Chemical and mineralogical evaluation of slag products derived from the pyrolysis/melting treatment of MSW

This paper provides the results of studies on the characteristics of novel material derived from pyrolysis/melting treatment of municipal solid waste in Japan. Slag products from pyrolysis/melting plants were sampled for the purpose of detailed phase analysis and characterization of heavy metal-containing phases using optical microscopy, electron probe microanalysis (EPMA), XRF and XRD. The study revealed that the slag material contains glass (over 95%), oxide and silicate minerals (spinel, melilite, pseudowollastonite), as well as individual metallic inclusions as the major constituents. A distinct chemical diversity was discovered in the interstitial glass in terms of silica content defined as low and high silica glass end members. Elevated concentrations of Zn, Cr, Cu, Pb and Ba were recorded in the bulk composition. Cu, Pb and Ba behave as incompatible elements since they have been markedly characterized as part of polymetallic alloys and insignificantly sulfides in the form of spherical metallic inclusions associated with tracer amounts of other elements such as Sb, Sn, Ni, Zn, Al, P and Si. In contrast, an appreciable amount of Zn is retained by zinc-rich end members of spinel and partially by melilite and silica glass. Chromium exhibits similar behavior, and is considerably held by Cr-rich spinel. The intense incorporation of Zn and Cr into spinel indicates the very effective enrichment of these two elements into phases more environmentally resistant than glass. There was no evidence, however, that Cu and Pb enter into the structure of the crystalline silicates or oxides that may lead to their easier leachability upon exposure to the environment.     

Influence of aeration modes on leachate characteristic of landfills that adopt the aerobic–anaerobic landfill method

As far as the optimal design, operation, and field application of the Aerobic–Anaerobic Landfill Method (AALM) are concerned, it is very important to understand how aeration modes (different combinations of aeration depth and air injection rate) affect the biodegradation of organic carbon and the transformation of nitrogen in landfill solid waste. Pilot-scale lysimeter experiments were carried out under different aeration modes to obtain detailed information regarding the influence of aeration modes on leachate characteristics. Results from these lysimeter experiments revealed that aeration at the bottom layer was the most effective for decomposition of organic carbon when compared with aeration at the surface or middle layers. Moreover, the air injection rate led to different nitrogen transformation patterns, unlike the lesser influence it has on organic carbon decomposition. Effective simultaneous nitrification and denitrification were observed for the aeration mode with a higher air injection rate (=1.0 L/min). On the other hand, the phenomenon of sequenced nitrification and denitrification could be observed when a low air injection rate (=0.5 L/min.) was employed. Finally, it is concluded that, for AALM, air injection with a higher air injection rate at the deepest layer near the leachate collection pipe tends to accelerate the stabilization of landfill waste as defined in terms of the enhancement of denitrification as well as organic carbon decomposition.     

Hydrothermal treatment of MSWI bottom ash forming acid-resistant material

To recycle municipal solid waste incinerator (MSWI) bottom ash, synthesis of hydrothermal minerals from bottom ash was performed to stabilize heavy metals. MSWI bottom ash was mixed with SiO(2), Al(OH)(3), and Mg(OH)(2) so its chemical composition was similar to that of hydrothermal clay minerals. These solid specimens were mixed with water at a liquid/solid ratio of 5. The reaction temperature was 200 degrees C, and reactions were performed for 24-240h. Generation of kaolinite/smectite mixed-layer clay mineral was found in the samples after the reaction of the mixture of bottom ash, SiO(2), and Mg(OH)(2). Calcium silicate hydrate minerals such as tobermorite and xonotlite were also generated. X-ray powder diffraction suggested the presence of amorphous materials. Leaching tests at various pHs revealed that the concentration of heavy metals in the leachates from MSWI bottom ash hydrothermally treated with SiO(2) and Mg(OH)(2) was lower than that in leachates from non-treated bottom ash, especially under acid conditions. Hydrothermal treatment with modification of chemical composition may have potential for the recycling of MSWI bottom ash.     

Atmospheric mercury emissions from waste combustions measured by continuous monitoring devices

Atmospheric mercury emissions have attracted great attention owing to adverse impact of mercury on human health and the ecosystem. Although waste combustion is one of major anthropogenic sources, estimated emission might have large uncertainty due to great heterogeneity of wastes. This study investigated atmospheric emissions of speciated mercury from the combustions of municipal solid wastes (MSW), sewage treatment sludge (STS), STS with waste plastics, industrial waste mixtures (IWM), waste plastics from construction demolition, and woody wastes using continuous monitoring devices. Reactive gaseous mercury was the major form at the inlet side of air pollution control devices in all combustion cases. Its concentration was 2.0–70.6 times larger than elemental mercury concentration. In particular, MSW, STS, and IWM combustions emitted higher concentration of reactive gaseous mercury. Concentrations of both gaseous mercury species varied greatly for all waste combustions excluding woody waste. Variation coefficients of measured data were nearly equal to or more than 1.0. Emission factors of gaseous elemental mercury, reactive gaseous mercury, and total mercury were calculated using continuous monitoring data. Total mercury emission factors are 0.30 g-Hg/Mg for MSW combustion, 0.21 g-Hg/Mg for STS combustion, 0.077 g-Hg/Mg for STS with waste plastics, 0.724 g-Hg/Mg for industrial waste mixtures, 0.028 g-Hg/Mg for waste plastic combustion, and 0.0026 g-Hg/Mg for woody waste combustion. All emission factors evaluated in this study were comparable or lower than other reported data. Emission inventory using old emission factors likely causes an overestimation.

