垃圾焚烧底渣中重金属的研究

采用Tessier四步分级提取法对垃圾焚烧飞灰中的4种重金属(锌、镍、铜、镉)的化学形态进行了研究。结果表明,金属Cd主要以底渣态的形式存在(占总镉质量的61.22%~62.41%),Ni,Zn以底渣态和铁锰氧化态为主,Cu主要以有机结合态为主(占总铜质量的60.97%~62.29%)。同时4种金属的生物有效性由高到低顺序依次为Ni,Cd,Zn,Cu。     

The leachability of heavy metals in hardened fly ash cement and cement-solidified fly ash

The effect of mix proportion, leachant pH, curing age, carbonation and specimen making method etc. on the leaching of heavy metals and Cr(VI) in fly ash cement mortars and cement-solidified fly ashes has been investigated. In addition, a method for reducing the leaching of Cr(VI) from cement-solidified fly ashes is proposed. The results mainly indicate that: (1) either Portland cement or fly ash contains a certain amount of heavy and toxic metals, and the leaching of them from hardened fly ash incorporated specimens exists and is increased with fly ash addition and water to cement ratio; (2) the leachability of some heavy metals is greatly dependent on leachant pH; (3) when carbonation of cement mortars occurs the leaching of chromium ions is increased; (4) the amount of heavy metals leached from cement-solidified fly ashes depends more on the kind of fly ash than their contents in fly ash; and (5) with ground granulated blast furnace slag addition, the leaching of Cr(VI) from solidified fly ashes is decreased.     

Removal of heavy metals from municipal solid waste incineration (MSWI) fly ash by traditional and microwave acid extraction

BACKGROUND: Municipal solid waste incinerator (MSWI) fly ash is regarded as hazardous waste because it contains various toxic metals. A previous study has shown that fly ash can be detoxified by removal of heavy metals. In this work, the extractability of heavy metals from MSWI fly ash by traditional and microwave acid extraction were compared. RESULTS: A 2^{4 ? 1} fractional factorial experimental design was adopted using acid concentration, extraction time, temperature, and liquid/solid (L/S) ratio as the experimental factors for traditional extraction, and acid concentration, extraction time, liquid/solid (L/S) ratio and microwave power as the experimental factors for microwave extraction. The traditional extraction results show that L/S played an important role in Zn, Cd extraction while L/S ratio and extractant concentration were important for Pb extraction. However, no controlling parameter was determined for Cu and Cr extraction. For the microwave extraction, it was shown that L/S was important for Pb and Zn and extractant concentration was important for Pb, Zn and Cd. The time and the power were not significant for the extractability of heavy metals. CONCLUSION: Hydrochloric acid was an effective extractant. Microwave heating promoted extraction and shortened extraction time. Microwave acid extraction treatment is a potentially feasible method for the removal of heavy metals from MSWI fly ash. Copyright © 2010 Society of Chemical Industry     

Electrokinetic remediation of bottom ash from municipal solid waste incinerator

The electrokinetic remediation was studied to verify the possibility to reclaim the bottom ash from municipal solid waste incineration (MSWI). In Italy, a production of 1 million tons per year of this kind of residue has been estimated, 90% of which is still landfilled. This work shows the results of four electrokinetic remediation tests for the removal of Pb, Cu, Zn, Cd and chlorides, using an open cell with graphite electrodes and without enhancing agents. The four tests have, respectively, been performed at a constant current density of 0.89, 1.67, 2.04 and 2.48 mA cm⁻², with duration of 42, 68, 47 and 40 h. Heavy metals occur in ashes in various forms, such as exchangeable, adsorbed, precipitated, organically complexed and residual phases. In order to determine the nature of any given system, in terms of specific chemical species and pertaining mobilities, sequential extraction analyses have been performed. The release of pollutants was investigated for treated and untreated ash. After treatment, the concentration of pollutants in the leachate was reduced by 31-83%, better results being obtained for chlorides. Both the low amount of heavy metal extracted and the increase of ash pH during the electrokinetic tests, suggest to use enhancing agents or a cation exchange membrane at the cathode, to prevent the precipitation of metals as hydroxides.     

