基于化学反应动力学机理的中等尺寸甲烷湍流扩散火焰的数值模拟

通过代码修改,在大涡模拟(LES)中嵌入气相化学反应速率、组分热力学性质和输运特性三大机理文件,严格意义上实现甲烷燃烧的四步简化机理与火灾动力学模拟软件(FDS)的成功对接。燃烧模型采用针对多组分燃料的涡耗散概念(EDC)模型,模拟0.3m直径的甲烷湍流扩散火焰,并分别与基于无限快反应速率的总包单步和两步化学反应预测结果对比。分析预测结果可知:四步机理能够很好的适应FDS框架,其模拟结果具有可靠性,时均温度、速度和主要反应物的预测结果高度一致;机理导入后可以预测CO2、H2O以及中间产物CO和H2的浓度,更合理地描述了火灾中气相产物的产生与输运过程。不同反应机制下主产物CO2和H2O浓度对比结果理想,在高温反应区内存在一定的差异,在高温反应区外呈现出高度的一致性。     

活化赤泥除氟剂的制备及除氟性能试验研究

分别采用(NH4)2HPO4,NH4HCO3,NaHCO3等对赤泥进行活化处理,并制备成球形颗粒,同时研究了活化剂浓度、焙烧温度、焙烧时间等对赤泥除氟剂吸附性能的影响。结果表明：在活化剂质量浓度为10%左右、焙烧温度500℃,焙烧时间2 h时制备的除氟剂具有较好的除氟效果,且采用(NH4)2HPO4,NH4HCO3,NaHCO3对赤泥进行活化处理制备的除氟剂能分别使溶液中氟离子的质量浓度从19 mg/L分别降低到0.085,0.13及0.19 mg/L,相应地除氟剂的吸附容量均达0.94 mg/g以上。     

Effects of hydrogen addition on propagation characteristics of premixed methane/air flames

An experimental study has been conducted to investigate the effects of hydrogen addition on the fundamental propagation characteristics of methane/air premixed flames at different equivalence ratios in a venting duct. The hydrogen fraction in the methane–hydrogen mixture was varied from 0 to 1 at equivalence ratios of 0.8, 1.0 and 1.2. The results indicate that the tendency towards flame instability increased with the fraction of hydrogen, and the premixed hydrogen/methane flame underwent a complex shape change with the increasing hydrogen fraction. The tulip flame only formed when the fraction of hydrogen ranged from 0 to 50% at an equivalence ratio of 0.8. It was also found that the flame front speed and the overpressure increased significantly with the hydrogen fraction. For all equivalence ratios, the stoichiometric flame (Φ = 1.0) has the shortest time of flame propagation and the maximum overpressure.     

Removal of cyanide in aqueous solution by oxidation with hydrogen peroxide in presence of activated alumina

This work is dedicated to the removal of free cyanide from aqueous solution by oxidation with hydrogen peroxide H₂O₂ catalyzed by neutral activated alumina. Effects of initial molar ratio [H₂O₂]₀/[CN^?]₀, catalyst amount, pH, and temperature on cyanide removal have been examined. The presence of activated alumina has increased the reaction rate showing thus, a catalytic activity. The rate of removal of cyanides increases with rising initial molar ratio [H₂O₂]₀/[CN^?]₀ but decreases at pH 10 to 12. Increasing the alumina amount from 1.0 to 30 g/L has a beneficial effect, and increasing the temperature from 20 °C to 35 °C improves cyanide removal. The kinetics of cyanide removal has been found to be of pseudo-first-order with respect to cyanide and the rate constants have been determined.     

阴极原位产H2O2强化光电催化降解水中EDTA的研究

本研究构建了以活性碳纤维(Activated Carbon Fiber,ACF)为阴极,TiO_2/Ti与Ru O_2/Ti为双阳极的光电催化体系.该体系中,Ru O_2/Ti电阳极和TiO_2/Ti光阳极均有氧化作用,可同时氧化降解污染物;且电阳极具有较强析氧作用,能产生大量O_2;ACF阴极具有还原作用,可将体系中产生的O_2原位还原为H_2O_2;H_2O_2在紫外光下产生·OH,进而强化光电催化与电催化氧化过程,实现对水中乙二胺四乙酸二钠(EDTA)的高效去除.本论文详细考察了电流密度、pH、曝气等因素对EDTA降解效果的影响.结果表明,在EDTA初始浓度为300 mg·L~(-1)、溶液初始pH=4.84、电流密度为12 m A·cm~(-2)和光电流密度为0.012 m A·cm~(-2)的条件下,反应90 min后,EDTA降解率高于90%.该催化体系实现了EDTA的高效降解.     

3种磷代阻燃剂在室内外灰尘中的粒径分布规律及人体暴露评估

磷代阻燃剂(Phosphorus flame retardants,PFRs)是目前被广受关注的一类新型有机污染物.探究了北京市5类典型室内外灰尘中3种PFRs(三(2-丁氧乙基)磷酸酯(Tris(2-butoxyethyl)phosphate,TBOEP)、磷酸三(2-氯乙基)酯(Tris(chloroethyl)phosphate,TCEP)、磷酸三(2-氯异丙基)酯(Tris(2-chloroisopropyl)phosphate,TCIPP))的污染特征、粒径分布规律及人体暴露水平.结果显示,3种PFRs在宾馆灰尘中的污染水平均最高,在道路灰尘中最低.PFRs在不同类型灰尘中的粒径分布特征存在显著差异.宾馆员工和儿童对灰尘中PFRs的暴露水平较高,需引起重视.     

