烧结法提取沸腾炉渣中的铝和铁

近年来,热电厂和钢厂产生了大量的沸腾炉渣.这些炉渣不仅占用了大量的土地,还污染了土壤、地下水和大气.由于该沸腾炉渣中氧化铝的含量很高,因此,评估其氧化铝提取的可利用性是必要的.本文对内蒙古包头钢铁厂的沸腾炉渣进行了粒径分布试验和化学成分分析试验.X-荧光分析显示,该炉渣中SiO2含量为42.60%,Al2O3含量为32.60%,Fe2O3含量为2.43%,CaO含量为2.16%,K2O含量为0.74%,MgO含量为0.44%,Na2O含量为0.16%,TiO2含量为0.88%,还有一些其他痕量元素.将沸腾炉渣和石灰及精煤混合制成小球,然后在约1 000 ℃下烧结.取不同烧结时间的样品,用硫酸浸取,得到含铝离子和铁离子的溶液.试验结果表明,使用浓度为4 mol·L-1的硫酸,在80 ℃下浸取烧结球样品(质量比为50%沸腾炉渣:40%精煤:10%石灰),24 h可以得到铝和铁的最大提取率,分别为86.50%和94.60%.滤渣可以作为固化材料用于高速公路的路基建设或水泥生产中的添加剂.     

A generalised sorption model for the concentration dependent uptake of caesium by argillaceous rocks

A three-site cation exchange model is proposed to describe the concentration dependent uptake of Cs on natural argillaceous rock systems. Major premises in the model are that the sorption of Cs is dominated by the illite mineral component in the rock and that there is a fixed relationship between the site capacities of the three site types denoted as frayed edge, type II and planar sites. The definition of a “reference illite” with a cation exchange capacity of 0.2 equiv. kg^-1 allows the three site capacities to be fixed in the model calculations over the weight fraction of illite in the argillaceous rocks. Up to Cs equilibrium concentrations of 10^-3 M sorption occurs predominantly on the frayed edge and type II sites (higher affinity sites), with the planar site type playing only a minor role. Competition with Cs for sorption on the former two site types arises predominantly from monovalent cations such as K, Rb and NH₄ which have low hydration energies. H and Na (except at high concentrations) are considerably less competitive and bivalent cations such as Mg, Ca and Sr are effectively non-competitive. A consistent set of selectivity coefficients for Cs with respect to K, Rb, NH₄ and Na was derived from analyses and modelling of a wide range of Cs sorption data available in the open literature on pure illites from many different sources. The model was tested against four Cs sorption isotherm data sets determined on argillaceous rocks: Boom clay, Oxford clay, Palfris marl and Opalinus clay. The water chemistries and illite contents given in these experiments allowed the Cs sorption isotherms to be predicted. It is concluded that the Cs sorption model presented here, in which there are no free parameters, can be used to predict the uptake of Cs at equilibrium concentrations below 10^-3 M to within a factor of 2 to 3 in natural argillaceous rock systems.     

Improved characterisation of inorganic components in airborne particulate matter

We set up a microanalytical procedure for non-volatile ions by ion chromatography (IC) and for elements by energy-dispersive X-ray fluorescence (ED-XRF) and inductively coupled plasma optical emission spectroscopy (ICP-OES). We analysed NO₃, SO₄, NH₄, Na, Mg, Ca, Fe, S, Zn, As, Cd, Cu, Mn, Ni, Pb, Sb, Se, Ti, and V. The use of complementary techniques yields reliable data for both trace and crustal elements, overcoming the analytical restrictions characteristic of the individual techniques. Some elements determined by two or by all three techniques can be used as data quality markers. The application of the procedure to a short PM_2.5 monitoring campaign is also described, aimed to the identification of fireworks tracers.     

海口市生活垃圾焚烧飞灰特性与重金属形态分析研究

生活垃圾焚烧飞灰因富合多种毒性物质而被列入危险废物名录.不同地区生活垃圾焚烧飞灰元素组成存在差异.论文研究了海口市生活垃圾焚烧飞灰的基本特性及重金属形态.结果表明,飞灰中Pb浸出值超过危险废物判别值的6倍之多,Pb、Cd和Zn的浸出值均超过生活垃圾填埋场限值.与As和Hg相比,Cu、Zn、Cr、Pb和Cd碳酸盐结合态的比例略高,在酸性条件下极易释放,对周围环境构成威胁.     

铬渣浸溶Cr(Ⅵ)溶解释放规律研究-以锦州堆场铬渣为例

通过锦州地区铬渣样品静态浸溶实验,测定不同固液比、浸出时间、浸取剂pH及组成、振荡速度、铬渣粒度大小、温度等因素对铬渣中Cr(VI)溶解释放的影响,揭示铬渣中Cr(VI)析出、释放机理。结果显示,稀释作用在不同固液比浸出中起主导作用,随固液比的降低,Cr(VI)浸出浓度逐渐降低,但是Cr(VI)浸出总量却在增加;随着浸出时间的增大,浸出Cr(VI)浓度随之增大;铬渣浸出液碱性很高,在铬渣溶解释放过程中,随酸性增强Cr(VI)溶解量相应增大,体现强的酸中和能力;随着振荡速度增加,Cr(VI)溶解释放速度明显加快;粒径越小,铬酸盐的溶解释放速度越快,溶解作用越充分;铬渣的浸出为吸热反应过程,铬渣溶解度随温度升高而增大。铬渣中Cr(Vl)溶解释放速率服从菲克(Fick)扩散定律。研究结果为铬渣危害的评价、监测及铬渣污染有效防治提供参考。     

