煤泥燃烧过程中汞的迁移行为研究

采用在线汞测试方法，以山西省低热值煤电厂中掺烧的煤泥为研究对象，利用实验室小型流化床，研究煤泥中汞的热转化行为差异及共性特征、影响煤泥热转化过程中汞迁移的关键因素，以揭示煤泥热转化过程中汞污染物的迁移机理。结果表明，同一种煤泥，相同气氛，800、900、1 000 ℃下，燃烧温度对煤泥中的汞的释放比例没有变化；相同温度，汞的释放比例为氮气>空气>氧气。3种煤泥在相同燃烧条件下，汞的释放特征相似，元素汞的释放量和释放比例差异较大。释放量与煤泥中的汞含量正相关，释放比例与煤泥中汞的赋存形态有一定关系。     

干巴菌中部分重金属元素及无机砷、 甲基汞含量分析

目的检测干巴菌中5种重金属总砷、总汞、铅、镉、铬及无机砷和甲基汞的含量,探讨干巴菌对重金属的生物富集作用。方法采用电感耦合等离子体质谱法检测总砷、总汞、铅、镉含量,采用液相原子荧光光度计联用检测无机砷、甲基汞的含量。结果 31份干巴菌样品中总砷、总汞、铅、镉的检出率均为100%,无机砷的检出率为50%,甲基汞在全部样品中均未检出。昆明的干巴菌样品中砷含量较高,达0.46 mg/kg;曲靖的干巴菌中铅含量有0.9997 mg/kg;镉含量较高,为0.46 mg/kg。结论总体来看不同地区的干巴菌中总砷、总汞、镉、铬、无机砷和甲基汞的含量处于较低水平,但铅含量偏高。干巴菌对重金属没有特异性吸收富集能力。     

载气热提取法测定熔敷金属中扩散氢收集条件的探究

探究了GB/T 3965—2012《熔敷金属中扩散氢测定方法》中载气热提取法收集条件对测定扩散氢含量的影响,并与水银法进行了对比。研究结果表明,样本炉温设定为400℃,A型试块的内部温度大约在51 min时稳定在358℃左右,B型试块内部温度大约在27 min时稳定在391℃左右;载气热提取法电信号曲线收集结束点的电信号及斜率均接近0时获得的结果与水银法具有较好的一致性。     

Reduced texaphyrin: A ratiometric optical sensor for heavy metals in aqueous solution

We report here a water-soluble metal cation sensor system based on the as-prepared or reduced form of an expanded porphyrin, texaphyrin. Upon metal complexation, a change in the redox state of the ligand occurs that is accompanied by a color change from red to green. Although long employed for synthesis in organic media, we have now found that this complexation-driven redox behavior may be used to achieve the naked eye detectable colorimetric sensing of several number of less-common metal ions in aqueous media. Exposure to In(III), Hg(II), Cd(II), Mn(II), Bi(III), Co(II), and Pb(II) cations leads to a colorimetric response within 10 min. This process is selective for Hg(II) under conditions of competitive analysis. Furthermore, among the subset of response-producing cations, In(III) proved unique in giving rise to a ratiometric change in the ligand-based fluorescence features, including an overall increase in intensity. The cation selectivity observed in aqueous media stands in contrast to what is seen in organic solvents, where a wide range of texaphyrin metal complexes may be prepared. The formation of metal cation complexes under the present aqueous conditions was confirmed by reversed phase high-performance liquid chromatography, ultra-violet-visible absorption and fluorescence spectroscopies, and high-resolution mass spectrometry.     

UV/TiO_2光催化氧化工艺脱汞的试验研究

UV/TiO_2光催化技术在TiO_2催化剂的作用下可将烟气中Hg~0氧化脱除。利用自制的UV/TiO_2氧化试验台研究了影响Hg~0去除率的相关因素,结果表明,在无催化剂和有紫外灯情况下可脱除少量Hg~0;Hg~0去除率随催化剂活性组分含量的增加而上升,但上升速率逐渐下降;在温度(50～200)℃范围内,Hg~0去除率无明显变化;Hg~0去除率随着Hg~0初始浓度的升高逐渐下降;Hg~0去除率随着烟气中氧含量先上升后趋于不变。UV/TiO_2氧化工艺脱汞可为燃煤电厂烟气脱汞提供理论指导。     

