CN1576356A - 通过用于煤的锰添加剂来降低烧煤产生的飘尘中的碳含量 - Google Patents

通过用于煤的锰添加剂来降低烧煤产生的飘尘中的碳含量 Download PDF

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CN1576356A
CN1576356A CNA2004100712375A CN200410071237A CN1576356A CN 1576356 A CN1576356 A CN 1576356A CN A2004100712375 A CNA2004100712375 A CN A2004100712375A CN 200410071237 A CN200410071237 A CN 200410071237A CN 1576356 A CN1576356 A CN 1576356A
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J·W·罗斯
S·A·法克托尔
R·I·戴维逊
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Abstract

一种用于降低由燃烧煤和含锰化合物的混合物产生的碳和飘尘的方法和添加剂。锰化合物在燃烧室之前或在燃烧室中与煤混合。锰化合物可以是无机或有机金属化合物。有机金属化合物可以包括甲基环戊二烯基三羰基锰。

Description

通过用于煤的锰添加剂来降低烧煤产生的飘尘中的碳含量
技术领域
本发明涉及一种方法和添加剂，用于降低由烧煤产生的飘尘中的碳含量。本方法和添加剂具体涉及在烧煤之前或过程中将含锰化合物混入煤中。
背景技术
飘尘中的碳是由含烃的燃料，包括煤的不完全燃烧产生的。为了降低从燃烧室排放的飘尘总量，希望降低灰分中的碳。与高碳飘尘相比，低碳飘尘也更容易处理，且更容易被常用于控制颗粒排放的静电沉淀器所捕获。
已知有若干种方法用于在煤炉中降低飘尘中的碳。一种现有的解决手段是增加注入燃烧室的空气量。虽然这种方法降低了飘尘中的碳含量，但该方法通常导致不希望的NOx排放增加。还已知通过向煤或燃烧室中加入镁或钙以降低飘尘中的碳。但这些金属必须以非常高的浓度加入才有效。不幸的是，大量钙和镁将导致体系中的其它问题，诸如结垢。
一种金属-锰通常大量存在于煤中。在某些情况下，在煤中天然存在几百ppm锰。但是，没有观察到煤中固有的锰导致灰分碳的减少。
发明内容
本发明涉及一种用于降低由烧煤产生的飘尘中碳含量的添加剂和方法。该添加剂包括含锰的化合物，包括但不限于无机和有机金属锰化合物。“含锰化合物”和“锰化合物”在本文中可以互换。
附图说明
图1描述了引入锰添加剂而导致灰分碳的量随时间的变化。
图2描述了飘尘中的锰。
具体实施方式
在一个实施方案中，含锰化合物在进入燃烧室之前或在燃烧室中与煤混合。为了增强锰作为燃烧反应的催化剂的有效性，与煤混合的锰化合物必须使锰以单核或小簇的方式获得。按照这种方式，更多的锰在燃烧过程中分散在煤(碳)颗粒上或其中。
因此，在本文的一个实施方案中提供了一种降低由烧煤产生的飘尘中碳含量的方法，该方法包括将煤与含有含锰化合物的添加剂混合，形成其混合物；以及在燃烧室中燃烧所述混合物；锰化合物以降低在燃烧室中由烧煤产生的飘尘中碳含量的有效量存在。
假定天然存在于煤中的大量锰由于锰与诸如硫或磷以结晶或粗晶形式结合在一起而不具有降低飘尘中碳含量的可评估效果。因此，没有大量的单核或小簇锰原子能够实现分散，以环绕并催化煤(碳)颗粒的燃烧。因此，天然存在的锰对于燃烧的影响似乎可以忽略不计。
此处的术语“单核”化合物包括锰原子或锰原子的小簇与基本上有机可溶性的化合物相结合的情况。一个例子是溶于各种有机溶剂的有机金属锰化合物。具有金属原子“小簇”的化合物可以包括，例如那些具有约2-约50个锰原子的物质。在该备选方案中，金属原子仍然充分分散或可分散成为燃烧反应的有效催化剂。当讨论单核和小簇原子的溶解度时，此处的术语“溶解度”既是指常规意义上的完全溶解，也是指部分溶解或者悬浮或分散于流体或液体介质中。只要锰原子适当地分散为单个原子或最多50个原子的簇，锰原子就足以为燃烧反应提供可靠的催化效果。
单核化合物的例子包括无机和有机金属化合物。在本发明的实施方案中，优选的有机金属化合物包括在其组分中含有有机和无机配体的化合物，所述配体包括醇、醛、酮、酯、酐、磺酸盐、膦酸酯、螯合物、酚盐、环烷酸盐、冠醚、羧酸、酰胺、乙酰丙酮化物及其混合物。含有锰的有机金属化合物包括但不限于三羰基锰化合物。例如，在美国专利4568357、4674447、5113803、5599357和5944858，以及欧洲专利466512B1中教导了这样的化合物。
