Dioxin emissions from waste incinerators

Mechanisms that have been proposed to account for the emission of PCDD/PCDF from municipal waste incinerators were evaluated in the light of extensive experimental data obtained from the Quebec City municipal solid waste incinerator by Environment Canada. It was found that PCDD/PCDF emissions were closely related to the quantity of material entrained by the combustion gases.     

Thermal behavior of PCDD/PCDF in fly ash from municipal incinerators

The effect of thermal treatment of fly ash on the behaviour of PCDD/PCDF was studied in the range between 120 and 600° C. Annealing at 300° C (2 hrs) resulted in an increase of PCDD/PCDF concentration by a factor of 10 to 15. At 600° C degradation to concentrations below 0.1 ng/g is observed.     

Generation of PCDD/F in fly ash from municipal solid waste incinerators

Fly ash from municipal solid waste incinerators (MSWIs) has been characterized in terms of polychlorinated dibenzyl-p-dioxin and polychlorinated dibenzofuran (PCDD/F) content. Increasing values of PCDD/Fs have been found to correlate with decreasing temperatures of sampling points in flue gas treatment lines of the plants, confirming other researchers' findings about temperature as the major controlling parameter for the PCDD/F formation. Measured PCDD/F ratios show that de novo synthesis is the dominant formation mechanism. The increasing trends of particulate-bound PCDD/Fs can be explained not only through the dominant de novo synthesis process but also considering the adsorption of gaseous PCDD/Fs on fly ash deposits, even outside the typical de novo synthesis temperature ranges. The effective role of a post-combustor unit, imposed by Italian law to destroy PCDD/ Fs, also needs to be carefully reconsidered.     

Extraction of heavy metals from MSW incinerator fly ash using saponins

An extraction process with saponins was evaluated for removing heavy metals from MSW (municipal solid waste) incinerator fly ashes. Two different fly ashes, A and B, were treated on a laboratory scale with three triterpene-glycoside type of saponins, M, Q, and T, in the pH range 4-9. The results were compared with those of the HCI and EDTA treatment. The treatment with saponins extracted 20-45% of Cr from the fly ashes. Saponins were also effective in extracting Cu from fly ash A attaining 50-60% extraction. Saponin T extracted 100% of Pb from fly ash A at pH around 4. The extraction of Zn with the saponin treatment was similar to that of the HCl treatment. Further, Cr, Cu, Pb, and Zn were fractionated by sequential extraction to investigate the effect of saponins on each fraction. Extraction behavior of other elements during the saponin treatment was also studied. The leaching test on the residues received after the saponin treatment showed that the fly ashes were successfully detoxified to meet the landfilling guideline.     

垃圾焚烧飞灰中不同粒径的毒性特性

对广州市某垃圾焚烧发电厂的焚烧飞灰进行粒径分级毒性分析研究。主要研究了粒径在35～1 000μm范围内的飞灰的腐蚀性和短期浸出毒性,包括Cr、Cd、Mg、Pb、Mn、Fe、Cu、Zn、Ni、Co等重金属,SO24-,Cl-,NO3--N和NO2--N,同时也研究了飞灰的物质组成和矿物特性。研究结果表明,所有粒径飞灰的浸出液pH值在12.3～12.5之间,属于有腐蚀性的危险废物,重金属Mg、Pb、Zn的浸出浓度最高,分别为168.78、53.94和86.40 mg/L。飞灰浸出液和含量最高分别达到8.87g/L和1.38 g/L,同时浸出液中测出一定量的硝态氮和亚硝态氮,证明飞灰吸附了垃圾焚烧过程中产生的氮氧化物气体。另外,研究得出飞灰的基本组成元素为Ca、Si、Cl、K、Na、S、Al、Mg和Fe,而重金属则以Zn、Pb、Mn、Cu、Cr等为主。矿物相主要为含硅和钙的化合物及NaCl和KCl等氯化物。     

Adsorption and chlorination of dibenzo-p-dioxin and 1-chlorodibenzo-p-dioxin on fly ash from municipal incinerators

Adsorption and chlorination reactions for dibenzo-p-dioxin (DD) and 1-chlorodibenzo-p-dioxin (1-MCDD) on fly ash were characterized quantitatively using laboratory-based simulation of stack emissions with air and HCl-air atmospheres. Influences of contact time and temperature were studied and results showed behavior of DD and 1-MCDD consistent with that for 1,2,3,4-tetrachlorodibenzo-p-dioxin. Di-, tri-, and tetra-chlorinated dioxins were major compounds produced from heterogenous phase reactions of DD and 1-MCDD with HCl in air. Total conversion through reactions alone were as high as 81% and 58% respectively.     