Implications Although waste combustion is one of major anthropogenic sources of atmospheric mercury emission, estimated emission might have large uncertainty due to great heterogeneity of wastes. This study investigated speciated mercury emissions from the combustions of municipal solid wastes, sewage treatment sludge with/without waste plastics, industrial waste mixtures, waste plastics from construction demolition, and woody wastes using continuous monitoring devices. Reactive gaseous mercury was the major form in all combustion cases and its concentration in the gas had large fluctuation. All emission factors evaluated in this study were comparable or lower than other reported data. Emission inventory using old emission factors likely causes an overestimation.     

Field study of nitrous oxide production with in situ aeration in a closed landfill site

Nitrous oxide (N₂O) has gained considerable attention as a contributor to global warming and depilation of stratospheric ozone layer. Landfill is one of the high emitters of greenhouse gas such as methane and N₂O during the biodegradation of solid waste. Landfill aeration has been attracted increasing attention worldwide for fast, controlled and sustainable conversion of landfills into a biological stabilized condition, however landfill aeration impel N₂O emission with ammonia removal. N₂O originates from the biodegradation, or the combustion of nitrogen-containing solid waste during the microbial process of nitrification and denitrification. During these two processes, formation of N₂O as a by-product from nitrification, or as an intermediate product of denitrification. In this study, air was injected into a closed landfill site and investigated the major N₂O production factors and correlations established between them. The in-situ aeration experiment was carried out by three sets of gas collection pipes along with temperature probes were installed at three different distances of one, two and three meter away from the aeration point; named points A-C, respectively. Each set of pipes consisted of three different pipes at three different depths of 0.0, 0.75 and 1.5 m from the bottom of the cover soil. Landfill gases composition was monitored weekly and gas samples were collected for analysis of nitrous oxide concentrations. It was evaluated that temperatures within the range of 30–40°C with high oxygen content led to higher generation of nitrous oxide with high aeration rate. Lower O₂ content can infuse N₂O production during nitrification and high O₂ inhibit denitrification which would affect N₂O production. The findings provide insights concerning the production potentials of N₂O in an aerated landfill that may help to minimize with appropriate control of the operational parameters and biological reactions of N turnover.

Implications: Investigation of nitrous oxide production potential during in situ aeration in an old landfill site revealed that increased temperatures and oxygen content inside the landfill site are potential factors for nitrous oxide production. Temperatures within the range of optimum nitrification process (30–40°C) induce nitrous oxide formation with high oxygen concentration as a by-product of nitrogen turnover. Decrease of oxygen content during nitrification leads increase of nitrous oxide production, while temperatures above 40°C with moderate and/or low oxygen content inhibit nitrous oxide generation.     

Characterization of chlorine and heavy metals for the potential recycling of bottom ash from municipal solid waste incinerators as cement additives

Bottom ash is an inevitable by-product from municipal solid waste (MSW) incineration plants. Recycling it as additives for cement production is a promising disposal method. However, the heavy metals and chlorine are the main limiting factors because of the potential environmental risks and corrosion of cement kilns. Therefore, investigating heavy metal and chlorine characteristics of bottom ash is the significant prerequisite of its reuse in cement industries. In this study, a correlative analysis was conducted to evaluate the effect of the MSW components and collection mode on the heavy metal and chlorine characteristics in bottom ash. The chemical speciation of insoluble chlorine was also investigated by synchrotron X-ray diffraction analysis. The results showed that industrial waste was the main source of heavy metals, especially Cr and Pb, in bottom ash. The higher contents of plastics and kitchen waste lead to the higher chlorine level (0.6 wt.%–0.7 wt.%) of the bottom ash. The insoluble chlorine in the MSW incineration bottom ash existed primarily as AlOCl, which was produced under the high temperature (1250°C) in incinerators.

