选择性催化还原脱硝催化剂的实验与机理研究
摘要
随着世界范围内氮氧化物排放标准的日益严格,选择性催化还原(Selective Catalytic Reduction, SCR)催化剂成为国内外各科研机构的研究热点。本文以化学分析纯颗粒状SCR催化剂为基础,采用实验研究和理论分析相结合的方法,分析了V2O5-WO3-MoO3/TiO2四元催化剂脱硝反应机理,并比较了该催化剂与V2O5-WO3/TiO2、V2O5-MoO3/TiO2三元催化剂脱硝性能的差异；从比表面积、比孔体积、平均孔径、物相组成、晶粒尺寸等微观角度对催化剂物理化学特性进行了研究,优化了V2O5-WO3-MoO3/TiO2四元催化剂的成分配比；以工业纯原料替换化学分析纯原料制备了蜂窝状催化剂,研究了药品纯度对催化剂脱硝性能的作用效果,并对成型工艺进行了优化；通过在山东某燃煤电厂300MW机组锅炉尾部所建造的SCR脱硝试验台研究了燃煤电厂真实排烟环境下空速、催化剂用量、温度、氨氮比、初始浓度、积灰时间、催化剂寿命等因素对工业纯蜂窝状V2O5-WO3-MoO3/TiO2四元催化剂脱硝性能的影响；通过Lister Petter TR1重型直喷式单缸柴油机尾气SCR脱硝试验台研究了柴油机真实尾气环境下工业纯颗粒状V2O5-WO3-MoO3/TiO2四元催化剂的脱硝性能以及在运行过程中活性降低的规律。
1.以化学分析纯偏钒酸铵、钨酸铵、钼酸铵、锐钛型钛白粉为主要成分,制备了颗粒状V2O5-WO3-MoO3/TiO2四元催化剂,利用标准气模拟烟气组成研究了该催化剂的脱硝性能,研究结果表明：在活性物质总负载量相同的情况下,同时负载W和Mo的四元催化剂脱硝效率高于单一负载W或Mo三元催化剂的脱硝效率；W可以有效提高催化剂高温区间活性,抑制Mo在高温区间的副反应发生,Mo可以有效提高催化剂低温区间活性,弥补W在低温区间活性不足,从而拓宽催化剂活性温度窗口；当V负载量为1.0%w/w,W负载量为4.5%w/w,Mo负载量为4.5%w/w时,催化剂具有最佳性能,其各部分物性均匀,颗粒致密,粒径大小一致,且具有完整的微孔结构；焙烧温度对催化剂比表面积、比孔体积、平均孔径、结晶度、物相转变和催化活性均有重要影响,催化剂在35℃焙烧具有最佳活性,峰值达到99.1%,但化学结构不稳定,在450℃焙烧具有稳定结构且结晶完全,活性物质溶入锐钛型Ti02晶格效果最佳,但活性峰值降至89.1%,采用350℃+450℃二次焙烧方法所得催化剂具备稳定化学结构,与450℃焙烧的催化剂相比,比表面积增大5.0%,比孔体积增大1.9%,平均孔径减小1.5%,催化剂活性峰值提升3.0%,温度窗口拓宽约40℃
2.以各项工业纯度原料分别替换分析纯度原料进行脱硝效率对比试验,所用催化剂中V负载量为1.0%w/w,W负载量为4.5%w/w,Mo负载量为4.5%W/w,研究结果表明：工业纯H2C2O4会造成催化剂严重失活,采用工业纯V、W、Mo和分析纯H2C2O4制备所得催化剂具有较低的制备成本和较高的脱硝效率和较宽的活性温度窗口,可以很好地解决催化剂制造成本和脱硝性能之间的矛盾。催化剂的成型性能与成型模具结构、成型剂种类和胚料制备工艺均有密切关系,通过完善成型工艺可以提高催化剂胚料的致密性和均匀性,经粉体筛分,胚料碾压、捶打,静置封存处理后所制得的催化剂胚料具有较好的蜂窝状成型性能、较强的硬度以及耐磨性。
3.利用燃煤电厂烟气脱硝试验台研究了系统运行参数对催化剂脱硝性能的影响效果,研究结果表明：空速增大,催化剂脱硝效率总体趋势是降低的,但在一定空速范围内催化剂活性较高且较为稳定；当脱硝效率达到80.0%以上时,增大SCR脱硝系统中催化剂的用量脱硝效率提高不明显,却会造成SO2氧化率不断升高,且增长速率不断增大,同时会导致脱硝成本较高,SCR脱硝系统中催化剂的用量应根据各燃煤电厂设计标准及排放要求布置,寻求最佳脱硝效率与催化剂体积的比值,避免单一追求脱硝效率导致其它资源的浪费。