CN101925781B - 在压缩前进行烟气过滤的含碳燃料燃烧工艺 - Google Patents
在压缩前进行烟气过滤的含碳燃料燃烧工艺 Download PDFInfo
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Abstract
本发明涉及一种用于燃烧含碳燃料的方法,其使用产生燃烧烟气的燃烧单元,所述烟气也包含二氧化碳(CO2)、固体颗粒以及选自H2O、N2、O2、Ar、NOx以及SOx的至少一种杂质,其特征在于,该方法包括以下步骤:a)使燃烧烟气过滤以获得小于1mg/m3的固体颗粒浓度;b)压缩经在步骤a)过滤的燃烧烟气;c)净化经在步骤b)压缩的燃烧烟气以至少部分地除去杂质中的一种;以及d)回收富CO2气流。
Description
技术领域
本发明涉及一种用于含碳燃料的燃烧的工艺,其特征在于,烟气(废气)被过滤以使得在压缩、净化以及储存或运输之前固体颗粒浓度小于1mg/m3。
背景技术
气候变化构成了最大的环境挑战之一。大气中二氧化碳浓度的增加是全球变暖的主要原因。源于人类的CO2基本上通过热电站中化石燃料的燃烧排放到大气中。
热电站通过燃烧燃料释放热能,该热能可用于产生蒸汽以及可选的机械能或电能。烟气将大量的CO2排放到大气中。
为了对抗CO2排放,一种技术将目标设定为捕集在含碳燃料的燃烧过程中排放的CO2以将其运输和/或储存到地下。然而,为了使这种CO2捕集成为可能,一些烟气必须在净化之前被压缩至通常为约4至60巴(bar)的绝对压力,然后进一步被压缩至通常为100至200巴的绝对压力以便储存。
用于将如此大量的气体压缩至如此压缩水平的该技术目前要求使用离心式压缩机,其中装有叶片的叶轮离心地喷出气体。为减少能量消耗,这些压缩机为多级的,在每一级使用制冷剂来使气体降至环境温度。
压缩叶轮和级间换热器两者都容易被燃烧所产生的固体颗粒弄脏。这些颗粒可能会堵塞换热器并降低它们的热性能。至于压缩机叶轮,可能由于在叶轮上不均匀的质量增加而变得不平衡。这导致机械轴的失衡、振动以及潜在的机器损坏。
用于压缩如此大量的气体的另一技术是所谓“轴向”技术,其中高速旋转的、与固定的定子翅片交错的转子翅片沿着机器转子的轴线压缩气体。在该技术中,固体颗粒的存在,尤其是通过侵蚀,导致翅片上的材料损失。
因此该形势面临着集尘问题。术语“集尘”应理解成指的是其中烟或气体通过气体/固体分离而将其包含的相当大一部分固体除去的任何活动或工艺。执行此任务的设备或器械系列被称为集尘器或除尘器。
如由B.Siret在题为“Dépoussiérage et dévésiculage[Dust and mistcollection]”,(《工程技术》(Techniques de l’Ingénieur),J 3580,1至26页)的文献中所述,传统上采用的用于在燃烧含碳燃料时解决灰尘收集问题的这些技术存在有不同类型,这些不同类型中如下技术区别在于:
-静电过滤器,其中从烟气流除去带电颗粒;
-袋式过滤器,其中烟气通过滤布;
-旋风分离器,其中颗粒通过离心作用和加速作用而分离;以及
-洗涤器,其中使烟气与液体喷淋器接触。
这些技术用来使锅炉出口处的灰尘含量从每立方米几克或几十克的常规水平降低至低一千倍的水平——与关于排放至大气中的常用标准相一致,但始终大于1mg/m3。
然而,对于1mg/m3或更高的烟气灰尘含量,压缩操作将经受尤其是中间制冷剂的堵塞的问题,需要停工以频繁维修。此外,这使得压缩性能降低。
由此,提出这样一个问题:如何提供一种具有改进的烟气处理、尤其是适于离心式压缩机技术的处理的用于含碳燃料的燃烧的工艺。
发明内容
根据本发明的一种解决方案是一种用于含碳燃料的燃烧的工艺,该工艺采用燃烧单元,该燃烧单元产生烟气,除了二氧化碳(CO2)以外,所述烟气还包括固体颗粒和选自以下的至少一种杂质:水、氮气、氧气、氩气、氮氧化物(NOX)以及硫氧化物(SOX),氮氧化物包括一氧化氮和二氧化氮,硫氧化物包括二氧化硫,其特征在于,执行以下步骤:
a)使烟气过滤以获得小于1mg/m3的固体颗粒浓度;
b)压缩经在步骤a)过滤的烟气;
c)净化经在步骤b)压缩的烟气以至少部分地除去杂质中的一种;以及
