A comparative investigation of NdSrCu_(1-x) Co_x O_(4-δ) and Sm_(1.8) Ce_(0.2) Cu_(1-x) Co_x O_(4-δ) (x:0–0.4) for NO decomposition

A series of single-phase T-structured NdSrCu 1-x Co x O 4-δ with oxygen vacancies and T -structured Sm 1.8 Ce 0.2 Cu 1-x Co x O 4-δ (x: 0–0.4) with oxygen excess were prepared using ultrasound-assisted citric acid complexing method, and characterized by means of techniques such as thermogravimetric analysis and NO temperature-programmed desorption (NO-TPD). The catalytic activities of these materials were evaluated for the decomposition of NO. It was found that the NdSrCu 1-x Co x O 4-δ catalysts were of oxygen vacancies whereas the Sm 1.8 Ce 0.2 Cu 1-x Co x O 4-δ ones possessed excessive oxygen (i.e., over-stoichiometric oxygen); with a rise in Co doping level, the oxygen vacancy density of NdSrCu 1-x Co x O 4-δ decreased while the over-stoichiometric oxygen amount of Sm 1.8 Ce 0.2 Cu 1-x Co x O 4-δ increased. The NO-TPD results revealed that NO could be activated much easier over the oxygen-deficient perovskite-like oxides than over the oxygen-excessive perovskite-like oxides, with the NdSrCuO 3.702 catalyst showing the best efficiency in activating NO molecules. Under the conditions of 1.0% NO/helium, 2800 hr -1 , and 600–900°C, the catalytic activity of NO decomposition followed the order of NdSrCuO 3.702 NdSrCu 0.8 Co 0.2 O 3.736 NdSrCu 0.6 Co 0.4 O 3.789 Sm 1.8 Ce 0.2 Cu 0.6 Co 0.4 O 4.187 Sm 1.8 Ce 0.2 Cu 0.8 Co 0.2 O 4.104 Sm 1.8 Ce 0.2 CuO 4.045 , in concord with the sequence of decreasing oxygen vacancy or oxygen excess density. Based on the results, we concluded that the higher oxygen vacancy density and the stronger Cu 3+ /Cu 2+ redox ability of NdSrCu 1-x Co x O 4-δ account for the easier activation of NO and consequently improve the catalytic activity of NO decomposition over the catalysts.     

哈尔滨市大气主要污染物浓度变化与城市发展因素影响分析研究

采用Daniel趋势检验法对哈尔滨市近年来SO2、NO2和PM10年均浓度变化趋势分析,并对城市总人口与经济、产业结构、民用汽车保有量和能源状况五个城市发展因素进行数据统计分析,用SPSS探究城市发展过程中影响大气污染的因素及相关性.结果表明:浓度变化趋势是SO2明显上升;NO2缓慢上升;PM10整体明显下降,但在2013年点突增至了0.119 mg/m3.SO2与NO2显著相关,相关系数为0.533.经统计,哈尔滨人口经济发展、产业结构调整较为缓慢,全市民用汽车保有量增加并未对NO2浓度影响显著,能源结构依然以煤为主,虽然能源强度提升,但也存在着煤质、散煤的问题.哈尔滨市各城市发展因素与污染物浓度关联度不显著.     

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.     

外源NO介导Cu~(2+)胁迫下番茄幼苗活性氧与内源NO代谢的研究

采用营养液培养方法,研究Cu~(2+)胁迫下外源一氧化氮(nitric oxide,NO)介导的番茄幼苗活性氧及NO代谢途径。结果表明:在Cu~(2+)胁迫下,番茄叶片和根系氧自由基含量增加,NO释放量以及硝酸还原酶(nitrate reductase,NR)和一氧化氮合酶(nitric oxide synthase,NOS)活性降低。外源NO能提高Cu~(2+)胁迫下番茄叶片NR和NOS活性,促进NO的产生,根系NOS活性及NO产量也同时上升。外源NO使精氨酸含量显著增加,而Hb(牛血红蛋白,NO清除剂)可部分抵消NO的促进作用,使Cu~(2+)+SNP+Hb处理下番茄精氨酸含量显著下降。可见,外源NO的加入可通过酶促和非酶促途径促进Cu~(2+)胁迫下NO的合成,介导NO信号调控网络,调节内源NO、精氮酸和活性氧代谢途径,从而缓解过多Cu~(2+)引起的氧化伤害。     

大气PM_（2.5）在线监测仪对SO_4~（2-）、NO_3~-和NH_4~＋的测定评价

通过两套大气细颗粒物（PM2.5）水溶性离子在线监测仪与蜂巢式固气分离器膜采样系统作对比,评估了在线监测仪器对主要水溶性组分SO24-、NO3-和NH4＋的测定结果.美国URG公司生产的在线连续监测分析系统（AIM URG-9000B）对NH4＋和NO3-的监测结果较好,但对SO24-的测定结果存在明显高估,其原因是AIM的平板溶蚀器系统无法完全去除大气中高浓度SO2,从而对SO24-的测定结果有干扰.为解决这一问题,进行了一系列实验,结果表明采用两个溶蚀器串联并用5 mmol.L-1H2O2＋5 mmol.L-1NaOH混合溶液作吸收液时,高浓度的SO2（甚至达到260μg.m-3）可以被完全吸收而对SO24-的测定结果不产生影响.由荷兰能源研究所（ECN）、Metrohm和Applikon共同研制的在线气体组分及气溶胶监测系统（MARGA,ADI2080）对NH4＋和SO24-的监测结果较好,可以满足实验要求;但NO3-的测定结果偏高,其准确性需作进一步评估.新型监测仪器在不同大气环境中投入使用前需进行对比测试,以确定其准确性和精确性.     

