废轮胎胶粉再燃脱硝性能的研究
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摘要
煤粉燃烧过程中生成的氮氧化物(NO_x)是电站锅炉排放的主要污染物之一，严重威胁着大气环境和人类健康。为了解决电站锅炉排放的NO_x对环境的污染问题，许多控制NO_x的技术应运而生，其中再燃脱硝是一种很有效的方法。常规的再燃燃料为天然气和低阶煤粉。天然气的价格昂贵，煤粉也是化石能源，且效率难以突破，主要原因是煤中赋存于杂环结构中的N以char-N的形式存在，在燃烬段重新生成NO_x导致总效率不能提高。寻找一种高效的能够取代天然气和煤粉的替代再燃燃料具有学术意义和工程应用价值。
随着我国经济的迅速发展，我国每年生产和消费的轮胎快速增加。同时，废轮胎作为一种难以处理的固体废弃物，也正在以很高的速度增加，带来环境污染问题和资源浪费问题。废轮胎为不熔或难熔性高分子弹性材料，具有很强的抗热、抗生物、抗机械性，并难以降解，废旧轮胎的处理已经成为一个全球性的环境问题。废轮胎的主要成分橡胶和碳都是宝贵的资源，而且废轮胎具有非常高的热值，挥发份含量高达60％以上，含N、S相对很低，理论上是一种非常好的再燃燃料。为此本文选用废旧轮胎胶粉作为研究对象，研究其作为再燃燃料的再燃脱硝性能。
首先通过热重实验，通过TG/DTG，DSC与质谱仪联用等方法研究了废轮胎胶粉、煤粉在氮气气氛下的热解特性和挥发份释放特性。结果发现废轮胎胶粉的最大失重率可达64.3％，其热解行为比神华煤粉的热解行为更加容易进行、热解挥发份析出特性更好、热解温度更低、热解温度范围更小。同时废轮胎胶粉热解时释放出来的气体以对NO_x具有较强还原性C_mH_n和H_2为主，C_mH_n先释放出来，H_2后释放出来，因此废轮胎胶粉是一种非常好的再燃燃料。本文同时对废轮胎胶粉进行了热解动力学的研究，用模型计算了有关热解动力学参数，分析了热解过程中试样的反应机理。
随后在小型热态炉中对废轮胎胶粉进行了再燃实验。对再燃燃料化学计量比SR2、初始NO浓度、停留时间和炉膛温度等因素对废胶粉再燃脱硝性能的影响进行了研究。再燃实验结果发现：1)．废轮胎胶粉在一定条件下脱硝效率高达95％左右，与同条件下天然气的再燃脱硝效率一样好，因此废轮胎胶粉完全可以取代天然气作为大型电厂燃煤锅炉的再燃燃料。2)．废轮胎胶粉再燃的最佳再燃区化学计量比SR2在0.8～0.9，废胶粉在炉内达到最佳脱硝效率时的停留时间要比一般的煤粉所需的停留时间短，在0.30s时达到最佳脱硝效率，最佳再燃温度为1150℃。3)．废轮胎胶粉2段再燃脱销实验表明，随着三次风的加入，炉膛出口NO浓度升高，但仍然能够在一定条件下达到85.0％左右的脱硝效率。
最后采用计算流体力学软件FLUENT分别模拟废旧轮胎胶粉和煤粉小型多功能热态炉中的燃烧过程，研究了化学计量比、炉膛温度、燃料粒径和燃料量等对NO排放规律的影响。实验结果发现：1)．废轮胎胶粉比神华煤粉更加容易燃烧，两种燃料的NO在小型热态实验炉中的析出特性，出现一个先增加后减少的趋势。2)．随着温度的增加，神华煤粉的NO生成量缓慢升高，而废轮胎胶粉的NO生成量降低；随着化学计量比的增加，废轮胎胶粉和神华煤粉的NO生成量增加；废轮胎胶粉的细度对NO生成量影响较大，细度越细，NO生成量越少。
研究结果发现，基于废轮胎胶粉的燃料纯再燃条件下具有和天然气一样优良的再燃脱硝效果，和某种物质混合燃烧时，在2段燃烧条件下，最终的NO脱除率可高达85.0％，接近于相同条件下天然气的2段再燃燃烧结果，而远远高于相同条件下低阶煤粉的再燃燃烧结果。它表明，本文研究的废轮胎胶粉可以取代天然气和煤粉，是一种优良的替代再燃燃料。本文的研究结果对于高品位利用废轮胎具有重要的工程指导价值。
Nitrogen oxides (NO_x) is one of the major pollutant emission from coal-fired power plant boilers and gives a serious threat to the atmosphere and man-kind's health. The research on NO_x control has been one of the hot topics around the world in the past 2 decades. Many technologies have been developed to reduce NO emission, among which reburning is one of the most promising technologies. Usually natural gas and low-rank coal are used as the typical reburning fuel. But natural gas is very expensive and coal is a fossil fuel that is not renewable. Therefore, it's important to find a new and efficient alternate reburning fuel for boilers taking place of natural gas and low-rank coal.
