CN1576357A - 利用锰在煤燃烧器中同时减少灰分中的nox和碳 - Google Patents
利用锰在煤燃烧器中同时减少灰分中的nox和碳 Download PDFInfo
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Abstract
本发明涉及一种添加剂和一种通过使用至少一种含锰添加剂来同时降低由煤燃烧所产生的灰碳和NOx产量水平的方法。在烧煤通用炉中使用含锰添加剂可以导致减少的灰碳量和减少的NOx排放。
Description
技术领域
本发明涉及一种添加剂和一种通过向燃料中添加有效量的锰化合物来同时减少由含煤燃料燃烧所产生的NOX和灰碳(carbon)的方法。
背景技术
在锅炉、焚烧炉和通用炉中燃烧燃料如燃油或煤时,获得高燃烧效率和低污染排放的能力是极为重要的。提高燃烧效率的最直接的方法之一就是增加助燃空气的量以保证碳-碳、碳-氢和碳-杂原子键完全氧化生成燃烧产物二氧化碳和水。燃烧产物中较高的二氧化碳量意味着提高的燃烧效率以及灰烬中较低的碳含量。不幸的是增加助燃空气的量会促进NOX的形成。也就是说,随着助燃空气的增加,燃烧效率(减少灰烬中的碳)与NOX产量成反比,从而当其中一种增加时,另一种减少。这个问题在采用废气循环的燃烧系统如通称为助燃气体循环(FGR)的系统中尤其明显。通过降低火焰温度,FGR降低了NOX,但代价是灰烬中的碳的增加。由于这种在环境压力下的燃烧所产生的传统燃烧学认为在NOX和未燃烧的碳之间存在一种折衷,即用来降低NOX的方法必然会升高未燃烧碳的量,反之亦然。已知含金属的添加剂在不同的燃烧系统中能实现其中的一个方面,但不能同时实现两个方面。为避免这种矛盾,以前以及常规的努力通常需要向每种碳烬和NOX独立地施加一系列的多重方法,以将它们置于控制之下或保持在可接受的水平。
发明内容
在一个具体实施方案中,本发明涉及通过使用至少一种含锰添加剂化合物同时改进燃煤设备的碳烬(即减少灰烬中的碳)和NOX产量水平的方法。如本文所述,在燃煤设备如通用炉中使用一种含锰添加剂,可以获得较少的灰中的碳含量以及较低的NOX排放。
应当理解,上述一般说明和下述详细说明都只是示范性和解释性的,都是为了对权利要求所述的本发明提供进一步的解释。
附图简述
图1说明了含锰添加剂在减少NOX中的表现。
图2说明了通过使用含锰添加剂减少了灰中的碳和一氧化碳。
具体实施方式
属于在环境压力下燃烧的传统燃烧学认为在NOX和未燃烧的碳之间存在一种折衷,即用来降低NOX的方法必然会提高未燃烧的碳的水平,反之亦然。
在本说明书的一个具体实施方案中,含锰添加剂与一种特别是含煤的燃料结合。含锰添加剂促进了整个燃烧过程中—既包括燃烧系统的高温区域也包括低温区域(即温度高达3600°F的焰锋和温度低至550°F的焰锋谷)—改进的碳燃烧(即降低了灰中的碳)。
另一方面,NOX的减少只在低于显著的热NOX形成温度范围(高于2500°F)之外的温度下的焰锋处形成。低于约2500°F,NOX与氧在含锰燃烧副产物微粒(烟灰或粉尘)的碳氧化中相互竞争。锰促进了此碳氧化反应,当NOX为氧源和温度下降时该反应较快。这种通过锰催化的NOX的碳氧化在低至约550°F的温度仍有效。即使在高空气对燃料比(即氧超过化学计量,或燃料缺乏)燃烧条件下,这种NOX减少的化学反应仍可以在含碳微粒如煤烟或飘尘上进行。这是因为含碳微粒上的环境是燃料富集型的,是减少NOX所必需的条件。从而,与含碳微粒(燃料富集型)混合在一起的锰可以利用助燃氧或NOX为氧化剂催化碳燃烬。这样,在NOX减少的同时灰中的碳也降低了。使用含锰添加剂时一氧化碳(CO)水平也降低了,这说明在将碳转化为氧化程度更高的二氧化碳燃烧产物时表现了改进的燃烧效率。
因此在本说明书的另一实施方案中,提出了一种同时降低由煤燃烧所产生的飘尘中的碳量、NOX量和一氧化碳量的方法,该方法包括将煤和含有含锰化合物的添加剂混合形成其混合物;将所述混合物在燃烧室中燃烧;存在的含锰化合物的量足以有效地降低由煤在燃烧室中燃烧所产生的飘尘中的碳量、NOX量和一氧化碳量。