d)回收富CO2气流。
优选地,在步骤b),烟气被压缩至高于4巴的压力。
优选地,在步骤b)使用的压缩通过离心式压缩机产生。
在步骤a)优选获得小于500μg/m3、更优选小于300μg/m3的固体颗粒浓度。
依情况而定,根据本发明的工艺可具有以下特征之一:
-烟气在步骤a)被过滤以获得小于100μg/m3的固体颗粒浓度;
-使用过滤筒执行步骤a)的过滤;
-在步骤a)之前烟气含有的水不饱和或者在过滤步骤a)之前执行烟气减饱和步骤;
-在烟气的第一次压缩之后执行步骤a);
-在过滤步骤a)的下游和步骤c)的上游使用至少一个换热器;
-燃烧单元是利用空气作为助燃剂(comburant,氧化剂)的单元,在该单元中通过吸收烟气中的CO2执行CO2捕集,这被称为“燃烧后”捕集;
-燃烧单元是利用氮含量相对于空气较少的气体作为助燃剂的全氧燃烧单元;
-步骤a)的过滤在步骤a)和步骤c)之间通过静态过滤完成;
-自静态过滤输出的烟气具有小于10μg/m3的固体颗粒浓度;
-在烟气具有高于100℃的温度的情况下,在过滤步骤a)的下游采用选自板式换热器、管翅式换热器以及铝钎焊式换热器的至少一个换热器;
-在烟气具有低于100℃的温度的情况下,在过滤步骤a)的下游采用塑料换热器;
-在过滤步骤a)的下游采用紧凑型换热器;
-在过滤步骤a)的下游使用填料洗涤塔和/或填料蒸馏塔,用于至少部分地除去选自SO2、NO2、N2、O2、Ar和N2O4的杂质中的至少一种;
-在过滤步骤a)的上游和/或过滤步骤a)的下游使用脱硫步骤和/或冷却步骤以通过使水冷凝而去除水;
-全氧燃烧烟气被分成至少两部分:再循环到燃烧单元中的第一部分和经历步骤b)、c)和d)的第二部分,仅第二部分经历脱硫步骤和/或冷却步骤以通过使水冷凝而去除水;
-在经脱硫的烟气的第一部分再循环到锅炉中之前所有烟气经历至少一次脱硫步骤,而经脱硫的烟气的第二部分经历步骤a)、b)、c)和d);
-含碳燃料是煤,第一烟气部分在返回到锅炉之前经历第二次脱硫步骤;
-所有燃烧烟气在过滤步骤a)之前经历第一次脱硫步骤,然后在过滤步骤a)之后、在分成两部分之前经历第二次脱硫步骤,第一烟气部分再循环到锅炉中,第二烟气部分经历步骤b)、c)和d)。
应注意到,在全氧燃烧的情况下,烟气的再循环部分可以达到烟气的80%。
术语“燃烧后”应理解成指的是常规的在空气中燃烧的工艺,随后是(例如通过胺吸收或氨吸收)从烟气分离CO2。
例如可以通过使用含有石灰或氢氧化钠的溶液执行脱硫步骤。
可以使用过滤筒执行过滤步骤a)(称为“精细过滤”)。其在0℃和300℃之间、优选100℃和200℃之间的温度下执行。术语“过滤筒”指的是由以柱状形式使用的褶状纤维介质构成的过滤筒。此过滤器技术以小占用空间提供大的过滤面积,并且对于相同流速的待处理气体产生的压降较低。这是因为褶皱操作使得在具有给定截面的管线中使用的过滤器面积增大,从而使得可以降低气体在过滤器中流过的速度,由此减小压降。
在过滤之后,过滤筒使用富CO2流体或者甚至空气清除堵塞物。此富CO2流体可由步骤b)和/或步骤d)产生。
术语“紧凑型换热器”应理解成指的是紧凑度大于700m2/m3的换热器,紧凑度定义为换热表面积与换热器体积的比。
管翅式换热器包括能提高热交换系数的管。存在各种类型的管翅式换热器。在本发明的情况下,可以例如使用成行或片分布的由管束构成的翅片管组,具有良好的热交换系数的传热流体流过所述翅片管组。
“板式换热器”应理解成指的是主表面式换热器或次表面式换热器。主表面式换热器由波纹状的、带有肋片或钉齿的板形成。板的外形设计可以各式各样,但其始终具有两个功能,即通过接触点的倍增而强化热传递并维持压力。在主表面式换热器中存在具有熔焊或钎焊板的换热器,使得可以在高于150℃的温度下使用这些主换热表面。在本发明的情况下,由于过滤步骤a)的在先使用,可以使用这些换热器而不用担心结垢。次表面式换热器使用褶状或波纹状的翅片。
A.Bontemps等人的题为“Echangeurs de chaleur[Heat exchangers]″,(《工程技术》(Techniques de l’Ingénieur),B 2 3241,3至4以及7至13页)的文献中描述了各种类型的管翅式换热器和板式换热器。