Waste tires are increasing rapidly as solid waste disposal and it's difficult to carry out the management problems associated with the waste tire disposal. It's necessary to investigate new techniques for its utilization as resources. After reviewing briefly on the present techniques for the recycle of waste tires, the author proposed the use of waste tires as a fuel to reduce both air emission and solid waste by applying them as a reburning fuel for NO_x reduction. Ultimate analysis of typical waste tire showed that it contains more than 80% carbon content, less than 2% nitrogen and sulfur, very little moisture and ash. The heating value of waste tires per kilogram is 69% more than that of wood, 10% more than that of bituminous and 4% more than that of coke. Waste tires meet the volatility and reactivity requirements and are low in both nitrogen and sulfur. Beyond its good combustion characteristics, it's also very attractive using waste tires as an alternative fuels for reburning because there are large mass of waste tires requiring disposal. These properties make waste tires a potentially good fuel for reburning NO_x control. This technology can dispose waste tires at a maximum extent by clean utilization of waste tire as a useful energy resource.
First, a thermo-gravimetric analyzer (TGA) was used to study the pyrolysis performance experimentally at the beginning step. In a thermo-gravimetric analyzer, a series of experiments were conducted. The pyrolysis tests of pulverized waste tire and pulverized coal in an inert atmosphere of nitrogen gas were conducted respectively to study their pyrolysis characteristics. The results show that the lost of weight of pulverized waste tire is as high as 64.3%. Compared to pulverized coal, the pyrolysis of pulverized waste tire is much easier, it can be carried out at relatively lower temperature. A DSC combined with a mass-spectrum was used to study the volatile release during the tire's pyrolysis. It's found that the yield of volatile gases is about 40% during pyrolysis of waste tires and the content of the volatile gases are mainly CO,H_2,CH_4,C_2H_4 etc, which are all good reburning fuels. A mathematical model was established to calculate the parameters of its pyrolysis.
Second, experiments were carried out on an ceramic flow reactor to study the reburning performance of waste tire powder at 1150℃. The results show that under the typical reburning conditions, the NO reduction efficiency of pulverized waste tire can achieve about 95%, which is as high as that by nature gas at the same conditions. The best stoichiometric ratio in the reburning zone of waste tire is 0.8～0.9, the residence time of waste tire is much shorter than pulverized coal's, the best reduction efficiency of waste tire appears at residence time is 0.3s, and the best temperature of waste tire reburning is 1150℃. In order to study the burnout of waste tire, a 2-stage test rig was established and several mixed fuel based on waste tire were experimentally investigated. The results showed that the NO emission increased when the OFA add to the furnace for tire only, which is also true for natural gas and coal reburning due to the burnout of HCN and/or coal char-N. When special matters were added to the tire, the mixes fuel gave very good results. At the typical reburning and burnout conditions, the reduction efficiency for one mixed fuel was as high as 85%, which is far beyond that by coal and similar to that by natural gas. The results showed that waste tire can be used as a new and efficient reburning fuel for NO reduction..
Finally, the author used FLUENT software to simulate the combustion process of pulverized waste tire and coal. Compared to pulverized coal, the combustion of waste tire can be much easier, the NO separate out characteristics of both fuel is resemble, the NO concentration will increases firstly, and decreases later along the axis of the furnace. 2). When the temperature increases, the NO concentration increases a little bit when pulverized coal is burned, while the NO concentration decreases when waste tire is burned. The NO concentration of both fuel increase when the stoichiometric ratio increase; When the particle diameter decreases, the NO concentration of waste tire decreases.