可以使用的适合的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，包括这些化合物中的两种或多种的混合物。例如在室温下是液体的环戊二烯基三羰基锰，诸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体混合物、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。
在例如美国专利2818417的文献中描述了这些化合物的制备，此处将该专利全文引作参考。
此处有用的锰化合物的其它例子是那些具有约2-约50个原子的小簇的化合物。
可以使用此处描述的化合物的燃烧体系包括能够燃烧，或者诸如煤的含烃燃料能够在其中燃烧的任何或所有内部和外部燃烧装置、机械、发动机、涡轮发动机、锅炉、焚烧炉、蒸发燃烧炉、固定式燃烧炉等。烧煤的加热炉，特别是较大的体系全部是单独设计的。但是，大部分加热炉具有初级空气流，其将煤送入并通过研磨工序并最终送入加热炉中的燃烧室。在加热炉中，还可以有一个或多个次级空气流，其将空气送入燃烧室。
根据此处的实施方案，锰化合物可以在进入燃烧室之前或同时与煤混合。例如，锰化合物可以注入初级空气流，以在燃烧室之前与煤混合。或者，锰化合物可以与次级空气流一起注入并在燃烧室中与煤混合。最后，含有锰化合物的添加剂可以单独注入煤中或直接注入燃烧室。在任何备选方案中，条件是在煤中得到含有锰化合物的有效添加剂混合物，以使锰原子存在或产生催化活性。添加剂可以是液态，使其与液体燃料互溶，并易于通过雾化喷嘴和轻度加热而分散于燃烧空气中。或者，含锰的添加剂也可以是流体(但不需要是液体)固体或粉末材料的一部分。
锰化合物对煤的处理比例是约1-约500ppm重量。处理比例也可以是约5-约100ppm重量锰。在进一步的实施方案中，锰对煤的处理比例是约20ppm重量。
实施例：
分析用于本实施例的煤，发现其锰含量是约700ppm wt。为了确定基线，在大应用功率(600MW)设备单元的加热炉中燃烧这种煤，并以固定的时间间隔测量飘尘的锰含量和灰分碳(CIA)。所述灰分中锰含量是约500ppm wt，CIA是约6wt％。随后，以约20ppm wt的处理比例将含锰添加剂(Greenburn2001HF燃烧催化剂)加入燃烧空气中。观察到飘尘中的锰含量从约500ppm的基线上升至约600ppm wt的平均水平。同时，CIA也从约6wt％的基线水平下降至约4.1wt％的较低平均水平。计算出CIA下降了约28％。结论是，添加剂中的锰对于碳的燃尽具有活性，但存在于煤中的天然形式是完全惰性的。
图1阐述了本发明通过向煤的燃烧中引入含锰添加剂而在减少灰分碳方面的优点。图2阐述了向煤的燃烧中引入含锰添加剂之后，飘尘中二氧化锰的增加。
可以理解的是，无论是以单数或复数形式，在本说明书或权利要求中任何一处的化学名称所指的反应物和组分等同于它们在与其它物质进行接触之前用化学名称或化学类型(例如碱燃料、溶剂等)所指的存在形式。无论在得到的混合物或溶液或反应介质中发生了怎样的化学变化、转化和/或反应(如果发生的话)，所述变化、转化和/或反应是在根据本公开所要求的条件下将特定的反应物和/或组分放在一起的自然结果。因此，反应物和组分等同于进行所需化学反应(诸如形成有机金属化合物)或形成所需组合物(诸如添加剂浓缩物或加料燃料混合物)而引入的成分。还可以认知的是，添加剂组分可以单独地，和/或作为用于形成预制添加剂组合物和/或亚组合物的组分的形式加入或掺入基础燃料中。因此，即使以下权利要求是以现在时提及物质、组分和/或成分(“包括”、“是”等)，所述物质、组分或成分也是指其恰好根据本公开，与一种或多种其它物质、组分和/或成分最初掺合或混合之前那一刻的存在形式。因此，物质、组分或成分在所述掺合或混合操作的过程中或恰好在其之后，通过化学反应或转化丧失其原始特性这一事实是正确理解和识别本公开及其权利要求的全部要义。
在本说明书中多处提及了美国专利、公开的外国专利申请和公开的技术文献。如同在本文中完全阐述地将所有这些引用的文献全文引入本公开。
本发明容许在实际中进行变化。因此，上述描述并非用于限制，也不应视为将本发明限制为上述特定实施方案。而其意图涵盖的内容是在后续的权利要求及其在法律意义上的等同方案中所列举的。
专利权人不意图向公众贡献任何公开的实施方案，并且在字面意义上未落入权利要求范围中的任何已公开改型或变型的范围，在等同理论下应视作本发明的一部分。

