环境中全氟有机物的毒性、检测分析及降解

自全氟有机物广泛使用50多年以来,已经在世界范围内发现一定浓度的全氟有机物,各国研究人员针对该类物质特别是全氟辛酸(PFOA)、全氟辛烷基磺酸(PFOS)进行了一定的研究.介绍了该类物质的污染现状,阐述了全氟有机物的毒性、检测分析技术及降解技术,在此基础上提出了今后的研究方向.     

高能等离子体分解CO_2气体研究

为治理温室气体ＣＯ_２，本工作在低温常压条件下，利用超高压脉冲电晕放电产生的高能量（２０～５０ｅＶ）非平衡等离子体作用于ＣＯ_２气体分子，使ＣＯ_２分子化学结合键断裂，在定向化学反应作用下，将ＣＯ_２气体分解成单原子气体分子Ｏ_２和单质固体微粒Ｃ。ＣＯ_２分解率在９０％以上。     

新能源汽车需求市场培育的政策取向:供给侧抑或需求侧

政策支持是促进新能源汽车消费市场等商业化条件成熟的重要手段。近年来,中央和一些地方政府在新能源汽车需求市场培育的"供给侧"和"需求侧"都先后出台了相应的市场培育政策。"供给侧"和"需求侧"的政策功能与效果不完全相同,地方政府在选择和应用新能源汽车需求培育政策时面临着诸多困惑。论文尝试将基尼系数分解法引入到新能源汽车需求市场"供给侧"和"需求侧"政策实施效果的区域差异分析中,分析了我国培育新能源汽车消费市场培养"供给侧"和"需求侧"政策取向的分布情况以及现阶段政策取向所面临的困惑,应用我国新能源汽车试点推广城市数据开展了实证研究。结果表明,"供给侧"政策着力于改善新能源汽车消费市场供给体系的质量和效率,为需求市场持续发展提供驱动力量;"需求侧"政策着力于激发新能源汽车消费的积极性和购买能力,为需求市场持续发展提供拉动力量。"供给侧"和"需求侧"政策在不同收入水平区域试点城市中的实施效果存在差异,高收入区域试点城市"供给侧"和"需求侧"政策都有着明显效果,但是"供给侧"政策效果更为显著;中等收入区域试点城市"需求侧"政策效果十分显著,"供给侧"政策效果相对较弱;收入稍低区域试点城市则以"供给侧"政策效果更为显著,"需求侧"政策效果相对较弱。我国新能源汽车市场培育在"供给侧"和"需求侧"政策取向上应因地制宜,各有侧重点。     

Evaluation of thermal properties and process hazard of three ionic liquids through thermodynamic calculations and equilibrium methods

Industrial and new energy applications of ionic liquids (ILs) may have to be used at high temperatures conditions, such as in batteries and fuel applications, which may cause thermal hazards. However, there are few studies on the thermal hazards of ILs. To ensure the thermal safety of ILs processes, three commonly used ILs were selected for analysis: 1-butyl-3-methylimidazolium nitrate ([Bmim]NO₃), 1-butyl-2,3-dimethylimidazolium nitrate ([Bmmim]NO₃), and 1,3-dimethylimidazolium nitrate ([Mmim]NO₃). The process hazards under adiabatic conditions demonstrated that [Bmmim]NO₃ and [Mmim]NO₃ have extensive explosion hazards. The self-reaction characteristics determined by the isothermal test indicated that the ILs are nth reactions, and the thermal decomposition features were also determined by thermogravimetric analysis. The data were obtained with a nonlinear thermodynamic model and used to establish the basic thermal hazards of the three ILs. In addition, based on the thermal equilibrium theory, the critical safety parameters can be inferred. The effects of heat transfer in 25.0 g and 50.0 g containers were discussed. The results show that [Mmim]NO₃ will produce a thermal runaway reaction at a lower temperature (<100 °C) and has the shortest reaction time (<1 day), which means [Mmim]NO₃ is considered to be the most hazardous material among the three ILs studied.     

