焦炭还原NO反应若干影响因素的研究
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摘要
电站锅炉燃煤排放的烟气是大气污染的NOx的主要来源。当前,我国NOx污染越加严重,为此,发展电站锅炉燃煤NOx控制技术势在必行。目前,NOx的控制技术方法较多,但是在我国,由于自身技术条件限制,只有少数几种技术较为实用。其中作为炉内低NOx燃烧技术的再燃技术是一项较经济有效的NOx控制技术,可行性大,易推广。再燃区中发生的NO-焦炭异相还原反应在煤粉再燃还原NO时是不可忽视的反应。研究再燃区中煤焦孔隙结构、焦炭中催化金属、锅炉内烟气成分对于NO-焦炭反应的影响,对于揭示NO-焦炭反应机理具有重要的意义。
本文首先在能够模拟真实烟气环境的携带流反应器EFR中制备焦炭,之后利用一维沉降炉DTF实验平台进行焦炭还原NO的实验。实验利用压汞仪和自动吸附仪等仪器测量了煤焦的孔隙结构,研究了在高温还原性气氛中不同煤种的煤焦孔隙结构参数和孔径分布特征,发现不同煤种的煤焦结构参数有很大差异,低阶煤种的煤焦具有较大的比表面积、孔容积及孔隙率,从而具有较强的反应性。同时研究了高温条件下烟气成分对于NO-焦炭反应的影响,实验发现O2对NO-焦炭反应具有抑制作用,与之相反,CO、SO2对反应具有促进作用。
本文应用统计学中相关分析的方法进行分析并提出了一个标准相关系数X来分析焦炭中的不同催化金属浓度在1273~1573K温度范围内对焦炭反应性的影响,得到各金属催化活性的顺序从强到弱为:Mg、K、Na、Ca、Fe。其中Mg在焦炭中的浓度虽然很低,但却具有非常强的催化活性。不同煤种和NO反应的活化能范围为65~137 ,不同煤种的活化能值的差异主要是由于金属催化剂的存在造成的。煤焦中的金属催化剂能够通过降低反应的活化能大大提高焦炭反应性。同时,本文还提出了另一个标准参数mkJ/molc来分析主要的金属氧化物对焦炭反应性的影响。催化金属成分含量的提高能明显加快焦炭对NO的还原,并随着mc的增大,焦炭反应性呈线性增大。
通过本文对焦炭结构、催化金属及烟气成分对于NO-焦炭反应的影响规律的研究,为进一步研究NO-焦炭的反应机理提供了理论指导。
Currently, the pollution caused by NOx emitting from coal-fired boiler power plant becomes more and more serious. Reburning which is considered as an effective technique to control NOx emitting is studied widely. Since NO-char reaction plays a very significant role in the reburning technique, a detailed study about the char pore structure, gas composition and catalytic effect of metal on the NO-char reaction at high temperature has been conducted in this paper.
Five coal chars were prepared in a flat flame flow reactor (FFR) which can simulate the temperature and gas composition of a real pulverized coal combustion environment. Reactivity of these chars with NO in the temperature range of 1273–1573K has been characterized by experiments in a high-temperature drop tube furnace (DTF). The characteristics of char pore structure under high-temperature reducing condition have been studied. The pore structure of chars was measured by mercury porosimetry and nitrogen adsorption. Via the study on the pore structure parameters and pore diameter distribution of different coal-chars in the expariment, the following conclusions were obtained. Low-rank coal-char has larger specific surface area, pore volume, porosity and higher reactivity than high-rank coal-char. And also, the experiment has found that at high temperature O2 prevented the NO-char reaction, whereas CO and SO2 had an enhanced effect.
Two normalized parameters ( X and mc) are proposed to analyze the effect of inherent metal content on char reactivity. The inherent metal catalysts in chars, such as magnesium, potassium, sodium, calcium and iron can significantly increase reactivity of char by reducing the activation energy. The reactivity of NO-char reaction increases with mc value monotonously and linearly in a certain range. Experimental results showed that the catalytic activity of magnesium, potassium, sodium, calcium and iron at the temperatures of 1273–1573 K were in decreasing sequence. In this study, the magnesium which was rarely studied in other literatures appears to have a great catalytic effect on the reduction of NO by chars.
