超临界反应的应用

采用环境友好的溶剂在超临界状态下进行的化学反应,能加快化学反应速率,提高反应的产率和选择性,方便地实现反应分离过程的一体化,该技术以其独特的优越性获得了广泛研究与关注。笔者简述了近年来超临界反应在石油化工、环境保护、生物柴油制备领域的应用。     

装置级突发事故应急预案编制的思考与对策

结合石化企业装置生产特点,分析装置级突发事故应急预案编制中存在的不足和问题,并对应急预案编制的思路和处置对策进行了深入地探讨.     

高温状态下受热时间对膨润土物性指标的影响∗

高温状态下膨润土的物性指标变化是高放核废物深地质处置库设计的重要参数之一。通过高温状态下不同受热时间MX80钠基膨润土的比重、液塑限、自由膨胀率试验,研究了受热时间对膨润土基本物性指标的影响规律;并通过热重分析(TGA)、X衍射(XDR)、电镜扫描(SEM)试验,从微观角度对上述变化规律进行了合理解释。研究结果表明:随着受热时间的增加,膨润土的比重、液塑限、自由膨胀率在受热15～30天内急剧下降,降幅分别为2.5%、3.1%和28.3%,之后各值变化量很小;高温状态下,膨润土的矿物成分转化、结合水脱附、微观形貌改变是膨润土物性指标发生变化的根本原因,三者之间相互作用和彼此影响。     

Beyond hypoxia：Occurrence and characteristics of black blooms due to the decomposition of the submerged plant Potamogeton crispus in a shallow lake

Organic matter-induced black blooms(hypoxia and an offensive odor) are a serious ecosystem disasters that have occurred in some large eutrophic shallow lakes in China. In this study, we investigated two separate black blooms that were induced by Potamogeton crispus in Lake Taihu, China. The main physical and chemical characteristics, including color- and odor-related substances, of the black blooms were analyzed. The black blooms were characterized by low dissolved oxygen concentration(close to 0 mg/L), low oxidation-reduction potential, and relatively low pH of overlying water. Notably higher Fe2+and∑S2-were found in the black-bloom waters than in waters not affected by black blooms. The black color of the water may be attributable to the high concentration of these elements, as black FeS was considered to be the main substance causing the black color of blooms in freshwater lakes. Volatile organic sulfur compounds, including dimethyl sulfide, dimethyl disulfide, and dimethyl trisulfide, were very abundant in the black-bloom waters. The massive anoxic degradation of dead Potamogeton crispus plants released dimethyl sulfide, dimethyl disulfide, and dimethyl trisulfide, which were the main odor-causing compounds in the black blooms. The black blooms also induced an increase in ammonium nitrogen and soluble reactive phosphorus levels in the overlying waters. This extreme phenomenon not only heavily influenced the original lake ecosystem but also greatly changed the cycling of Fe, S, and nutrients in the water column.     

Carbonyl emissions from heavy-duty diesel vehicle exhaust in China and the contribution to ozone formation potential

Fifteen heavy-duty diesel vehicles were tested on chassis dynamometer by using typical heavy duty driving cycle and fuel economy cycle. The air from the exhaust was sampled by 2,4- dinitrophenyhydrazine cartridge and 23 carbonyl compounds were analyzed by high performance liquid chromatography. The average emission factor of carbonyls was 97.2 mg/km, higher than that of light-duty diesel vehicles and gasoline-powered vehicles. Formaldehyde, acetaldehyde, acetone and propionaidehyde were the species with the highest emission factors. Main influencing factors for carbonyl emissions were vehicle type, average speed and regulated emission standard, and the impact of vehicle loading was not evident in this study. National emission of carbonyls from diesel vehicles exhaust was calculated for China, 2011, based on both vehicle miles traveled and fuel consumption. Carbonyl emission of diesel vehicle was estimated to be 45.8 Gg, and was comparable to gasolinepowered vehicles （58.4 Gg）. The emissions of formaldehyde, acetaldehyde and acetone were 12.6, 6.9, 3.8 Gg, respectively. The ozone formation potential of carbonyls from diesel vehicles exhaust was 537 mg O3/km, higher than 497 mg O3/km of none-methane hydrocarbons emitted from diesel vehicles.     

