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-14.2μg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4.5μgm3.     

Adsorption characteristics and mechanism of Cr （Ⅵ） on chitoan-yttrium porous microsphere

以壳聚糖和Y2（OH）5NO3为原料通过乳液交联法制备了壳聚糖-钇（Ch—Y）复合微球,通过扫描电镜、透射电镜、X射线衍射、红外光谱等方法对其表面形貌、结构进行了表征.探讨了溶液的pH值、反应时间、投加量、离子初始浓度对其吸附性能的影响.研究结果表明,壳聚糖-钇（Ch—Y）复合微球在pH值为3的酸性环境中对Cr（Ⅵ）保持了较高的吸附能力,吸附容量为52.39mg·g-1,其吸附行为符合Langmuir吸附等温模型;通过吸附机理的研究,发现壳聚糖-钇（Ch—Y）对Cr（Ⅵ）吸附是化学吸附静电吸附协同氧化Cr（Ⅵ）离子作用来实现的.     

利用SCIAMACHY遥感资料研究我国NO2柱 浓度及其时空分布

利用SCIAMACHY/ENVISAT 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.     

Effect of CeO2 and Al2O3 on the activity of Pd/Co_3O_4/cordierite catalyst in the three-way catalysis reactions (CO/NO/CnHm)

The present article studies the effect of CeO₂ and Al₂O₃ on the activity of Pd/Co₃O₄/cordierite catalyst in conversion of NO, CO, C_nH_m. The catalysts were characterized by temperature programmed reduction with hydrogen, X-ray diffraction, X-ray photoelectron spectroscopy and transmission electron microscopy. It is shown that the effect of CeO₂ on the properties of Pd/Co₃O₄/cordierite catalyst depends on preparation method. The catalyst obtained by co-deposition of cerium and cobalt oxides has higher activity in CO oxidation (CO + O₂ and CO + NO) and total hexane oxidation (C₆H₁₄ + O₂). Such phenomenon is probably caused by more than stoichiometric amount of formed oxygen vacancies, an increase in both mobility of surface oxygen and dispersity of components in the catalytic composition. It is demonstrated that CeO₂ addition promotes the SO₂ resistance of Pd/Co₃O₄/cordierite. The second support decreases the activity of Pd/Co₃O₄/cordierite catalyst in the reactions of CO and C₆H₁₄ with oxygen because of CoAl₂O₄ formation.     

Novel Co-Mg-Al-Ti-O catalyst derived from hydrotalcite-like compound for NO storage/decomposition

Catalysts of Co_1.5Mg_1.5/Al_0.9Ti_0.1O and Co_1.5Mg_1.5/AlO were successfully prepared by calcinations of corresponding hydrotalcite-like compounds at 800℃ for 4 hr. The derived oxides were of spinel phase and a small quantity of Ti substitution did not change the crystal purity. Their catalytic performance for the NO storage/decomposition was investigated. Ti incorporation enhanced the NO decomposition activity while has an opposite effect on the storage capacity of catalyst. In situ FT-IR spectra of the catalysts showed that the final adsorption species on the catalysts was coordinated nitrates/nitrites. In addition, NO storage/decomposition mechanism has been discussed on the basis of these observations.     

FeⅡ(EDTA)络合协同RDB去除NO废气效能及过程分析

为进一步提高一氧化氮(NO)的去除效率,在新型生物转鼓反应器(rotating drum biofilter,RDB)中,以FeⅡ(EDTA)络合协同RDB生物转鼓的耦合技术强化难水溶性NO的气液传质速率,提高生物还原效能为目标进行了研究.结果表明,适量FeⅡ(EDTA)被添加到RDB底部营养液后,能迅速吸收气相中的NO并生成FeⅡ(EDTA)-NO络合物,进而可通过反硝化实现同步脱氮和络合剂再生.在转速0.5 r.min-1、空床停留时间(EBRT)57.7 s、温度30℃、pH 7～8的实验条件下,RDB的净化效能随络合剂的投加而显著改善;FeⅡ(EDTA)质量浓度从0增至500 mg.L-1后,NO去除率从61.1%提高到97.6%,去除负荷从16.2 g.(m3.h)-1上升到26.7 g.(m3.h)-1.分析了FeⅡ(EDTA)络合协同净化NO的反应过程,建立了NO净化效率与FeⅡ(EDTA)添加浓度的关联方程,可较好地拟合实验数据.     

胶州湾及邻近海域表层海水中一氧化氮浓度分布及其影响因素探讨

2011年2～3月利用化学发光法对胶州湾及邻近海域表层海水中一氧化氮(NO)浓度进行了监测.结合水文、化学和生物等要素的同步观测资料,对该海域NO浓度分布及其影响因素进行了探讨.结果表明,胶州湾内表层海水中NO浓度为0.080～0.493 nmol.L-1,平均值为(0.292±0.146)nmol.L-1,胶州湾外NO浓度为未检出～0.435 nmol.L-1,平均值为(0.160±0.130)nmol.L-1.总体来说,胶州湾表层海水中NO浓度呈现出自湾内向湾外递降的分布趋势,陆地径流和人为活动可能对NO浓度的分布造成一定程度的影响.胶州湾及邻近海域表层海水中NO浓度比开阔大洋高1个数量级.周日变化研究表明,NO浓度具有一定的变化特征,最大值出现在15:00,这可能主要受光照的影响.影响NO浓度分布的因素比较复杂,可能主要受亚硝酸盐、光强和pH等因素的影响.结果表明,2011年春季胶州湾及邻近海域表层海水是大气NO的源,通量约为1.09×10-15 mol.(cm2.s)-1.     

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.     

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.     

活性焦脱硫脱硝的机理研究

采用质谱仪在线检测的方法,研究了不同组成的模拟烟气在活性焦上的吸附行为;并应用SEM、FT-IR、XPS、BET等手段表征了活性焦的结构性质。结果表明,活性焦脱硫脱硝性能与活性焦的孔隙结构和表面化学特性密切相关,孔容是决定污染物初期脱除率的主要因素;表面官能团则在污染物的化学吸附上发挥着重要作用,是吸附、催化的活化中心;二氧化硫较一氧化氮优先吸附在活性焦上;烟气中氧气或水蒸汽的单独存在对脱硫脱硝均不会有明显的影响,当烟气中同时存在氧气和水蒸汽时,活性焦的脱硫脱硝效果可明显改善;氨的存在既可将一氧化氮还原为氮气,又能增强活性焦脱除二氧化硫的效果。