Effect of pretreatment on Pd/Al2O3 catalyst for catalytic oxidation of o-xylene at low temperature

The effect of pretreatment on Pd/Al₂O₃ catalysts for the catalytic oxidation of o-xylene at low temperature was studied by changing the pretreatment and testing conditions. The fresh and pretreated Pd/Al₂O₃ catalysts were characterized by transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD). The results showed that the pretreatment dramatically changed the Pd/PdO ratio and then significantly affected the Pd/Al₂O₃ activity; while the pretreatment had not much influence on Pd particle size. The Pd/Al₂O₃ pre-reduced at 300℃/400℃, which has fully reduced Pd species, showed the highest activity; while the fresh Pd/Al₂O₃, which has fully oxidized Pd species, presented the worst performance, indicating the Pd chemical state plays an important role in the catalytic activity for the o-xylene oxidation. It is concluded that metallic Pd is the active species on the Pd/Al₂O₃ catalyst for the catalytic oxidation of o-xylene at low temperature.     

上海市秋季大气VOCs对二次有机气溶胶的生成贡献及来源研究

2011年9月1日～11月21日在上海市城区对大气中颗粒物质量浓度和挥发性有机物体积分数进行了在线连续观测.期间共出现4次大气污染过程:PD1(9月20～23日)、PD2(10月5～9日)、PD3(10月13～18日)、PD4(11月10～14日).本测点大气PM2.5的平均浓度分别为(45±16)、(76±46)、(57±36)和(122±92)μg·m-3,VOCs的体积分数分别为(30.87±30.77)×10-9、(32.09±30.69)×10-9、(34.04±28.13)×10-9和(44.27±31.58)×10-9;烷烃、烯烃、芳香烃的体积分数分别占TVOC的53.58%、27.89%、10.96%;用OH消耗速率(LOH)和臭氧生成潜势(OFP)评估了VOCs大气化学反应活性.结果表明,烯烃和芳香烃是本测点秋季大气VOCs中对LOH和OFP贡献最大的关键活性组分.利用气溶胶生成系数FAC和OC/EC比值法估算上海市SOA的生成潜势,两种方法得出的SOA浓度值分别为1.43μg·m-3和4.54μg·m-3,比值法明显较高,这主要是本研究测得的SOA前体物偏少所致.其中芳香烃不仅是OFP的关键活性组分,而且也是SOA的重要前体物.应用PMF模型对VOCs进行源解析,确定了秋季上海市大气中VOCs的6个主要的污染来源,分别为汽车尾气(24.30%)、不完全燃烧(17.39%)、燃料挥发(16.01%)、LPG/NG泄露(15.21%)、石油化工(14.00%)、涂料/溶剂的使用(13.09%).汽车尾气和涂料/溶剂等源排放的VOCs中富含OFP关键活性组分和SOA重要前体物,它们对VOCs浓度的贡献占TVOC的37.39%,这些排放源应列入未来上海市大气复合污染控制的优先范围.     

Compilation of reaction kinetics parameters determined in the Key Development Project for Air Pollution Formation Mechanism and Control Technologies in China

A compilation of new advances made in the research field of laboratory reaction kinetics in China's Key Development Project for Air Pollution Formation Mechanism and Control Technologies was presented. These advances are grouped into six broad, interrelated categories, including volatile organic compound (VOC) oxidation, secondary organic aerosol (SOA) formation, new particle formation (NPF) and gas-particle partitioning, ozone chemistry, model parameters, and secondary inorganic aerosol (SIA) formation, highlighting the laboratory work done by Chinese researchers. For smog chamber applications, the current knowledge gained from laboratory studies is reviewed, with emphasis on summarizing the oxidation mechanisms of long-chain alkanes, aromatics, alkenes, aldehydes/ketones in the atmosphere, SOA formation from anthropogenic emission sources, and oxidation of aromatics, isoprene, and limonene, as well as SIA formation. For flow tube applications, atmospheric oxidation mechanisms of toluene and methacrolein, SOA formation from limonene oxidation by ozone, gas-particle partitioning of peroxides, and sulfuric acid-water (H₂SO₄-H₂O) binary nucleation, methanesulfonic acid-water (MSA-H₂O) binary nucleation, and sulfuric acid-ammonia-water (H₂SO₄-NH₃-H₂O) ternary nucleation are discussed.     

