城市生活垃圾焚烧炉SNCR脱硝技术研究
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摘要
随着人类文明的进步和人口的增长,生活垃圾的产生量不断增加,对环境造成的污染日益加剧,已成为我国社会经济持续发展和生态文明建设的一大阻碍。垃圾焚烧技术由于其占地小、垃圾减量化稳定化无害化程度高、能量利用率高等优点而得到迅速发展。虽然我国采用焚烧处理生活垃圾起步较晚,但在引进、消化和吸收国外先进技术的基础上,基本完成了机械炉排焚烧炉的国产化和大型化的发展过程。同时,国家的相关政策和污染控制标准也将对垃圾焚烧的二次污染控制提出更高的要求。其中氮氧化物是城市生活垃圾焚烧烟气中主要的大气污染物之一,已成为研究垃圾焚烧二次污染的研究热点。因此,针对我国城市生活垃圾成分特点,研究符合中国国情的科学型、实用型垃圾焚烧炉脱硝方法已成为摆在从事生活垃圾焚烧处理技术研究人员面前的一项重要任务。
从国外及国内的发展经验看,SNCR脱硝技术由于其投资及运行成本较其他脱硝技术低、改造方便、比较适用于烟气中NOX含量和所需还原率较低的燃烧设备,适宜生活垃圾焚烧炉脱硝。本文针对我国垃圾多成分和多形态、高水分和高挥发分、低热值和低固定碳的特点,对垃圾焚烧炉SNCR脱硝技术进行了理论、实验、数值模拟、生命周期和经济性研究。
利用干燥箱模拟垃圾在固定床上的干燥过程,在100~200℃温度区间,分别对不同的单元垃圾及混合垃圾进行了干燥实验。结果表明,垃圾试样的厚度越厚,干燥速率越小,干燥时间越长。不同的干燥模型适合不同的垃圾试样:对于垃圾混样,Two term exponential和Page模型拟合效果较好;对于白菜茎,Page模型拟合效果较好;对于土豆块,Two term exponential、Page和Attenuation Index equation模型拟合效果较好;对于桔子皮,Page模型拟合效果较好。垃圾试样的扩散系数介于1.62×10~(-9) m~2/s~4.53×10~(-6) m~2/s,活化能介于12.66 kJ/mol~17.25 kJ/mol之间。垃圾不同含水率对氮氧化物生成产生一定的影响。随着含水率的增加,挥发分析出最大质量百分比增加,氮氧化物生成浓度降低,NO生成最大量与挥发分几乎同时达到最大值。
在电加热管式流动反应器中以氨气作为还原剂,对SNCR脱硝反应的影响因素和不同气体添加剂的SNCR反应进行了实验研究。分析得出SNCR合适的温度窗口在875~1000℃范围内;最佳氨氮摩尔比为1.5;NO初始浓度和O_2浓度在实际运行中对SNCR的影响较小;加入CO、CH_4和H_2添加剂都能使最佳反应温度降低;加入CO和CH_4后对最大脱硝率没有明显的影响,而加入H_2后使最大脱硝率明显的降低;添加剂CO和H_2使温度窗口明显变窄,而CH_4使温度窗口有所增宽;加入CO、CH_4和H_2后,NH_3逃逸量降低;综合考虑各方面的影响,三种气体中CH_4为较合适的添加剂。
运用FLIC固相模拟软件和FLENT气相模拟软件分别模拟垃圾床层焚烧特性与燃烧室燃烧特性,并和实际运行数据进行对比,验证了数学模型的可靠性,并就不同的炉排速度、富氧气氛和含水率的影响进行了计算,结果表明:随着炉排运动速度的增加,挥发分开始析出位置距燃料入口越来越远,烟气温度降低,NO_X生成量减少而CO生成量增加;富氧气氛下,与传统的运行气氛相比,炉膛出口烟气温度、NO生成量与CO生成量都有所增加;随着垃圾含水率的增加,烟气温度升高,炉膛出口CO浓度、NO_X浓度增加,而氧气含量降低。
采用CFD技术对SNCR喷嘴布置与优化进行研究。包括SNCR脱硝方法中喷嘴布置方式、喷射口数量、位置、喷射速度等。结果显示:炉膛内适宜SNCR反应的区域位于折焰角下方;在折焰角附近烟气流动速度梯度较大,流速分布较均匀,适合SNCR喷嘴布置;在折焰角下方,前后炉墙布置4个喷口、左右炉墙布置2个喷口,并以80m/s的速度喷入还原剂,还原剂与烟气混合较均匀,能达到较高的脱硝效果。
以某垃圾焚烧厂实施的SNCR脱硝技术为研究对象,采用LCA方法,对该技术整个生命周期的环境影响进行评价,包括SNCR脱硝技术整个生命周期的能源消耗和对环境的影响。结果表明:SNCR运行过程中污染物排放量最大;从能源的消耗过程来看,主要是原材料生产过程消耗量最大,SNCR脱硝技术的环境负荷为4686人当量,该技术减少酸化470人当量,减少富营养化874人当量。
运用费用—效益原理,对SNCR脱硝技术进行技术经济评价,动态计算了垃圾焚烧发电厂投资的烟气脱硝装置的年费用及主要影响因素对脱硝技术经济指标的影响。可以得出以下结论:对于投资费用而言,SNCR脱硝装置的设备购置费在各项投资费用中所占比例最大,达到82.91%;对于SNCR脱硝装置的年运行费用,还原剂费用在所有成本中所占比例最大,达到SNCR脱硝年运行费用的31.8%,SNCR脱硝装置的年费用为133.93万元,脱除每吨NO_X费用为8542.95元。随着年利用小时数的增加,年费用呈线性增加,而脱硝单位费用减小;随着还原剂价格的增加,年费用和脱硝单位费用均呈线性增加;随着排污费用的增加,年费用和脱硝单位费用均呈下降趋势。