Presence of nitro-chlorinated dioxins on fly ash from municipal incinerators and from laboratory production through reactions between NO2 and T4CDD on fly ash

Treatment of tetrachlorodibenzo-p-dioxin (T₄CDD) on municipal incinerator fly ash at 30 to 150°C for 10 minutes using 5% (Vol/Vol) NO₂ in air resulted in production of nitro-T₄CDD. Percent conversion was between 40% at 50°C to 100% at 150°C. Nitro-T₄CDD produced in the laboratory was unstable in hexane/methanol or hexane/acetone solutions and decomposed at ?5°C with half-lives of 8–10 days^?1 to the original T₄CDD.Fly ash from a municipal incinerator in Toronto, Ontario was extracted using toluene/methanol for 12 hrs in a Soxhlet extractor. Condensate of this extract was analyzed using capillary gas chromatography with flame ionization, nitrogen-selective, and mass spectrometric detectors. Retention times for nitro-T₄CDD, multi-ion selected ion monitoring, and nitrogen detector response were used as supporting evidence for the presence of nitro-chlorinated dioxins as naturally occurring in this sample.     

添加垃圾焚烧飞灰冷固小球的工业烧结实验

将垃圾焚烧飞灰添加进烧结冷固球团配料进行造球,对冷固小球的成分及强度进行分析,结果表明,添加垃圾焚烧飞灰冷固小球化学组成稳定,重金属浸出毒性远低于危险废物鉴别标准,落下强度较基准期略微降低,但符合运输、贮存的要求.并对添加了飞灰的冷固小球对其后续烧结、冶炼工序的影响进行分析,结果表明,用添加飞灰的冷固小球进行烧结所得烧结矿的转鼓强度、落下强度及常规化学成分较基准期没有太大变化,添加飞灰进行造球、烧结,对其后续冶炼工序的顺行几乎没有影响,所带来的额外的环境污染微乎其微.     

Emission of heavy metals from animal carcass incinerators in Taiwan

The metal emissions from three incinerators burning different feedstock in Taiwan were characterized in this study. It was found that the Incinerators A and B, treating pig carcasses and animal (including pigs) carcasses, respectively, had much higher metal concentrations in stack flue gases than Incinerator C that combusted medical wastes. However, Incinerator A obtained relative lower metal contents in fly ash and bottom ash than the other two incinerators, mainly because the former used a much lower feedstock rate (although burning at a lower temperature) than the latter. For all the incinerators, (1) Fe, Ni, Pb, and Zn were dominant in both the fly ash and bottom ash while most of the Cd and Pb (more volatile) were present in the fly ash; (2) Fe emission factor was the highest and Zn/Pb/Ni/Cr emission factors were greater than those of Mn/Cd/Cu; (3) the Cu emission factors in bottom ash were relatively higher in comparison with those in fly ash; and (4) indicatory metals were the same (Fe, Zn, Pb, and Cu). The metal emission factors obtained from the livestock incinerators were much higher than those reported from MSW incinerators. Likewise, crematories that burn human cadavers must create similar pollution issues since metal supplements are part of human's normal diets. This causes an environmental concern and this work has important ramifications both in technical and regulatory decisions.     