利用响应面法优化皂角苷浸提飞灰中重金属的处理条件

通过响应面法对皂角苷浸提飞灰中Cu、Zn、Pb和Cd 4种重金属的实验条件进行优化,选取pH、皂角苷浓度、离子强度、温度、时间和固液比6个因素进行中心组合设计,使用design-expert8.0软件进行数据拟合,建立了Cu、Zn、Pb和Cd去除总量的工艺数学模型,通过方差分析得到6个因素对浸提液中4种重金属去除总量的主效应关系为： pH>固液比>离子强度>皂角苷浓度>温度>时间。对重金属去除总量数据进行design-expert8.0软件优化,得到皂角苷浓度为41.2g·L^-1、时间为13.54 h、离子强度为0.64 mol·L^-1、pH为2、固液比为1%和温度为23.4℃时,重金属总去除量达最大值,Cu、Zn、Pb和Cd的去除率分别达到55.12%、6.20%、17.80%和78.11%。     

硅铝调控与晶种诱导对水热稳定飞灰中重金属的协同影响

研究了选取的粉煤灰、膨润土、高岭土、硅藻土作为外源硅铝调理剂添加与雪硅钙石人工晶种诱导对150℃水热法稳定垃圾焚烧飞灰中重金属Pb、Zn、Cu、Cd、Cr的协同影响。飞灰由于富钙而低硅铝的元素特征,导致其在水热条件下无法直接合成沸石类,Pb的浸出浓度仍然超标;当单一或混合添加硅铝调理剂添加量为10%时,其水热产物中有水钙铝榴石或加藤石生成;提高添加量至30%时,均有目标雪硅钙石的生成,这与30%添加量下飞灰中Ca/（Al+Si）元素比接近雪硅钙石的理想元素比值0.67~1.20直接相关。混合添加30%的粉煤灰与硅藻土为最佳选择,水热产物Pb的浸出浓度降低至0.30 mg·L^-1,且在此基础上再添加3%的诱导晶种可加速从第6 h开始即合成雪硅钙石,并使Pb的浸出浓度下降到最低值0.28 mg·L^-1。硅铝调控（30%的复合硅铝调理剂,其中粉煤灰：硅藻土为1：1）与晶种诱导的协同影响下高效生成雪硅钙石,并显著抑制Pb、Zn等在水热过程中向液相的转移、降低其在水热液相中的浓度,使飞灰中的重金属在水热后确实稳定于水热固相产物中而非迁移至水热液相造成污染转移,真正实现了飞灰中重金属的固定化。     

Comparison of the fixation of heavy metals in raw material, clinker and mortar using a BCR sequential extraction procedure and NEN7341 test

The release potential and leaching behavior of five heavy metals (As, Cd, Cr, Cu and Pb) in raw material, clinker and mortar were studied by the three-step sequential extraction procedure proposed by the commission of the European Communities Bureau of Reference (BCR) and NEN7341 leaching test. The results of two experimental methods were compared to show the fixation difference of heavy metals among three kinds of samples. The results of NEN7341 leaching test show that the maximum leached concentration of cement products is low and the leached fraction of five heavy metals represents less than 15% of the total heavy metal content of the cement product. To refer to the bulk content as a criterion of environmental impact is not appropriate. The results of sequential extraction procedures show that the bonding forms of heavy metals change a lot in three samples. The contamination factor (Cf) and the leached fraction of each element in three samples indicate that all the elements are better fixed in cement products than in raw material due to calcination and hydration. To most elements, the relative metal retention is higher in mortar than in clinker. Compared within the five analyzed elements, Cd is better retained and Cu is worse retained in the same kind of sample.     

柱淋滤模式下生活垃圾焚烧炉渣中Cu2+和Zn2+浸出规律

垃圾焚烧炉渣是一种活性材料,在其储存、预处理及应用等过程与雨水频繁接触时,炉渣中重金属随着水域环境发生迁移和浸出现象。本研究采用连续柱淋滤试验装置模拟自然降雨,开展了0～5mm和5～10mm焚烧炉渣的动态淋滤毒性浸出分析,重点研究了pH和降雨强度对Cu²⁺和Zn²⁺的浸出影响。结果表明,动态淋滤过程中,淋滤液pH变化对Cu²⁺和Zn²⁺的浸出水平影响显著,且在酸性较强淋滤液作用下Cu²⁺浸出水平比Zn²⁺更强,与Ⅴ类地表水环境浓度限值对比,在整个淋滤时间内Cu²⁺浸出浓度严重超标,在炉渣工程应用时需预防相关的环境风险;原生炉渣粒径大小与重金属浸出水平无直接相关性,但是0～5mm细炉渣中可浸出Zn²⁺含量更高,这与细颗粒物中Zn赋存形态和可溶出态含量较高有关;淋滤强度对重金属浸出水平影响主要反应了动态淋滤过程液固比和水分运移速率情况,当较低淋滤强度时具有低液固比,溶出液中重金属含量较高。     

