Dehalogenation Potential of Municipal Waste Incineration Fly Ash

BACKGROUND, AIMS AND SCOPE: In the first part of this paper the main principles which control the dehalogenation of polychlorinated aromatic compounds on municipal waste incineration fly ash (MWI-FA) have been discussed and the model fly ash of similar dehalogenation activity has been proposed. Even if both systems show comparable dehalogenation properties, the main question concerning the postulated identical reaction mechanism in both cases is left unanswered. The other very important point is to what extent is this dechlorination mechanism thermodynamically controlled. The same problem is often discussed in the literature also for the de novo synthetic reactions. From the data it is clear that metallic copper plays a decisive role in the mechanism of the dehalogenation reaction. Although the results reported in the first part strongly support the idea that copper acts in this dechlorination as the reaction component, in contrast to its generally accepted catalytic behaviour, we believed that additional support for this conclusion can be obtained with the help of a thermodynamic interpretation of the mechanism of the reaction. RESULTS AND DISCUSSION: The pathways of hexachlorobenzene dechlorination on MWI-FA and model fly ash were studied in a closed system at 260-300 degrees C under nitrogen atmosphere. These pathways were the same for both systems, with the following prevailing sequences: hexachlorobenzene --> pentachlorobenzene --> 1,2,3,5-tetrachlorobenzene --> 1,3,5-trichlorobenzene --> 1,3-dichlorobenzene. Thermodynamic calculations were carried out by using the method of minimization total Gibbs energy of the whole system. In the calculations, the following reaction components were taken into account: all gaseous chlorinated benzenes, benzene, hydrogen chloride, a gaseous trimer Cu3Cl3, and also Cu2O and CuCl2 as solid components. The effect of the reaction temperature and the amount of copper and water vapour were considered as well. The effect of reaction temperature was determined from the data calculated for the 500 to 750 K temperature region. The effect of the initial composition was determined for the molar amounts of copper = 0.01-3 moles and water vapour = 0.2 to 3 moles per mole of chlorobenzene isomer CONCLUSIONS: The results of hexachlorobenzene dechlorination by MWI-FA and model fly ash under comparable reaction conditions allow us to conclude that both dechlorinations proceed via the same dechlorination pathways, which can be taken as an evidence of the identical dehalogenation mechanism for both systems. The relative percentual distribution of the dehalogenated products depends on the temperature, but not on the initial amount of water vapour or copper metal. On the other hand, the initial amount of copper substantially affects the conversion of the dehalogenation as well as the molar ratio of Cu3Cl3 to HCl in the equilibrium mixture. Comparison of the experimental with thermodynamic results supports the idea that dehalogenation reactions are thermodynamically controlled. RECOMMENDATIONS AND OUTLOOK: Thermodynamic analysis of the dehalogenation reactions may prove useful for a wide range of pollutants. The calculations concerning polychlorinated biphenyls and phenols are under study.     

铬渣的固化/稳定化研究

探讨了用水泥粘结剂对铬渣进行稳定化的方法。结果表明，把高炉矿渣和粉煤灰加入水泥基材中对铬渣进行固化，固化体抗压强度达到30MPa以上，浸出毒性大大降低，浸了同液中六价铬浓度在容许范围内，建议可以综合利用。     

电厂冲灰水回用于冷却循环水系统的试验研究

火电厂冲灰水经絮凝沉降和反渗透处理后用作电厂循环冷却水 ,经多项试验证明 ,此工艺方法技术可行 ,灰水处理回用后不会增加冷却水系统结垢和腐蚀 ,且回用灰水代替部分地下水增加了明显的经济效益。     

添加粉煤灰对污泥比阻影响的研究

污泥脱水是污泥处理中重要的一环。本研究采用电厂废弃物粉煤灰对未脱水污泥改性，经过改性的污泥比阻降低，改善污泥脱水性能，并对产生这一现象的机制进行了探讨。     

基于精细化观测的沙尘通量分布特征

研究沙尘随高度的变化特征对揭示沙尘物质在近地层分布特征具有重要意义。为揭示0—80 m沙尘通量的垂直分布规律,在野外实测的基础上,选取2008年7月20日、8月7日、8月19日、8月29日4次沙尘天气,对贴地层（0—0.05 m）、中间层（0.05—2 m）、近地层（2—80 m）的沙尘通量进行对比分析。结果表明：贴地层（0—0.05 m）,沙尘通量随着高度的增高呈增加趋势,最大值为1604.29 g?mm^?2。中间层（0.05—2 m）,沙尘通量随高度分布的关系为幂函数关系,且随着高度的升高沙尘通量减小,决定系数R²值均在0.9以上。近地层（2—80 m）,沙尘通量随高度增加呈分段函数分布,32 m、48 m处为沙尘通量的拐点高度。由此看出,研究沙尘通量对阐明沙尘输送机制非常重要,不仅可加强对沙尘输送的定量研究,还可为沙尘输送的数值模拟提供重要参数。     

Phytotoxicity and groundwater impacts of leaching from thermal treatment residues in roadways

