基于远程在线监控车载终端的柴油车NOx排放等级诊断研究

远程在线监控车载终端集成了远程通讯模块、卫星定位模块、发动机OBD信息解析模块,能够实时读取车辆排放相关运行信息,但无法直接判断车辆NO_x排放情况.为了快速、准确地评估车辆排放情况,诊断和监测NO_x高排放车,同时为了克服有些重型柴油车监测数据中缺失进气流量、燃油流量、车速等重要的实时信息,无法计算出车辆NO_x排放因子的问题.本文提出了由NO_x浓度分布特征驱动的高排放重型柴油车识别算法,通过远程在线监控车载终端设备获取车辆的发动机信息和SCR系统运行信息,运用NO_x浓度分布计算车辆每天NO_x排放浓度占比,通过系统聚类法对车辆NO_x排放浓度占比进行聚类,结果聚为优、良、中、差4类.利用车辆NO_x排放浓度区间分布及其聚类结果分别作为训练集的输入和输出,选择BP神经网络作为训练算法,训练获得的模型分类准确率为90%,利用训练好的模型判断在用柴油车NO_x排放等级,从而识别及监测NO_x高排放车辆.研究结果可为柴油车NO_x高排放诊断及监测提供依据,有助于监管部门能够快速识别NO_x高排放车辆.     

CuxCe1-xO2/γ-Al2O3催化剂催化燃烧甲苯性能的研究

以γ-Al₂O₃ 为载体,以复合氧化物Cu_xCe_1-xO₂为活性组分,其中,x=0.1,0.2,0.4,0.6,0.8,通过浸渍法制备了一系列Cu_xCe_1-xO₂/γ-Al₂O₃催化剂.在固定床反应器中评价了催化剂对甲苯的催化活性,通过XRD、SEM对催化剂进行表征,并运用ICP-MS分析并计算Cu、Ce的摩尔比以及活性组分的负载量.结果表明,在Cu_xCe_1-xO₂/γ-Al₂O₃催化剂中Cu、Ce摩尔比的实际值与理论值相近,活性组分的负载量在19%以上,而且对甲苯都有较好的低温催化活性,其中当x=0.2时,即Cu_0.2Ce_0.8O₂/γ-Al₂O₃催化剂对甲苯的催化活性最高,其中T₁₀=160 ℃,T₉₀=265 ℃;当甲苯的进口浓度在700~3000 mg·m^-3时,进口浓度对Cu_0.2Ce_0.8O₂/γ-Al₂O₃催化剂的催化活性影响较小,且经过连续80 h的稳定性操作后转化率仍然保持在90%以上.     

NOx和VOC自然源排放及其对中国地区对流层光化学特性影响的数值模拟研究

利用Williams等和Guenther等的模型估计中国地区NO_x和VOC的自然源排放.所得清单显示土壤NO_x排放总量（以N计）为225.75 Gg;植被VOC年排放总量（以C计）为13.23 Tg,其中异戊二烯、单萜烯、其它VOC分别为7.77、1.86、3.60 Tg;排放有明显季节变化和空间变化.运用中尺度气象模式MM5以及光化学模式Calgrid研究这些排放在不同季节对对流层化学的影响.结果表明,O₃、NO_x、HNO₃和PAN的全国平均浓度在土壤NO_x排放影响下分别增加15.3%、15.7%、25.5%和6.5%;在植被VOC排放影响下改变5.6%、-4.9%、-19.3％和142.3％;在两者综合影响下增加26.1%、8.8%、4.3%和177.9%;浓度变化在夏季明显强于其它季节.自然源对中国地区光化学污染物空间分布有不同程度的影响,这种影响同区域气象条件、源排放和NMHC/NO_x比值等因素有关.NO_x和VOC的自然源排放对光化学特性影响显著,在光化学模拟过程中不容忽视.     