可用于过滤步骤a)中的另一技术是基于通过由塑料例如PPS(聚苯硫醚)、聚酯和PTFE(聚四氟乙烯)制成的介质执行的过滤。这些塑料能实现亚微过滤水平,而与此同时,依情况而定,能经得起介于50℃和200℃之间的温度。
术语“静态过滤器”应理解成指的是粗和/或细过滤器,优选细过滤器,或先粗后细过滤器的组合。术语“细过滤器”应理解成指的是根据欧洲标准EN 779:2002的F5至F9等级的过滤器。这可以是例如袋式静态过滤器或盒式静态过滤器,通常测量尺寸为24英寸乘以24英寸(约610mm乘以610mm)。术语“粗过滤器”应理解成指的是G1至G4等级的过滤器。
根据本发明的静态过滤器可以跟随有HEPA或ULPA过滤器。根据欧洲标准EN 1822-1:1998,1822-2:1998以及1822-3:1998,HEPA过滤器是H10至H14等级的过滤器,ULPA过滤器是U15至U17等级的过滤器。
根据本发明的工艺采用被供给含碳燃料的燃烧单元。优选地,该燃料是煤,但其可以是基于碳原子的任何燃料,即油残渣、碳氢化合物、天然气、生物质、生活垃圾,等。
燃烧优选地是全氧燃烧(oxycombustion),也就是说,其中助燃剂为氮含量相对于空气较少并且富含CO2的气体的燃烧。此脱氮通过例如在低温风煤气分离单元中将空气分离成富氧馏分和富氮馏分而实现。富氧馏分与富CO2烟气的再循环部分混合以形成助燃剂。此馏分的氧浓度一般大于空气。应注意,全氧燃烧也可以在纯氧中进行,即,没有用一部分富CO2烟气稀释。那么其氧含量通常介于85%和99.9%。
具体实施方式
下面将借助于附图1和2更详细地描述本发明。
图1示出根据本发明的总体工艺,该工艺采用煤粉锅炉,该锅炉通过氮含量比空气更低的助燃剂运行,其特征在于,所有烟气经历脱硫步骤。
空气1被供给进入风煤气分离单元2,该风煤气分离单元然后生产氧气3。氧气3经由CO2再循环管线送至混合器4,在混合器4中氧气3可以与富CO2的再循环气体6混合。来自混合器4的助燃剂5然后被供给进入煤粉锅炉7,该锅炉然后通过氮含量比空气更低的助燃剂运行。
燃料8(这里指原煤)在被供给到煤粉锅炉7中之前首先被送入粉碎机10。
来自锅炉的蒸汽在汽轮机11中膨胀,该汽轮机输出机械功。此功通过交流发电机12转变成(电)能量。
烟气13可经历各种处理:汞(未示出)和氮氧化物的去除19、集尘14以及脱硫和/或冷却15。
这些全氧燃烧的烟气的第一部分6可以被再循环到锅炉中以降低燃烧中的氧含量并且因此降低燃烧温度。
非再循环的烟气(即,第二烟气部分)在被送入CO2压缩和净化单元(CPU)16之前利用过滤筒20过滤。在压缩步骤16之前,烟气可经历洗涤9以便除去SOX和/或NOX和/或通过直接接触使它们冷却以通过冷凝从中除去一些水。
来自CPU单元16的经净化的CO217然后可被装瓶和/或运输和/或储存。
集尘14应理解成指的是利用常规技术的集尘:例如通过静电过滤器或袋式滤器进行的集尘。
图2示出了根据本发明的一种采用煤粉锅炉并以氮含量比空气更低的助燃剂运行的工艺,其特征在于所有的烟气在过滤步骤a)之前经历第一次脱硫步骤,然后在被分成两部分——再循环到锅炉中的第一烟气部分和经历步骤b)、c)和d)的第二烟气部分——之前经历第二次脱硫步骤。
此工艺与前述工艺的不同之处在于:
-在被送入洗涤器9以除去SOX和/或NOX和/或通过直接接触被冷却以通过冷凝从中除去一些水之前,所有烟气利用过滤筒20过滤;
-第一烟气部分6可以在通过洗涤器9之后再循环到锅炉中;以及
-非再循环的烟气(第二烟气部分)被送入CO2压缩和净化单元(CPU)16。
应注意,可以预期中间方案,即,介于在图1的情况下所述的方案和在图2的情况下所述的方案之间。例如,去往粉碎机的助燃剂部分可要求除水步骤以使包含在煤中的水蒸发,而另一部分助燃剂5不需要此处理并因此被再循环,如图1中的那样。
图3提供了根据本发明的工艺的步骤a)、b)、c)和d)的更具体的描述。
为了简化描述,烟气过滤为“精细过滤”以获得小于1mg/m3的固体颗粒浓度。