With the progress of human civilization and the growth of population, the amount of municipal solid waste has become increasing and environment pollution more seriously; it has become a major obstacle for social economy sustainable development and ecological civilization construction. For the reaseas that smaller land acquisition, higher level of reduction, stability, harmless, energy utilization efficiency, and the waste incineration technology has become rapidly development. Although municipal solid waste incineration with a late starts, our country has completed the localization and large-scale of the mechanical grate incinerator based on introduction, digestion and absorption of foreign advanced technology. Meanwhile, relevant policies and pollution control standards in our contury will also put forward higher requirements for second pollution control. Nitrogen oxides are one of the major air pollutants of municipal solid waste incineration, and have become a research hotspot of secondary pollution. Therefore, based on characteristics of municipal solid waste in our country, it has become an important task for researchers working on municipal solid waste incineration to study NO_X removal method with science and practeical based on Chinese national conditions.
From foreign and domestic development experience, the SNCR de-NO_X technology is suitable for municipal solid waste, for the reaseas that lower investment and operation cost than other de-NO_X technology, easy to reconstruct, more suitable for the sombustion equipment with lower NO_X content and reduction rate. For the characteristics of multi-conponent, multi-form, high moisture, high volatile, low heating value and fixed carbon of municipal solid waste in our contury, this paper studied SNCR NO_X removal technology of municipal solid waste by theoretical analysis, experimental, numerical simulation, life cycle and economical assessment.
Regarding drying oven as fixed bed, during 100~200℃, this paper made drying experiment for different units and mixed waste. The results showed that the thicker of waste sample resulted in the lower drying rate and the longer drying time. Different dying models for different waste samples: Two term exponential and Page models for mixed waste; Page model for cabbage stem and orange peel. Effective diffusivity of waste samples is in the range of 1.62×10~(-9)m~2/s~4.53×10~(-6)m~2/s and activation energy is 12.66kJ/mol~17.25kJ/mol. Different moisture content affects the nitrogen oxides. With the increasing of moisture content, volatile maximum mass percentage increased, the NO_X concentration reduced, and the NO and volatile almost simultaneously reached maximum.