另一实施方案提供了一种同时降低由煤燃烧所产生的一氧化碳量和NOX量的方法,该方法包括将煤和含有含锰化合物的添加剂混合形成其混合物;将所述混合物在燃烧室中燃烧;存在的含锰化合物的量足以有效地降低由煤在燃烧室中燃烧所产生的一氧化碳量和NOX量。
另一实施方案提供了一种同时降低由煤燃烧所产生的飘尘中的碳量和NOX量的方法,该方法包括在至少1ppm含锰添加剂的存在下煤,由此,由所述煤燃烧所产生的飘尘中的碳量和NOX量相对于含锰添加剂不存在的情况下煤燃烧所产生的飘尘中的碳量和NOX量都得以降低。
另一个实施方案提供了一种在以FGR模式下运行时稳定燃烧的方法。当燃烧炉在FGR速度下运行以显著降低NOX时,通常会遇到由FGR造成的温度较低的火焰所导致的燃烧不稳定。这种不稳定导致了燃烧效率低和羟、一氧化碳和高碳含量(烟和飘尘)颗粒的增多。从而提供了一种通过在存在至少1ppm含锰添加剂的情况下燃烧煤来稳定煤燃烧的方法,由此,由所述煤燃烧所产生的飘尘中的碳量和NOX量相对于不存在含锰添加剂的情况下煤燃烧所产生的飘尘中的碳量和NOX量都得以降低,燃烧稳定性相对于不存在含锰添加剂时也得以提高。
在本文中可用作煤添加剂的含锰化合物的例子包括无机化合物和有机金属化合物。可用于本发明的无机锰化合物可以包括一种或多种锰的氧化物、锰的硫酸盐和锰的磷酸盐。
在本发明的一个实施方案中,优选的有机金属化合物包括醇、醛、酮、酯、酐、磺酸盐、膦酸盐、环烷酸盐、螯合物、苯酚盐、冠醚、羧酸、酰胺、乙酰丙酮化物及其混合物。含锰有机金属化合物包括三羰基锰化合物。这种化合物在例如美国专利US4,568,357;US4,674,447;US5,113,803;US5,599,357;US5,944,858和欧洲专利EP466512B1中有记述。
可用的适当三羰基锰化合物包括环戊二烯基三羰基锰、甲基环戊二烯基三羰基锰、二甲基环戊二烯基三羰基锰、三甲基环戊二烯基三羰基锰、四甲基环戊二烯基三羰基锰、五甲基环戊二烯基三羰基锰、乙基环戊二烯基三羰基锰、二乙基环戊二烯基三羰基锰、丙基环戊二烯基三羰基锰、异丙基环戊二烯基三羰基锰、叔丁基环戊二烯基三羰基锰、辛基环戊二烯基三羰基锰、十二烷基环戊二烯基三羰基锰、乙基甲基环戊二烯基三羰基锰、茚基三羰基锰等等,包括两种或多种这些化合物的混合物。一个例子是室温下为液态的环戊二烯基三羰基锰如甲基环戊二烯基三羰基锰、乙基环戊二烯基三羰基锰、环戊二烯基三羰基锰和甲基环戊二烯基三羰基锰的液态混合物、甲基环戊二烯基三羰基锰和乙基环戊二烯基三羰基锰的混合物等等。
这些化合物的制备在文献中有记述,如美国专利US2,818,417,其公开内容在此完全引入。
可以使用本说明书所记述的含锰的煤添加剂化合物的燃烧体系包括任何和所有可以烧或其中可以烧烃类燃料如煤的内燃和外燃设备、机器、发动机、涡轮发动机、锅炉、焚化炉、蒸汽炉、固定式炉等。烧煤锅炉,特别是大的系统,都是独特设计的。但是多数都具有将煤输入和通过研磨过程并最终输入炉子的燃烧室的初级气流。在炉内,可以有一个或多个同样向燃烧室内输送空气的二级气流。
含锰的煤添加剂化合物可以在进入燃烧室之前或同时与煤进行混合。例如可以将锰化合物注入初级气流中以使其在燃烧室前与煤混合。或者可以将锰化合物随二级气流注入并在燃烧室中与煤混合。最后,具有锰化合物的添加剂可以单独注入煤中和直接注入燃烧室中。在所有情形下,都有条件使具有锰化合物的添加剂在煤中有效混合从而使锰原子可以存在并可用于催化活性。添加剂可以是液态形式以易于与液态燃料混合,并通过喷雾嘴和微热轻易分散于燃烧空气中。
锰化合物在煤中的添加率在1-约500ppm之间。或者添加率任选地为5-100ppm的锰。在另一实施方案中锰对煤的添加率为20ppm。
以下实施例对本发明的某些方面作进一步说明,但并不限制本发明。
实施例