The use of coal fly ash (CFA), municipal solid waste incinerator bottom ash (MSWIBA) and flue gas desulfurization residue (FGDR) in road construction has become very common owing to its economical advantages. However, these residues may contain toxic constituents that pose an environmental risk if they leach out and flow through the soil, surface water and groundwater. Therefore, it is necessary to assess the ecotoxicity and groundwater impact of these residues before decisions can be made regarding their utilization for road construction. In this study, the physico-chemical characteristics, leaching and phytotoxicity of these residues were investigated. Specifically, multivariate analyses were used to evaluate the contributions of the leaching constituents of the CFA, MSWIBA and FGDR leachates to the germination index of wheat seeds. B, Ba, Cr, Cu, Fe and Pb were found to be more toxic to the wheat seeds than the other heavy metals. Furthermore, the leached concentrations of the constituents from the CFA, MSWIBA and FGDR were below the regulatory threshold limits of the Chinese identification standard for hazardous wastes. Analyses conducted using a numerical groundwater model (WiscLEACH) indicated that the predicted field concentrations of metals from the CFA, MSWIBA and FGDR increased with time up to about 30 years at the point of compliance, then decreased with time and distance. Overall, this study demonstrated that the risks resulting from MSWIBA, CFA and FGDR leaching could be assessed before its utilization for road construction, providing crucial information for the adoption of these alternative materials.     

不同活化条件下粉煤灰中锂的酸碱溶出特性

粉煤灰提取氧化铝作为其资源高值利用的重要途径之一引起广泛关注.由于粉煤灰中还含有一定丰度Li（锂）元素,在提取氧化铝的同时实现Li的协同提取对于进一步提高粉煤灰的资源利用效益意义重大.为认识粉煤灰中Li的溶出特性,分别考察了原粉煤灰、CaO煅烧活化粉煤灰和Na₂CO₃煅烧活化粉煤灰中Li在酸性溶液和碱性溶液中的溶出特性,并采用XRD（X-射线衍射）分析了粉煤灰浸取前后的物相变化,结合Li溶出率的变化,阐释了Li在不同浸出条件下溶出率差异的原因.结果表明:在相同浸出温度（100℃）下粉煤灰直接在酸性溶液和碱性溶液中的溶出率相对较低,分别仅为28%和36%;而经CaO和Na₂CO₃活化后粉煤灰中Li的溶出率显著提高,活化后粉煤灰中Li在酸性溶液中的溶出率可达到98%和86%,均高于碱性溶液中Li的溶出率（86%和67%）.XRD的分析结果进一步表明,部分Li可能赋存于非晶相或晶相表面,这部分Li易于被酸或碱直接浸出;部分Li可能镶嵌在莫来石、石英等晶相内部,不易被溶出,经CaO和Na₂CO₃助剂活化后,部分Li又重新嵌入到钙黄长石、霞石等新生成物相的晶格中,而这些物相更易于与酸反应,因而酸性溶液中Li的溶出率普遍高于碱性溶液中的结果.      

粉煤灰提铝中间产物合成4A分子筛对氨氮的吸附行为研究

采用粉煤灰提铝中间产物合成4A分子筛,利用XRD、SEM、热重分析、化学成分分析、阳离子交换容量对4A分子筛进行表征.考察吸附时间、pH、分子筛投加量、氨氮初始浓度、共存阳离子对其吸附性能的影响,研究其对模拟废水中氨氮的吸附效果,并结合准二级动力学方程、吸附等温线研究吸附性能和机理.结果表明,初始浓度为50 mg·L~(-1)、4A分子筛投加量为5 g·L~(-1)、pH值为6~9、吸附时间为80 min时氨氮去除率可达71.34%;随着氨氮初始浓度升高,其去除率降低,吸附容量增加;共存阳离子Na~+、K~+、Ca~(2+)对NH_4~+有强烈的竞争吸附,Mg~(2+)无明显竞争作用.吸附过程符合准二级动力学方程和Freundlich模型.Langmuir吸附等温线显示最大吸附容量为20 mg·g~(-1).     

钢铁行业不同物料的二英生成分布及机理探讨

钢铁行业是我国二噁英的第一大排放源,但对不同钢铁生产过程二英的生成排放认识有所欠缺.本文系统探究了钢铁行业不同物料的二噁英生成能力和同系物分布特征.结果表明,烧结飞灰的二英生成能力最强,而烧结生料生成二噁英能力最弱.3种污泥(连铸、热轧、冷轧)和烧结生料的二英生成途径相似,4种飞灰(电炉、转炉、高炉一次、高炉二次)之间也有相似的二英生成途径,而烧结飞灰则与其他物料均不同.所有物料中,有毒2,3,7,8-PCDD同系物之间存在极强的相关性,且氯酚合成二噁英路径也被发现存在于钢铁生产过程中.     

改性粉煤灰在处理锑矿选矿废水中的应用

针对锑矿选矿废水中锑和丁基黄原酸钠严重超标的问题,用酸改性粉煤灰对其进行吸附处理.试验结果表明,当改性粉煤灰处理选矿废水的最佳质量体积比(g.mL-1)为1:100,pH值为3,静置时间为4h时,可以将选矿废水中的锑浓度从28.611mg.L-1降到0.05mg.L-1以下,去除率达99.8%以上;废水中的丁基黄原酸钠浓度可从0.373mg.L-1降到0.02mg.L-1以下,去除率达95.0%以上.处理废水后的改性粉煤灰用硫酸-硝酸浸提,浸出液中重金属离子浓度均低于国家浸出毒性标准,表明改性粉煤灰是一种很好的锑矿选矿废水处理剂.