Taking ammonia as the reducing agent, this paper studied the effect factors and additives of SNCR technology in electric heating reactor. The results showed that the right temperature window was in the range of 875~1000℃; the normalized stoichiometric ratio was 1.5; the initial NO concentration and O_2 concentration had little effect on SNCR in the actural operation; the CO, CH_4 and H_2 reduced the best reaction temperation; CO and CH_4 had little effect on reducing maximum de-NO_X efficiency, but H_2 was the opposite. CO and H_2 made the temperature window narrower, but CH_4 widener; CO, CH_4 and H_2 reduced the amount of NH_3 slip. Considering the various factors, CH_4 was the best appropriate additives.
Using the solide phase mathematic modeling–FLIC and gas phase modeling–FLUENT, this paper numerical simulated the characteristics of bed combustion and over-bed combustion. The results of numerical simulated were compared with actual operation data, and verified the reliability of the mathematical model. Furthermore, this paper calculated the effect of grate speed, rich- oxygen atmosphere and moisture content on combustion. The results showed that with the increasing of grate speed, the position of volatile starting emission was farther away from the fuel inlet, the gas temperature reduced, the amount of NO formation and CO formation were increased; with the increasing the moisture in waste, the gas temperature increased, the CO concentration and NO_X concentration increased but O_2 concenctration reduced.
This paper studied nozzle arrangement and optimization of SNCR technology, including nozzle arrangement, number of jet, location and speed. The results showed that the suitable area of SNCR reaction located under the furnace arch where the gas flows gradient is larger and velocity more uniform; under the furnace arch, 4 jet were arranged in front and back furnace wall, 2 jet in left and right funace wall, jet speed was 80 m/s, the reducing agent and gas mixed well and got higher de-NO_X efficiency.
To study the whole life cycle environment assessment of the SNCR technology in a waste combustion plant, this paper used the LCA method. The assessment included energy comsumption and environment assessment. The results showed that the emission in SNCR operation process was maximal; for energy comsumption, the material product process was the main contributer. The environment load of SNCR technology was 4686 PET_(2000), acidification and nutrient enrichment reduced 470PET_(2000) and 874PET_(2000) respectively.
To assess of technical and economic of SNCR technology, this paper dynamic calculated annual cost of de-NO_X equipment in a waste combustion plant and main effect factors on technical and economic indicator. For investment, the results showed that the purchase cost was the main contributor in all kinds of investments, and reached 82.91%; for annual cost, the cost of reducing agent was the main contributor, and reached 31.8%; the annual cost of SNCR technology was 1.3393millon yuan, NO_X removal cost per ton was 8542.95yuan. With the increasing of number of utilize hours, the annual cost increased linearly, while the cost of removal unit NO_X reduced; with the increasing of reducing agent cost, annual cost and removal unit NO_X cost increased linearly; with the increasing of fine fee, both annual cost and removal unit NO_X cost reduced.
