Effects of calcination temperature on physicochemical property and activity of CuSO4/TiO2 ammonia-selective catalytic reduction catalysts

CuSO_4/TiO_2 catalysts with high catalytic activity and excellent resistant to SO_2 and H_2 O,were thought to be promising catalysts used in Selective catalytic reduction of nitrogen oxides by NH_3.The performance of catalysts is largely affected by calcination temperature.Here,effects of calcination temperature on physicochemical property and catalytic activity of CuSO_4/TiO_2 catalysts were investigated in depth.Catalyst samples calcined at different temperatures were prepared first and then physicochemical properties of the catalyst were characterized by N2 adsorption-desorption,X-ray diffraction,thermogravimetric analysis,Raman spectra,Fourier-transform infrared spectroscopy,X-ray photoelectron spectroscopy,temperature-pro grammed desorption of NH_3,temperature-programmed reduction of H_2 and in situ diffuse reflectance infrared Fourier transform spectroscopy.Results revealed that high calcination temperature had three main effects on the catalyst.First,sintering and anatase transform into rutile with increase of calcination temperature,causing a decrement of specific surface area.Second,decomposition of CuSO_4 under higher calcination temperature,resulting in disappears of Br(?)nsted acid sites(S-OH),which had an adverse effect on surface acidity.Third,CuO from the decomposition of CuSO_4 changed surface reducibility of the catalyst and favored the process of NH_3 oxidation to nitrogen oxides(NO_x).Thus,catalytic activity of the catalyst calcined under high temperatures(≥600℃) decreased largely.     

Will polycentric cities cause more CO2 emissions? A case study of 232 Chinese cities

From 2000 to 2010 China experienced rapid economic development and urbanization. Many cities in economically developed areas have developed from a single-center status to polycentricity. In this study, we used exploratory spatial data analysis (ESDA) to identify the population centers, which identified 232 cities in China as having urban centers. COMP was used to represent urban agglomeration, and POLYD (representing how far is the city's sub-centers to the main center), POLYC (representing the number of a city's centers), and POLYP (representing the population distributed between the main center and the sub-centers) were used to indicate urban polycentricity. Night light data were used to determine the CO₂ emissions from various cities in China. A mixed model was used to study the impact of urban aggregation and polycentric data on the CO₂ emission efficiency in 2000 and 2010. The study found that cities with higher compactness were distributed in coastal areas, and the cities with higher multicentricity were distributed in the Yangtze River Delta and Shandong Province. The more compact the city was, the less conducive it was to improving CO₂ emission efficiency. Polycentric development of the city was conducive to improving the CO₂ emission efficiency, but the number of urban centers had no significant relationship with the CO₂ emission efficiency. Our research showed that the compactness and multicentricity of the city had an impact on the CO₂ emission efficiency and provided some planning suggestions for the low carbon development of the city.     

Ozone pollution characteristics and sensitivity analysis using an observation-based model in Nanjing, Yangtze River Delta Region of China

Ground-level ozone (O₃) has become a critical pollutant impeding air quality improvement in Yangtze River Delta region of China. In this study, we present O₃ pollution characteristics based on one-year online measurements during 2016 at an urban site in Nanjing, Jiangsu Province. Then, the sensitivity of O₃ to its precursors during 2 O₃ pollution episodes in August was analyzed using a box model based on observation (OBM). The relative incremental reactivity (RIR) of hydrocarbons was larger than other precursors, suggesting that hydrocarbons played the dominant role in O₃ formation. The RIR values for NO_X ranged from –0.41%/% to 0.19%/%. The O₃ sensitivity was also analyzed based on relationship of simulated O₃ production rates with reductions of VOC and NO_X derived from scenario analyses. Simulation results illustrate that O₃ formation was between VOCs-limited and transition regime. Xylenes and light alkenes were found to be key species in O₃ formation according to RIR values, and their sources were determined using the Positive Matrix Factorization (PMF) model. Paints and solvent use was the largest contributor to xylenes (54%), while petrochemical industry was the most important source to propene (82%). Discussions on VOCs and NO_X reduction schemes suggest that the 5% O₃ control goal can be achieved by reducing VOCs by 20%. To obtain 10% O₃ control goal, VOCs need to be reduced by 30% with VOCs/NO_X larger than 3:1.     

