无机离子与胡敏酸对零价铁去除水中Pb（Ⅱ）、Hg（Ⅱ）的影响

研究了Ca2+、Cl-和胡敏酸(HA)对零价铁(ZVI)去除水中Pb(Ⅱ)、Hg(Ⅱ)的影响及其动力学特征,应用X-射线衍射分析(XRD)初步探讨了ZVI对Pb(Ⅱ)、Hg(Ⅱ)的去除机制.结果表明,ZVI主要通过吸附-共沉淀作用去除水中的Pb(Ⅱ),氧化还原作用去除Hg(Ⅱ).随着Ca2+浓度的增加,Hg(Ⅱ)和Pb(Ⅱ)的去除率分别呈逐渐升高和轻微下降的趋势;增加Cl-浓度有利于Hg(Ⅱ)的去除,但Pb(Ⅱ)去除率增加不明显;Pb(Ⅱ)、Hg(Ⅱ)去除率随HA浓度的增加分别呈缓慢升高和缓慢下降的趋势.当Cl-、Ca2+和HA共存时,Pb(Ⅱ)、Hg(Ⅱ)的去除率分别达到99.71%和97.95%.在Cl-、Ca2+、HA单独存在和共存时,ZVI去除Pb(Ⅱ)、Hg(Ⅱ)的过程均符合准一级反应动力学特征;Pb(Ⅱ)的去除速率常数以5 mg·L-1HA单独存在时最大(0.0240 min-1),而Hg(Ⅱ)以0.80 mmol·L-1Ca2+单独存在时最大(0.0169 min-1).     

不同粒径零价铁活化过硫酸钠氧化降解酸性橙7的影响及动力学研究

以偶氮染料酸性橙7(AO7)为目标污染物,研究了不同粒径零价铁(包括1 mm-ZVI、150μm-ZVI、50 nm-ZVI)对活化过硫酸钠(PS)氧化降解AO7的影响,并探讨了这3种不同粒径的零价铁活化体系中AO7的降解动力学及中间产物.结果表明,3种粒径零价铁均可以高效活化PS氧化降解AO7,反应90 min后,1 mm-ZVI、150μm-ZVI和50 nm-ZVI活化体系对AO7的去除率分别为43%、97%和100%.AO7动力学方程拟合结果表明,1 mm-ZVI和150μm-ZVI活化PS降解AO7是一级反应,50 nm-ZVI活化体系中AO7的降解是二级反应,这3种粒径零价铁活化PS降解AO7的速率常数大小顺序为50 nm-ZVI>150μm-ZVI>1 mm-ZVI.反应过程中1 mm-ZVI反应后主要生成α-Fe2O3和少量Fe3O4,150μm-ZVI表面的腐蚀产物主要是Fe3O4,而50 nm-ZVI的主要氧化物为α-Fe2O3和α-FeOOH.GC/MS检测出AO7降解中间产物有2-萘酚、邻甲酚、3-甲基-4-乙基苯酚、邻苯二甲酰亚胺、邻苯二甲酸等,AO7溶液吸收光谱的变化特征及GC/MS检测结果表明3种粒径零价铁活化PS氧化降解AO7的途径可能存在差异.     

高炉炼铁工艺细颗粒物PM2.5排放特性分析

采用静电低压撞击器(electrical low pressure impactor,ELPI)对高炉出铁场、矿槽除尘后细微颗粒物(PM2.5)的粒径及质量浓度分布进行在线分析.结果表明,出铁场除尘后PM2.5粒数浓度在105~106cm-3数量级范围内,主要为粒径小于0.1μm的颗粒物,而矿槽除尘后PM2.5粒数浓度在104~105cm-3数量级范围内,主要为粒径1.0μm以下的颗粒物,质量浓度呈单峰分布;PM2.5化学组成分析表明水溶性离子SO2-4、K+、Ca2+含量较高,分别为10.32%~28.55%、10.36%~12.15%、3.97%~15.4%;主量元素主要为Fe、Si、Al,含量分别为16.8%~31.62%、2.24%~8.76%、1.24%~5.89%;含碳组分OC和EC在PM2.5中的含量也较为丰富,分别为2.7%~4.6%和0.8%~1.3%.PM2.5单体颗粒形态主要为球状颗粒和不规则颗粒.高炉出铁场、矿槽除尘后PM2.5的排放因子分别为0.045~0.085 kg·t-1、0.042~0.071 kg·t-1.     