全氧燃烧的烟气101经历精细过滤103和在直接接触塔105中的洗涤/冷却。在此塔中可以除去SOX和/或NOX。由于精细过滤,低压洗涤塔可以是填充塔/填料塔,因为常规过滤将会导致填料结垢。那么将必须非常频繁地清洁该塔或者使用能够较不易结垢但是导致更高压降的托盘。经冷却的烟气107在于换热器111中冷却之前进入第一压缩级109,然后在于换热器115中再次冷却之前进入第二压缩级113。由于精细过滤,这些换热器111和115可以是翅片式或板式或紧凑型换热器。流体117的压力通常介于4和60巴的绝对压力之间、优选介于15和35巴的绝对压力之间。根据压力选用压缩级的数量。每一压缩级可由一个或多个离心轮组成。然后流体117进入高压洗涤/冷却塔119,然后在经历在吸附器123中的吸附脱汞步骤之前在吸附器121中干燥。由于精细过滤,高压洗涤塔可具有填料。然后所获得的流体125在换热器127和128中经历部分冷凝。由于精细过滤,这些换热器可由钎焊铝制成。在某些情况下,足以防止压缩机结垢的此精细过滤对于这样的换热器的使用可能是不够的。此外,干燥和吸附脱汞步骤可能将固体颗粒引入流体中。可以对流体125进行辅助过滤,例如使用烧结金属筒。经部分地冷凝的流体被分成富CO2液体馏分和通常富N2、Ar、O2的蒸气馏分。液体馏分在蒸馏塔137中膨胀并且使其富含有CO2。气态流体139被从蒸馏塔中抽出、在换热器127中加热并然后可选地在压缩机171中压缩以及在换热器127的上游再循环以便提高CO2产量。液体流体141可选地在被引入蒸馏塔155之前在换热器127中膨胀和蒸发以净化去除尚未通过先前的净化步骤除去的密度大的化合物,如SO2和NO2/N2O4。由于使用精细过滤,蒸馏塔可以是填充塔/填料塔。富含密度大的化合物的液体馏分157从此塔提取出来,富CO2馏分产生并在压缩机151中压缩以备在通常介于100和200巴之间的绝对压力下储存。气态馏分133在换热器127中被加热并在涡轮机163中在一个或多个步骤中膨胀,所述气态馏分已经在换热器161中被预热,从而以压力形式回收能量。然后此流体进入加热器165并用来使吸附器121再生。
作为一个示例,根据本发明的燃烧工艺可使用产生全氧燃烧烟气的全氧燃烧单元,该全氧燃烧烟气包括约55%CO2、20%H2O、20%N2、5%O2、和氩以及少量其它杂质,所述工艺的特征在于,在步骤d)回收包括至少90%CO2、优选至少95%CO2的气态流。
根据本发明的工艺尤其具有以下优点:
-换热器的使用比光滑管更有效,所述光滑管是唯一能在灰尘含量大于1mg/m3的情况下使用的换热器,
-更好的压缩,
-在给定的时间周期中更少地为维修保养而停工,
-使用装配有填料而不是托盘的洗涤塔和/或蒸馏塔,这造成更低的压降,也提高了***的能量效率,以及
-就固体颗粒而言最终产品的纯度提高,从而减少了下游设备、尤其是管线中的污垢。
Claims (21)
1.一种用于含碳燃料的燃烧的方法,该方法采用燃烧单元,该燃烧单元产生烟气,除了二氧化碳(CO2)以外,所述烟气还包括固体颗粒和选自以下的至少一种杂质:水、氮气、氧气、氩气、氮氧化物(NOX)以及硫氧化物(SOX),氮氧化物包括一氧化氮和二氧化氮,硫氧化物包括二氧化硫,其特征在于,执行以下步骤:
a)使烟气过滤以获得小于1mg/m3的固体颗粒浓度;
b)压缩经在步骤a)过滤的烟气;
c)净化经在步骤b)压缩的烟气以至少部分地除去杂质中的一种;以及
d)回收富CO2气流。
2.根据权利要求1所述的方法,其特征在于,烟气在步骤a)被过滤以获得小于100μg/m3的固体颗粒浓度。
3.根据权利要求1和2中任一项所述的方法,其特征在于,使用过滤筒执行步骤a)的过滤。
4.根据权利要求1和2中任一项所述的方法,其特征在于,在步骤a)之前烟气含有的水不饱和或者在过滤步骤a)之前执行烟气减饱和步骤。
5.根据权利要求1和2中任一项所述的方法,其特征在于,在烟气的第一次压缩之后执行步骤a)。
6.根据权利要求1和2中任一项所述的方法,其特征在于,在过滤步骤a)的下游和步骤c)的上游使用至少一个换热器。
7.根据权利要求1和2中任一项所述的方法,其特征在于,所述燃烧单元是利用空气作为助燃剂的单元,在该单元中通过吸收烟气中的CO2执行CO2捕集。