精细化工园区工艺过程VOCs产生量核算方法

挥发性有机物(VOCs)是目前影响我国大气环境质量的关键污染物之一.工业源已成为中国最主要的VOCs排放源,其中化工行业的VOCs排放贡献尤为突出.化工企业已经大量集聚于化工园区内,因此化工园区的VOCs控制至关重要.本研究以典型精细化工园区——杭州湾上虞经济技术开发区为例,通过分析精细化工生产模式及VOCs产生原理,建立了基于工艺过程的VOCs产生量核算方法,对投料、升温、化学反应产生气体带出、清洗吹扫、真空抽气、泄压释放和蒸发逸散等生产过程的VOCs产生量进行了核算;同时运用化工流程模拟软件Aspen进行了前述生产过程VOCs产生量估算;运用2种方法对案例园区14种典型产品各工艺过程的VOCs产生特征进行了分析,并对两种方法的核算结果进行了比较.结果发现,除泄压释放环节外,两种方法的结果差异在±22%以内.进而对该园区典型企业的代表性产品进行计算方法应用,可得到精准的VOCs产生关键环节和组分.案例研究表明这一方法在定量的化工生产参数支持下估算精细化工工艺过程的VOCs产生量具有较好的精准性、简便性和可靠性.     

Ethylenediurea (EDU) pretreatment alleviated the adverse effects of elevated O3 on Populus alba “Berolinensis” in an urban area

Ethylenediurea(EDU)has been used as a chemical protectant against ozone(03).However,its protective effect and physiological mechanisms are still uncertain.The present study aimed to investigate the changes of foliar visible injury,physiological characteristics and emission rates of volatile organic compounds(VOCs)in one-year-old Populus alba"Berolinensis"saplings pretreated with EDU and exposed to elevated O_3(EO,120μg/m~3).The results showed that foliar visible injury symptoms under EO were significantly alleviated in plants with EDU application(p0.05).Under EO,net photosynthetic rate,the maximum photochemical efficiency of PSII and the photochemical efficiency of PSII of plants pretreated with 300 and600 mg/L EDU were similar to unexposed controls and significantly higher compared to EOstressed plants without EDU pretreatment,respectively.Malondialdehyde content was highest in EO without EDU and decreased significantly by 14.9%and 21.3%with 300 and600 mg/L EDU pretreatment,respectively.EDU pretreatment alone increased superoxide dismutase activity by 10-fold in unexposed plants with further increases of 88.4%and 37.5%in EO plants pretreated with 300 and 600 mg/L EDU pretreatment,respectively(p0.05).Abscisic acid content declined under EO relative to unexposed controls with the effect partially reversed by EDU pretreatments.Similarly,VOCs emission rate declined under EO relative to unexposed plants with a recovery of emission rate observed with 300 and 600 mg/L EDU pretreatment.These findings provided significant evidence that EDU exerted a beneficial effect and protection on the tested plants against 03 stress.     

Atmospheric photochemistry and secondary aerosol formation of urban air in Lyon, France

Photochemical aging of volatile organic compounds (VOCs) in the atmosphere is an important source of secondary organic aerosol (SOA). To evaluate the formation potential of SOA at an urban site in Lyon (France), an outdoor experiment using a Potential Aerosol Mass (PAM) oxidation flow reactor (OFR) was conducted throughout entire days during January-February 2017. Diurnal variation of SOA formations and their correlation with OH radical exposure (OHexp), ambient pollutants (VOCs and particulate matters, PM), Relative Humidity (RH), and temperature were explored in this study. Ambient urban air was exposed to high concentration of OH radicals with OHexp in range of (0.2–1.2)×10¹² molecule/(cm³?sec), corresponding to several days to weeks of equivalent atmospheric photochemical aging. The results informed that urban air at Lyon has high potency to contribute to SOA, and these SOA productions were favored from OH radical photochemical oxidation rather than via ozonolysis. Maximum SOA formation (36 µg/m³) was obtained at OHexp of about 7.4 × 10¹¹molecule/(cm³?sec), equivalent to approximately 5 days of atmospheric oxidation. The correlation between SOA formation and ambient environment conditions (RH & temperature, VOCs and PM) was observed. It was the first time to estimate SOA formation potential from ambient air over a long period in urban environment of Lyon.     