Oxidation reactivity of 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE) by Compound I model of cytochrome P450s

Alternative brominated flame retardants (BFRs) have become prevalent as a consequence of restrictions on the use of polybrominated diphenyl ethers (PBDEs). For risk assessment of these alternatives, knowledge of their metabolism via cytochrome P450 enzymes is needed. We have previously proved that density functional theory (DFT) is able to predict the metabolism of PBDEs by revealing the molecular mechanisms. In the current study, the reactivity of 1,2-bis(2,4,6-tribromophenoxy)ethane and structurally similar chemicals with the Compound I model representing the active site of P450 enzymes was investigated. The DFT calculations delineated reaction pathways which lead to reasonable explanations for products that were detected by wet experiments, meanwhile intermediates which cannot be determined were also proposed. Results showed that alkyl hydrogen abstraction will lead to bis(2,4,6-tribromophenoxy)ethanol, which may undergo hydrolysis yielding 2,4,6-tribromophenol, a neurotoxic compound. In addition, a general pattern of oxidation reactivity regarding the 2,4,6-tribromophenyl moiety was observed among several model compounds. Our study has provided insights for convenient evaluation of the metabolism of other structurally similar BFRs.     

The presence and partitioning behavior of flame retardants in waste, leachate, and air particles from Norwegian waste-handling facilities

Flame retardants in commercial products eventually make their way into the waste stream.Herein the presence of flame retardants in Norwegian landfills, incineration facilities and recycling sorting/defragmenting facilities is investigated. These facilities handled waste electrical and electronic equipment(WEEE), vehicles, digestate, glass, combustibles, bottom ash and fly ash. The flame retardants considered included polybrominated diphenyl ethers(∑BDE-10) as well as dechlorane plus, polybrominated biphenyls, hexabromobenzene,pentabromotoluene and pentabromoethylbenzene(collectively referred to as ∑FR-7). Plastic,WEEE and vehicles contained the largest amount of flame retardants(∑BDE-10: 45,000–210,000 μg/kg; ∑FR-7: 300–13,000 μg/kg). It was hypothesized leachate and air concentrations from facilities that sort/defragment WEEE and vehicles would be the highest. This was supported for total air phase concentrations(∑BDE-10: 9000–195,000 pg/m~3 WEEE/vehicle facilities, 80–900 pg/m~3 in incineration/sorting and landfill sites), but not for water leachate concentrations(e.g., ∑BDE-10: 15–3500 ng/L in WEEE/Vehicle facilities and 1–250 ng/L in landfill sites). Landfill leachate exhibited similar concentrations as WEEE/vehicle sorting and defragmenting facility leachate. To better account for concentrations in leachates at the different facilities, waste-water partitioning coefficients, Kwastewere measured(for the first time to our knowledge for flame retardants). WEEE and plastic waste had elevated Kwastecompared to other wastes, likely because flame retardants are directly added to these materials. The results of this study have implications for the development of strategies to reduce exposure and environmental emissions of flame retardants in waste and recycled products through improved waste management practices.     

基于同位素证据的夏季风水汽影响区域分界

以影响我国大陆干湿状况的孟加拉湾和南海两股水汽的疑似交界影响区域之一的云南省、广西壮族自治区为研究区,借助稳定性同位素质谱仪MAT253测定2014年16个点、239个有效样本的雨季大气降水的氢氧稳定同位素组成,完成了基于GIS平台的δD、δ18O空间格局分析,实现了中国夏季风西南水汽和东南水汽的交互区域界定。主要研究结果有三点:(1)2014年雨季及6月中下旬一次降水过程δD和δ18O空间变化格局基本一致,因为夏季风大气降水δD和δ18O均沿水汽输送路径不断衰减;(2)大气降水氢氧稳定同位素空间分布主要受降雨量效应和大陆效应的影响,哀牢山高大地形阻隔及云南高原正地形水汽截留作用可能是其数值发生突变的主要原因;(3)2014年夏季的西南水汽在越过哀牢山后与东南水汽在红河、个旧、蒙自附近交互影响使δD和δ18O发生显著变化,6月中下旬一次降水过程中的氢氧同位素数值在红河、个旧附近达到最低,两者互为验证红河、个旧应该是西南水汽和东南水汽影响区域分界。     

The solution phase complexing of atrazine by fulvic acid: Equilibria at 25°c

Abstract

The solution phase complexing equilibria of atrazine by fulvic acid at 25°C±1.° have been investigated over the pH range of 1.3 to 6.0. Experiments with 0.1MKC1 and chelated Cu(II) are compared with those without metal ions. The use of a fulvic acid having calibrated acidic and Cu(II) chelation properties has made it possible to obtain stoicheometricly “exact”; chemical information. This is correlated with previous hydrolysis kinetics work. It is concluded that atrazine is hydrogen bonded in a labile equilibrium, to an identifiable set of protonated carboxyl groups, which act as Brönsted acid catalysts for hydrolysis. 0.1M KC1 changes (1‐α_A), the degree of protonation of the carboxyl groups, without otherwise affecting the atrazine complexing. Cu(II) chelation both reduces and weakens the complexing through a combination of carboxyl group blocking, and fulvic acid aggregation. Simple equations are presented for predictive calculations.