2010~2015年我国水泥工业NOx排放清单及排放特征

基于我国2011~2015年水泥企业逐条生产线基础信息、活动水平及控制技术等数据,建立了水泥工业NO_x排放量计算方法和动态排放数据库.利用该方法,计算了2011~2015年逐条水泥生产线NO_x排放量,分析了2010~2015年我国水泥工业NO_x排放特征.结果表明,我国水泥工业NO_x排放量变化范围为168~199万t,自2010年的169万t增加到2012年的199万t,达到排放峰值,随后逐年下降,到2015年与2010年基本持平.水泥工业NO_x排放的地区分布不均衡,2015年安徽、四川、河南、湖南、云南、山东是排放量最大的省份,占全国排放总量的40%,上海、内蒙、山西、新疆、湖南、云南、四川是单位熟料NO_x排放强度最大的省份.从生产线规模来看,规模≥ 4000 t·d^-1的熟料生产线产量占比和NO_x排放量占比均最大,分别为68.5%和66.5%,单位熟料NO_x平均排放强度最低.水泥生产工艺结构的转变及水泥工业降氮脱硝工作的开展是影响水泥工业大气NO_x排放特征的主要因素.     

SO2对MnOx/PG催化剂低温脱硝的影响机理研究

采用等体积浸渍法制备了锰氧化物负载凹凸棒石(MnO_x/PG)低温SCR催化剂,通过SO₂暂态响应、程序升温表面反应(TPSR)等实验技术研究了烟气中SO₂对催化剂SCR脱硝活性的影响行为.采用程序升温脱附(TPD)、BET比表面及孔径分布测定、XPS等表征技术对催化剂硫中毒的机理及化学本质进行了深入分析.结果表明,低温下烟气中SO₂对MnO_x/PG催化剂的SCR脱硝活性存在显著的抑制作用,催化剂中毒主要由烟气中SO₂的催化氧化引起.一方面SO₂氧化为SO₃后与NH₃及H₂O竞争反应形成复杂的硫酸铵盐堵塞催化剂孔道,另一方面与活性组分MnO₂结合形成MnSO₄使得部分活性组分形态发生变迁.其中硫酸铵盐的形成可通过适当的热处理得以去除,而MnSO₄则不可恢复,但催化剂SCR活性却显著增加,表明MnSO₄的形成不是催化剂失活的主要因素.吸附态的硫可显著增加催化剂表面酸性,因此对SCR活性有促进作用.催化剂失活主要机理为:由气相SO₂的连续氧化并与NH₃相结合形成硫酸铵盐,并且在低温下难以分解,以致堵塞催化剂活性中心.     

超细煤粉在氧化条件下NOx的释放特性实验研究

采用DTG(热重/差热分析仪)和GC-MS(气相色谱质谱联用仪)对鹤岗煤超细化煤粉进行燃烧试验,分析了粒径、氧气浓度、升温速率对NO_x释放的影响.结果表明,不同粒径的鹤岗煤在氧气浓度为20％的燃烧条件下,NO_x的析出均为单峰曲线;粒径对煤粉燃烧NO_x释放有重要影响,超细化煤粉可以减少NO_x的排放;在5、10、20 ℃/min升温条件下,随升温速率的增大NO和NO₂的析出量也增加,并且NO的最大析出速率对应的温度随着升温速率的提高也提高;随着燃烧气氛氧气浓度的增高,NO_x的析出量相应增加,并且NO_x的最大析出速率对应温度相应降低.     