与实验室模拟烟气相比,真实烟气中脱硝效率对温度的变化更敏感,高温区间脱硝效率随温度变化剧烈,但对NH3的敏感度较低,当氨氮比达到0.9时催化剂的脱硝效率大于70.0%,运行中增大NH3投入体积可以进一步提高NOx转化率,同时降低S02氧化率。本课题所制备的V2O5-WO3-MoO3/TiO2四元催化剂对NOx初始浓度的变化具有较强的适应性,在300-1700ppm范围内,脱硝效率均大于70.0%。催化剂的脱硝效率会随着积灰时间的延长而不断降低,同时随着催化剂运行时间的延长,脱硝效率呈现先急剧下降,后缓慢降低的变化趋势,在运行第1个月内下降较快,平均每运行78h脱硝效率降低1.0%,在运行2-12月内下降较为平缓,平均每运行740h脱硝效率降低1.0%。
4.利用柴油机尾气脱硝试验台研究了柴油机运行工况对所研制催化剂脱硝性能的影响,研究结果表明：柴油机SCR反应器内空速增大,所研制催化剂脱硝效率和脱硝反应副产物N20浓度呈现单一下降趋势,而NH3逸出浓度增大；柴油机负载增大,催化剂脱硝效率呈现下降趋势,且脱硝效率下降速率递增,同时脱硝反应副产物N20浓度不断减小,而NH3逸出浓度不断增大；不同负载下催化剂的脱硝效率均受反应温度影响较大,但脱硝效率随反应温度的变化趋势相似,仅变化幅值不同；柴油机负载变化会导致催化剂活性温度窗口(脱硝效率>70%)发生较大变化,同时导致副反应NH3/N2O起始温度和N20生成量一起变化；随着NH3投入量的增加,催化剂脱硝效率先升高后保持不变,而副反应产物N20的生成浓度不断增大且增大速率均匀,NH3逃逸量不断增长且增长速率逐渐变大。随着柴油机运行时间的延长,催化剂表面积碳量增加,催化剂脱硝效率缓慢降低,但积碳量对催化剂的脱硝效率的影响程度较弱；柴油机启动、停机次数增加会加速催化剂脱硝效率的降低,并使得副反应NH3/N2O进行程度减弱,同时导致NH3逃逸率增大。
本课题得到山东省科技发展计划：选择性催化还原烟气脱销用高效催化剂的失活机理和工业应用研究(NO.2011GSF11716)和山东电力集团科技项目：大容量燃煤锅炉氮氧化物NOx排放控制技术实验研究(NO.2008ZB-19)的资助。本文作者在英国伯明翰大学期间实验及生活得到国家留学基金委的资助(NO.2011622102)。
Selective catalytic reduction (SCR) catalyst for NOx reduction becomes the research focus of domestic and foreign research institutions with the emission standards developing stricter in the worldwide.
In this study, the powder SCR catalyst prepared with analytical pure chemicals was researched by experiment and theoretical analysis. The denitration reaction mechanism of V2O5-WO3-MoO3/TiO2catalyst was studied and its denitration performance was compared with V2O5-WO3/TiO2and ViO5-MoO3/TiO2catalysts. The physical and chemical properties of V2O5-WO3-MoO3/TiO2catalyst was analyzed based on its microscopic characterizations, such as specific surface area, pore volume, mean pore diameter, phase composition and grain size. Also, the mass percentage of each chemical in the catalyst was optimized.