Decomposition of 2,2',4,4',5,5'-hexachlorobiphenyl with iron supported on an activated carbon from an ion-exchange resin

An activated carbon (AC) containing a high concentration (374 mg g⁻¹) of Fe was prepared by carbonization of an ion-exchange resin. To examine its chemical reactivity as a catalyst to decompose 2,2′,4,4′,5,5′-hexachlorobiphenyl (PCB-153), the decomposition parameters of temperature and time were varied under air or N₂. Decomposition at 350 °C was achieved within 15 min under air and 30 min under N₂, and the efficiency of PCB-153 decomposition was 99.7% and 98.0%, respectively. An analysis of inorganic chloride ions revealed that PCB-153 was mineralized effectively during the decomposition. The Brunauer-Emmett-Teller (BET) surface area and pore volume of the AC were measured to assess the adsorption capacity before and after the decomposition. The differences between decomposition under air and N₂ reflected the differences in the BET surface and pore volume measurements. A decomposition pathway was postulated, and the reactive characteristics of chlorine atoms loaded on the benzene rings followed the order of para > meta > ortho, which agrees with the calculated results from a density functional theory study.     

Decomposition and oxidation of sodium 3,5,6-trichloropyridin-2-ol in sub- and supercritical water

Sodium 3,5,6-trichloropyridin-2-ol (STCP) is a necessary precursor compound for the production of chlorpyrifos and triclopyr, which are extensively used as pesticide and herbicide, respectively. In the process of STCP production, however, large amount of wastewater containing STCP is discharged, which causes increasingly environmental concerns. Therefore, it is of great significance to develop a rapid and effective method for the disposal of containing STCP contaminants. In this work, the thermal decomposition of STCP in sub- and supercritical water was investigated using a continuous tubular reactor. While STCP was stable below 280 °C, it could be effectively decomposed at elevated temperature. FT-IR spectra of the decomposition products indicated that the pyridine ring structure in the STCP molecule was stable even at temperatures up to 400 °C. The decomposition reaction was mainly caused by the substitution of Cl groups in the STCP molecule with OH groups, resulting in polyhydroxylated pyridines as the major decomposition product. Moreover, high pressure favored the substitution reaction. To completely decompose STCP into non-toxic or low toxic compounds, supercritical water oxidation (SCWO) was employed to evaluate the oxidation of STCP using H₂O₂ as an oxidant. It was found that STCP could be completely oxidized to H₂O, CO₂ and corresponding inorganic ammonium salts with an oxidation rate of 99%.     

Application of human factors evaluation in engineering design and safe operation of dense phase ethylene treaters

Ethylene treaters are widely used in the petrochemical industry to remove impurities from ethylene feedstock imported from pipeline networks or storage caverns. The safety concerns of dense phase ethylene treaters due to the reactive and highly flammable nature of ethylene are well known and studied. Under certain conditions, ethylene may self-polymerize and decompose violently with heat release. Under other conditions, ethylene will auto-refrigerate, generating cold liquids that may cause potential brittle fracture hazards. Therefore, dense phase ethylene treaters present design challenges with the unique combination of high temperature decomposition and cold temperature brittle fracture hazards.Due to these safety concerns, it is important to select the appropriate engineering design options for dense phase ethylene treaters and the associated regeneration facilities. Totally automated treater regeneration systems add complexity and instrument maintenance requirements while manually operated systems rely heavily on operator training and procedures. Unfortunately, little or no information or design guidance is available from published research findings in the literature on the evaluation and risk assessment of current industrial design options and practices for dense phase ethylene treaters.This paper presents a systematic risk assessment method to evaluate the engineering design and safe operation options for dense phase ethylene treaters. The proposed risk assessment method integrates human factors task analysis into the traditional HAZOP, LOPA and fault tree analysis to allow evaluation of automated, manual and hybrid approaches with a goal of selecting and optimizing design options to ensure plant safety. This approach provides a realistic assessment of the operational risk and allows identification of fit-for-purpose risk reduction. Applying this systematic risk assessment approach, a simpler and more cost effective design solution can be justified, thereby avoiding the need for a high integrity protective system.     