2013年1月华北地区重霾污染过程SO2和NOx的CMAQ源同化模拟研究

以2006年中国地区的INTEX-B排放清单为基础,采用CMAQ模式污染源同化方法,反演更新了2013年1月重霾污染过程华北地区的SO₂和NO_x排放源;应用WRF-CMAQ模式以及2006年INTEX-B初始排放源和2013年1月改进的排放源,分别模拟了1月9-15日和28-31日两次持续重霾污染过程的SO₂和NO₂浓度,并与华北地区47个环境监测站点实测值进行对比,重点分析了基于初始源和同化反演源的模拟效果及其改进原因;本文亦采用2012年清华大学编制的东亚地区MEIC排放清单评估了SO₂和NO_x同化反演源的合理性.分析结果表明:①CMAQ模式污染源同化方法可适用于重霾污染过程,即采用同化反演源模拟的SO₂、NO₂浓度时空变化特征与实测值较一致,而且可反映SO₂、NO_x排放源强的动态变化特征;②基于同化反演源的SO₂、NO₂浓度模拟效果明显优于2006年INTEX-B排放源,其时间变化趋势与实测值较一致,而且可模拟重霾污染过程SO₂、NO₂浓度的峰值;③采用反演源模拟的SO₂、NO₂浓度空间区分布特征与实测值较一致,而且可较好反映重污染区的极值分布特征;④经污染源同化改进后SO₂、NO₂模拟浓度与实测值的相关系数有所提高,误差明显减小;SO₂的改进效果略优于NO₂,这与污染源对两种污染物浓度的影响差异有关;⑤初始源中SO₂、NO_x排放源的空间分布和强度与2012年清华大学编制的排放源强差异较大,而同化反演源的空间分布和强度均接近于上述2012年排放源,较好反映出重点地区的高污染源分布特征.本文研究结果将为改进重霾污染过程的空气质量预报、减小自下而上建立的排放源清单不确定性、评估SO₂、NO_x等排放源的影响效应以及不同气象条件下区域排放源的动态调控等提供新技术途径和研究思路.     

苏州市初夏臭氧污染成因及年际变化

以2017~2021年的5~6月苏州市城区站点的大气污染物浓度为研究对象,分析了臭氧（O₃）、氮氧化物（NO_x）、总氧化剂（O_x）、一氧化碳（CO）和挥发性有机物（VOCs）等污染物的变化特征,利用基于观测的模型（OBM）研究了O₃污染成因及其年际变化,解析了环境空气VOCs的主要来源及其变化趋势.结果表明：①近年来苏州O_x平均体积分数以及NO_x和CO平均浓度整体呈下降趋势,但VOCs的体积分数整体呈上升趋势;O₃污染天光化学反应前体物浓度水平仍较高,且显著高于优良天.②近年来苏州O₃生成处于VOCs控制区;苏州市VOCs和NO_x长期减排比例应不低于5∶1,在VOCs控制方面应注重对芳香烃和烯烃的减排.③源解析结果显示,工业排放、汽油车尾气和柴油机尾气是苏州市VOCs的主要排放源;近年来工业排放源和溶剂使用源有所下降,但汽油车尾气源和油气挥发源贡献率上升明显,且上述两类污染源排放VOCs的O₃生成潜势较高.④综合分析各排放源对O₃生成潜势的贡献发现,溶剂使用源和汽油车尾气源的VOCs排放是影响苏州市O₃生成的关键因素.     

基于随机森林的北京城区臭氧敏感性分析

明确臭氧（O₃）与前体物的非线性关系是O₃防控措施制定的基础和关键.基于北京城区站点2020年4~9月O₃、挥发性有机物（VOCs）、氮氧化物（NO_x）和气象要素在线观测,分析了O₃及其前体物污染特征,利用随机森林（RF）模型结合SHAP值探究了影响O₃的关键因素,并通过多情景分析探讨了O₃-VOCs-NO_x敏感性.相关性分析结果显示O₃小时浓度与温度（T）呈显著正相关,与TVOCs和NO_x呈显著负相关;但从每日结果来看,O₃与T、TVOCs和NO_x均呈显著正相关.RF模型模拟的O₃浓度与实测值吻合较好,进一步计算了各个特征变量的SHAP值,结果显示T和NO_x对O₃影响最高,但前者是正向影响,而后者是负向影响.以观测期间O₃污染天的NO_x和VOCs平均值为基础情景,设置了对应不同NO_x和VOCs的多种情景,并利用RF模型计算不同情景下的O₃,得到O₃等值线（EKMA曲线）,结果显示北京城区O₃-VOCs-NO_x敏感性处于VOCs控制区,与基于观测的盒子模型（OBM）得到的结果一致,这说明RF模型可以用作O₃-VOCs-NO_x敏感性分析的一种补充方法.     

