光氧化反应脱汞技术发展综述

燃煤电厂烟气中汞污染的控制技术研究是目前重要的环保课题之一。气相元素汞成为大气中汞污染的主要来源。文章分析了光氧化反应脱汞技术(包括光化学氧化反应和光催化氧化反应)的反应机理,认为光化学氧化反应技术脱汞均是在紫外光作用下,产生具有强氧化性的基态原子或自由基,将难以脱除的Hg0氧化为高价汞,再通过配套的电除尘器等设备将高价汞捕集,进而达到汞污染控制的目的。不同的是,在光化学氧化反应中,汞的氧化需要借助于电厂烟气中的O2、H2O等成分,而在光催化氧化反应中,反应需要在光催化剂(TiO2或TiO2负载复合物等)的催化作用下进行。阐述了光氧化反应汞脱除技术研究进展。光氧化反应脱汞技术的汞脱除率均可达到60%~70%,具备设备简单、无二次污染等优点。     

燃煤电厂大气汞排放控制的必要性与防治技术分析

目前,汞已经成为温室气体和持久性有机物后又一引人关注的全球性化学污染物,汞污染和控制问题成为全球环境问题的新热点和前沿研究领域.2002年,联合国环境规划署(UNEP)专门对全球汞污染状况进行了评估,指出"人为活动的汞排放已经明显改变了全球汞的自然循环,对人类健康和生态系统构成了严重威胁".     

道南膜技术测定Ca(NO3)2溶液体系中汞的化学形态

虽然道南膜技术(DMT)已经成功用于土壤/溶液中多种重金属自由态离子浓度的测定,但DMT技术测定Hg的形态尚未解决.采用DMT测定Ca(NO3)2溶液体系中Hg化学形态.实验结果表明,Hg在阳离子交换膜内的吸附除静电吸附外还存在结合力更强的化学吸附,Hg在阳离子交换膜内扩散成为Hg跨膜传输受阻的主要因素,限制道南膜技术用于Hg形态测定.Hg2+和Hg(OH)2都表现出在阳离子交换膜上的强烈吸附,供端(Donor)Hg损失达50%以上.缩短试验时间至8h以内,可在一定程度上降低Hg吸附.计算结果表明,由于大量的Hg滞留在阳离子交换膜内,在计算受端(Acceptor)Hg浓度时引入滞留系数补偿供端Hg的损失,较好地预测了Ca(NO3)2溶液体系中Hg的化学形态.     

铜坑矿区蔬菜和土壤汞污染研究及来源解析

为了深入了解铜坑矿区的汞污染状况,就矿区内蔬菜、土壤中的汞进行了含量研究,指出了矿区汞污染传播途径以及可能造成居民受汞污染的途径,最后针对矿区内不同污染程度的尾砂坝、山地、农田、住宅等不同地区提出了针对性的治理方案。     

中美淡水生物区系中汞物种敏感度分布比较

通过收集无机汞对中国与美国淡水水生生物的毒性数据,构建了脊椎动物(包括鱼类)、无脊椎动物(包括节肢动物和非节肢无脊椎动物)及所有物种对汞的物种敏感度分布(SSD:species sensitivity distributions)曲线,并在此基础上对中国和美国不同类别生物对汞的敏感性分布进行了分析.结果表明:中国与美国各类生物及所有物种对汞的SSD敏感性分布曲线没有显著差异.然而,中国淡水水生物种对汞短期暴露的HC5(hazardous concentration for 5% of the species)较美国淡水物种的阈值小,尤其是非节肢无脊椎动物,汞对美国非节肢动物的HC5值是我国对应物种的7.4倍.在保护95%的物种水平下,中国不同类别试验生物对汞的敏感性排序为无脊椎动物>脊椎动物,其中节肢动物>非节肢无脊椎动物>鱼类;而对应的美国生物对汞的敏感性排序无脊椎动物>脊椎动物,其中节肢动物>鱼类>非节肢无脊椎动物.另外,中美所有节肢动物对汞的敏感性要强于所有鱼类和所有非节肢无脊椎动物.所以在使用所有物种推导水质基准时应考虑其中各类别物种敏感度分布的影响,且需要注意采用美国淡水水生物种推导的水质基准可能会对我国淡水水生物种造成"保护不足".     

蝉中汞含量及其分布特征研究

研究了葫芦岛氯碱-有色冶金化工区蝉汞、膜翅汞及蝉蜕汞的含量,比较了蝉与其它昆虫汞含量的差异,探讨了汞在蝉体内的分布特征.结果表明,蝉汞含量很高,平均值为2.64 mg.kg-1,远高于对照点地区蝉汞含量(平均为1.00 mg.kg-1);蝉中汞的分布特征为蝉汞膜翅汞(平均为0.98 mg.kg-1)蝉蜕(平均为0.50 mg.kg-1);不同性别蝉体质量、汞含量存在显著差异,雌性蝉体质量(平均为1.11 g)显著高于雄性(平均为0.54 g);雌性蝉汞含量(平均为1.34 mg.kg-1)要显著低于雄性汞含量(平均为3.38 mg.kg-1);不同采样点中蝉汞含量差异明显,但是膜翅汞含量差异较小;蝉汞含量与土壤汞含量之间不存在显著的相关关系.蝉汞含量低于生命周期较长的蜻蜓汞含量,但是却远高于生命周期较短的其它昆虫,反映了环境汞污染在长生命周期昆虫的累积效应.     