从国外及国内的发展经验看,SNCR脱硝技术由于其投资及运行成本较其他脱硝技术低、改造方便、比较适用于烟气中NOX含量和所需还原率较低的燃烧设备,适宜生活垃圾焚烧炉脱硝。本文针对我国垃圾多成分和多形态、高水分和高挥发分、低热值和低固定碳的特点,对垃圾焚烧炉SNCR脱硝技术进行了理论、实验、数值模拟、生命周期和经济性研究。
利用干燥箱模拟垃圾在固定床上的干燥过程,在100~200℃温度区间,分别对不同的单元垃圾及混合垃圾进行了干燥实验。结果表明,垃圾试样的厚度越厚,干燥速率越小,干燥时间越长。不同的干燥模型适合不同的垃圾试样:对于垃圾混样,Two term exponential和Page模型拟合效果较好;对于白菜茎,Page模型拟合效果较好;对于土豆块,Two term exponential、Page和Attenuation Index equation模型拟合效果较好;对于桔子皮,Page模型拟合效果较好。垃圾试样的扩散系数介于1.62×10~(-9) m~2/s~4.53×10~(-6) m~2/s,活化能介于12.66 kJ/mol~17.25 kJ/mol之间。垃圾不同含水率对氮氧化物生成产生一定的影响。随着含水率的增加,挥发分析出最大质量百分比增加,氮氧化物生成浓度降低,NO生成最大量与挥发分几乎同时达到最大值。
在电加热管式流动反应器中以氨气作为还原剂,对SNCR脱硝反应的影响因素和不同气体添加剂的SNCR反应进行了实验研究。分析得出SNCR合适的温度窗口在875~1000℃范围内;最佳氨氮摩尔比为1.5;NO初始浓度和O_2浓度在实际运行中对SNCR的影响较小;加入CO、CH_4和H_2添加剂都能使最佳反应温度降低;加入CO和CH_4后对最大脱硝率没有明显的影响,而加入H_2后使最大脱硝率明显的降低;添加剂CO和H_2使温度窗口明显变窄,而CH_4使温度窗口有所增宽;加入CO、CH_4和H_2后,NH_3逃逸量降低;综合考虑各方面的影响,三种气体中CH_4为较合适的添加剂。
运用FLIC固相模拟软件和FLENT气相模拟软件分别模拟垃圾床层焚烧特性与燃烧室燃烧特性,并和实际运行数据进行对比,验证了数学模型的可靠性,并就不同的炉排速度、富氧气氛和含水率的影响进行了计算,结果表明:随着炉排运动速度的增加,挥发分开始析出位置距燃料入口越来越远,烟气温度降低,NO_X生成量减少而CO生成量增加;富氧气氛下,与传统的运行气氛相比,炉膛出口烟气温度、NO生成量与CO生成量都有所增加;随着垃圾含水率的增加,烟气温度升高,炉膛出口CO浓度、NO_X浓度增加,而氧气含量降低。
采用CFD技术对SNCR喷嘴布置与优化进行研究。包括SNCR脱硝方法中喷嘴布置方式、喷射口数量、位置、喷射速度等。结果显示:炉膛内适宜SNCR反应的区域位于折焰角下方;在折焰角附近烟气流动速度梯度较大,流速分布较均匀,适合SNCR喷嘴布置;在折焰角下方,前后炉墙布置4个喷口、左右炉墙布置2个喷口,并以80m/s的速度喷入还原剂,还原剂与烟气混合较均匀,能达到较高的脱硝效果。
以某垃圾焚烧厂实施的SNCR脱硝技术为研究对象,采用LCA方法,对该技术整个生命周期的环境影响进行评价,包括SNCR脱硝技术整个生命周期的能源消耗和对环境的影响。结果表明:SNCR运行过程中污染物排放量最大;从能源的消耗过程来看,主要是原材料生产过程消耗量最大,SNCR脱硝技术的环境负荷为4686人当量,该技术减少酸化470人当量,减少富营养化874人当量。
运用费用—效益原理,对SNCR脱硝技术进行技术经济评价,动态计算了垃圾焚烧发电厂投资的烟气脱硝装置的年费用及主要影响因素对脱硝技术经济指标的影响。可以得出以下结论:对于投资费用而言,SNCR脱硝装置的设备购置费在各项投资费用中所占比例最大,达到82.91%;对于SNCR脱硝装置的年运行费用,还原剂费用在所有成本中所占比例最大,达到SNCR脱硝年运行费用的31.8%,SNCR脱硝装置的年费用为133.93万元,脱除每吨NO_X费用为8542.95元。随着年利用小时数的增加,年费用呈线性增加,而脱硝单位费用减小;随着还原剂价格的增加,年费用和脱硝单位费用均呈线性增加;随着排污费用的增加,年费用和脱硝单位费用均呈下降趋势。
With the progress of human civilization and the growth of population, the amount of municipal solid waste has become increasing and environment pollution more seriously; it has become a major obstacle for social economy sustainable development and ecological civilization construction. For the reaseas that smaller land acquisition, higher level of reduction, stability, harmless, energy utilization efficiency, and the waste incineration technology has become rapidly development. Although municipal solid waste incineration with a late starts, our country has completed the localization and large-scale of the mechanical grate incinerator based on introduction, digestion and absorption of foreign advanced technology. Meanwhile, relevant policies and pollution control standards in our contury will also put forward higher requirements for second pollution control. Nitrogen oxides are one of the major air pollutants of municipal solid waste incineration, and have become a research hotspot of secondary pollution. Therefore, based on characteristics of municipal solid waste in our country, it has become an important task for researchers working on municipal solid waste incineration to study NO_X removal method with science and practeical based on Chinese national conditions.
