料能够优先吸附二氧化碳,而从所述废气流中分离含高浓度二氧化碳的气流包括如下步骤:
-让废气流渗透到所述气体半透性材料中,以吸附至少所述废气流中所含二氧化碳的相关部分,并获得低二氧化碳含量的渗透气流。
-分散所述低二氧化碳含量的渗透气流,和
-从所述气体半透性材料中解吸至少相应部分的二氧化碳,这样获得含高浓度二氧化碳的气流。
从如下参照附图对本发明执行方法而做的陈述性描述及其非限定性实例,将会使本发明从燃烧废气中回收二氧化碳方法的特征和优点变得更清楚。
附图简述
-图1显示了本发明从燃烧废气中分离和回收二氧化碳方法的实施方案的方块图。
发明详述
参照附图,方块1指的是用空气燃烧燃料,特别是矿物燃料的家用或工厂设备。
方块2指的是冷却方块1内燃烧产生的高温废气流的热交换器。
该废气流的气体组成主要包括二氧化碳、水、氧气和氮气以及,在有限程度上,氮和硫氧化物(SOx和Nox)。
方块3指的是适合将方块2中冷却的废气流压缩到所需压力的压缩单元。方块3是任选的,而当使用PSA型分子筛或中空纤维膜来分离二氧化碳时,方块3变得非常重要,因为此时必须适当地压缩待处理的废气。
如果使用TSA型分子筛,可以省略方块3,或者作为替代,方块3可以由一个简单的风扇组成。
方块4是气体半透性材料,例如膜或分子筛,用于从来自方块2或方块3的废气流中分离含高浓度二氧化碳的气流,本说明中稍后将解释这点。
方块5是另一个适合对来自方块4的含高浓度二氧化碳的气流进行压缩的压缩单元。
方块6是另一个热交换器,适合加热部分来自方块4的含高浓度二氧化碳的气流。
流线7指示在方块1内燃烧产生的高温废气流。
然后该废气流被输送到方块2,在那儿被冷却至20℃~80℃。
流线8表示来自方块2的冷却气流。如果方块4的气体半透性材料由中空纤维膜或PSA型分子筛组成,首先在方块3中在1abs bar~20abs bar的压力下压缩废气流8,然后再如流线9所示,输送到方块4中。
与之相反,如果方块4的气体半透性材料由TSA型分子筛组成,可以省略方块3,因此方块2出来的废气流8被直接输送到方块4。
方块4的气体半透性材料用于从废气流8或9中分离含高浓度二氧化碳的气流。
优选该材料由TSA型分子筛组成,这种分子筛允许优先通过氮气,同时吸附含氧的混合气体组分,即主要是二氧化碳、水和氧气。
因此,如流线10所示,在方块4出口处获得的气流主要包括氮气,该气流被分散到大气中。
为了使方块4中吸附的二氧化碳和其他氧化的化合物解吸出来,中断进入方块4的废气流8或9,并再生方块4中的中空纤维膜或分子筛。
在使用中空纤维膜或PSA型分子筛的情况下,再生是通过降低方块4中的压力(减压)而进行的,以分离该材料中吸附的二氧化碳。
在使用TSA型分子筛的情况下,再生是按照本说明稍后解释的方式进行的。
如流线11所示,从再生步骤获得气流,结果是其中的二氧化碳浓度比废气流8或9中的要高。气流11中方块4所吸附的其他气体成分的浓度也高于废气流8或9中这些成分的浓度。
然后,可以使用含高浓度二氧化碳的气流11作为在合适的工业工序中供给的原材料,可以直接供给或者经过进一步处理后再供给。或者,可以将气流11液化或以合适的方式储存,以备以后根据特定的需要使用。
例如,可以在方块5中压缩气流11至合适的压力,这样获得的气流,如流线12所示,可以被直接用作生产尿素或甲醇的装置的供给原材料。
无论如何,必须从气体成分气流11中完全或部分清除诸如氧气和氮或硫氧化物(SOx、NOx)之类的物质,然后才可以安排使气流11在合适的操作条件下通过一个或多个膜或分子筛,和/或用其他类型的分离系统来处理气流11。
在这种情况下,可以将从上述气体成分中完全或部分纯化的气流11在方块5中压缩,并在生产尿素或甲醇的装置中作为供给原材料。
本实例中,流线13所示的含高浓度二氧化碳的气流部分11,在方块6中被加热,并通过流线14输送到方块4,以再生TSA-型分子筛。
备选地,上述再生方法中可以使用高温水蒸汽。
再生意味着气体成分的解吸,特别是TSA-型分子筛的微孔中保留的二氧化碳,这些二氧化碳在气流11中被回收。
很显然本领域的技术人员可以对本发明的方法进行多处修改,来达到具体而特殊的要求,所有这些都属于如下权利要求所限定的本发明的保护范围。
Claims (4)
1.从可燃物氧化产生的废气中分离和回收二氧化碳的方法,该方法包括如下步骤:
-将废气流输送到气体半透性材料,这些气体半透性材料是TSA型分子筛或活性炭,
-通过所述气体半透性材料从所述废气流中分离出含高浓度二氧化碳的气流,和
-至少使用部分含高浓度二氧化碳的气流作为工业生产装置中供给的原材料和/或将至少部分所述含二氧化碳的气流储存起来。
2.权利要求1的方法,其中所述气体半透性材料能够优先吸附二氧化碳,而从所述废气流中分离含高浓度二氧化碳的气流包括如下步骤:
-让废气流渗透到所述气体半透性材料中,以至少吸附所述废气流中所含二氧化碳的相关部分,并获得低二氧化碳含量的渗透气流,
-分散所述低二氧化碳含量的渗透气流,和
-从所述气体半透性材料中解吸至少相应部分的二氧化碳,这样获得含高浓度二氧化碳的气流。
3.前述权利要求任一条中的方法,其中所述的可燃物是矿物燃料。
4.前述权利要求任一条中的方法,其中所述工业生产装置是生产氨和尿素或者甲醇的装置。
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WO2002083272A1 (en) | 2002-10-24 |
UA75646C2 (en) | 2006-05-15 |
US20040123737A1 (en) | 2004-07-01 |
EP1377359B1 (en) | 2009-12-02 |
CA2442119A1 (en) | 2002-10-24 |
BR0208815A (pt) | 2004-03-09 |
ES2337344T3 (es) | 2010-04-23 |
ATE450307T1 (de) | 2009-12-15 |
BR0208815B1 (pt) | 2011-11-29 |
CA2442119C (en) | 2011-09-20 |
EP1249264A1 (en) | 2002-10-16 |
RU2349371C2 (ru) | 2009-03-20 |
DE60234582D1 (de) | 2010-01-14 |
EP1377359A1 (en) | 2004-01-07 |
US7153344B2 (en) | 2006-12-26 |
CN1520333A (zh) | 2004-08-11 |
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