影响大气汞化学过程的敏感因子分析

为了分析汞在大气中的化学行为,在一个化学模式中加入汞的气相、气液平衡和液相反应,模拟大气汞及其化合物的演变规律,并分析了气象因子(云、光解率、温度)和化学因子(气态O3、H2O2、HO2、OH和气态零价汞Hg0(g))的初始体积分数对各形态汞及其化合物浓度和Hg0(g)转化率的影响.模拟结果表明,在中等大气污染条件下,Hg0(g)的每小时平均转化率为2.91%.敏感性试验结果表明,云量、光解率、温度、O3和Hg0(g)的初始体积分数对不同形态汞的影响较为显著.云量的增加、光解率的增加、臭氧初始体积分数的升高,各形态汞的平衡时间缩短,除气态氧化汞和一价汞离子外,其他形态汞的平衡浓度均会降低,Hg0(g)的转化率增加.温度增加将抑制Hg0(g)的转化.Hg0(g)的初始体积分数增加,各形态汞的浓度升高,但其平均转化率没有显著变化.不同因子对汞化学过程的相对作用对区域或全球大气汞的环境模拟具有指导意义.     

Efficiency of white lupin in the removal of mercury from contaminated soils： Soil and hydroponic experiments

This study examined the ability of the white lupin to remove mercury (Hg) from a hydroponic system (Hg concentrations 0, 1.25, 2.5, 5 and 10 μmol/L) and from soil in pots and lysimeters (total Hg concentration (19.2 ± 1.9) mg/kg availability 0.07%, and (28.9 ± 0.4) mg/kg availability 0.09%, respectively), and investigated the accumulation and distribution of Hg in different parts of the plant. White lupin roots efficiently took up Hg, but its translocation to the harvestable parts of the plant was low. The Hg concentration in the seeds posed no risk to human health according to the recommendations of the World Health Organization, but the shoots should not be used as fodder for livestock, at least when unmixed with other fodder crops. The accumulation of Hg in the hydroponically-grown plants was linear over the concentration range tested. The amount of Hg retained in the roots, relative to the shoots, was almost constant irrespective of Hg dose (90%). In the soil experiments, Hg accumulation increased with exposure time and was the greater in the lysimeter than in the pot experiments. Although Hg removal was the greater in the hydroponic system, revealing the potential of the white lupin to extract Hg, bioaccumulation was the greatest in the lysimeter-grown plants; the latter system more likely reflects the true behaviour of white lupin in the field when Hg availability is a factor that limits Hg removal. The present results suggest that the white lupin could be used in long-term soil reclamation strategies that include the goal of profitable land use in Hg-polluted areas.     

Evaluation of mercury speciation and removal through air pollution control devices of a 190 MW boiler

Air pollution control devices (APCDs) are installed at coal-fired power plants for air pollutant regulation. Selective catalytic reduction (SCR) and wet flue gas desulfurization (FGD) systems have the co-benefits of air pollutant and mercury removal. Configuration and operational conditions of APCDs and mercury speciation a ect mercury removal e ciently at coal-fired utilities. The Ontario Hydro Method (OHM) recommended by the U.S. Environmental Protection Agency (EPA) was used to determine mercury speciation simultaneously at five sampling locations through SCR-ESP-FGD at a 190 MW unit. Chlorine in coal had been suggested as a factor a ecting the mercury speciation in flue gas; and low-chlorine coal was purported to produce less oxidized mercury (Hg2+) and more elemental mercury (Hg0) at the SCR inlet compared to higher chlorine coal. SCR could oxidize elemental mercury into oxidized mercury when SCR was in service, and oxidation e ciency reached 71.0%. Therefore, oxidized mercury removal e ciency was enhanced through a wet FGD system. In the non-ozone season, about 89.5%–96.8% of oxidized mercury was controlled, but only 54.9%–68.8% of the total mercury was captured through wet FGD. Oxidized mercury removal e ciency was 95.9%–98.0%, and there was a big di erence in the total mercury removal e ciencies from 78.0% to 90.2% in the ozone season. Mercury mass balance was evaluated to validate reliability of OHM testing data, and the ratio of mercury input in the coal to mercury output at the stack was from 0.84 to 1.08.     

上海市夏季湿沉降汞的时空分布规律及其影响因素

为研究上海市夏季湿沉降汞的时空分布特征,按月采集了2008年夏季(6～8月)5个采样点的大气湿沉降样品,经过王水+BrC1水浴消解、SnCl2还原后,用原子荧光测汞仪测试了样品中的总汞、溶解态汞和颗粒态汞浓度并对结果加以分析。结果表明,上海市夏季各采样点湿沉降中总汞、溶解态汞和颗粒态汞的平均浓度变化范围大,分别为0.13～0.39μg/L、0.04～0.22μg/L、0.09～0.18μg/L,总体上各形态汞的浓度都较高。湿沉降总汞的浓度在时间上表现为6月份较低而7、8月份较高的特征,在空间上是浦东最高,普陀其次,宝山最低;颗粒态汞占总汞的比例大,并且在不同降水类型中所占总汞的比例不同,在梅雨期锋面雨中所占比例较少而在对流雨中所占比例较大;总汞的沉降量与降水量成明显的正相关关系。大气湿沉降中各形态汞的浓度受控因素较多,其中在重要排放源和市中心下风向地区汞的浓度偏高,这需要在节能减排上下功夫,从源头治理汞的污染。