The conclusion could be drawn from this thesis as the following: the waste tire powder is as good as natural gas for reburning NO control. When mixed with a special matter, the final NO reduction ratio can be as high as 85% during the reburning and burnout 2-stage combustion experiment, which is similar to that by natural gas and much high than that by typical coal reburning. The results suggested that waste tire powder can be used as a new and efficient reburning fuel for NO reduction.
随着我国经济的迅速发展，我国每年生产和消费的轮胎快速增加。同时，废轮胎作为一种难以处理的固体废弃物，也正在以很高的速度增加，带来环境污染问题和资源浪费问题。废轮胎为不熔或难熔性高分子弹性材料，具有很强的抗热、抗生物、抗机械性，并难以降解，废旧轮胎的处理已经成为一个全球性的环境问题。废轮胎的主要成分橡胶和碳都是宝贵的资源，而且废轮胎具有非常高的热值，挥发份含量高达60％以上，含N、S相对很低，理论上是一种非常好的再燃燃料。为此本文选用废旧轮胎胶粉作为研究对象，研究其作为再燃燃料的再燃脱硝性能。
首先通过热重实验，通过TG/DTG，DSC与质谱仪联用等方法研究了废轮胎胶粉、煤粉在氮气气氛下的热解特性和挥发份释放特性。结果发现废轮胎胶粉的最大失重率可达64.3％，其热解行为比神华煤粉的热解行为更加容易进行、热解挥发份析出特性更好、热解温度更低、热解温度范围更小。同时废轮胎胶粉热解时释放出来的气体以对NO_x具有较强还原性C_mH_n和H_2为主，C_mH_n先释放出来，H_2后释放出来，因此废轮胎胶粉是一种非常好的再燃燃料。本文同时对废轮胎胶粉进行了热解动力学的研究，用模型计算了有关热解动力学参数，分析了热解过程中试样的反应机理。
随后在小型热态炉中对废轮胎胶粉进行了再燃实验。对再燃燃料化学计量比SR2、初始NO浓度、停留时间和炉膛温度等因素对废胶粉再燃脱硝性能的影响进行了研究。再燃实验结果发现：1)．废轮胎胶粉在一定条件下脱硝效率高达95％左右，与同条件下天然气的再燃脱硝效率一样好，因此废轮胎胶粉完全可以取代天然气作为大型电厂燃煤锅炉的再燃燃料。2)．废轮胎胶粉再燃的最佳再燃区化学计量比SR2在0.8～0.9，废胶粉在炉内达到最佳脱硝效率时的停留时间要比一般的煤粉所需的停留时间短，在0.30s时达到最佳脱硝效率，最佳再燃温度为1150℃。3)．废轮胎胶粉2段再燃脱销实验表明，随着三次风的加入，炉膛出口NO浓度升高，但仍然能够在一定条件下达到85.0％左右的脱硝效率。
最后采用计算流体力学软件FLUENT分别模拟废旧轮胎胶粉和煤粉小型多功能热态炉中的燃烧过程，研究了化学计量比、炉膛温度、燃料粒径和燃料量等对NO排放规律的影响。实验结果发现：1)．废轮胎胶粉比神华煤粉更加容易燃烧，两种燃料的NO在小型热态实验炉中的析出特性，出现一个先增加后减少的趋势。2)．随着温度的增加，神华煤粉的NO生成量缓慢升高，而废轮胎胶粉的NO生成量降低；随着化学计量比的增加，废轮胎胶粉和神华煤粉的NO生成量增加；废轮胎胶粉的细度对NO生成量影响较大，细度越细，NO生成量越少。
研究结果发现，基于废轮胎胶粉的燃料纯再燃条件下具有和天然气一样优良的再燃脱硝效果，和某种物质混合燃烧时，在2段燃烧条件下，最终的NO脱除率可高达85.0％，接近于相同条件下天然气的2段再燃燃烧结果，而远远高于相同条件下低阶煤粉的再燃燃烧结果。它表明，本文研究的废轮胎胶粉可以取代天然气和煤粉，是一种优良的替代再燃燃料。本文的研究结果对于高品位利用废轮胎具有重要的工程指导价值。
Nitrogen oxides (NO_x) is one of the major pollutant emission from coal-fired power plant boilers and gives a serious threat to the atmosphere and man-kind's health. The research on NO_x control has been one of the hot topics around the world in the past 2 decades. Many technologies have been developed to reduce NO emission, among which reburning is one of the most promising technologies. Usually natural gas and low-rank coal are used as the typical reburning fuel. But natural gas is very expensive and coal is a fossil fuel that is not renewable. Therefore, it's important to find a new and efficient alternate reburning fuel for boilers taking place of natural gas and low-rank coal.