高效液相色谱-电感耦合等离子体质谱法测定鱼肉中甲基汞、乙基汞含量的不确定度评定

目的 评定采用高效液相色谱-电感耦合等离子体质谱(High performance liquid chromatography combined with inductively coupled plasma-mass spectrometry, HPLC-ICP-MS)法检测鱼肉中甲基汞、乙基汞含量的不确定度。方法 分析整个检测过程中存在的不确定度因素，建立数学模型，分别从称样量、稀释体积、标准溶液、标准曲线拟合以及方法回收率等几个方面进行分析，对测量结果的不确定度进行评定。结果 影响测量结果的不确定度主要来源于样品前处理和标准曲线拟合。鱼肉样品中结果表示分别为：甲基汞含量（0.48±0.046） mg/kg；乙基汞含量为（0.34±0.051） mg/kg, k=2。结论 该方法准确度高，适用于鱼肉中甲基汞、乙基汞的检测，为提高数据准确性提供有效指导。     

不同煤阶煤孔隙特征及其吸附能力响应

我国是煤炭资源大国，煤层气储量规模相当可观，但煤储层又具有低孔、低渗的不足，照搬国外或常规石油天然气的开采程序和方法已被证实是走不通的。应结合实际，根据不同地质条件、不同煤阶的开采程序，进行孔隙特征研究。煤孔隙特征、连通性和吸附能力对煤层气开采影响尤为重要，为研究煤孔隙结构特征随煤变质程度的变化关系及其吸附能力的响应特点，采取不同地区不同变质程度煤样，进行压汞测试和等温吸附实验。实验结果表明，煤孔隙度和平均孔径均随变质程度增加呈现降低—升高—降低的趋势；煤中孔隙连通性随煤变质程度增加逐渐变差；随煤变质程度增加，其最大吸附能力也呈现降低—升高—降低的总体趋势。     

微波消解-原子荧光光谱法同时测定香辛料中砷、汞含量

目的 建立微波消解-原子荧光光谱法同时测定香辛料中砷、汞含量的方法。方法 样品加入硝酸和双氧水, 微波消解后加热浓缩, 冷却后加入硫脲与抗环血酸混合溶液, 加水定容, 使用原子荧光光谱仪进行测定。结果 砷和汞分别在0~20.0 μg/L和0~2.0 μg/L浓度范围与荧光强度呈良好的线性关系, 相关系数均大于0.9997。砷和汞的方法检出限分别为0.0026和0.0006 mg/kg; 精密度和重复性实验的相对标准偏差(relative standard deviations, RSD)小于5%; 加标回收率分别为93.2%和103.0%; 对国家标准物质(GBW 10020柑橘叶)检测结果均在标准认定值范围。结论 该法操作简单、检出限低、准确度高, 适合香辛料中砷、汞含量的检测。     

Visualizations of Mercury Methylation and Dynamic Transformations by In Vivo Imaging

Visualization of Hg(II) and MeHg in their native contexts is significant for examining mercury poisoning, while it is challenging because of indistinguishable fluorescent (FL) signals during FL imaging. Herein, visualizations of mercury methylation and dynamic transformations of Hg(II) and MeHg are achieved in living biological systems. Well distinguishable FL responses (blue emission for Hg(II), yellow emission for MeHg) are obtained by a double‐response FL probe (DPAHB) without any interference. As demonstrated by experimental and computational studies, the distinguishable signals are attributed to selective binding with DPAHB and different inhibition of excited‐state proton transfer. Through control tests for live‐dead markers, mercury methylation is demonstrated to be employed in living biological systems. Therefore, the methylation and dynamic transformations of both ions are monitored in zebrafish by imaging, and these results are confirmed by traditional high‐performance liquid chromatography‐based methods. The methylation of Hg(II) to MeHg, dynamic transformations and final accumulations of both species in zebrafish tissues are visualized successfully. This method is also convenient for fast evaluation of detoxification reagents. This is the first visualization of in vivo mercury methylation and dynamic transformation of both species and is effective for studying pathological processes in their native contexts.     

300MWCFB锅炉配套半干法烟气脱硫的汞排放试验研究

某300 MW循环流化床(CFB)锅炉采用炉内脱硫、SNCR、预电除尘器和烟气循环流化床半干法脱硫装置实现了超低排放。对不同工况下不同位置的烟气汞浓度和灰渣等固体副产物中的汞含量进行测试分析,研究结果表明:燃煤在循环流化床锅炉燃烧产生的汞主要以气态汞和颗粒汞形式存在;锅炉负荷提高,烟气中气态汞和颗粒汞浓度均有所提高,炉内脱硫对原始汞排放特性几乎没有影响;烟气循环流化床半干法脱硫装置可脱除71%～77%的气态汞和86%～88%的颗粒汞;采用预电除尘器与烟气循环流化床半干法脱硫结合的超低排放路线,总汞脱除率可达到82%～87%,使烟囱排放的汞浓度不高于1.5μg/m~3。副产物分析结果表明,烟气中脱除的汞主要富集于粉煤灰和半干法脱硫灰中。