Recycling of bottom ash from biomass combustion in porcelain stoneware tiles: Effects on technological properties,phase evolution and microstructure

This work aims to evaluate the use of bottom biomass ash as an alternative raw material in porcelain stoneware bodies. For this purpose, ash coming from a biomass thermoelectric power plant in Emilia-Romagna (Italy) was selected and its chemical, mineralogical and thermal properties determined. Data indicated its technological role as a flux, so it was introduced in a porcelain stoneware batch in partial replacement of feldspars and experimented at laboratory scale. A bottleneck, relative to the rheological behavior of the slips, was overcome by a slight deflocculant increase. The powder compacts were fired from 1000° to 1220 °C in order to follow the evolution of the technological properties, phase composition (XRPD-Rietveld) and microstructure (SEM). The introduction of ash allowed to lower the firing temperature by 20 °C, while keeping the technological properties comparable with those of the benchmark. Moreover, the mineralogical and microstructural data revealed different sintering kinetics.     

Analysis of fly ash heavy metal content and disposal in three thermal power plants in India

The study investigates the heavy metal content of fly ash and bottom ash from three major power plants in North India, using flame atomic absorption spectrometry. It also studies the prevalent disposal methods used at these sites. The ashes were analysed for the presence of Cr, Mn, Pb, Zn, Cu, Ni and Co and detectable levels of all were found in both fly ash and bottom ash. The concentrations of Cr and Zn were highest while Co concentration was less. The wet disposal method is used in two of the power plants (site 1 and site 3). Neither of the sites uses ash pond lining in the construction of the ash ponds, hence leaching of the heavy metals is possible. Site 2 has adopted 100% dry disposal system which allows better utilization but incurs additional costs. Better management practices, increased utilization and proper disposal practices need to be undertaken to minimize the adverse environmental impact.     

掺烧生活垃圾焚烧飞灰和炉渣对水泥熟料矿物组成的影响

分别对掺烧20%生活垃圾焚烧炉渣的熟料和掺烧10%生活垃圾焚烧飞灰的熟料进行化学成分分析、相萃取、XRD分析与岩相分析,并与用化学纯试剂配料煅烧的基准样熟料进行对比研究。研究结果发现,受灰渣中较高含量的硫、氯等阴离子的影响,熟料KH值会降低;受灰渣当中微量重金属元素的影响,掺烧灰渣熟料的铁相中有少量C2F存在,并且其C4AF特征峰的d值增大。     

Effects of heavy metals and polyelectrolytes in humic substance coagulation under saline conditions

Charge neutralisation plays a major role in heavy metal and humic substance removal in water treatment. Humic substances have no readily identifiable structure and they consist of anionic macromolecules of low to moderate molecular weight. Humic substances are easily coagulated using cationic metals and polyelectrolytes. Different concentrations of humic substances have been coagulated with different concentrations of heavy metals and/or polyelectrolytes. The charge neutralisation was determined using U.V. spectrophotometer. Humic substance removal increased with increasing salinity level until reaching a point where HS destabilization is considered complete and salinity no longer play a role in HS removal. Humic substance removal increased with increasing heavy metals concentration and precipitation was experienced at high concentrations of heavy metals (15–20 mg/L) and low concentration of humic substances (10 mg/L). In addition, HS removal also increased with increasing polyelectrolyte concentration. Diallydimethylammonium chloride (PDADMAC) polyelectrolyte was more effective in humic substance coagulation compared to copolymer of dimethyl aminoethyl acrylate (CoAA). The addition of heavy metals in polyelectrolyte coagulation increased humic substance removal due to the combined charge neutralization of the metals and polyelectrolytes.     

Migration,transformation and solidification/stabilization mechanisms of heavy metals in glass-ceramics made from MSWI fly ash and pickling sludge