The honeycomb catalyst of V2O5-WO3-MoO3/TiO2was prepared with industrial pure chemicals to investigate the impurities effects on the denitration performance, which were contained in the chemicals. Meanwhile, the forming process was optimized during the honeycomb catalyst preparation. The denitration performance of honeycomb V2O5-WO3-MoO3/TiO2catalyst under actual flue gas was tested on a SCR DeNOx test bench which was built at a300MW unit of a coal-fired power plant in Shandong Province. In this test, the effects of space velocity, catalyst volume, reaction temperature, NH3to NOx ratio, NOx initial concentration, soot depositing time, and catalyst life on the catalyst denitration performance were revealed.
The denitration performance of powder V2O5-WO3-MoO3/TiO2catalyst was researched under the exhaust of a Lister Petter TR1heavy direct injection single-cylinder diesel engine, and the catalyst deactivation mechanism during diesel engine operation was analyzed.
1. The powder V205-W03-Mo03/Ti02catalyst was prepared with analytical pure chemicals of ammonium vanadate, ammonium tungstate, ammonium molybdate and anatase titanium dioxide. The denitration performance of this catalyst was researched under simulated flue gas composed of NO, SO2, O2and N2. The research results show that, the Denitration efficiency of the catalyst loading W and Mo is higher than the catalyst only loading W or Mo, when the same total amount of active substance is loaded. In high temperature range, W can effectively enhance the activity of the catalyst and inhibit the side reactions caused by Mo. In low temperature range, Mo can effectively improve the activity of the catalyst to compensate for the insufficient activity of W. Thereby the temperature window of the catalyst loading both W and Mo is broadened. The catalyst has best denitration performance with uniform and dense particles and complete microporous structure under V load at1.0%w/w, W load at4.5%w/w, Mo load at4.5%w/w. The sintering temperature has close relationship with the characterizations of the catalyst, such as specific surface area, pore volume, average pore diameter, degree of crystallization, phase transform and catalytic activity. The catalyst sintered at350℃had the highest Denitration efficiency of99.1%, but its chemical structure was not stable. The catalyst sintered at450℃had a stable chemical structure and complete crystallization with the active material dissolved into the anatase TiO2lattice, but its Denitration efficiency reduced to89.1%. The catalyst, sintered by350℃+450℃two-stage sintering method, had a stable chemical structure, and its specific surface area increased by5.0%, pore volume enlarged by1.9%, average pore diameter reduced by1.5%, Denitration efficiency peak increased by3.0%, and the temperature window approximately broadened by40℃compared with the catalyst sintered at450℃.
2. The Denitration efficiency of the catalyst prepared with industrial pure chemicals and analytical pure chemicals were tested and compared. The research results show that, the industrial pure H2C2O4causes the catalyst serious deactivation, and the catalyst prepared with industrial purity of V, W, Mo and analytical purity of H2C2O4has low cost, high Denitration efficiency and wide temperature window. Forming properties have close relationship with the mold structure, the forming agent type and the precursor preparation process. The density and uniformity of the precursor can be improved by optimizing the forming process. After powder screening, rolling, beating and sealed storing, the precursor has preferable honeycomb-forming properties, strong hardness and abrasive resistance.