Investigation to meet China II emission legislation for marine diesel engine with diesel methanol compound combustion technology

In order to reduce the pollutant emission and alleviate the pressure of petroleum resources shortage and greenhouse gas emission at the same time, the use of clean and renewable alternative fuel for marine engines is a promising option. In this study, a marine diesel engine, which was modified to run in diesel methanol compound combustion (DMCC) mode, was investigated. After the diesel injection parameters were calibrated, and combined with a sample after-treatment device DOC (diesel oxidation catalyst), the engine could meet the requirements of China II legislation. The overall MSP (methanol substitute percent) reached 54.1%. The value of each pollutant emission was much lower than that in China II emission legislation, and there was almost no methanol and formaldehyde emissions. When methanol was injected into the inlet manifold, the intake air temperature decreased a lot, as well as the exhaust gas temperature, which were beneficial to increase engine thermal efficiency and improve engine room environment. Compared with the engine running in pure diesel mode, when the engine ran in diesel/methanol dual fuel mode, the combustion phase was advanced, and the combustion duration became shorter. Therefore, the engine thermal efficiency increased, and fuel consumption decreased significantly.     

Photodegradation of Hexafluoropropylene Oxide Trimer Acid under UV Irradiation

As a novel alternative to traditional perfluoroalkyl substances (PFASs), including perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS), hexafluoroproplyene oxide trimer acid (HFPO-TA) has been detected worldwide in surface water. Moreover, recent researches have demonstrated that HFPO-TA has stronger bioaccumulation potential and higher hepatotoxicity than PFOA. To treat these contaminants e.g. PFOA and PFOS, some photochemical techniques by adding exogenous substances had been reported. However, there is still no report for the behavior of HFPO-TA itself under direct UV irradiation. The current study investigated the photo-transformation of HFPO-TA under UV irradiation in aqueous solution. After 72 hr photoreaction, 75% degradation ratio and 25% defluorination ratio were achieved under ambient condition. Reducing active species, i.e., hydrated electrons and active hydrogen atoms, generated from water splitting played dominant roles in degradation of HFPO-TA, which was confirmed by different effects of reaction atmospheres and quenching experiments. A possible degradation pathway was proposed based on the products identification and theoretical calculations. In general, HFPO-TA would be transformed into shorter-chain PFASs, including hexafluoropropylene oxide dimer acid (HFPO-DA), perfluoropropionic acid (PFA) and trifluoroacetate (TFA). This research provides basic information for HFPO-TA photodegradation process and is essential to develop novel remediation techniques for HFPO-TA and other alternatives with similar structures.     

基于TMVOC的地下水位波动带苯系物迁移转化模拟

为探究水位波动情况下苯系物的迁移转化规律,提高石油污染场地地下水污染治理精度,以西北某傍河石化场地为研究对象,基于TMVOC模型对特征污染物苯系物开展泄漏模拟,通过情景模拟比较水位波动对苯系物迁移转化的影响,并从污染分布、相间转化等方面,解析地下水位稳定和波动状态下苯系物迁移转化过程差异.结果表明:①TMVOC模型较好地模拟了水位波动状态下苯系物迁移转化过程.②相较于水位稳定状态下,水位波动作用下苯系物污染深度增加0.5 m,污染面积增加25%,总质量增加12 kg.③水位稳定和波动状态下苯系物"气-液-NAPL（Non-Aqueous Phase Liquids）相"占比分别为0.17%、2.03%、97.8%和0.04%、3.69%、96.27%.④NAPL相苯系物饱和度分布与苯系物质量分布呈正相关,水位波动造成NAPL相初始饱和度降低,且初始水位面以下NAPL相饱和度升高.⑤对于苯而言,水位波动状态下非饱和带中苯在液相中的质量是水位稳定状态下的1.11倍,饱和带为10.15倍.研究显示,水位波动显著地影响了苯系物的迁移转化过程,促进了苯系物的溶解,并使更多的苯系物残留在地下介质中.      

污泥腐殖酸对Cd2+的吸附特性

为了促进污水处理厂剩余污泥的资源化利用,探索S-HA（sludge-based humic acid, 污泥腐殖酸）对溶液中重金属Cd2+的吸附特性.采用国际腐殖酸协会（IHSS）推荐的方法提取S-HA,通过元素分析、FT-IR（傅里叶红外光谱分析）和SEM-EDS（外观形态分析）等方法,考察溶液pH和共存阳离子对吸附过程的影响,并对吸附过程分别进行了吸附动力学模型、等温吸附模型和吸附热力学模型拟合,同时通过对比S-HA吸附前后的红外光谱和扫描电镜-能谱图片,探索S-HA对Cd2+的吸附机制.结果表明:①S-HA表面呈松散的簇团状,含有大量的羧基、醇羟基和酚羟基等含氧官能团,芳香度较高,含有较多的脂肪链结构;S-HA在吸附水中Cd2+的过程中,Cd2+与S-HA表面上的酚羟基、羧基等官能团发生了络合作用.②S-HA对Cd2+的吸附量随溶液pH升高而增加,溶液中Na+、NH₄+和Ca2+等共存阳离子的存在不利于S-HA对Cd2+的吸附,其中Ca2+的存在对S-HA吸附Cd2+影响最大.③S-HA对Cd2+的吸附由快吸附、慢吸附和吸附平衡3个阶段组成,吸附平衡时间为12 h;吸附过程符合准二级动力学模型,其整体吸附速度由液膜扩散和颗粒内扩散共同控制;吸附等温线符合Freundlich等温吸附模型,25℃下的最大吸附量为19.29 mg/g,Cd2+在S-HA上的吸附是自发吸热反应.研究显示:污水处理厂剩余污泥提取的S-HA对Cd2+具有较好的吸附效果;S-HA对Cd2+的吸附过程同时存在着物理吸附和化学吸附;高pH对S-HA吸附Cd2+有促进作用,而高离子强度对S-HA吸附Cd2+有抑制作用.      

