CN101918108A - 燃煤锅炉的排气处理系统及其运行方法 - Google Patents
燃煤锅炉的排气处理系统及其运行方法 Download PDFInfo
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Abstract
本发明的燃煤锅炉的排气处理系统包括:向作为燃料(F)而使用煤炭的燃煤锅炉的排气喷雾氯化氢(33)的HCl喷雾装置(32)、向喷雾氯化氢后的排气中添加氨(12)以通过氨脱硝除去氮氧化物并将汞氧化的脱硝装置(13)、将除去氧化物后的气体中的热量回收的空气预热器(14)、将热量回收后的气体中的烟尘除去的集尘器(15)、向除尘后的气体中喷雾活性炭(22a)的活性炭喷雾装置(22)、捕集吸附了汞的活性炭的袋式除尘器(21)、将除去活性炭后的排气中的硫氧化物除去的脱硫装置(16)、将脱硫后的气体向外部排出的烟囱(17)、为了向脱硫装置(16)内的料浆吸收液供给空气而测量氧化还原电位的ORP计(19)。
Description
技术领域
本发明涉及一种从锅炉的排气中除去汞的燃煤锅炉的排气处理系统及其运行方法。
背景技术
由于在火力发电厂等的作为燃烧装置的锅炉的排气中含有毒性高的汞,所以从过去开始对用于从排气中除去汞的系统进行了各种研究。
通常,在锅炉中设置有用于从排气中除去硫磺成分的湿式脱硫装置。对于在这样的锅炉中作为排气处理装置附设脱硫装置而成的排烟处理设备,排气中的氯(Cl)成分含量越多,水中可溶的二价的金属汞的比例就越高,利用所述脱硫装置可容易捕集汞的事实已广为人知。
因此,近年来,对于将还原NOx的脱硝装置以及将碱吸收液作为SOx的吸收剂的湿式脱硫装置进行组合以处理该金属汞的方法、装置,进行了各种各样的设计(专利文献1)。
作为处理排气中的金属汞的方法,虽然基于活性炭、硒过滤器等吸附剂的除去方法为公众所知,但是仍然需要特殊的吸附除去手段,上述的除去方法不适用于发电厂排气等的大容量排气处理(专利文献2)。
在此,图7是表示燃煤锅炉的排气处理系统的示意图。
如图7所示,现有的排气处理系统包括通过所添加的氨12而除去来自燃煤锅炉11的排气中的氮氧化物的脱硝装置13、将除去氮氧化物后的气体中的热量回收的空气预热器14、将热量回收后的气体中的烟尘除去的集尘器15、利用石灰/石膏法将除尘后的气体中的硫氧化物除去的同时将氧化汞除去的气液接触式的脱硫装置16、将脱硫并且除去汞后的净化气体向外部排出的烟囱17,在集尘器15的下游侧设置有袋式除尘器21,并从活性炭喷雾装置22向气体通道内供给活性炭22a,从而将气体中汞吸附除去。需要说明的是,附图中,符号18为空气。通过供给该空气18可以调整脱硫装置16内的氧化还原电位。
专利文献1:日本特开2007-7612号公报
专利文献2:日本特开2005-230810号公报
然而,在为了除去汞而使用活性炭吸附方法的情况下,存在活性炭喷雾装置以及将其捕集的袋式除尘器的设备费用高、另外喷雾的粉末活性炭的费用也高的问题。
例如,如果将除去汞的活性炭喷雾装置的设备费用与10年间的运行经费相比,存在比从其他途径购买汞的排放权的费用高的情况。
这是因为吸附汞的活性炭虽然被袋式除尘器所分离,但是其废弃的费用高。
因此,作为基于活性炭吸附法从排气中除去汞的对策,迫切期待其运行费用的低廉化。
发明内容
鉴于上述问题,本发明的目的在于提供能够从燃煤锅炉的排气中有效地除去汞、并能实现运行费用低廉化的燃煤锅炉的排气处理系统及其运行方法。
为了解决上述问题,本发明的第一方案的燃煤锅炉的排气处理系统包括:除去来自燃煤锅炉的排气中的氮氧化物的脱硝装置、回收除去氮氧化物后的气体中的热量的空气预热器、除去热量回收后的气体中的烟尘的集尘器、通过石灰/石膏法除去除尘后的气体中的硫氧化物并除去氧化汞的气液接触式的脱硫装置、将脱硫后的气体向外部排出的烟囱,其特征在于,在该排气处理系统中,在脱硝装置的上游侧喷雾氯化氢,并在所述集尘器的下游侧喷雾活性炭,从而吸附气体中的汞。