3. The operating parameters effects on the catalyst denitration performance were researched on the SCR DeNOx test bench which was built at a300MW unit of a coal-fired power plant in Shandong Provence. The research results show that the overall trend of the catalyst denitration efficiency is reduced with the space velocity increasing, but within a certain range, the denitration efficiency is relative stable. When the denitration efficiency reaches80.0%, increasing the amount of catalyst used in the SCR system to improve the denitration efficiency is not effective, but it will result in SO2oxidation increase, meanwhile, it will result in higher cost of the SCR system. The volume of catalyst used in the SCR system should be arranged according to the design standards and emission requirements for each coal-fired power plant. The ratio of the catalyst denitration efficiency to catalyst volume should be optimized to avoid other resources wasting by singlely pursuiting the high denitration efficiency. Compared with the results in the simulated flue gas, the denitration efficiency in the actual flue gas is more sensitive to temperature variation, and the denitration efficiency change is larger with temperature varying at the high-temperature range. The denitration efficiency, however, is less sensitive to NH3concentration variation, which reach70.0%at NH3:NOx of0.9. The denitration efficiency can be improved by enlarging NH3:NOx and the SO2oxidation will decrease at the same time. The V2O5-WO3-MoO3/TiO2catalyst has strong adaptability to the change of the NOx initial concentration, and its denitration efficiency is larger than70.0%with the NOx initial concentration in the range of300-1700ppm. The denitration efficiency of the catalyst reduces with the soot depositing time extension, and it declines sharply at the beginning of the catalyst continuous operation. In the first month of the catalyst continuous operation, the denitration efficiency decreases by1.0%per78h, in the range of2to12months, the denitration efficiency decreases by1.0%per740h.
4. The effect of the diesel engine operating parameters on the catalyst denitration performance was researched with the exhaust of a Lister Petter TR1heavy direct injection single-cylinder diesel engine. The results show that, the denitration efficiency and the by-product N2O concentration decrease with the space velocity increase, while the NH3slip increases. With the diesel engine load increasing, the denitration efficiency declines and the decline rate keeps on rising, at the same time, the by-product N2O concentration decreases and the NH3slip increases continuously. Under different loads, the catalyst denitration efficiencies are all greatly influenced by the reaction temperature and the trends of denitration efficiency varying with reaction temperature rising are similar, but the varying values are quite different. Diesel engine load change can lead the catalyst temperature window (denitration efficiency>70%) varying largely, at the same time, the starting temperature of NH3/N2O side reaction and the N2O concentration change together. With the increase of NH3volume, the denitration efficiency increases first and then remains unchanged, while the concentration of by-product N2O increases