调质对垃圾焚烧飞灰烧结处理的影响

为提高经磷酸预处理后的焚烧飞灰在烧结处理过程中的烧结体机械强度,研究了添加SiO2或粉煤灰进行调质,其添加比例对烧结温度和烧结体性能的影响。同时进一步研究了利用硼酸钠作为助熔剂对焚烧飞灰烧结试验影响。结果表明,在烧结温度为1 150℃时,添加30%或者更低比例的SiO₂,或添加20%比例的粉煤灰,焚烧飞灰烧结体已经具有足够的抗压强度和致密化程度。添加5%的硼酸钠时,坯体烧结温度在1 050℃,而添加10%的硼酸钠时烧结温度可降低至980℃。     

某典型生活垃圾焚烧企业烟气中二噁英类变化特征

本文选取了1家典型的生活垃圾焚烧企业作为研究对象,分别采集了净化前和净化后的烟气,结果表明:净化后的烟气中二噁英毒性当量浓度均低于0.1 ng TEQ/Nm 3,去除效率为98.3%;净化前二噁英主要以“从头合成”为主,净化后变化成“前驱物合成”为主;无论是烟气净化前还是净化后,O 8CDD、1,2,3,4,6,7,8-H 7CDD和1,2,3,4,6,7,8-H 7CDF,占比都是最大的;通过相关性分析,1,2,3,4,7,8-H 6CDF质量浓度与I-TEQ相关性最高,可作为二噁英潜在的测定指示物。通过对比研究净化前后的烟气,初步掌握了二噁英工艺流程中变化特征,为企业焚烧控制技术和环境管理提供了数据支持。     

Comparison of CaO’s effect on the fate of heavy metals during thermal treatment of two typical types of MSWI fly ashes in China

Both grate and fluidized bed incinerators are widely used for MSW incineration in China. CaO addition for removing hazardous emissions from MSWI flue gas changes the characteristics of fly ash and affects the thermal behavior of heavy metals when the ash is reheated. In the present work, two types of MSWI fly ashes, sampled from both grate and fluidized bed incinerators respectively, were thermal treated at 1023–1323 K and the fate of heavy metals was observed. The results show that both of the fly ashes were rich in Ca and Ca-compounds were the main alkaline matter which strongly affected the leaching behavior of heavy metals. Ca was mostly in the forms of Ca(OH)₂ and CaCO₃ in the fly ash from grate incinerator in which nascent fly ash particles were covered by Ca-compounds. In contrast, the content of Ca was lower in the fly ash from fluidized bed incinerator and Ca was mostly in the form of CaSO₄. Chemical reactions among Ca-compounds caused particle agglomeration in thermal treated fly ash from grate incinerator, restraining the heavy metals volatilization. In thermal treated fly ash from fluidized bed incinerator, Ca was converted into aluminosilicates especially at 1323 K which enhanced heavy metals immobilization, decreasing their volatile fractions as well as leaching concentrations. Particle agglomeration hardly affected the leaching behavior of heavy metals. However, it suppressed the leachable-CaCrO₄ formation and lowered Cr leaching concentration.     

Online measurements of low-volatile organic chlorine for dioxin monitoring at municipal waste incinerators

In this study, an automatic sampling device and an analysis device have been developed for the measurement of low-volatile organic chlorine (LVOCl) in flue gas. The concentrations of dioxins (polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans, and dioxin-like polychlorinated biphenyls) have been estimated by online measurements of LVOCl at a municipal solid waste incinerator (MSWI) using these devices. The LVOCl concentration at the outlet of the selective catalyst reactor (SCR) of the MSWI increased momentarily up to 95 μg Cl m⁻³ during the startup period of the MSWI; subsequently, it gradually decreased to less than 1.0 μg Cl m⁻³ after 50 h from the start of waste feeding. The concentration of toxic equivalent quantity (TEQ)-Dioxins at the SCR outlet had a linear positive relationship with the LVOCl concentrations. Moreover, the level of TEQ-Dioxins concentration can be estimated by using this relationship with LVOCl. From our results, since the LVOCl concentrations in a flue gas can thus be automatically analyzed every hour by online measurements, the operators of an MSWI would be able to monitor approximate TEQ-Dioxin emissions on a daily basis.     

Impacts of natural weathering on the transformation/neoformation processes in landfilled MSWI bottom ash: a geoenvironmental perspective

Natural weathering processes are significant mechanisms that noticeably affect the fundamental nature of incineration ash residues. To provide a greater understanding of these processes, a MSWI (mono)landfill site in the north east of the US was selected as the target for systematic investigation of the natural weathering of bottom ash residues. Samples of various ages were collected from locations A (1 yr), B (10 yrs), C (13-14 yrs) and D (20 yrs) of the landfill in 2009. We investigated the phase transformation of the collected bottom ash particles, neoformation processes as well as the behavior and distribution of certain heavy metals (Cu, Pb, Zn, Ni, and Cr) in the neoformed phases using optical microscopy, SEM-EDX, and bulk examinations. Key findings: at the preliminary stage, the waste metallic particles (Al, Fe, and Cu) and unstable minerals such as lime, portlandite, ettringite and hydrocalumite convert to oxide and hydroxide (hydrate) phases, calcite, alumina gel and gypsum. At the intermediate stage, the decomposition of melt products including magnetite spinels and metallic inclusions is triggered due to the partial dissolution of the melt glass. At the longer time horizon it is possible to track the breakdown of the glass phase, the extensive formation of calcite and anhydrite, Al-hydrates and more stable Fe-hydrates all through the older ash deposits. Among the dominant secondary phases, we propose the following order based on their direct metal uptake capacity: Fe-hydrates>Al-hydrates>calcite. Calcite was found to be the least effective phase for the direct sorption of heavy metals. Based on overall findings, a model is proposed that demonstrates the general trend of ash weathering in the landfill.     