中温期和高温期污泥堆肥物料中典型氟喹诺酮类抗生素去除的影响因素

污泥处理后土地利用是氟喹诺酮类抗生素（fluoroquinolones,FQs）进入土壤环境的主要途径之一。好氧堆肥具有高效去除FQs、削减其环境风险的潜力,但目前对于堆肥过程中各阶段物料FQs去除影响因素的研究仍较少。该研究在制备典型城市污泥好氧堆肥获取其中温期、高温期物料的基础上,向堆肥中添加2种典型的FQs（ofloxacin,OFL;norfloxacin,NOR）,在不同FQs初始浓度（0,2.5,5.0 mg/kg）、含水率（50%、60%、70%）和通风量（0,15 mL/min）条件下,进行56 d的抗生素去除试验,控制各堆肥物料在其对应堆肥阶段温度（中温期物料,35℃;高温期物料,55℃）。结果表明:2种物料中FQs去除率均随着初始浓度上升而逐步下降,中温期物料最佳初始FQs浓度分别为5.0 mg/kg（OFL）、2.5 mg/kg（NOR）,对于高温期物料两者均为2.5 mg/kg;中温期物料中,FQs去除率随含水率增加先上升后下降,最佳含水率均为60%,高温期物料中,FQs去除率随含水率升高而逐步增加;2种物料中,通风量15 mL/min下的FQs去除率均明显高于未通风处理。与中温期物料对比,高温期物料中FQs去除过程需要较低的初始浓度和较高的含水率;在2种物料中,充分通风下FQs的去除率均明显高于未通风处理。     

含油污泥处理技术进展

石油工业生产的特征固体废物——含油污泥,是一种由石油烃、水、固体颗粒物和其他物质（如重金属）组成的固态/半固态复合物,因毒性和易燃性被归入危险废物管理。我国含油污泥年产量高达500万t,其中含有15%~50%的石油烃。含油污泥的处理要兼顾无害化和资源化。基于其组成、性质和危害,介绍了含油污泥的油品资源化分离法（离心、溶剂萃取、热解）和无害化剩余含油残渣处理法（焚烧、固化、生物处理）等国内外常用的处理方法。大体上,含油污泥的处理思路为,首先预处理降低含水率、提高含油率,再经油品分离法回收含油污泥中的石油烃,最后无害化处理剩余含油残渣。讨论了各方法的特点以及国内外研究进展,提出了含油污泥处理技术的发展建议。     

Concentrations and chemical compositions of PM10 during hazy and non-hazy days in Beijing

In order to study the concentrations of major components,characteristics and comparison in hazy and non-hazy days of PM_(10) in Beijing,aerosol samples were collected at urban site in Beijing from December 29,2014 to January 22,2015.Heavy metals like Zn,Pb,Mn,Cu,As,V,Cr and Cd were deeply studied considering their toxic effects on human being;nine water-soluble inorganic ions(SO_4~(2-),NO_3~-,NH_4~+,Na~+,K~+,Cl~-,Ca~(2+) and Mg~(2+)) and carbon fractions(OC and EC) were also analyzed.The concentrations of heavy metals were 1.03–1.98 times higher in hazy days than those in non-hazy days,mainly due to biomass burning and coal burning.The trends in total heavy metals concentrations were basically consistent with the trends in PM concentrations except for two obvious periods(12.29–12.30;1.14–1.15);but when air masses accumulated locally or around Beijing,trends in PM concentrations and heavy metals were opposite.The proportion for NO_3~-/SO_4~(2-) indicated that mobile sources such as automobiles were important reasons for haze in Beijing.Correlation between OC and EC during non-hazy days was strong(R~2= 0.95) but it was low(R~2= 0.67) during hazy days,and large variations for OC/EC values occurred in hazy days.The calculated mass concentration of SOC is 2.58 μg/m~3,which only accounted for 10.1% of the OC concentration.When air masses from the far north-west,they decreased PM concentration in Beijing and they were relatively clean;however,those from the near east,south-east and south of the mainland increased PM concentration and they were dirty.