Waste tires are increasing rapidly as solid waste disposal and it's difficult to carry out the management problems associated with the waste tire disposal. It's necessary to investigate new techniques for its utilization as resources. After reviewing briefly on the present techniques for the recycle of waste tires, the author proposed the use of waste tires as a fuel to reduce both air emission and solid waste by applying them as a reburning fuel for NO_x reduction. Ultimate analysis of typical waste tire showed that it contains more than 80% carbon content, less than 2% nitrogen and sulfur, very little moisture and ash. The heating value of waste tires per kilogram is 69% more than that of wood, 10% more than that of bituminous and 4% more than that of coke. Waste tires meet the volatility and reactivity requirements and are low in both nitrogen and sulfur. Beyond its good combustion characteristics, it's also very attractive using waste tires as an alternative fuels for reburning because there are large mass of waste tires requiring disposal. These properties make waste tires a potentially good fuel for reburning NO_x control. This technology can dispose waste tires at a maximum extent by clean utilization of waste tire as a useful energy resource.
First, a thermo-gravimetric analyzer (TGA) was used to study the pyrolysis performance experimentally at the beginning step. In a thermo-gravimetric analyzer, a series of experiments were conducted. The pyrolysis tests of pulverized waste tire and pulverized coal in an inert atmosphere of nitrogen gas were conducted respectively to study their pyrolysis characteristics. The results show that the lost of weight of pulverized waste tire is as high as 64.3%. Compared to pulverized coal, the pyrolysis of pulverized waste tire is much easier, it can be carried out at relatively lower temperature. A DSC combined with a mass-spectrum was used to study the volatile release during the tire's pyrolysis. It's found that the yield of volatile gases is about 40% during pyrolysis of waste tires and the content of the volatile gases are mainly CO,H_2,CH_4,C_2H_4 etc, which are all good reburning fuels. A mathematical model was established to calculate the parameters of its pyrolysis.
Second, experiments were carried out on an ceramic flow reactor to study the reburning performance of waste tire powder at 1150℃. The results show that under the typical reburning conditions, the NO reduction efficiency of pulverized waste tire can achieve about 95%, which is as high as that by nature gas at the same conditions. The best stoichiometric ratio in the reburning zone of waste tire is 0.8～0.9, the residence time of waste tire is much shorter than pulverized coal's, the best reduction efficiency of waste tire appears at residence time is 0.3s, and the best temperature of waste tire reburning is 1150℃. In order to study the burnout of waste tire, a 2-stage test rig was established and several mixed fuel based on waste tire were experimentally investigated. The results showed that the NO emission increased when the OFA add to the furnace for tire only, which is also true for natural gas and coal reburning due to the burnout of HCN and/or coal char-N. When special matters were added to the tire, the mixes fuel gave very good results. At the typical reburning and burnout conditions, the reduction efficiency for one mixed fuel was as high as 85%, which is far beyond that by coal and similar to that by natural gas. The results showed that waste tire can be used as a new and efficient reburning fuel for NO reduction..
Finally, the author used FLUENT software to simulate the combustion process of pulverized waste tire and coal. Compared to pulverized coal, the combustion of waste tire can be much easier, the NO separate out characteristics of both fuel is resemble, the NO concentration will increases firstly, and decreases later along the axis of the furnace. 2). When the temperature increases, the NO concentration increases a little bit when pulverized coal is burned, while the NO concentration decreases when waste tire is burned. The NO concentration of both fuel increase when the stoichiometric ratio increase; When the particle diameter decreases, the NO concentration of waste tire decreases.
The conclusion could be drawn from this thesis as the following: the waste tire powder is as good as natural gas for reburning NO control. When mixed with a special matter, the final NO reduction ratio can be as high as 85% during the reburning and burnout 2-stage combustion experiment, which is similar to that by natural gas and much high than that by typical coal reburning. The results suggested that waste tire powder can be used as a new and efficient reburning fuel for NO reduction.
引文
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