In consideration of recycling solid waste to achieve high value-added products, glass-ceramics have been fabricated from municipal solid waste incineration (MSWI) fly ash, pickling sludge (PS), and waste glass (WG) by melting at 1450 °C firstly to achieve parent glass and then crystallizing at 850 °C. Results demonstrated that heavy metals have been well solidified in the prepared glass-ceramics, and relatively/extremely low leaching concentrations of heavy metals have been detected. The synthetic toxicity index of heavy metals has been greatly reduced from 7-18 to <3.2 after crystallization treatment, and the leaching concentrations of Cr, Ni, Zn, Cu, and Pb are 0.15, 0.05, 0.26, 0.12, 0.19 mg L^-1 respectively. Chemical morphology analysis, principal component analysis, TEM and EPMA were utilized to clarify the migration, transformation, and solidification mechanism of heavy metals from the as-received solid wastes. The major heavy metals, Cr and Ni which is responsible for the most toxicity, mainly exist in form of the oxidation state and residual state in parent glass, while the residual state in the glass-ceramics. The solidification performance was mostly positively correlated with the form of residue state, which the stability of heavy metals in glass-ceramics is improved. The solidification mechanism of heavy metals in glass-ceramics could be explained by the combination of chemical solidification/stabilization and physical coating. The TEM and EPMA confirmed that Cr and Ni mainly exist in the spinel crystalline (NiCr₂O₄, Fe_0.99Ni_0.01Fe_1.97Cr_0.03O₄) by solid solution or chemical substitution, and a small amount of Cr in the diopside phase. Pb, Cu, and Zn are homogenously dispersed in the glass-ceramics, which is considered as physical coating solidification.     

Comparing different methods of analysing sewage sludge, dewatered sewage sludge and sewage sludge ash

The following article compares different ways of characterising sewage sludge. Against the background of sludge recycling in agriculture as well as treatment with subsequent phosphorus recovery in mind, the article starts by collating and evaluating the levels of phosphorus, heavy metals, chlorine and sulphur in sludge as reported in the literature. Sewage sludge from the sewage treatment plant at Kaditz in Dresden was analysed using standardised and adjusted methods, which produced different results. In the course of this analysis the results were produced by using elemental analysis, atomic absorption spectroscopy, X-ray fluorescence spectroscopy (X-RFA) and ion chromatography (IC). The second part of the article therefore seeks reasons for the differences in the findings and tries to give solution statements. The article closes by calculating transfer coefficients for selected parameters during the incineration process and solid-liquid separation and weighing up the analysis techniques compared. Basically this article will show significant differences in sludge composition and the effects on the specific elements by ashing or mechanical dewatering of the different sludges. An essential attention obtains the analysis by using the X-RFA.     

Potential utilization of oil sludge incineration bottom ash for glass-ceramics: Crystallization kinetics,properties and toxicological evaluation

The bottom ash (OIBA) generated from the incineration of hazardous oil sludge is classified as a hazardous waste. In this work, the OIBA was applied as raw material to prepare SiO₂-Al₂O₃-CaO system glass-ceramics by melt-sintering with the addition of waste glass wool (GW). The effects of basicity (CaO/SiO₂ ratio, 0.52-1.05) and sintering temperature (900–1050 °C) on the crystallization kinetics, properties, microstructure, leaching concentrations of heavy metals and potential toxicity of glass-ceramics were investigated. The results showed that the crystallization pattern was two-dimensional crystallization, and with the decrease of basicity, the main crystalline phase evolved from gehlenite to diopside. And the glass-ceramics with basicity of 0.88 and sintering temperature of 950 °C exhibited the best comprehensive properties, including density (2.72 g/cm³), water absorption (0.06%), compressive strength (452.45 MPa) and chemical corrosion resistance. In addition, the reduction of heavy metal leaching concentration indicates that produced glass-ceramics showed excellent solidification effect on heavy metals, the low toxicity of glass-ceramics leaching solution to the wheat seeds and Artemia suggests the environmental protection characteristics of OIBA-based glass-ceramics. These findings proved that the glass-ceramics produced by OIBA and GW could be a promising method to dispose hazardous waste with preparing high value-added construction materials.     

Recovery of vanadium and nickel in fly ash from heavy oil

Recovery of vanadium and nickel from an oil fly ash is studied in a two-step leaching process, carried out under ambient pressure without calcination. In the leaching, nickel is dissolved with NH₄Cl in the first step, followed by vanadium leaching with Na₂CO₃ in the second step. Both leachants depress the dissolution of iron and aluminium from the ash and hence the selective leachings are feasible. Nickel was recovered in 87% yield from the leach liquor by precipitation with Na₂S, the purity of NiS being over 99% on the basis of the target metals (V, Ni, Fe, Al and Mg). For the recovery of vanadium, which has a relatively low concentration in the leach liquor, solvent extraction with TOA is preferable to concentration, prior to crystallization with NH₄Cl. The experimental data showed that the vanadium concentration of the stripping solution is increased by about 15 times that of the leach liquor, which results in 78% yield as NH₄VO₃ crystals.     