Selective reduction of NO by photo-SCR with ammonia in an annular fixed-film photoreactor

Gaseous NO was photocatalytically reduced at room temperature by photo-assisted selective catalytic reduction (photo-SCR) with ammonia over TiO₂ in this study. NO reduction efficiency and N₂ selectivity were determined from gases composition at the outlet stream of photoreactor. Effect of operating conditions, e.g. light intensity and inlet concentrations of ammonia and oxygen, on the NO reduction efficiency and N₂ selectivity were discussed to determine the feasible operating condition for photocatalytic reduction of NO. Experimental results showed that selective catalytic reduction of NO with ammonia over TiO₂ in the presence of oxygen was a spontaneous reaction in dark. The photoirradiation on the TiO₂ surface caused remarkable photocatalytic reduction of NO to form N₂, NO₂, and N₂O under 254 nm UV illuminations, while almost 90% of N₂ selectivity was achieved in this study. The ammonia and oxygen molecules played the roles of reductant and oxidant for NO reduction and active sites regeneration, respectively. The reduction of NO was found to be increased with the increase of inlet ammonia and oxygen concentrations until specific concentrations because of the limited active sites on the surface of TiO₂. The kinetic model proposed in this study can be used to reasonably describe the reaction mechanism of photo-SCR.     

2006─2010年环保重点城市主要污染物浓度变化特征

利用2006─2010年全国环保重点城市的空气质量日报数据,分析了大气ρ(SO2)、ρ(NO2)和ρ(PM10)的变化特征. 结果表明:从年际变化看,ρ(SO2)和ρ(PM10)呈下降趋势,ρ(NO2)变化不显著.从季节变化看,ρ(SO2)、ρ(NO2)和ρ(PM10)均呈冬季高、夏季低的特征.从浓度谱分布看,全国大气中ρ(SO2)、ρ(NO2)和ρ(PM10)分别集中在0～0.150、0～0.100和0～0.250 mg/m3范围内,ρ(SO2)和ρ(PM10)谱峰区间逐渐向低浓度范围偏移,高浓度事件逐渐减少,表明SO2和PM10污染得到较明显的控制,而ρ(NO2)谱峰变化不大.从浓度变化看,山西ρ(SO2)、ρ(NO2)和ρ(PM10)下降最明显,年变化率分别为-11.2、-3.6和-14.2 μg/m3;青海ρ(SO2)、山东ρ(NO2)和ρ(PM10)的上升趋势最明显,年变化率分别为4.4、2.7和4.5 μg/m3.      

利用SCIAMACHY遥感资料研究我国NO2柱浓度及其时空分布

利用SCIAMACHYENVISAT 2003—2009年月均观测数据,结合1∶4 000 000行政区划图,得到了近7 a来我国城市级别NO₂柱浓度的时空分布和变化趋势,并采用Seasonal Mann-Kendall非参数检验方法对各城市的变化趋势进行了显著性分析. 结果表明:我国NO₂分布东高西低,NO₂柱浓度高值区主要分布在京津冀及环渤海区域、长江三角洲北部及广东省等地区. 近7 a来我国北部和中部地区的NO₂增长趋势显著,NO₂柱浓度平均值最高和增速最快的前20个城市主要分布在江苏、山东和安徽等省的二级城市郊县和小城市. 与统计年鉴工业废气排放数据的比较表明,工业废气排放与NO₂柱浓度及其时空分布具有较好的一致性. 这种新的NO₂污染格局应该引起重视并采取有针对性的污染监管措施.      

NO在分子筛ZSM-5催化剂上催化氧化动力学研究

研究了常温下NO在疏水型高硅分子筛ZSM-5上的氧化反应. 结果发现,NO在分子筛ZSM-5表面氧化的同时,伴随着明显的吸附过程,待吸附饱和后释放出NO2.相比于活性炭,高硅分子筛ZSM-5上NO氧化受水汽影响较小,303K饱和湿气下,NO稳态转化率只比干气下降低6%.在排除内、外扩散影响的条件下,于等温积分反应器中研究了稳定阶段NO氧化的本征动力学,根据不同温度下X~W/FA0及NO分压数据,计算了反应速率,建立简化的动力学模型并获得了反应速率方程,结果表明其拟合复相关系数较高.     

南充市城市空气质量变化及达标分析

为了掌握南充市近年来城市空气质量变化及其达标情况,对南充市城区2008～2012年SO2、NO2和PM10的质量浓度数据进行统计分析,并计算各个站点的空气污染指数和空气质量指数。结果表明,3种污染物浓度值都有明显的下降趋势,S02浓度在0．002～0．052mg／m^3之间变化;N02浓度值从0．042mg／m^3下降到0．029mg／m^3;PM10浓度在0．060～0．063mg／m^3之间波动。南充市空气质量冬季较差,夏季较好。在5个监测点中,炼油厂空气质量最差,优良率为92．9％（85．1％）;高坪空气质量最好,优良率为99．1％（98．3％）。相关性分析表明,南充市空气污染源主要是工业燃煤和机动车尾气。