测试在300兆瓦(MW)的燃煤通用炉中进行。时长46天的测试粗分成几个阶段。第一个阶段作为基准线,不使用含锰添加剂,第二阶段使用含锰添加剂,持续时间与基准线阶段相同。含锰添加剂注入燃气体再循环流中。由于含锰添加剂的引入,观察到NOX水平从平均189ppm降到155ppm,降低18%。同时,由于含锰添加剂的引入,灰中的碳量从平均约20.4%降到9.4%,降低约54%。在这种类型的燃烧中,用一种方法或单一添加剂同时降低NOX和灰中的碳是意料不到的。
附图1和2显示了上述实施例中使用一种含锰添加剂同时降低燃烧产物中灰中的碳和NOX的结果。附图2显示了上述实施例中使用一种含锰添加剂同时降低燃烧产物中灰碳、NOX和一氧化碳的结果。该数据采自在整个阶段内都燃烧同样的煤的燃煤单元,且是基于200MW±10MW时的日平均值。“GB”代表向燃烧单元中引入被称为Greenburn 2001HF燃烧催化剂的含锰的煤添加剂。从这些结果可以看出,NOX、灰碳和一氧化碳显著地同时降低。NOX最终降低17%,飘尘碳含量降低48%,助燃气体一氧化碳降低30%。
应当理解,在此说明书或权利要求书中任何一处用化学名称指代的反应物和组分,无论是单数还是复数,都应认为与另一种用化学名称或化学类别(例如基础燃料、溶剂等)所指代的关连之前都已经存在。在所得混合物或溶液或反应介质中发生的化学变化、转化和/或反应(如果有的话)并不重要,因为这些变化、转化和/或反应是将特定的反应物和/或组分在本公开所要求遵从的条件下放在一起的自然结果。因此无论是在进行期望的化学反应(如有机金属化合物的形成)还是在形成期望的组成(如添加剂浓缩物或添加的燃料混合物)中,反应物和组分都被认为是要被放在一起的成分。还应认识到,添加剂组分可以本身单独地或作为形成预形成添加剂组合物和/或子组合物的组分加入到基础燃料中或者与其混合。因此,尽管在下面的权利要求书中提到物质、组分和/或成分时可能是现在时,但对这些物质、组成或成分的指代就好像它在首次混合或与一种或多种根据本公开所述的其它物质、组成和/或成分混合之前已经存在。所述物质、组成和/或成分在上述混和或混合操作之中或之后已经通过化学反应或转化失去了其原始特性这一事实对于准确理解和评价说明书以及下述权利要求并不重要。
在本说明书的很多地方,引用了许多美国专利、公开的外国专利申请和公开的技术论文。所有这些引用文献都特别完全引入本公开,如同在此完全公开。
本发明在实施中容许有许多变化。因此上述说明不是要限制,也不应被解释成要限制本发明于上文所公开的具体实施例。相反,所要覆盖的范围陈述于随后的权利要求书,并且其等同物在法律上是允许的。
专利权人并不是要将所公开的任何实施方案献给公众,就这方面来说,所有公开的改进和变化就字面上来说可能不在权利要求书的范围内,但它们在等同的原则下被认为是本发明的一部分。
Claims (21)
1.一种同时降低由煤燃烧所产生的飘尘中的碳量和NOX量的方法,该方法包括:
将煤和含有含锰化合物的添加剂混合,形成其混合物;
将所述混合物在燃烧室中燃烧;
含锰化合物的存在量要足以有效地降低由煤在燃烧室中燃烧所产生的飘尘中的碳量和NOX量。
2.根据权利要求1的方法,其中所述的锰化合物是有机金属化合物。
3.根据权利要求2的方法,其中所述有机金属化合物的有机部分衍生自选自醇、醛、酮、酯、酐、磺酸盐、膦酸盐、环烷酸盐、螯合物、苯酚盐、冠醚、羧酸、酰胺、乙酰丙酮化物及其混合物的物质。
4.根据权利要求2的方法,其中所述的有机金属化合物包含甲基环戊二烯基三羰基锰。
5.根据权利要求2的方法,其中所述的锰化合物选自环戊二烯基三羰基锰、甲基环戊二烯基三羰基锰、二甲基环戊二烯基三羰基锰、三甲基环戊二烯基三羰基锰、四甲基环戊二烯基三羰基锰、五甲基环戊二烯基三羰基锰、乙基环戊二烯基三羰基锰、二乙基环戊二烯基三羰基锰、丙基环戊二烯基三羰基锰、异丙基环戊二烯基三羰基锰、叔丁基环戊二烯基三羰基锰、辛基环戊二烯基三羰基锰、十二烷基环戊二烯基三羰基锰、乙基甲基环戊二烯基三羰基锰、茚基三羰基锰等等,包括两种或多种这些化合物的混合物。