松花江(黑龙江省段)流域水环境承载力指标体系构建研究

针对流域水环境承载力指标体系亟待解决的问题,介绍了流域水环境承载力指标体系构建进展与存在的问题,提出了流域水环境承载力指标体系构建的改进措施,对松花江流域水环境承载力指标体系构建,提出了改进指标体系的构建原则、构建程序,分析影响因素,提出流域水环境承载力内涵,从水资源量、水资源消耗量、水资源质量影响三方面出发选取了指标,构建了松花江流域水环境承载力的三层递阶层次结构的指标体系,为评价与预测该流域水环境承载力奠定理论基础。     

基于距离相关系数和支持向量机回归的PM2.5浓度滚动统计预报方案

针对目前空气质量统计预报方法存在的主要缺陷,本文提出了距离相关系数和支持向量机回归相结合的统计预报方案DC-SVR.利用淮安市2013年1—12月PM_(2.5)观测资料和常规气象观测资料,首先在选入预报当日气象要素的基础上,增加选取前期污染物和气象要素作为预报因子,再采用距离相关系数分季节从预报因子中筛选出重要预报因子,最后采用支持向量机回归对PM_(2.5)浓度值进行逐日滚动统计预报.研究发现,淮安地区气温和气压对PM_(2.5)的距离相关性要高于其他气象要素,夏秋季PM_(2.5)与气象要素的距离相关性较春冬季好.基于距离相关系数和支持向量机回归建立DC-SVR模型,PM_(2.5)的试预报值和实测值的全年相关系数高达0.76,平均偏差仅为1.13μg·m~(-3),平均绝对误差为23.47μg·m~(-3).通过与支持向量机回归、人工神经网络的统计预报效果对比,DC-SVR模型有效降低预报因子维数且能自适应选取最佳参数,预报精度显著优于其他3种统计预报方案,可为业务化预报提供参考.     

Important role of reaction field in photodegradation of deca-bromodiphenyl ether: Theoretical and experimental investigations of solvent effects

Photolysis of deca-bromodiphenyl ether (BDE-209) was investigated in tetrahydrofuran, dichloromethane, isopropanol, acetone, ethanol, methanol, acetonitrile and dimethylsulfoxide. Noticeable differences of the photolytic rates and quantum yields were found in the diverse solvents. Different to the previous deductions, hydrogen donating efficiency and electron donating efficiency of solvents were not the decisive factors for the photolytic rate in this study, which was proved by the fast photolysis of BDE-209 in CCl₄, a solvent without hydrogen and difficult to donate electrons. Besides hydrogen addition process, intermolecular polymerization might occur during the photolysis. Density functional theory (DFT) calculation was performed to understand the molecular properties of BDE-209 in different solvents. The lowest singlet vertical excitation energy (E_ex) and the average formal charge on Br () of BDE-209, reflecting the difficulty for the excitation of BDE-209 and for the departing of Br atom, respectively, were changed by the reaction fields formed by the different solvents. E_ex and linearly correlated with the photolytic activity (log k). This study is helpful to better understand the photolytic behavior of BDE-209 in different media.     

石油类污染物自然衰减能力现场试验验证研究

在北京地区某加油站开展的前期石油类污染物自然衰减现场试验的基础上,进一步开展了验证试验,结果表明本次试验得到的挥发性有机物(VOCs)变化趋势及O2、CO2含量沿土壤深度分布和前期试验结果呈现相同的规律,说明基于自然衰减法设计实施的加油站现场试验检测分析结果可靠,试验方法具有合理性、可操作性及可重复性.进一步的理论分析对前期试验结果进行了验证,得出以下结论:(1)通过氧平衡和碳平衡计算对加油站土壤内的自然衰减方式进行评价,验证了该加油站地下土壤中实际发生的微生物降解既有需氧降解也有厌氧降解；(2)利用有机物的一级衰减模型对该污染现场土壤中石油类污染物的降解速率和半衰期进行计算表明,2次试验计算得到的石油类污染物的半衰期基本一致,该污染现场石油类污染物的半衰期为50 d左右；(3)在此基础上,对该加油站包气带土壤的自然衰减能力和环境质量进行评价,2次试验结果均表明该污染现场在自然衰减的作用下已经不存在环境风险.     

循环流化床锅炉燃煤技术热电厂生命周期评价

运用生命周期评价方法,应用Gabi5.0软件对采用循环流化床锅炉燃煤技术的热电企业进行资源耗竭和环境影响分析,计算各生产单元生命周期清单的全球变暖潜值、酸化效应潜值、富营养化潜值、非生物资源耗竭潜值、人体毒性潜值以及光化学烟雾和臭氧生成潜值等主要环境影响类型,对燃煤发电过程进行生命周期评价。结果表明,全球变暖和非生物资源耗竭为发电运行过程中主要的环境影响因素,分别占53%和15.05%;锅炉燃烧阶段的环境影响最重,占整个生命周期影响值的77.12%,并且除生物耗竭潜值外的其他5项指标均为发电运行阶段各个单元中最高。采用SNCR脱硝技术减少燃烧过程中NOx的排放量,并对该技术方案进行生命周期评价,比较方案实施前后的环境影响。