表生风化淋滤迁移过程的Cd同位素分馏及其指示意义

利用Cd同位素来示踪Cd污染源是近年发展起来的一个新的同位素示踪体系,具有极大的优越性。然而,在利用Cd同位素示踪污染源的研究中,表生风化淋滤作用是否会导致同位素分馏,目前还没有研究报导,限制了Cd同位素在示踪污染源方面的应用。通过对Pb-Zn矿山主要固体污染源的表生风化淋滤过程进行模拟实验表明,无论是淋滤实验还是可交换态Cd实验,淋滤液总体上较残留态富集Cd的重同位素,其中尤以硫化矿最为明显,其Cd同位素分馏可达0.50‰(δ^114/110Cd)。此外, Cd的淋滤率与淋滤产生的Cd同位素分馏总体呈负相关关系。因此,我们认为在利用Cd同位素端元模型示踪污染源时,必须充分考虑表生风化淋滤作用可能带来的影响。     

含砷废渣高温烧结过程砷的矿物相结构变化与环境释放行为

研究了含砷废渣高温烧结过程引起的砷挥发和砷发生的矿物相结构变化,并分析了烧结体的砷浸出释放行为.在10MPa下加压成型制样,进空气流量为2 000 mL·min-1,烧结温度1 000～1 350℃,烧结时间60 min.结果表明,烧结温度对砷挥发的影响很小,As的固定率保持在90%以上,但对砷浸出毒性的影响明显.烧结温度低于1 000℃时,FeAsS被氧化生成钙砷、铝砷和铁砷,以Ca3（AsO4）2矿物相为主,导致砷的浸出释放水平提高;烧结温度达到1 200℃,Ca3（AsO4）2被玻璃熔融态所包围,并被转换为硅钙砷酸盐化学键接,导致砷的浸出水平显著降低.从烧结体的环境安全性考虑,最佳烧结温度为1 200℃.     

沸石掺量对磷酸镁水泥固化模拟放射性核素Sr的影响

研究了不同沸石掺量对磷酸镁水泥固化模拟放射性核素Sr的影响,测试了固化体的基本性能及抗浸出性,并采用X射线衍射仪、傅立叶变换红外光谱仪、综合热分析仪和扫描电子显微镜对固化体物相和微观结构进行分析.结果表明:掺入沸石的固化体仍具有优异的力学性能,一定范围内,沸石掺量增大,固化体的抗冻融性、抗浸泡性及抗浸出性增强;掺入沸石后固化体力学性能下降的原因是水化产物的结晶程度及整体性下降,当沸石掺量超过一定程度,水化产物含量降低也会导致固化体力学性能下降;沸石的高吸附性、沸石及磷酸镁水泥水化凝胶的双重保护,以及掺入沸石后磷酸镁水泥固化体机械阻滞作用的增强使固化体在掺入沸石后固化性能得到显著改善.     

凤眼莲源生物炭对土壤As、Hg、Cd溶出特性与化学形态的影响

以我国典型水生入侵植物凤眼莲为前体制备了生物炭(BCW)和负载铁生物炭(BCW-Fe),在对其理化特性进行充分表征的基础上,系统分析了这2类生物炭对金矿冶炼区酸性复合污染土壤中As、Hg、Cd的钝化修复效果.水浸与酸浸实验表明,5%(质量分数)BCW与5%(质量分数)BCW-Fe处理分别使土壤As浸出浓度降低91.4%~91.6%和64.9%~96.8%,Hg浸出浓度由0.03~0.04μg·L-1降低至0~0.02μg·L~(-1);而2种材料对Cd的钝化优势分别出现在中性和酸性浸出条件下.重金属形态分析结果显示,2种生物炭处理均使As、Hg、Cd由植物可利用性较高的可交换态和碳酸盐结合态向较为稳定的铁锰氧化物与有机物结合态转化.其中,BCW与BCW-Fe的加入分别使可交换态与碳酸盐结合态As总量减少0.3%和3.1%,使这2种非稳态Hg总量分别减少2.3%和3.4%,使这2种形态Cd总量分别减少7.7%和14.9%.综合以上研究结果,凤眼莲负载铁生物炭提供了一种能够在我国广泛分布的酸雨沉降地区内实现对复合污染土壤中As、Hg、Cd同步稳定钝化的有效材料,与此同时,该方法有利于实现对入侵植物的有效管理和应用土地系统进行长期固碳.     

Long-term leaching of uranium from different waste matrices

A semi-dynamic leaching test was carried out for metallurgical wastes and ore samples from the uranium and copper mining industry over a 142 day period using distilled water and 0.1N NaNO(3) as solvents. Laser fluorimetry was used as the analytical technique to determine the total uranium content in the leachates. The cumulative leach fraction (CLF) of uranium release from the samples was calculated to be 0.22, 0.22, 0.07 and 0.39% for rock, uranium tailings, copper kinker ash samples and copper tailings respectively using distilled water as solvent and 0.31, 0.27, 0.05 and 0.59% for the same matrices using 0.1N NaNO(3). The release of mobile uranium fraction was very slow, being faster in the initial stage and then attained a near steady state condition. The diffusion coefficient and bulk release of uranium from the samples have been calculated. The processes governing the release of uranium from these matrices have been identified to be surface wash-off and diffusion. Hence the use of weak solvents (leach out the mobile/exchangeable fraction of uranium) under semi-dynamic conditions aids the determination of leaching parameters and identification of the leaching mechanism for mobile uranium fraction from different matrices by slow leaching processes.