生活垃圾焚烧飞灰重金属的受热特性

研究了飞灰重金属在不同煅烧温度下的挥发情况及其存在形态.结果表明:重金属挥发能力由强到弱依次为Hg＞Pb＞As、Cd＞Zn＞Cr、Ni、Cu;其中Hg、Pb、As和Cd属易挥发重金属,在1 150 ℃时几乎全部挥发;Zn属较易挥发重金属,1 150 ℃时的挥发率在40%～50%;Cr、Ni和Cu属难挥发重金属,在1 150 ℃的挥发率不超过10%;在400～1 150 ℃,随温度的升高,部分Zn、Hg、Cu、Pb、Cd、Ni和As由可溶态向残渣态、铁锰氧化态转化;在400～900 ℃,随温度的升高Cr可溶态比例减少,而在900～1 150 ℃,随温度的升高其可溶态比例增加.     

采用烧结法降低垃圾焚烧飞灰浸出毒性的研究

采用电感耦合等离子体发射光谱仪（ICP-AES）对垃圾焚烧飞灰和造粒烧结后试样中重金属的浸出量进行分析.研究表明,随着烧结时间的增加和烧结温度的提高,大多数重金属浸出毒性都有所降低.对造粒后的飞灰物料进行低温烧结处理,烧结工艺参数可初步定为造粒直径为15mm,烧结温度为950℃-1100℃,烧结时间约为20min.     

Quantification of the resource recovery potential of municipal solid waste incineration bottom ashes

Municipal solid waste incineration (MSWI) plays an important role in many European waste management systems. However, increasing focus on resource criticality has raised concern regarding the possible loss of critical resources through MSWI. The primary form of solid output from waste incinerators is bottom ashes (BAs), which also have important resource potential. Based on a full-scale Danish recovery facility, detailed material and substance flow analyses (MFA and SFA) were carried out, in order to characterise the resource recovery potential of Danish BA: (i) based on historical and experimental data, all individual flows (representing different grain size fractions) within the recovery facility were quantified, (ii) the resource potential of ferrous (Fe) and non-ferrous (NFe) metals as well as rare earth elements (REE) was determined, (iii) recovery efficiencies were quantified for scrap metal and (iv) resource potential variability and recovery efficiencies were quantified based on a range of ashes from different incinerators. Recovery efficiencies for Fe and NFe reached 85% and 61%, respectively, with the resource potential of metals in BA before recovery being 7.2%ww for Fe and 2.2%ww for NFe. Considerable non-recovered resource potential was found in fine fraction (below 2 mm), where approximately 12% of the total NFe potential in the BA were left. REEs were detected in the ashes, but the levels were two or three orders of magnitude lower than typical ore concentrations. The lack of REE enrichment in BAs indicated that the post-incineration recovery of these resources may not be a likely option with current technology. Based on these results, it is recommended to focus on limiting REE-containing products in waste for incineration and improving pre-incineration sorting initiatives for these elements.     

烧结条件对垃圾焚烧飞灰中重金属固定率的影响

研究了烧结试验条件的变化对焚烧飞灰中重金属分布的影响规律,并进一步探讨了焚烧飞灰烧结过程中重金属的固定途径和固定效应。结果表明:烧结温度的升高会导致重金属挥发率的升高,Pb的挥发率从1 050℃的97.1%升高到1 180℃的99.7%;而Zn的挥发率从1 050℃的35.5%升高至55.2%。通过降低焚烧飞灰中氯盐含量,能够降低Zn与Pb的挥发速率。对原飞灰和水洗灰,延长烧结时间会造成Zn与Pb的挥发率升高而固定率下降。磷酸灰的变化情况与原飞灰及水洗灰不同,Zn与Pb的固定率随烧结时间的延长出现了小幅度的增加。     

垃圾焚烧飞灰中重金属的污染特性

以广西和重庆某生活垃圾焚烧厂的焚烧飞灰为研究对象,研究了飞灰中重金属的化学形态、不同粒径下飞灰中重金属含量及浸出毒性。结果表明:广西垃圾焚烧飞灰中含有5种重金属,且都是以残渣态为主要存在形态;重庆垃圾焚烧飞灰中Cr以残渣态为主要存在形态,Zn、Cu和Cd以醋酸可提取态为主要存在形态,具有较大的潜在毒性,毒性较强的Pb只以醋酸可提取态和可还原提取态两种形态存在,危险性非常高,Mn以可还原提取态为主要存在形态。两地飞灰中含量较高的重金属元素都表现出向小颗粒富集趋势。随飞灰颗粒粒径的减小,各重金属浸出量基本呈增加趋势。相比之下,重庆的垃圾焚烧飞灰中Zn、Cu、Pb和Cd的含量和浸出量都高于广西飞灰。广西飞灰中各粒级的飞灰中各元素浸出量均不超标,而重庆飞灰各粒级的飞灰中Zn、Pb和Cd的浸出量严重超标,表明重庆飞灰属于典型危险废物。