Claims (20)

1.一种降低由烧煤产生的飘尘中的碳含量的方法，该方法包括
将煤与含有含锰化合物的添加剂混合，形成其混合物；以及
在燃烧室中燃烧所述混合物；
含锰化合物以降低在燃烧室中由烧煤产生的飘尘中的碳含量的有效量存在。
2.权利要求1所述的方法，其中锰化合物是有机金属化合物。
3.权利要求2所述的方法，其中有机金属化合物的有机部分由选自醇、醛、酮、酯、酐、磺酸盐、膦酸酯、螯合物、酚盐、环烷酸盐、冠醚、羧酸、酰胺、乙酰丙酮化物及其混合物的材料产生。
4.权利要求2所述的方法，其中有机金属化合物包括甲基环戊二烯基三羰基锰。
5.权利要求2所述的方法，其中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，包括这些化合物中的两种或多种的混合物。
6.权利要求1的方法，其中含锰化合物选自锰氧化物、硫酸锰以及磷酸锰。
7.权利要求1所述的方法，其中锰化合物是煤的约20ppm。
8.权利要求1所述的方法，其中锰化合物是煤的约5-100ppm。
9.权利要求1所述的方法，其中锰化合物是煤的约1-500ppm。
10.权利要求1所述的方法，其中将添加剂引入携带煤进入燃烧室的空气流中。
11.权利要求1所述的方法，其中锰化合物包括单核化合物。
12.一种降低由烧煤产生的飘尘中的碳含量的方法，该方法包括
在燃烧室中燃烧煤和包括含锰化合物的添加剂；
含锰化合物以降低在燃烧室中由烧煤产生的飘尘中的碳含量的有效量存在，其中添加剂是与煤各自单独直接引入燃烧室的。
13.权利要求12所述的方法，其中将添加剂引入烟道气循环流。
14.权利要求12所述的方法，其中将添加剂引入送到燃烧室中的次级空气流中。
15.一种降低由烧煤产生的飘尘中的碳含量的方法，该方法包括
将煤与含有锰化合物的添加剂混合，形成其混合物；
将煤和添加剂的混合物引入烧煤的燃烧室中；
在燃烧室中燃烧混合物；并且
锰化合物以降低在燃烧室中由烧煤产生的飘尘中的碳含量的有效量存在。
16.一种用于降低由烧煤产生的飘尘中的碳含量的煤添加剂，所述添加剂包括锰化合物，其中在燃烧之前，将锰化合物以占煤的约1-500ppm的处理比例加入煤中。
17.权利要求16所述的煤添加剂，其中在燃烧之前，锰化合物以占煤的约5-100ppm的处理比例加入煤中。
18.权利要求16所述的煤添加剂，其中在燃烧之前，锰化合物以占煤的约20ppm的处理比例加入煤中。
19.一种降低由烧煤产生的飘尘中的碳含量的方法，该方法包括
将煤与含有含锰化合物的添加剂混合，形成其混合物；以及在燃烧室中燃烧所述混合物；含锰化合物以降低在燃烧室中由烧煤产生的飘尘中的碳含量的有效量存在。
20.一种降低由烧煤产生的飘尘中的碳含量的方法，该方法包括
在至少1ppm含锰添加剂存在下燃烧煤，由此使燃烧所述煤产生的飘尘中，碳的量相对于在不存在含锰添加剂的情况下烧煤产生的飘尘中的碳含量有所降低。
CNB2004100712375A 2003-07-18 2004-07-16 通过用于煤的锰添加剂来降低烧煤产生的飘尘中的碳含量 Expired - Fee Related CN100503793C (zh)

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