关中盆地NO2和SO2对颗粒物污染的协同效应

基于WRF-Chem模式模拟了关中盆地2019年1月2—14日一次颗粒物污染事件,评估了NO_x和SO₂减排及其在颗粒物污染中的协同作用对PM_2.5污染的影响。敏感性实验结果表明：NO_x减排可使PM_2.5中硝酸盐含量下降,但大气中O₃浓度上升,大气氧化能力增强,其他二次组分上升,导致PM_2.5下降不明显;SO₂人为源减排可使硫酸盐质量浓度下降,但由于硫酸盐在PM_2.5中占比较低,当SO₂减排75%时,PM_2.5仅下降1.74%;当减排比例较高时,NO_x和SO₂同时减排更有利于颗粒物污染防治。PM_2.5质量浓度在NO_x和SO₂同时减排75%时比分开减排75%时多下降0.75%,主要是硫酸盐下降所致;对气溶胶含水量进行分析,发现NO_x对气溶胶含水量影响较大,当NO_x减排75%时,气溶胶含水量可下降15.51%;此外,NO_x和SO₂同时减排比分开减排时气溶胶含水量更低,更不利于二次颗粒物生成。     

Real-world fuel efficiency and exhaust emissions of light-duty diesel vehicles and their correlation with road conditions

The real-world fuel efficiency and exhaust emission profiles of CO, HC and NO_x for light-duty diesel vehicles were investigated. Using a portable emissions measurement system, 16 diesel taxies were tested on different roads in Macao and the data were normalized with the vehicle specific power bin method. The 11 Toyota Corolla diesel taxies have very good fuel economy of (5.9 ± 0.6) L/100 km, while other five diesel taxies showed relatively high values at (8.5 ± 1.7) L/100 km due to the variation in transmission systems and emission control strategies. Compared to similar Corolla gasoline models, the diesel cars confirmed an advantage of ca. 20% higher fuel efficiency. HC and CO emissions of all the 16 taxies are quite low, with the average at (0.05 ± 0.02) g/km and (0.38 ± 0.15) g/km, respectively. The average NO_x emission factor of the 11 Corolla taxies is (0.56 ± 0.17) g/km, about three times higher than their gasoline counterparts. Two of the three Hyundai Sonata taxies, configured with exhaust gas recirculation (EGR) + diesel oxidation catalyst (DOC) emission control strategies, indicated significantly higher NO₂ emissions and NO₂/NO_x ratios than other diesel taxies and consequently trigger a concern of possibly adverse impacts on ozone pollution in urban areas with this technology combination. A clear and similar pattern for fuel consumption and for each of the three gaseous pollutant emissions with various road conditions was identified. To save energy and mitigate CO₂ emissions as well as other gaseous pollutant emissions in urban area, traffic planning also needs improvement.     

High NO2/NOx emissions downstream of the catalytic diesel particulate filter: An influencing factor study

Diesel vehicles are responsible for most of the traffic-related nitrogen oxide (NO_x) emissions, including nitric oxide (NO) and nitrogen dioxide (NO₂). The use of after-treatment devices increases the risk of high NO₂/NO_x emissions from diesel engines. In order to investigate the factors influencing NO₂/NO_x emissions, an emission experiment was carried out on a high pressure common-rail, turbocharged diesel engine with a catalytic diesel particulate filter (CDPF). NO₂ was measured by a non-dispersive ultraviolet analyzer with raw exhaust sampling. The experimental results show that the NO₂/NO_x ratios downstream of the CDPF range around 20%–83%, which are significantly higher than those upstream of the CDPF. The exhaust temperature is a decisive factor influencing the NO₂/NO_x emissions. The maximum NO₂/NO_x emission appears at the exhaust temperature of 350°C. The space velocity, engine-out PM/NO_x ratio (mass based) and CO conversion ratio are secondary factors. At a constant exhaust temperature, the NO₂/NO_x emissions decreased with increasing space velocity and engine-out PM/NO_x ratio. When the CO conversion ratios range from 80% to 90%, the NO₂/NO_x emissions remain at a high level.     