and increase rate keeps stable, at the same time, the NH3slip increases and the increase rate rises gradually. With the diesel engine operation time extension, the carbon content on the catalyst surface area increases and the catalyst denitration efficiency decreases slowly, but the effect of carbon deposition on denitration efficiency is weak. Diesel engine start-up, shut-down times increase accelerates the reduction of catalyst denitration efficiency, meanwhile, the side reaction of NH3/N2O becomes weak, and the NH3slip increases.
This study is funded by shandong province science and technology development plan:high efficiency selective catalytic reduction catalyst deactivation mechanism research and industrial application (NO.2011GSF11716) and Shandong Power Ltd technology projects:NOx emissions control technology research on large capacity coal fired boilers (NO.2008ZB-19). The author's experiment and life at the university of Birmingham, UK is supported by China Scholarship Council (NO.2011622102).
1.以化学分析纯偏钒酸铵、钨酸铵、钼酸铵、锐钛型钛白粉为主要成分,制备了颗粒状V2O5-WO3-MoO3/TiO2四元催化剂,利用标准气模拟烟气组成研究了该催化剂的脱硝性能,研究结果表明：在活性物质总负载量相同的情况下,同时负载W和Mo的四元催化剂脱硝效率高于单一负载W或Mo三元催化剂的脱硝效率；W可以有效提高催化剂高温区间活性,抑制Mo在高温区间的副反应发生,Mo可以有效提高催化剂低温区间活性,弥补W在低温区间活性不足,从而拓宽催化剂活性温度窗口；当V负载量为1.0%w/w,W负载量为4.5%w/w,Mo负载量为4.5%w/w时,催化剂具有最佳性能,其各部分物性均匀,颗粒致密,粒径大小一致,且具有完整的微孔结构；焙烧温度对催化剂比表面积、比孔体积、平均孔径、结晶度、物相转变和催化活性均有重要影响,催化剂在35℃焙烧具有最佳活性,峰值达到99.1%,但化学结构不稳定,在450℃焙烧具有稳定结构且结晶完全,活性物质溶入锐钛型Ti02晶格效果最佳,但活性峰值降至89.1%,采用350℃+450℃二次焙烧方法所得催化剂具备稳定化学结构,与450℃焙烧的催化剂相比,比表面积增大5.0%,比孔体积增大1.9%,平均孔径减小1.5%,催化剂活性峰值提升3.0%,温度窗口拓宽约40℃
2.以各项工业纯度原料分别替换分析纯度原料进行脱硝效率对比试验,所用催化剂中V负载量为1.0%w/w,W负载量为4.5%w/w,Mo负载量为4.5%W/w,研究结果表明：工业纯H2C2O4会造成催化剂严重失活,采用工业纯V、W、Mo和分析纯H2C2O4制备所得催化剂具有较低的制备成本和较高的脱硝效率和较宽的活性温度窗口,可以很好地解决催化剂制造成本和脱硝性能之间的矛盾。催化剂的成型性能与成型模具结构、成型剂种类和胚料制备工艺均有密切关系,通过完善成型工艺可以提高催化剂胚料的致密性和均匀性,经粉体筛分,胚料碾压、捶打,静置封存处理后所制得的催化剂胚料具有较好的蜂窝状成型性能、较强的硬度以及耐磨性。
3.利用燃煤电厂烟气脱硝试验台研究了系统运行参数对催化剂脱硝性能的影响效果,研究结果表明：空速增大,催化剂脱硝效率总体趋势是降低的,但在一定空速范围内催化剂活性较高且较为稳定；当脱硝效率达到80.0%以上时,增大SCR脱硝系统中催化剂的用量脱硝效率提高不明显,却会造成SO2氧化率不断升高,且增长速率不断增大,同时会导致脱硝成本较高,SCR脱硝系统中催化剂的用量应根据各燃煤电厂设计标准及排放要求布置,寻求最佳脱硝效率与催化剂体积的比值,避免单一追求脱硝效率导致其它资源的浪费。与实验室模拟烟气相比,真实烟气中脱硝效率对温度的变化更敏感,高温区间脱硝效率随温度变化剧烈,但对NH3的敏感度较低,当氨氮比达到0.9时催化剂的脱硝效率大于70.0%,运行中增大NH3投入体积可以进一步提高NOx转化率,同时降低S02氧化率。本课题所制备的V2O5-WO3-MoO3/TiO2四元催化剂对NOx初始浓度的变化具有较强的适应性,在300-1700ppm范围内,脱硝效率均大于70.0%。催化剂的脱硝效率会随着积灰时间的延长而不断降低,同时随着催化剂运行时间的延长,脱硝效率呈现先急剧下降,后缓慢降低的变化趋势,在运行第1个月内下降较快,平均每运行78h脱硝效率降低1.0%,在运行2-12月内下降较为平缓,平均每运行740h脱硝效率降低1.0%。
4.利用柴油机尾气脱硝试验台研究了柴油机运行工况对所研制催化剂脱硝性能的影响,研究结果表明：柴油机SCR反应器内空速增大,所研制催化剂脱硝效率和脱硝反应副产物N20浓度呈现单一下降趋势,而NH3逸出浓度增大；柴油机负载增大,催化剂脱硝效率呈现下降趋势,且脱硝效率下降速率递增,同时脱硝反应副产物N20浓度不断减小,而NH3逸出浓度不断增大；不同负载下催化剂的脱硝效率均受反应温度影响较大,但脱硝效率随反应温度的变化趋势相似,仅变化幅值不同；柴油机负载变化会导致催化剂活性温度窗口(脱硝效率>70%)发生较大变化,同时导致副反应NH3/N2O起始温度和N20生成量一起变化；随着NH3投入量的增加,催化剂脱硝效率先升高后保持不变,而副反应产物N20的生成浓度不断增大且增大速率均匀,NH3逃逸量不断增长且增长速率逐渐变大。随着柴油机运行时间的延长,催化剂表面积碳量增加,催化剂脱硝效率缓慢降低,但积碳量对催化剂的脱硝效率的影响程度较弱；柴油机启动、停机次数增加会加速催化剂脱硝效率的降低,并使得副反应NH3/N2O进行程度减弱,同时导致NH3逃逸率增大。
本课题得到山东省科技发展计划：选择性催化还原烟气脱销用高效催化剂的失活机理和工业应用研究(NO.2011GSF11716)和山东电力集团科技项目：大容量燃煤锅炉氮氧化物NOx排放控制技术实验研究(NO.2008ZB-19)的资助。本文作者在英国伯明翰大学期间实验及生活得到国家留学基金委的资助(NO.2011622102)。
Selective catalytic reduction (SCR) catalyst for NOx reduction becomes the research focus of domestic and foreign research institutions with the emission standards developing stricter in the worldwide.