6.根据权利要求1的方法,其中所述的含锰化合物选自锰的氧化物、锰的硫酸盐和锰的磷酸盐。
7.根据权利要求1的方法,其中所述的锰化合物占煤的约20ppm。
8.根据权利要求1的方法,其中所述的锰化合物占煤的约5-100ppm。
9.根据权利要求1的方法,其中所述的锰化合物占煤的约1-500ppm。
10.根据权利要求1的方法,其中所述的添加剂被引入将煤送入燃烧室的空气流中。
11.一种同时降低由煤燃烧所产生的飘尘中的碳量和NOX量的方法,该方法包括:
将煤和含有含锰化合物的添加剂混合,形成其混合物;
将所述混合物在燃烧室中燃烧;
含锰化合物的存在量要足以有效地降低由煤在燃烧室中燃烧所产生的飘尘中的碳量和NOX量,其中添加剂与煤分开直接引入燃烧室中。
12.根据权利要求11的方法,其中所述添加剂被引入燃气循环流中。
13.根据权利要求11的方法,其中所述添加剂被引入输入到燃烧室中的二级气流中。
14.一种同时降低由煤燃烧所产生的飘尘中的碳量和NOX量的方法,该方法包括:
将煤和含有含锰化合物的添加剂混合,形成其混合物;
将煤与添加剂的混合物引入到烧煤的燃烧室中;
将所述混合物在燃烧室中燃烧;和
含锰化合物的存在量要足以有效地降低由煤在燃烧室中燃烧所产生的飘尘中的碳量和NOX量。
15.一种用在同时减少由煤燃烧所产生的飘尘中的碳量和NOX量的煤添加剂,该添加剂包含一种锰化合物,其中锰化合物在燃烧前以煤的约1-500ppm的处理率加入煤中。
16.根据权利要求14所述的煤添加剂,其中所述锰化合物在燃烧前以煤的约5-100ppm的处理率加入煤中。
17.根据权利要求14所述的煤添加剂,其中所述锰化合物在燃烧前以煤的约20ppm的处理率加入煤中。
18.一种同时降低由煤燃烧所产生飘尘中的碳量、NOX量和一氧化碳量的方法,该方法包括将煤和含有含锰化合物的添加剂混合,形成其混合物;将所述混合物在燃烧室中燃烧;含锰化合物的存在量要足以有效地降低由煤在燃烧室中燃烧所产生的飘尘中的碳量、NOX量和一氧化碳量。
19.一种同时降低由煤燃烧所产生的一氧化碳量和NOX量的方法,该方法包括:
将煤和含有含锰化合物的添加剂混合,形成其混合物;
将所述混合物在燃烧室中燃烧;
含锰化合物的存在量要足以有效地降低由煤在燃烧室中燃烧所产生的一氧化碳量和NOX量。
20.一种同时降低由煤燃烧所产生的飘尘中的碳量和NOX量的方法,该方法包括在至少1ppm含锰添加剂的存在下燃烧煤,由此,由所述煤燃烧所产生的飘尘中的碳量和NOX量相对于含锰添加剂不存在的情况下煤燃烧所产生的飘尘中的碳量和NOX量都得以降低。
21.一种通过在至少1ppm含锰添加剂的存在下燃烧煤来稳定煤燃烧的方法,由此,由所述煤燃烧所产生的飘尘中的碳量和NOX量相对于不存在含锰添加剂的情况下煤燃烧所产生的飘尘中的碳量和NOX量都得以降低,而且燃烧稳定性相对于不存在含锰添加剂时煤的燃烧稳定性也得以提高。
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-
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- 2003-07-21 US US10/623,686 patent/US20050016057A1/en not_active Abandoned
-
2004
- 2004-06-10 CA CA002470690A patent/CA2470690A1/en not_active Abandoned
- 2004-06-11 ZA ZA2004/04661A patent/ZA200404661B/en unknown
- 2004-06-24 EP EP04014850A patent/EP1500692A1/en not_active Withdrawn