Determinants of CO2 emissions in Brazil and Russia between 1992 and 2011: A decomposition analysis

This paper deals with the decomposition analysis of energy-related CO₂ emissions in Brazil and Russia from 1992 to 2011. The refined Laspeyres index (RLI) method applied and both aggregated and sectoral changes in CO₂ emissions decomposed. Brazil’s and Russia’s economies divided into three economic sectors including agriculture, industry and services. Impact of four main factors, such as economic activity, employment, energy intensity, and carbon intensity in CO₂ emissions changes were analyzed. The aggregated decomposition analysis revealed that Brazil is still far from a decoupling between economic growth and carbon dioxide emissions where Russia achieved a substantial decline in carbon emissions mainly due to the improved energy intensity. The empirical findings of sectoral decomposition analysis emphasized that the economic activity was the major CO₂ increasing factor in Brazil’s economic sectors. On the other hand the economic activity effect followed a reducing impact in Russia’s sectoral emissions until 2000. The structural changes between sectors and their impacts on CO₂ emissions were captured by employment effect. Energy intensity and carbon intensity effects underlined that environmental sustainability widely neglected in Brazil and Russia during the study period. The results yield important hints for energy planning and sustainable environment.     

Decomposition of Al13 promoted by salicylic acid under acidic condition: Mechanism study by differential mass spectrometry method and DFT calculation

Decomposition of the polycation Al₁₃O₄(OH)₂₄(H₂O)₁₂⁷⁺ (Al₁₃) promoted by ligand is a vital subject to advance our understanding of natural and artificial occurrence and evolution of aluminum ions, especially in the case of acidic condition that dissolved Al³⁺ species can be released from the Al-bearing substances. However, the microscopic pathway of synchronous proton-promoted and ligand-promoted decomposition process for Al₁₃ is still in the status of ambiguity. Herein, we applied differential mass spectrometry method and DFT calculation to study the initial detailed process of Al₁₃ decomposition under the presence of proton and salicylic acid (H₂Sal). Mass results showed that the mononuclear Al³⁺-H₂Sal complexes dominated the resulting Al species, whereas the monodentate complex Al₁₃HSal⁶⁺ was not observed in the spectra. The difference of decomposition levels between the ligand/Al ratio 0.2 and 0.5 cases revealed that proton and ligand performed synergistic effect in initial Al₁₃ decomposition process, and the proton transfer determined the ring closure efficiency. The ring closure reaction is the prerequisite for the collapse of Al₁₃ structure and detachment of the mononuclear complex. DFT calculations reveal that hydrogen bond plays an important role in inducing the formation of chelated complex accompanying proton transfer. Attachment of protons at the bridging OH⁻ can elongate and weaken the critical bond between targeted Al³⁺ and µ₄-O^2- resulting from delocalization of electron pairs in the oxygen atom. These results demonstrate the detailed mechanism of Al₁₃ composition promoted by ligand and proton, and provide significant understanding for further application and control of Al₁₃.     

无锡市碳排放的因素分解模型及实证分析

在计算无锡市2000~2011年二氧化碳排放量的基础上,采用对数平均权重Divisia分解法,建立无锡市人均碳排放的因素分解模型,定量分析能源结构、能源效率、经济发展情况等因素对无锡市人均碳排放的影响。结果显示经济发展对拉动无锡人均碳排放的贡献率呈指数增长趋势,相比之下,能源效率及能源结构对碳排放的抑制作用并不明显。据此提出开发可再生能源,转变能源消费结构,发展清洁煤技术,提高能源利用率等对策。