有机膨润土负载纳米零价铁去除废水中的四氯乙烯研究

用具有良好吸附能力的有机膨润土作载体,通过FeSO4与NaBH4反应制得有机膨润土负载纳米零价铁(NZVI/CTMA-Bent).用XRD、TEM对NZVI/CTMA-Bent进行了表征,并将NZVI/CTMA-Bent用于四氯乙烯(PCE)的去除,考察了介质pH值、PCE初始质量浓度对其去除率的影响,并与相同铁含量的纳米零价铁(NZVI)进行了比较,测定反应中Cl-浓度的变化,采用GC/MS方法对反应产物进行了分析.结果表明:以有机膨润土作载体,可有效阻止NZVI的团聚,且对介质pH值有一定的缓冲作用;NZVI/CTMA-Bent与PCE反应120 min后,去除率接近100％,既高于相同铁含量的NZVI对PCE的去除率(54.8％),也优于NZVI和有机膨润土对PCE去除率的加和(86.5％);NZVI/CTMA-Bent与PCE反应几乎完全转变成乙烯.动力学研究表明,NZVI/CTMA-Bent、NZVI对PCE的反应均符合Langmuir-Hinshelwood方程,且反应速率与其对PCE的吸附性能呈正相关.     

电化学法处理聚驱采油废水的研究

采用电化学法处理油田开发三次采油过程中产生的聚驱采油废水,考察了pH值、反应时间、电流强度对污染物降解效果的影响.结果表明,pH=3.25时,COD和HPAM去除率最高,分别达到83.03％和98.66％;电流强度为0.8A时,COD及HPAM去除率最高,为85.24％和99.63％;pH=3.25、电流强度为0.8A时,COD及HPAM去除率随时间延长而增大,反应30 min后去除率基本不变.研究了处理过程中电流效率的变化,发现反应前10 min内电流效率最高,达23.63％;并通过投加与电化学溶出的新生态铁等量的铁盐絮凝剂(FeSO4)分析了电化学中电絮凝作用的贡献,酸性条件下电化学过程对COD去除率为83.79％,同等条件下,FeSO4混凝的COD去除率为70.31％,电化学作用过程中氧化、气浮及电场作用对COD的去除率贡献最高为13.48％,因此,电化学法处理聚驱采油废水的主要作用机理为电絮凝作用.研究表明,电化学法能有效降解聚驱采油废水.     

青岛大气气溶胶中铁的溶解度及其影响因素

大气气溶胶的干湿沉降带来的铁对海洋初级生产和固碳能力有着重要影响,但这种影响从根本上决定于沉降铁的溶解度.本文利用2012年12月在青岛连续采集的31个总悬浮颗粒物(TSP)样品,分析了其中微量元素Fe的总浓度和溶解态浓度,讨论了颗粒物浓度、气溶胶来源及酸化过程对Fe溶解度的影响.结果表明,气溶胶中Fe的总浓度和溶解态浓度分别为(3248±1683)ng·m-3和(43.3±16.4)ng·m-3,溶解度为0.57%~4.86%,平均为1.63%±1.02%.随着气溶胶中总Fe浓度的增加,Fe溶解度呈现规律性降低.气溶胶中Fe的溶解度与富集因子(EF)无相关关系,而与无机和有机酸性离子存在显著正相关关系.气团后向轨迹的聚类分析显示,观测期间,64.5%的气溶胶样品主要受北方沙尘源(DS)影响,35.5%的样品主要受到华北城市群等人为源(AS)影响.AS样品中Fe的溶解度平均为2.06%,高于DS样品中的1.36%.两组样品中Fe的EF值相当,但AS样品中酸性离子与溶解度的相关关系明显好于DS组,表明酸化过程可能是造成两组样品Fe溶解度差异的主要原因.     