本发明的第二方案的燃煤锅炉的排气处理系统包括:除去来自燃煤锅炉的排气中的氮氧化物的脱硝装置、回收除去氮氧化物后的气体中的热量的空气预热器、除去热量回收后的气体中的烟尘的集尘器、通过石灰/石膏法除去除尘后的气体中的硫氧化物并除去氧化汞的气液接触式的脱硫装置、将脱硫后的气体向外部排出的烟囱,其特征在于,在该排气处理系统中,在脱硝装置的上游侧喷雾氯化氢,并在所述集尘器的下游侧喷雾活性炭,吸附气体中的汞,将脱硫装置内的吸收液的氧化还原电位设为150mV以上。
本发明的第三方案的燃煤锅炉的排气处理系统,在本发明的第一或第二方案中,将含有汞的料浆吸收液向外部抽出,在分离石膏前添加凝集剂,从而凝集除去汞。
本发明的第四方案的燃煤锅炉的排气处理系统,在本发明的第一至第三方案中的任意一个中,使分离了石膏的分离液与活性炭、螯合物树脂、离子交换树脂、或者硫化物载体中的至少一个接触,以吸附除去汞。
本发明的第五方案的一种燃煤锅炉的排气处理系统的运行方法,其特征在于,该运行方法使用上述第一至第四方案中任意一种燃煤锅炉排气处理系统,在煤炭中的汞(Hg)/硫磺(S)的摩尔比为1.3×10-6以上的情况下,在脱硫装置的下游侧监视汞浓度,并根据该结果喷雾活性炭。
根据本发明,即使在将活性炭进行喷雾的情况下,也能实现运行费用的低廉化,并且能够长期间稳定地进行汞的吸附/固定化。
附图说明
图1是实施例1的燃煤锅炉的排气处理系统的示意图。
图2是气液接触塔中的ΔHg/ΔCaSO4和汞除去性能(气液接触塔出口的气体中汞浓度)的关系图。
图3是美国煤炭的烟煤的各30个采样的Hg/S比的合计图。
图4是美国煤炭的PRB炭的各30个采样的Hg/S比的合计图。
图5是实施例2的燃煤锅炉的排气处理系统的示意图。
图6是实施例3的燃煤锅炉的排气处理系统的示意图。
图7是现有的燃煤锅炉的排气处理系统的示意图。
附图标记说明
11 燃煤锅炉
12 氨
13 脱硝装置
14 空气预热器
15 集尘器
16 脱硫装置
17 烟囱
21 袋式除尘器
22a 活性炭
22 活性炭喷雾装置
23 上清液
24 石膏
41 固液分离装置
具体实施方式
以下,参照附图对本发明进行详细地说明。需要说明的是,本发明并不限于该实施例。另外,下述实施例中的构成要素中包括对于本领域技术人员而言为显而易见的结构或者与其实质相同的结构。
实施例1
以下,参照附图对本发明的实施例1的燃煤锅炉的排气处理系统进行说明。
图1是本发明的燃煤锅炉的排气处理系统的示意图。
该排气处理系统包括:向作为燃料F而使用煤炭的燃煤锅炉11的排气中喷雾氯化氢33的HCl喷雾装置32、向喷雾氯化氢后的排气中添加氨12以通过氨脱硝除去氮氧化物并将汞氧化的脱硝装置13、将除去氧化物后的气体中的热量回收的空气预热器14、将热量回收后的气体中的烟尘除去的集尘器15、向除尘后的气体中喷雾活性炭22a的活性炭喷雾装置22、捕集吸附了汞的活性炭的袋式除尘器21、将除去活性炭后的排气中的硫氧化物通过基于气液接触的石灰/石膏法除去并除去氧化汞的脱硫装置16、以及将脱硫后的气体向外部排出的烟囱17、为了向脱硫装置16内的料浆(スラリ)吸收液供给空气而测量氧化还原电位的ORP计19。
本实施例的燃煤锅炉的排气处理系统中,具有在上述脱硝装置13的上游侧喷雾氯化氢33的HCI喷雾装置32,并在烟道内喷雾氯化氢33,以促进脱硝装置13内的脱硝催化剂上的汞的氧化(Hg0-Hg2+)。
这是因为,氧化汞(Hg2)比零价汞(Hg0)容易被活性炭吸附,能够使汞吸附量(kgHg/kg活性炭)增加、使活性炭使用量(kg活性炭)减少。
吸附汞的活性炭由袋式除尘器21回收,并通过其他途径被废弃处理。
另外,使用ORP计19测量脱硫装置16的吸收液的氧化还原电位(ORP),将其氧化还原电位的测量值设为150mV以上。
这是因为,氧化汞(Hg2)在脱硫装置16内借由气液接触被气体吸收液(石灰石、石膏料浆)吸收,但是此时通过将ORP值调整为150mV以上(最好为200至300mV以上)能够抑制被吸收的氧化汞Hg2+的还原(Hg2+→Hg0)。