- 2004-07-01 AU AU2004203002A patent/AU2004203002A1/en not_active Abandoned
- 2004-07-06 MX MXPA04006613A patent/MXPA04006613A/es not_active Application Discontinuation
- 2004-07-14 JP JP2004207569A patent/JP2005042109A/ja active Pending
- 2004-07-16 KR KR1020040055415A patent/KR20050010711A/ko not_active Application Discontinuation
- 2004-07-19 BR BR0403581-0A patent/BRPI0403581A/pt not_active IP Right Cessation
- 2004-07-20 AR ARP040102565A patent/AR046397A1/es not_active Application Discontinuation
- 2004-07-20 RU RU2004122435/04A patent/RU2268915C1/ru not_active IP Right Cessation
- 2004-07-20 CN CNB2004100713359A patent/CN100503794C/zh not_active Expired - Fee Related
- 2004-07-20 SG SG200404304A patent/SG108965A1/en unknown
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102517121A (zh) * | 2012-01-05 | 2012-06-27 | 江南大学 | 一种提高煤炭燃烧热值的催化装置 |
CN102989510A (zh) * | 2012-12-24 | 2013-03-27 | 江南大学 | 一种用于污泥焚烧过程的催化剂 |
CN103146459A (zh) * | 2013-03-11 | 2013-06-12 | 江南大学 | 一种促进淤泥和煤粉混合物燃烧的催化剂 |
CN112403524A (zh) * | 2020-11-20 | 2021-02-26 | 雷夫·维本斯塔德 | 一种燃烧催化剂 |
Also Published As
Publication number | Publication date |
---|---|
SG108965A1 (en) | 2005-02-28 |
RU2004122435A (ru) | 2006-01-20 |
CA2470690A1 (en) | 2005-01-21 |
US20050016057A1 (en) | 2005-01-27 |
CN100503794C (zh) | 2009-06-24 |
KR20050010711A (ko) | 2005-01-28 |
RU2268915C1 (ru) | 2006-01-27 |
JP2005042109A (ja) | 2005-02-17 |
AU2004203002A1 (en) | 2005-02-10 |
AR046397A1 (es) | 2005-12-07 |
MXPA04006613A (es) | 2005-03-31 |
EP1500692A1 (en) | 2005-01-26 |
BRPI0403581A (pt) | 2005-06-28 |
ZA200404661B (en) | 2005-02-23 |
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