Carbonyl emissions from heavy-duty diesel vehicle exhaust in China and the contribution to ozone formation potential

Fifteen heavy-duty diesel vehicles were tested on chassis dynamometer by using typical heavy duty driving cycle and fuel economy cycle. The air from the exhaust was sampled by 2,4- dinitrophenyhydrazine cartridge and 23 carbonyl compounds were analyzed by high performance liquid chromatography. The average emission factor of carbonyls was 97.2 mg/km, higher than that of light-duty diesel vehicles and gasoline-powered vehicles. Formaldehyde, acetaldehyde, acetone and propionaidehyde were the species with the highest emission factors. Main influencing factors for carbonyl emissions were vehicle type, average speed and regulated emission standard, and the impact of vehicle loading was not evident in this study. National emission of carbonyls from diesel vehicles exhaust was calculated for China, 2011, based on both vehicle miles traveled and fuel consumption. Carbonyl emission of diesel vehicle was estimated to be 45.8 Gg, and was comparable to gasolinepowered vehicles （58.4 Gg）. The emissions of formaldehyde, acetaldehyde and acetone were 12.6, 6.9, 3.8 Gg, respectively. The ozone formation potential of carbonyls from diesel vehicles exhaust was 537 mg O3/km, higher than 497 mg O3/km of none-methane hydrocarbons emitted from diesel vehicles.     

稻田气溶胶NH3和气体NOx排放在线测定研究

气溶胶NH3和气体NOx是大气颗粒物和降水的主要成分,是形成气溶胶的关键物种.田间集约化氮肥施用是气溶胶NH3和气体NOx的一个重要来源,目前该领域的研究鲜有报道.2010年5月～2010年10月,在线监测了稻田施用尿素后气溶胶NH3和气体NOx的排放情况.监测系统的时间分辨率设置为1 h.在4次稻田施肥试验中,施肥后对气溶胶NH3排放和相应的气象因子连续采样20 d.在第4次施肥试验中,施肥后连续采样47 d,进而研究气体NOx的排放规律及其与气象因子的关系.结果表明,气溶胶NH3的排放因子分别为2.6%、5.5%、4.0%和1.6%,相应的排放通量分别为3.97、2.08、1.52和1.22 kg·hm-2.温度(空气温度和土壤温度)是影响稻田施肥气溶胶NH3排放的主要因子,而空气湿度和土壤水分对其排放的影响却不明确.通过分析监测数据可知,稻田施肥后NO2-N排放量与NO-N排放量的比值为9/4,气体NOx的排放因子和排放通量分别为0.14%和0.30 kg·hm-2.气象因子与气体NOx排放通量的关系也进行了初步探讨.     

Numerical evaluation of the effectiveness of NO2 and N2O5 generation during the NO ozonation process

Wet scrubbing combined with ozone oxidation has become a promising technology for simultaneous removal of SO₂ and NO_x in exhaust gas. In this paper, a new 20-species, 76-step detailed kinetic mechanism was proposed between O₃ and NO_x. The concentration of N₂O₅ was measured using an in-situ IR spectrometer. The numerical evaluation results kept good pace with both the public experiment results and our experiment results. Key reaction parameters for the generation of NO₂ and N₂O₅ during the NO ozonation process were investigated by a numerical simulation method. The effect of temperature on producing NO₂ was found to be negligible. To produce NO₂, the optimal residence time was 1.25 sec and the molar ratio of O₃/NO about 1. For the generation of N₂O₅, the residence time should be about 8 sec while the temperature of the exhaust gas should be strictly controlled and the molar ratio of O₃/NO about 1.75. This study provided detailed investigations on the reaction parameters of ozonation of NO_x by a numerical simulation method, and the results obtained should be helpful for the design and optimization of ozone oxidation combined with the wet flue gas desulfurization methods (WFGD) method for the removal of NO_x.     

Characterization of particulate matter from diesel passenger cars tested on chassis dynamometers