Flux characteristics of total dissolved iron and its species during extreme rainfall event in the midstream of the Heilongjiang River

The occurrence of extreme rainfall events and associated flooding has been enhanced due to climate changes, and is thought to influence the flux of total dissolved iron(TDI) in rivers considerably. Since TDI is a controlling factor in primary productivity in marine ecosystems, alteration of riverine TDI input to the ocean may lead to climate change via its effect on biological productivity. During an extreme rainfall event that arose in northeastern China in 2013, water samples were collected in the midstream of the Heilongjiang River to analyze the concentration and species of TDI as well as other basic parameters. The speciation of TDI was surveyed by filtration and ultrafiltration methods.Compared with data monitored from 2007 to 2012, the concentration of TDI increased significantly during this event, with an average concentration of 1.11 mg/L, and the estimated TDI flux reached 1.2 × 105 tons, equaling the average annual TDI flux level.Species analysis revealed that low-molecular-weight complexed iron was the dominant species, and the impulse of TDI flux could probably be attributed to the hydrological connection to riparian wetlands and iron-rich terrestrial runoff. Moreover, dissolved organic matter played a key role in the flux, species and bioavailability of TDI. In addition,there is a possibility that the rising TDI flux could further influence the transport and cycling of nutrients and related ecological processes in the river, estuary coupled with the coastal ecosystems, which merits closer attention in the future.     

混凝/催化氧化/微电解三元组合技术处理油田压裂废液

油田压裂废液成分复杂、粘度高、COD高且难降解,对环境造成较大污染。提出了化学混凝/催化氧化/微电解三元组合技术处理压裂废液的新方法,确定了各步骤的最佳工艺条件。结果表明,压裂废液经化学混凝/催化氧化/微电解三元组合技术处理后,粘度降至1.5 m Pa·s,COD去除率98%,COD150 mg/L,达到国家污水排放2级标准。各单元过程形成的泥饼浸出液分析结果符合GB 18599—2001《一般工业固体废物贮存、处置场污染控制标准》第一类技术要求。     

Explosion behaviour of metallic nano powders

This paper describes experiences and results of experiments with several metallic dusts within the nanometer range. The nano dusts (aluminium, iron, zinc, titanium and copper) were tested in a modified experimental setup for the test apparatus 20 L-sphere (also known as 20-L Siwek Chamber), that enables the test samples to be kept under inert atmospheric conditions nearly until ignition. This setup was already introduced in earlier papers by the authors. It was designed to allow the determination of safety characteristics of nano powders under most critical circumstances (e.g. minimisation of the influence of oxidation before the test itself). Furthermore the influence of passivation on explosion behaviour is investigated and additional tests with deposited dust were carried out to describe the burning behaviour of all dusts. For a better characterisation all samples were tested with a simultaneous thermal analysis (STA). To minimise the influence of oxidation all samples were handled at inert conditions until shortly before ignition or start of the test respectively.     

铁刨花-Fenton-絮凝工艺对染料生产废水中AOX、色度和TOC的去除效果研究

采用铁刨花-Fenton-絮凝工艺处理染料生产废水,考察了不同Fe~(2+)与H_2O_2摩尔比(1∶3~1∶15)、铁刨花反应时间(2~5h)、Fenton氧化反应时间(20~80 min)下可吸附性有机卤代物(AOX)、色度和总有机碳(TOC)的去除效果.结果表明,AOX、色度和TOC去除率随Fe~(2+)与H_2O_2摩尔比的降低先升高后减少,随铁刨花和Fenton反应时间的增加而持续升高.最优化条件为Fe~(2+)与H_2O_2摩尔比1∶8、铁刨花反应时间4 h和Fenton反应时间60 min,该条件下AOX、色度和TOC的去除率分别为94.2%、93.7%和27.2%.比较实验结果表明,铁刨花-Fenton-絮凝组合工艺对废水AOX、色度和TOC的去除效果远优于铁刨花处理、Fenton氧化、絮凝沉淀的单个技术或两两技术组合效果.GC-MS分析表明,废水中的有机卤代物和苯胺类污染物得到高效去除,此外硝基苯类、苯酚类、苯甲醛类、醚类、腈类和杂环化合物等有毒有害物质也均得到高效去除.叔丁醇捕获·OH实验表明·OH在Fenton反应中的主导作用.