8.根据权利要求1和2中任一项所述的方法,其特征在于,所述燃烧单元是利用氮含量相对于空气较少的气体作为助燃剂的全氧燃烧单元。
9.根据权利要求1和2中任一项所述的方法,其特征在于,步骤a)的过滤通过静态过滤完成。
10.根据权利要求9所述的方法,其特征在于,自静态过滤输出的烟气具有小于10μg/m3的固体颗粒浓度。
11.根据权利要求1和2中任一项所述的方法,其特征在于,在烟气具有高于100℃的温度的情况下,在过滤步骤a)的下游采用至少一个换热器。
12.根据权利要求11所述的方法,其特征在于,所述换热器选自板式换热器和管翅式换热器。
13.根据权利要求11所述的方法,其特征在于,所述换热器选自铝钎焊式换热器。
14.根据权利要求1和2中任一项所述的方法,其特征在于,在烟气具有低于100℃的温度的情况下,在过滤步骤a)的下游采用塑料换热器。
15.根据权利要求1和2中任一项所述的方法,其特征在于,在过滤步骤a)的下游采用紧凑型换热器。
16.根据权利要求1和2中任一项所述的方法,其特征在于,在过滤步骤a)的下游使用填料洗涤塔和/或填料蒸馏塔,用于至少部分地除去至少一种以下杂质:SO2、NO2、N2、O2、Ar和N2O4。
17.根据权利要求8所述的方法,其特征在于,在过滤步骤a)的上游和/或过滤步骤a)的下游使用脱硫步骤和/或冷却步骤以通过使水冷凝而去除水。
18.根据权利要求17所述的方法,其特征在于,全氧燃烧烟气被分成至少两部分:再循环到燃烧单元中的第一部分和经历步骤b)、c)和d)的第二部分,仅第二部分经历脱硫步骤和/或冷却步骤以通过使水冷凝而去除水。
19.根据权利要求17所述的方法,其特征在于,所有烟气经历至少一次脱硫步骤,然后经脱硫的烟气被分成两部分:经脱硫的烟气的第一部分再循环到锅炉中,而经脱硫的烟气的第二部分经历步骤a)、b)、c)和d)。
20.根据权利要求19所述的方法,其特征在于,所述合碳燃料是煤,第一烟气部分在返回到锅炉之前经历第二次脱硫步骤。
21.根据权利要求17所述的方法,其特征在于,所有燃烧烟气在过滤步骤a)之前经历第一次脱硫步骤,然后在过滤步骤a)之后、在分成两部分之前经历第二次脱硫步骤,第一烟气部分再循环到锅炉中,第二烟气部分经历步骤b)、c)和d)。
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PCT/FR2009/050078 WO2009095581A2 (fr) | 2008-01-28 | 2009-01-21 | Procede de combustion de combustibles carbones avec filtration des fumees de combustion avant compression |
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EP2235443A2 (fr) | 2010-10-06 |
CN101925781A (zh) | 2010-12-22 |
WO2009095581A3 (fr) | 2009-10-01 |
ZA201004131B (en) | 2011-04-28 |
US20100322843A1 (en) | 2010-12-23 |
WO2009095581A2 (fr) | 2009-08-06 |
US8715605B2 (en) | 2014-05-06 |
FR2926876B1 (fr) | 2010-03-05 |
PL2235443T3 (pl) | 2019-03-29 |
CA2712643C (fr) | 2016-03-15 |
JP2011514959A (ja) | 2011-05-12 |
JP5512547B2 (ja) | 2014-06-04 |
EP2235443B1 (fr) | 2018-10-24 |
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AU2009208873A1 (en) | 2009-08-06 |
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