In this study, the powder SCR catalyst prepared with analytical pure chemicals was researched by experiment and theoretical analysis. The denitration reaction mechanism of V2O5-WO3-MoO3/TiO2catalyst was studied and its denitration performance was compared with V2O5-WO3/TiO2and ViO5-MoO3/TiO2catalysts. The physical and chemical properties of V2O5-WO3-MoO3/TiO2catalyst was analyzed based on its microscopic characterizations, such as specific surface area, pore volume, mean pore diameter, phase composition and grain size. Also, the mass percentage of each chemical in the catalyst was optimized.
The honeycomb catalyst of V2O5-WO3-MoO3/TiO2was prepared with industrial pure chemicals to investigate the impurities effects on the denitration performance, which were contained in the chemicals. Meanwhile, the forming process was optimized during the honeycomb catalyst preparation. The denitration performance of honeycomb V2O5-WO3-MoO3/TiO2catalyst under actual flue gas was tested on a SCR DeNOx test bench which was built at a300MW unit of a coal-fired power plant in Shandong Province. In this test, the effects of space velocity, catalyst volume, reaction temperature, NH3to NOx ratio, NOx initial concentration, soot depositing time, and catalyst life on the catalyst denitration performance were revealed.
The denitration performance of powder V2O5-WO3-MoO3/TiO2catalyst was researched under the exhaust of a Lister Petter TR1heavy direct injection single-cylinder diesel engine, and the catalyst deactivation mechanism during diesel engine operation was analyzed.
1. The powder V205-W03-Mo03/Ti02catalyst was prepared with analytical pure chemicals of ammonium vanadate, ammonium tungstate, ammonium molybdate and anatase titanium dioxide. The denitration performance of this catalyst was researched under simulated flue gas composed of NO, SO2, O2and N2. The research results show that, the Denitration efficiency of the catalyst loading W and Mo is higher than the catalyst only loading W or Mo, when the same total amount of active substance is loaded. In high temperature range, W can effectively enhance the activity of the catalyst and inhibit the side reactions caused by Mo. In low temperature range, Mo can effectively improve the activity of the catalyst to compensate for the insufficient activity of W. Thereby the temperature window of the catalyst loading both W and Mo is broadened. The catalyst has best denitration performance with uniform and dense particles and complete microporous structure under V load at1.0%w/w, W load at4.5%w/w, Mo load at4.5%w/w. The sintering temperature has close relationship with the characterizations of the catalyst, such as specific surface area, pore volume, average pore diameter, degree of crystallization, phase transform and catalytic activity. The catalyst sintered at350℃had the highest Denitration efficiency of99.1%, but its chemical structure was not stable. The catalyst sintered at450℃had a stable chemical structure and complete crystallization with the active material dissolved into the anatase TiO2lattice, but its Denitration efficiency reduced to89.1%. The catalyst, sintered by350℃+450℃two-stage sintering method, had a stable chemical structure, and its specific surface area increased by5.0%, pore volume enlarged by1.9%, average pore diameter reduced by1.5%, Denitration efficiency peak increased by3.0%, and the temperature window approximately broadened by40℃compared with the catalyst sintered at450℃.