本文首先在能够模拟真实烟气环境的携带流反应器EFR中制备焦炭,之后利用一维沉降炉DTF实验平台进行焦炭还原NO的实验。实验利用压汞仪和自动吸附仪等仪器测量了煤焦的孔隙结构,研究了在高温还原性气氛中不同煤种的煤焦孔隙结构参数和孔径分布特征,发现不同煤种的煤焦结构参数有很大差异,低阶煤种的煤焦具有较大的比表面积、孔容积及孔隙率,从而具有较强的反应性。同时研究了高温条件下烟气成分对于NO-焦炭反应的影响,实验发现O2对NO-焦炭反应具有抑制作用,与之相反,CO、SO2对反应具有促进作用。
本文应用统计学中相关分析的方法进行分析并提出了一个标准相关系数X来分析焦炭中的不同催化金属浓度在1273~1573K温度范围内对焦炭反应性的影响,得到各金属催化活性的顺序从强到弱为:Mg、K、Na、Ca、Fe。其中Mg在焦炭中的浓度虽然很低,但却具有非常强的催化活性。不同煤种和NO反应的活化能范围为65~137 ,不同煤种的活化能值的差异主要是由于金属催化剂的存在造成的。煤焦中的金属催化剂能够通过降低反应的活化能大大提高焦炭反应性。同时,本文还提出了另一个标准参数mkJ/molc来分析主要的金属氧化物对焦炭反应性的影响。催化金属成分含量的提高能明显加快焦炭对NO的还原,并随着mc的增大,焦炭反应性呈线性增大。
通过本文对焦炭结构、催化金属及烟气成分对于NO-焦炭反应的影响规律的研究,为进一步研究NO-焦炭的反应机理提供了理论指导。
Currently, the pollution caused by NOx emitting from coal-fired boiler power plant becomes more and more serious. Reburning which is considered as an effective technique to control NOx emitting is studied widely. Since NO-char reaction plays a very significant role in the reburning technique, a detailed study about the char pore structure, gas composition and catalytic effect of metal on the NO-char reaction at high temperature has been conducted in this paper.
Five coal chars were prepared in a flat flame flow reactor (FFR) which can simulate the temperature and gas composition of a real pulverized coal combustion environment. Reactivity of these chars with NO in the temperature range of 1273–1573K has been characterized by experiments in a high-temperature drop tube furnace (DTF). The characteristics of char pore structure under high-temperature reducing condition have been studied. The pore structure of chars was measured by mercury porosimetry and nitrogen adsorption. Via the study on the pore structure parameters and pore diameter distribution of different coal-chars in the expariment, the following conclusions were obtained. Low-rank coal-char has larger specific surface area, pore volume, porosity and higher reactivity than high-rank coal-char. And also, the experiment has found that at high temperature O2 prevented the NO-char reaction, whereas CO and SO2 had an enhanced effect.
Two normalized parameters ( X and mc) are proposed to analyze the effect of inherent metal content on char reactivity. The inherent metal catalysts in chars, such as magnesium, potassium, sodium, calcium and iron can significantly increase reactivity of char by reducing the activation energy. The reactivity of NO-char reaction increases with mc value monotonously and linearly in a certain range. Experimental results showed that the catalytic activity of magnesium, potassium, sodium, calcium and iron at the temperatures of 1273–1573 K were in decreasing sequence. In this study, the magnesium which was rarely studied in other literatures appears to have a great catalytic effect on the reduction of NO by chars.
引文
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2冯俊凯,沈幼庭,杨瑞昌.锅炉原理及计算.科学出版社,2003
3吴少华,李争起,孙绍增,孙锐.低NOx排放的“风包粉”浓淡煤粉燃烧技术.机械工程学报. 2002, 38(1):108~111
4秦裕琨,孙锐,李争起,孙绍增,吴少华.径向浓淡旋流煤粉燃烧器流动特性研究及应用.电机工程学报. 2000, 20(9): 72~76
5秦明,吴少华,孙绍增,孙锐.六角切圆燃烧褐煤煤粉锅炉低NOx燃烧技术研究.电机工程学报. 2005, 25(1): 158~162
6孙锐,李争起,孙绍增,吴少华.四角切圆锅炉炉内煤粉燃烧过程数值模拟.机械工程学报, 2006, 24(8): 107~113
7郑巧生.巴威公司的低成本NOx控制技术.锅炉技术. 1995, (5): 27~30
8何季民.国外煤粉燃烧器技术的新进展.东方电气评论. 1995, 9(4)
9赵太平. PM浓淡燃烧器在400t/h锅炉上的应用.能源通讯. 1996, (2)
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