Characteristics, sources and health risks assessment of VOCs in Zhengzhou, China during haze pollution season

Zhengzhou is one of the most haze-polluted cities in Central China with high organic carbon emission, which accounts for 15%-20% of particulate matter (PM2.5) in winter and causes significantly adverse health effects. Volatile organic compounds (VOCs) are the precursors of secondary PM2.5 and O3 formation. An investigation of characteristics, sources and health risks assessment of VOCs was carried out at the urban area of Zhengzhou from 1st to 31st December, 2019. The mean concentrations of total detected VOCs were 48.8 ± 23.0 ppbv. Alkanes (22.0 ± 10.4 ppbv), halocarbons (8.1 ± 3.9 ppbv) and aromatics (6.5 ± 3.9 ppbv) were the predominant VOC species, followed by alkenes (5.1 ± 3.3 ppbv), oxygenated VOCs (3.6 ± 1.8 ppbv), alkyne (3.5 ± 1.9, ppbv) and sulfide (0.5 ± 0.9 ppbv). The Positive Matrix Factorization model was used to identify and apportion VOCs sources. Five major sources of VOCs were identified as vehicular exhaust, industrial processes, combustion, fuel evaporation, and solvent use. The carcinogenic and non-carcinogenic risk values of species were calculated. The carcinogenic and non-carcinogenic risks of almost all air toxics increased during haze days. The total non-carcinogenic risks exceeded the acceptable ranges. Most VOC species posed no non-carcinogenic risk during three haze events. The carcinogenic risks of chloroform, 1,2-dichloroethane, 1,2-dibromoethane, benzyl chloride, hexachloro-1,3-butadiene, benzene and naphthalene were above the acceptable level (1.0 × 10?6) but below the tolerable risk level (1.0 × 10?4). Industrial emission was the major contributor to non-carcinogenic, and solvent use was the major contributor to carcinogenic risks.     

中国涂料应用过程挥发性有机物的排放计算及未来发展趋势预测

基于各行业的涂料当前消费量和未来消费预测,以及各行业使用涂料的挥发性有机物(VOC)含量,建立了分省、分行业、分化学组分的排放清单模型,获得2005~2020年中国涂料应用过程的VOC排放清单.结果表明,2005年,我国涂料应用共排放VOC约1 883 kt,以苯系物、醇、酯、醚、酮5类化合物为主,平均增量反应活性指标(以O3/VOC计)约为3.6 g/kg,其中31%的VOC为有毒物质.如不加强控制,到2020年该部门VOC排放量将激增至5 673 kt;因此,国家应及时开展其排放控制行动.排放控制情景分析表明,通过提高涂料产品品质达到发达国家上世纪末水平,且要求新建规模企业安装有机废气末端处理设施,2020年该部门VOC排放量可控制在3 519 kt;通过进一步将建筑涂料和木器涂料改进到当前欧美发达国家先进水平,且规模企业均安装有机废气末端处理设施,2020年该部门VOC排放量有可能控制在2 243 kt.2种控制情景下所排放VOC的化学毒性和大气氧化活性均得到了有效改善.     

北京某小学室内外VOC浓度及有毒害物种识别

采用美国EPA推荐的TO14/15方法定量分析了北京市某小学室内外夏季观测的空气样品,得到82种挥发性有机物（VOCs）的浓度水平及组成特征,对其中可能危害儿童健康的有毒有害物质进行了识别.结果表明,室内总VOCs浓度高于室外,烷烃是含量最丰富物种,平均占室内外空气中定量VOCs总浓度的32.8%.室内外VOCs组成相似,异戊烷、苯、甲苯、丙醛、丙烯和二氯甲烷为浓度优势物种,受到室外源的影响较大,室内的对二氯苯、环己烷及间二氯苯较为特征,前2种物质室内/室外浓度比例平均值分别为65.8和10.5,间二氯苯室内平均浓度为2.02×10^-9（体积分数）,而室外浓度低于检测限,这3种物质可能来自室内源. 1, 3-丁二烯、氯乙烯、苯和氯甲烷4种物质在学校室内、室外及儿童家中都超过1×10^-6的癌症风险值,平均风险值分别为1.3×10^-5、 6.4×10^-6、 5.1×10^-6和3.3×10^-6,小学室外、室内及儿童家中的累积癌症风险超过1×10^-6的癌症风险值24～39倍.丙烯醛未确认具有致癌性,但具有毒有害性,在室内外及儿童家中超过基准浓度13～72倍.