2. The Denitration efficiency of the catalyst prepared with industrial pure chemicals and analytical pure chemicals were tested and compared. The research results show that, the industrial pure H2C2O4causes the catalyst serious deactivation, and the catalyst prepared with industrial purity of V, W, Mo and analytical purity of H2C2O4has low cost, high Denitration efficiency and wide temperature window. Forming properties have close relationship with the mold structure, the forming agent type and the precursor preparation process. The density and uniformity of the precursor can be improved by optimizing the forming process. After powder screening, rolling, beating and sealed storing, the precursor has preferable honeycomb-forming properties, strong hardness and abrasive resistance.
3. The operating parameters effects on the catalyst denitration performance were researched on the SCR DeNOx test bench which was built at a300MW unit of a coal-fired power plant in Shandong Provence. The research results show that the overall trend of the catalyst denitration efficiency is reduced with the space velocity increasing, but within a certain range, the denitration efficiency is relative stable. When the denitration efficiency reaches80.0%, increasing the amount of catalyst used in the SCR system to improve the denitration efficiency is not effective, but it will result in SO2oxidation increase, meanwhile, it will result in higher cost of the SCR system. The volume of catalyst used in the SCR system should be arranged according to the design standards and emission requirements for each coal-fired power plant. The ratio of the catalyst denitration efficiency to catalyst volume should be optimized to avoid other resources wasting by singlely pursuiting the high denitration efficiency. Compared with the results in the simulated flue gas, the denitration efficiency in the actual flue gas is more sensitive to temperature variation, and the denitration efficiency change is larger with temperature varying at the high-temperature range. The denitration efficiency, however, is less sensitive to NH3concentration variation, which reach70.0%at NH3:NOx of0.9. The denitration efficiency can be improved by enlarging NH3:NOx and the SO2oxidation will decrease at the same time. The V2O5-WO3-MoO3/TiO2catalyst has strong adaptability to the change of the NOx initial concentration, and its denitration efficiency is larger than70.0%with the NOx initial concentration in the range of300-1700ppm. The denitration efficiency of the catalyst reduces with the soot depositing time extension, and it declines sharply at the beginning of the catalyst continuous operation. In the first month of the catalyst continuous operation, the denitration efficiency decreases by1.0%per78h, in the range of2to12months, the denitration efficiency decreases by1.0%per740h.
4. The effect of the diesel engine operating parameters on the catalyst denitration performance was researched with the exhaust of a Lister Petter TR1heavy direct injection single-cylinder diesel engine. The results show that, the denitration efficiency and the by-product N2O concentration decrease with the space velocity increase, while the NH3slip increases. With the diesel engine load increasing, the denitration efficiency declines and the decline rate keeps on rising, at the same time, the by-product N2O concentration decreases and the NH3slip increases continuously. Under different loads, the catalyst denitration efficiencies are all greatly influenced by the reaction temperature and the trends of denitration efficiency varying with reaction temperature rising are similar, but the varying values are quite different. Diesel engine load change can lead the catalyst temperature window (denitration efficiency>70%) varying largely, at the same time, the starting temperature of NH3/N2O side reaction and the N2O concentration change together. With the increase of NH3volume, the denitration efficiency increases first and then remains unchanged, while the concentration of by-product N2O increases and increase rate keeps stable, at the same time, the NH3slip increases and the increase rate rises gradually. With the diesel engine operation time extension, the carbon content on the catalyst surface area increases and the catalyst denitration efficiency decreases slowly, but the effect of carbon deposition on denitration efficiency is weak. Diesel engine start-up, shut-down times increase accelerates the reduction of catalyst denitration efficiency, meanwhile, the side reaction of NH3/N2O becomes weak, and the NH3slip increases.
This study is funded by shandong province science and technology development plan:high efficiency selective catalytic reduction catalyst deactivation mechanism research and industrial application (NO.2011GSF11716) and Shandong Power Ltd technology projects:NOx emissions control technology research on large capacity coal fired boilers (NO.2008ZB-19). The author's experiment and life at the university of Birmingham, UK is supported by China Scholarship Council (NO.2011622102).
引文
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