Use of zeolite, coal bottom ash and fly ash as replacement materials in cement production

In this research, the effects of zeolite, coal bottom ash and fly ash as Portland cement replacement materials on the properties of cement are investigated through three different combinations of tests. These materials are substituted for Portland cement in different proportions, and physical properties such as setting time, volume expansion, compressive strength and water consistency of the mortar are determined. Then, these physical properties are compared with those of PC 42.5. The results showed that replacement materials have some effects on the mechanical properties of the cement. The inclusion of zeolite up to the level of 15% resulted in an increase in compressive strength at early ages, but resulted in a decrease in compressive strength when used in combination with fly ash. Also, setting time was decreased when zeolite was substituted. The results obtained were compared with Turkish Standards (TS), and it was found that they are above the minimum requirements.     

废水中EDTA与总重金属含量的同时测定

在被EDTA和重金属离子污染的废水中，由于它们之间的络合作用，很难用简单的方法测出二者的含量。本文在强酸性和加入助萃络合剂的条件下，使EDTA与重金属离子分离。采用离子缔合萃取法，将水中的重金属离子萃于有机相，用分光光度法可测定出水中EDTA的总浓度。另取一份平行样，加入过量且定量的EDTA标准溶液，同水中未与EDTA络合的重金属离子络合，再进行返滴定。通过萃取与返滴定的巧妙结合，可求出水中重金属离子的总量。本法操作简便、快速，不需大型仪器，特别适合于被EDTA和(或)重金属离子污染的废水测定。     

Rationale of lead immobilization by ball milling in synthetic soils and remediation of heavy metals contaminated tailings

In this work, the use of mechanical milling for the remediation of heavy metals in synthetic soils and tailings sampled from the mining area of “Barraxiutta”, SW of Sardinia, Italy is investigated. Specifically, Pb(II) contaminated synthetic soils of sandy, bentonitic and kaolinitic type are taken into account following the results obtained in previous works. Suitable sequential extraction procedures have been performed on both untreated and treated synthetic soils. It is found that mechanical loads which occur during collisions among milling media and soils are able to modify the distribution of Pb(II) onto the different solid fractions of contaminated synthetic soils. Specifically, for sandy soils the milling treatment induces a significant increase in Pb(II) content in the Fe–Mn oxides fraction. On the other hand, for bentonitic and kaolinitic soils, Pb(II) content in both carbonate and Fe–Mn oxide fractions is augmented after treatment. Such phenomena may contribute to Pb(II) immobilization efficiency since the heavy metal trans-speciation occurs in favor of fractions characterized by stronger bonds and lower solubility.As for the heavy metals contaminated tailings, their immobilization is obtained using both ball and attrition milling devices under specific ball to powder ratio values. The degree of metals immobilization is evaluated by analyzing the corresponding leachable fraction obtained through the Synthetic Precipitation Leaching Procedure (SPLP) proposed by EPA. X-ray diffraction and granulometric analyses revealed no significant alterations of the intrinsic character of the tailings after milling except for a relatively small increase in particles size.The increase in immobilization efficiency when tailings are mechanically treated may be due to specific phenomena induced during milling such as entrapment of heavy metals into aggregates, solid diffusion of metals into the crystalline reticulum of soil particles, the formation of new fresh surfaces onto which heavy metals may be irreversibly adsorbed as well as metal trans-speciation onto tailings fractions characterized by stronger bonds and lower solubility.     

垃圾焚烧飞灰重金属药剂稳定化研究进展

生活垃圾焚烧飞灰中存有大量高毒性的重金属物质,若不规范处置容易对土壤、地下水造成严重污染,目前通常采用添加化学药剂的方法来稳定飞灰中的重金属。本文在梳理国内外文献的基础上,归纳评述了飞灰重金属的性质、固化稳定化填埋工艺以及目前已被研究或应用的飞灰重金属稳定药剂,包括硫化钠、磷酸、无定形硅材料、铁化合物等无机药剂以及硫脲、EDTA接聚体、壳聚糖、氨基硫代羧酸盐等有机螯合剂,阐明了药剂作用机制和存在的问题,总结了不同药剂作用下的重金属稳定效果,同时针对新形势下的飞灰重金属稳定化要求进行了探讨,提出今后的研究方向为：选择特征性重金属药剂复配稳定飞灰;以改性、成环方式改良氨基硫代羧酸盐类物质（DTC）物质或以交联接枝等方式开发新型螯合剂。