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生活垃圾焚烧飞灰差异性特征对脱氯除盐效果影响研究——以重庆和天津飞灰为例

随着生活垃圾焚烧技术的普及,垃圾焚烧飞灰的资源化利用迫在眉睫,然而飞灰中的高浓度氯元素严重阻碍了其资源化进程.水洗技术作为常用的脱氯除盐技术,得到越来越多的应用,但除氯效果受飞灰自身性质特征影响较大.本研究从重庆和天津采集了两种理化性质具有较大差异的垃圾焚烧飞灰,在对其粒径分布、化学组成、矿物组成、pH值和浸出毒性等基本特征进行分析表征的基础上,采用水洗技术和碳酸化水洗技术对两种飞灰进行了脱氯处理.结果表明,重庆飞灰氯元素的赋存形态包括NaCl、KCl等可溶性氯盐,还含有较高浓度的难溶氯盐(如CaClOH、Friedel盐和Ca₆(CO₃)₂(OH)₇Cl),因此,水洗技术难以达到理想的脱氯效果,氯盐去除率最高为88%.在水洗过程中通入CO₂可以显著降低反应体系的pH值,促进难溶盐的转化和溶解,进而提高飞灰氯盐的去除率.重庆飞灰采用加速碳酸化水洗技术,氯盐去除率最高可达94%.天津飞灰中氯元素主要以可溶性氯盐的形式存在,难溶盐占比很少,因此,水洗技术可以达到较高的脱盐率(96%).采用加速碳酸化技术对天津飞灰进行处理,发现氯盐去除率较纯水洗技术反而有所降低,分析其主要原因可能与加速碳酸化过程中碳酸钙等物质的再沉淀对氯盐的裹挟作用有关.由此可知,飞灰自身性特征尤其是氯盐的赋存形态对于脱氯除盐技术的选择有重要影响.因此,实际资源化利用过程中,可根据飞灰性质来决定预处理手段,从而最大化提升效率和节约成本.     

Atmospheric mercury emissions from waste combustions measured by continuous monitoring devices

Atmospheric mercury emissions have attracted great attention owing to adverse impact of mercury on human health and the ecosystem. Although waste combustion is one of major anthropogenic sources, estimated emission might have large uncertainty due to great heterogeneity of wastes. This study investigated atmospheric emissions of speciated mercury from the combustions of municipal solid wastes (MSW), sewage treatment sludge (STS), STS with waste plastics, industrial waste mixtures (IWM), waste plastics from construction demolition, and woody wastes using continuous monitoring devices. Reactive gaseous mercury was the major form at the inlet side of air pollution control devices in all combustion cases. Its concentration was 2.0-70.6 times larger than elemental mercury concentration. In particular, MSW, STS, and IWM combustions emitted higher concentration of reactive gaseous mercury. Concentrations of both gaseous mercury species varied greatly for all waste combustions excluding woody waste. Variation coefficients of measured data were nearly equal to or more than 1.0. Emission factors of gaseous elemental mercury, reactive gaseous mercury, and total mercury were calculated using continuous monitoring data. Total mercury emission factors are 0.30 g-Hg/Mg for MSW combustion, 0.21 g-Hg/Mg for STS combustion, 0.077 g-Hg/Mg for STS with waste plastics, 0.724 g-Hg/Mg for industrial waste mixtures, 0.028 g-Hg/Mg for waste plastic combustion, and 0.0026 g-Hg/Mg for woody waste combustion. All emission factors evaluated in this study were comparable or lower than other reported data. Emission inventory using old emission factors likely causes an overestimation.     

Spectroscopic studies of the progress of humification processes in humic substances extracted from refuse in a landfill

Humic acids (HA) and fulvic acids (FA) extracted from refuse in a landfill at different landfill ages were characterized by elemental composition, GPC, FTIR, and (13)C CP/MAS NMR. The elemental composition analysis revealed high O/C and low H/C ratios in the FA, indicating a high proportion of O-alkyl and carboxylic acids in the FA. The M(w) and M(n) values and M(w)/M(n) ratios indicated that the HA had a higher molecular weight and were more homogeneous with respect to molecular weight. FTIR spectra showed that the FA had relatively more intense bands assigned to aliphatic structures and were abundant in oxygen-containing function groups. The analytical results of (13)C CP/MAS NMR suggested that there were more oxygenated aliphatic carbons and fewer aromatic carbons in the FA than in the HA. All the results demonstrated that the degree of humification increased with landfill age.     

Characterization of humic and fulvic acids extracted from landfill by elemental composition, 13C CP/MAS NMR and TMAH-Py-GC/MS

Humic acid (HA) and fulvic acid (FA) extracted from landfills at different landfill ages were characterized by elemental composition, (13)C CP/MAS NMR, and TMAH-Py-GC/MS. The elemental composition analysis revealed high O/C and low H/C ratios in the FA, indicating a high proportion of O-alkyl and carboxylic acids in the FA. The analytical results of (13)C CP/MAS NMR suggested that there were more oxygenated aliphatic carbons and fewer aromatic carbons in FA than in HA. The Py-GC/MS products showed that the HA and FA extracted from the refuse in the landfill were mainly composed of various lignin-derived compounds. Oxidized aromatic acid derivatives originated from the oxidation of side-chains of lignin-like compounds, and this process played a significant role in the process of HA and FA formation in the landfill. All of the results demonstrated that the degree of humification increased with landfill age.