Emission characterization of particle number as well as particle mass from three diesel passenger cars equipped with diesel particulate filter(DPF), diesel oxidation catalyst(DOC)and exhaust gas recirculation(EGR) under the vehicle driving cycles and regulatory cycle.Total particle number emissions(PNEs) decreased gradually during speed-up of vehicle from 17.3 to 97.3 km/hr. As the average vehicle speed increases, the size-segregated peak of particle number concentration shifts to smaller size ranges of particles. The correlation analysis with various particulate components such as particle number concentration(PNC),ultrafine particle number concentration(UFPNC) and particulate matter(PM) mass was conducted to compare gaseous compounds(CO, CO_2, HC and NOx). The UFPNC and PM were not only emitted highly in Seoul during severe traffic jam conditions, but also have good correlation with hydrocarbons and NOxinfluencing high potential on secondary aerosol generation. The effect of the dilution temperature on total PNC under the New European Driving Cycle(NEDC), was slightly higher than the dilution ratio. In addition, the nuclei mode(DP: ≤ 13 nm) was confirmed to be more sensitive to the dilution temperature rather than other particle size ranges. Comparison with particle composition between vehicle speed cycles and regulatory cycle showed that sulfate was slightly increased at regulatory cycle, while other components were relatively similar. During cold start test, semivolatile nucleation particles were increased due to effect of cold environment. Research on particle formation dependent on dilution conditions of diesel passenger cars under the NEDC is important to verify impact on vehicular traffic and secondary aerosol formation in Seoul.     

超声辅助法制备新型FeMOR分子筛催化NOx还原反应性能研究

采用超声辅助浸渍法成功合成了高铁含量的Fe MOR-5%-UL催化剂,并且测试其催化还原NO性能.研究发现在超声辅助条件下浸渍制得的催化剂可以引入更高比例的离子交换位上的孤立的Fe~(3+),这些铁离子具有更强的NO还原活性,因此超声辅助浸渍法制备的催化剂催化性能显著高于传统的离子交换法和浸渍法.其中活性最高的FeMOR-5%-UL催化剂在添加SO_2等多种气氛时,催化活性下降不显著.并且在持续100 h的汽车尾气条件下进行的稳定性实验中,FeMOR-5%-UL的催化活性没有明显下降.FeMOR-5%-UL的优异的催化活性和稳定性非常具有应用前景和研究价值.     

轻型柴油车实际道路瞬时排放模拟研究

系统介绍了CMEM模型及其计算原理.以轻型柴油车为研究对象,给出了模型的主要输入参数,并计算了车辆在实际道路上的瞬时排放结果,并根据实测数据对模拟结果进行了验证.测试车辆的CO、THC、NOx和CO2排放因子为0.81、0.61、2.09和193 g·km-1,相同线路模拟所得的排放因子分别为0.75、0.47、2.47和212 g·km-1,相关系数分别达到0.69、0.69、0.75和0.72.通过模拟发现,轻型柴油车在实际道路微观区域内的排放水平随交通条件和行驶状态波动明显,采用CMEM模型能够较好地反映该车排放随行驶工况的瞬时变化趋势.应用CMEM模拟发现,改善典型交叉口区域的交通条件后,轻型柴油车在模拟区域内的CO、THC、NOx和CO2排放量分别削减了50%、47%、45%和44%,排放改善效果显著.从研究结果来看,利用微观尺度模型来分析混合车流在一些典型交通区域的瞬时排放变化是必要的,也是可行的,对于评价道路交通规划的环境效果具有一定的指导意义.     

大气NOx测量准确性问题分析

采用美国热电公司的NO-N02-NOx分析仪(Model 42i TL)和NOy分析仪(Model 42i NOy),在2011年1月-10月期间,对北京城市大气中的NO、NOx和NOy进行了连续在线测量.两台仪器对NO的测量结果具有较高的一致性(r＞0.998,p＜0.01),说明两台仪器测量精度基本一致.将NOy分析仪(Model 42i NOy)采样口处安装和不安装颗粒物过滤膜两种条件下测量的NOy结果与NO-NO2-NOx分析仪所测的NOx结果分别进行了相关性分析([NOy] =0.989x[NOx],R2 =0.993;[NOy] =1.134 ×[NOx],R2=0.959),得出以下两个结论:①以颗粒态硝酸盐为代表的颗粒物是造成NOx与NOy偏差的主要原因,其所占比例在10％左右;②目前Model 42i-TL所测NOx的浓度水平较真实值偏高,其测量值更接近气态NOy的浓度水平.为估算NO2测值被高估的程度(以2011年8月6日-15日观测数据为例),用扣除部分气态NOz物种(HONO、HNO3、PAN、PPN)的修正方法,推论出在夏季N02被高估约7％(R2=0.968).