另外,即使在具有现有的活性炭喷雾装置的排气处理系统中,通过为了实现活性炭的使用量的降低而在脱硝装置的上游侧设置供给氯化氢的氯化氢供给装置并设置脱硫装置的气体吸收液的ORP计,使汞的吸附效率提高,通过简单的设备变更实现长期的活性炭喷雾量的降低,其结果是能够降低废弃活性炭量,促进排气处理系统运行费用大幅度地降低。
另外,在本实施例中虽设置有袋式除尘器21,但是也可以不设置袋式除尘器21而直接导入到脱硫装置16内,在从基于石灰/石膏法的吸收液除去石膏时同时将其排出。
另外,根据煤炭的炭的种类,汞(Hg)/硫磺(S)的摩尔比为1.3×10-6以上的情况下,采用监视在脱硫装置的下游侧的汞浓度、并根据其结果强制性地喷雾活性炭22的燃煤锅炉的排气处理系统的运行方法。
这是因为,通常,汞含量小的煤炭中,其汞(Hg)/硫磺(S)的摩尔比(称为Hg/S摩尔比)为1.3×10-6以下的情况下,仅通过氯化氢33的供给和ORP计的控制,就能够除去排气中的汞,但是在煤炭中的炭的种类发生变化而急剧变化到1.3×10-6以上的情况下,不能通过基于ORP计的控制,对应迅速除去汞的要求。
在这种情况下,基于ORP计19的控制稳定的期间,由于排气中的汞浓度上升,所以通过强制性地喷雾活性炭,能够暂时防止汞向外部飞散。
这是因为,煤炭中的汞(Hg)/硫磺(S)的摩尔比为1.3×10-6以上(molHg/molS)的情况下,相对于汞(Hg)的除去速度,石膏(CaSO4)的生成速度变得不足。
接下来,说明将Hg/S摩尔比规定为1.3×10-6的理由。
首先,根据ΔHg/ΔCaSO4=Δ汞除去量/Δ石膏生成量的关系,在图2中示出脱硫装置16的气液接触塔中的ΔHg/ΔCaSO4和汞除去性能(在气液接触塔出口的气体中的汞浓度)的关系。
根据该图,明确了在ΔHg/ΔCaSO4为2mgHg/kgCaSO4以下能够维持汞除去性能。
在汞(Hg)和石膏(CaSO4)中所包含的硫磺(S)起因于最上游的煤炭。
在此,如果换算ΔHg/ΔCaSO4=2mgHg/kgCaSO4,会有以下的结果。即,Hgmol/Smol=2mgHg/kgCaSO4×〔(1/200.59)×10-3molHg/mgHg〕/〔(1/136.144)×103molS/kgCaSO4〕=1.357×10-6molHg/molS
需要说明的是,将汞(Hg)的分子量设为200.59、将硫磺(S)的分子量设为32.066,将石膏(CaSO4)的分子量设为136.144。
因此,ΔHg/ΔCaSO42mgHg/kgCaSO4相当于1.3×10-6molHg/molS。
其结果是,作为Hg/S摩尔比的阈值规定1.3×10-6,因为在超过该阈值的情况下,汞除去性能会降低,所以有必要采取除去汞的对策。
进一步而言,图3以及图4是表示烟煤和PRB炭中的煤炭的含量比(Hg/S)与频率的关系图。
图3以及图4是对美国煤炭的烟煤以及PRB炭的各30个采样的Hg/S比合计后的图,1.36×10-6molHg/molS以下的比率在烟煤中为大约70%,在PRB炭中为大约27%。
即使在这种单独使用烟煤或者混合使用烟煤的情况下,也能够通过氯化氢的供给和ORP的控制高效地除去汞。另外,即使在煤炭的种类发生变化的情况下,通过喷雾活性炭即使汞浓度急剧上升也能够应对。
实施例2
图5是本发明的其他的燃煤锅炉的排气处理系统的示意图。
本实施例的排气处理系统包括:通过添加氨12除去来自燃煤锅炉11的排气中的氮氧化物的脱硝装置13、回收除去氮氧化物后的气体中的热量的空气预热器14、除去热量回收后的气体的烟尘的集尘器15、将除尘后的气体中的硫氧化物通过石灰/石膏法除去并除去氧化汞的气液接触式的脱硫装置16、以及将脱硫且除去汞后的净化气体向外部排出的烟囱17,在该排气处理系统中,将来自脱硫装置16的含有汞的料浆吸收液向外部抽出,在分离石膏前添加凝集剂,从而将汞凝集除去。
即,如图5所示,向从脱硫装置16抽出的含有汞的料浆吸收液添加凝集剂,在使该凝集剂凝集汞、利用固液分离装置41分离除去石膏24时,与石膏24一起也分离凝集剂,降低分离水中的汞浓度。