From foreign and domestic development experience, the SNCR de-NO_X technology is suitable for municipal solid waste, for the reaseas that lower investment and operation cost than other de-NO_X technology, easy to reconstruct, more suitable for the sombustion equipment with lower NO_X content and reduction rate. For the characteristics of multi-conponent, multi-form, high moisture, high volatile, low heating value and fixed carbon of municipal solid waste in our contury, this paper studied SNCR NO_X removal technology of municipal solid waste by theoretical analysis, experimental, numerical simulation, life cycle and economical assessment.
Regarding drying oven as fixed bed, during 100~200℃, this paper made drying experiment for different units and mixed waste. The results showed that the thicker of waste sample resulted in the lower drying rate and the longer drying time. Different dying models for different waste samples: Two term exponential and Page models for mixed waste; Page model for cabbage stem and orange peel. Effective diffusivity of waste samples is in the range of 1.62×10~(-9)m~2/s~4.53×10~(-6)m~2/s and activation energy is 12.66kJ/mol~17.25kJ/mol. Different moisture content affects the nitrogen oxides. With the increasing of moisture content, volatile maximum mass percentage increased, the NO_X concentration reduced, and the NO and volatile almost simultaneously reached maximum.
Taking ammonia as the reducing agent, this paper studied the effect factors and additives of SNCR technology in electric heating reactor. The results showed that the right temperature window was in the range of 875~1000℃; the normalized stoichiometric ratio was 1.5; the initial NO concentration and O_2 concentration had little effect on SNCR in the actural operation; the CO, CH_4 and H_2 reduced the best reaction temperation; CO and CH_4 had little effect on reducing maximum de-NO_X efficiency, but H_2 was the opposite. CO and H_2 made the temperature window narrower, but CH_4 widener; CO, CH_4 and H_2 reduced the amount of NH_3 slip. Considering the various factors, CH_4 was the best appropriate additives.
Using the solide phase mathematic modeling–FLIC and gas phase modeling–FLUENT, this paper numerical simulated the characteristics of bed combustion and over-bed combustion. The results of numerical simulated were compared with actual operation data, and verified the reliability of the mathematical model. Furthermore, this paper calculated the effect of grate speed, rich- oxygen atmosphere and moisture content on combustion. The results showed that with the increasing of grate speed, the position of volatile starting emission was farther away from the fuel inlet, the gas temperature reduced, the amount of NO formation and CO formation were increased; with the increasing the moisture in waste, the gas temperature increased, the CO concentration and NO_X concentration increased but O_2 concenctration reduced.
This paper studied nozzle arrangement and optimization of SNCR technology, including nozzle arrangement, number of jet, location and speed. The results showed that the suitable area of SNCR reaction located under the furnace arch where the gas flows gradient is larger and velocity more uniform; under the furnace arch, 4 jet were arranged in front and back furnace wall, 2 jet in left and right funace wall, jet speed was 80 m/s, the reducing agent and gas mixed well and got higher de-NO_X efficiency.
To study the whole life cycle environment assessment of the SNCR technology in a waste combustion plant, this paper used the LCA method. The assessment included energy comsumption and environment assessment. The results showed that the emission in SNCR operation process was maximal; for energy comsumption, the material product process was the main contributer. The environment load of SNCR technology was 4686 PET_(2000), acidification and nutrient enrichment reduced 470PET_(2000) and 874PET_(2000) respectively.
To assess of technical and economic of SNCR technology, this paper dynamic calculated annual cost of de-NO_X equipment in a waste combustion plant and main effect factors on technical and economic indicator. For investment, the results showed that the purchase cost was the main contributor in all kinds of investments, and reached 82.91%; for annual cost, the cost of reducing agent was the main contributor, and reached 31.8%; the annual cost of SNCR technology was 1.3393millon yuan, NO_X removal cost per ton was 8542.95yuan. With the increasing of number of utilize hours, the annual cost increased linearly, while the cost of removal unit NO_X reduced; with the increasing of reducing agent cost, annual cost and removal unit NO_X cost increased linearly; with the increasing of fine fee, both annual cost and removal unit NO_X cost reduced.
引文
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