凝集剂的添加可以在脱硫装置16的内部(40A)或者固液分离装置41的上游侧(40B)进行。
其结果是,能够降低返回到脱硫装置16的分离水中的零价的汞(Hg0)的浓度,并能够防止脱硫装置16内的汞的再次飞散。
实施例3
图6是本发明的其他的燃煤锅炉的排气处理系统的示意图。
本实施例的排气处理系统包括:通过添加氨12除去来自燃煤锅炉11的排气中的氮氧化物的脱硝装置13、回收除去氮氧化物后的气体中的热量的空气预热器14、除去热量回收后的气体的烟尘的集尘器15、将除尘后的气体中的硫氧化物通过石灰/石膏法除去并除去氧化汞的气液接触式的脱硫装置16、以及将脱硫且除去汞后的净化气体向外部排出的烟囱17,在该排气处理系统中,将来自脱硫装置16的含有汞的料浆吸收液向外部抽出,使用固液分离装置41分离石膏24,分离石24后,对于分离了石膏24的上清液23,在汞吸附除去装置42内使其与活性炭、螯合物树脂、离子交换树脂、或者硫化物载体等汞吸附材料向接触,以吸附除去汞。
其结果是,能够降低返回到脱硫装置16的分离水中的零价的汞(Hg0)的浓度,并能够防止脱硫装置16内的汞的再次飞散。
需要说明的是,在本实施例中,也可以结合添加图5的实施例2的凝集剂,以进一步提高除去汞的效果。
产业上的利用可能性
这样,根据本发明的排气处理系统以及运行方法,由于降低汞的再次分散,所以能够提高汞除去效率,从而适用于排气中的汞排出量受到规定限制的情况。
Claims (5)
1.一种燃煤锅炉的排气处理系统,包括:
除去来自燃煤锅炉的排气中的氮氧化物的脱硝装置、
回收除去氮氧化物后的气体中的热量的空气预热器、
除去热量回收后的气体中的烟尘的集尘器、
通过石灰/石膏法除去除尘后的气体中的硫氧化物并除去氧化汞的气液接触式的脱硫装置、以及
将脱硫后的气体向外部排出的烟囱,
所述排气处理系统的特征在于,
在脱硝装置的上游侧喷雾氯化氢,
并在所述集尘器的下游侧喷雾活性炭而吸附气体中的汞。
2.一种燃煤锅炉的排气处理系统,包括:
除去来自燃煤锅炉的排气中的氮氧化物的脱硝装置、
回收除去氮氧化物后的气体中的热量的空气预热器、
除去热量回收后的气体中的烟尘的集尘器、
通过石灰/石膏法除去除尘后的气体中的硫氧化物并除去氧化汞的气液接触式的脱硫装置、
以及将脱硫后的气体向外部排出的烟囱,
所述排气处理系统的特征在于,
在脱硝装置的上游侧喷雾氯化氢,
并在所述集尘器的下游侧喷雾活性炭而吸附气体中的汞,
将脱硫装置内的吸收液的氧化还原电位设为150mV以上。
3.如权利要求1或2所述的燃煤锅炉的排气处理系统,其特征在于,将含有汞的料浆吸收液向外部抽出,在分离石膏前添加凝集剂,从而凝集除去汞。
4.如权利要求1至3中任意一项所述的燃煤锅炉的排气处理系统,其特征在于,使分离了石膏的分离液与活性炭、螯合物树脂、离子交换树脂或者硫化物载体中的至少一种接触,以吸附除去汞。
5.一种燃煤锅炉的排气处理系统的运行方法,其特征在于,该运行方法使用权利要求1至4中的任意一种燃煤锅炉的排气处理系统,
在煤炭中的汞(Hg)/硫磺(S)的摩尔比为1.3×10-6以上的情况下,在脱硫装置的下游侧监视汞浓度,并根据该结果喷雾活性炭。
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US20110044872A1 (en) | 2011-02-24 |
US8071060B2 (en) | 2011-12-06 |
CN101918108B (zh) | 2013-06-05 |
JP2009166012A (ja) | 2009-07-30 |
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CA2711950A1 (en) | 2009-07-30 |
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