Dioxins and their fingerprint in size-classified fly ash fractions from municipal solid waste incinerators in China--mechanical grate and fluidized bed units

The distribution of polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDD/Fs), in brief dioxins, has seldom been addressed systematically in fly ash from municipal solid waste incinerators (MSWIs). This study shows the amount and fingerprint of PCDD/Fs in fly ash from four different Chinese MSWIs, that is, three mechanical grate units and one circulating fluidized bed unit. In these fly ash samples, dioxins-related parameters (international toxic equivalent quantity, total amount of PCDD/Fs, individual isomer classes, and 17 toxic 2,3,7,8-substituted congeners) all tend to increase with decreasing particle size for mechanical grate incinerators, yet only for the finest fraction for fluidized bed units. Moreover, the fluidized bed incinerator seems superior to grate incineration in controlling dioxins, yet a comparison is hampered by internal differences in the sample, for example, the fluidized bed fly ash has much lower carbon and chlorine contents. In addition, the presence of sulfur from mixing coal as supplemental fuel to the MSW may poison the catalytic steps in dioxins formation and thus suppress the formation of dioxins. With more residual carbon and chlorine in the fly ash, it is easier to form dioxins during cooling. Nevertheless, there is no apparent relation between Fe, Cu, and Zn contents and that of dioxins in fly ash.     

有机螯合剂与磷酸盐联合稳定垃圾焚烧飞灰中重金属的作用机理

为探讨二硫代氨基甲酸型有机螯合剂(FACAR)和重过磷酸钙(TSP)对垃圾焚烧飞灰中重金属Pb、Cd、Ni的稳定作用机制,对稳定前后的飞灰采用BCR连续提取法、X射线衍射(XRD)分析以及扫描电镜-能谱(SEM-EDS)联用等分析方法进行了表征。结果表明：投加质量分数5%的FACAR能有效稳定飞灰中Pb、Cd和Ni,其浸出浓度低于《生活垃圾填埋场污染控制标准》(GB 16889-2008)规定的浸出浓度限值;采用3% FACAR和3% TSP复配药剂处理,可使飞灰达到GB 16889-2008进场要求;经复合药剂稳定处理后的飞灰颗粒表面孔隙度明显降低,飞灰中Pb、Cd和Ni的形态均由不稳定态向稳定态转化。该复合稳定剂的稳定机制主要为螯合、共沉淀和吸附联合作用机制,其中,有机螯合剂中含硫官能团是影响重金属稳定的主要因素,且重金属具有优先与含硫官能团结合的特性。     

Influence of coexisting surface-active agents on leachability of dioxins in raw and treated fly ash from an MSW incinerator

The leaching behavior of dioxins from raw and treated fly ash (FA) under the coexistence of several types of surface-active agents (SAAs) was examined by batch leaching tests to obtain significant information not only for evaluating leachability of dioxins as hydrophobic organic pollutants (HOPs) under the severe environment in which SAAs coexist, but also for evaluating the reduction efficiency of dioxin-leachability from the treated FA. Enhancement of dioxin-leachability by sufficient addition of SAAs was observed in the leaching test, whereas addition of a smaller quantity depressed the leachability. The higher the degree of chlorination in PCDDs/PCDFs homologues, the more effectively the SAAs enhanced the leachability. Moreover, there was a large difference in the potential for leachability enhancement due to each surface activity, based on critical micelle concentration (CMC) of the SAAs although Aldrich humic acid enhanced the leachability at a much lower concentration than CMC. A comparison of the leachability in FA treated by several methods showed a difference in the reduction efficiency of leachability, depending on the adsorption of SAAs by each treated FA.     

热等离子体处理前后垃圾飞灰中重金属浸出浓度的变化及二恶英分布特性的差异

为探究热等离子体处理飞灰工艺工业应用的潜力,分析处理前后飞灰中9种重金属浸出浓度变化及二恶英的分布特性,基于处理量为5 t·d⁻¹的中试规模的热等离子体熔融系统,在1 550 ℃的处理温度下进行了飞灰处理实验。结果表明,不宜使用硫酸硝酸法检测玻璃态渣中As浸出浓度,硫酸根离子会与As在熔融过程中形成的砷酸钙和亚砷酸钙中的钙离子结合,导致As的浸出浓度增加;熔融处理后,除As外的其他重金属的浸出浓度均降至国家标准浓度限值以下;就太原地区而言,其垃圾飞灰中PCDFs的含量高于PCDDs,且低氯代呋喃含量高于高氯代呋喃;熔融处理后的垃圾飞灰中,二恶英毒性当量减少率为99.96%,降至0.546 6 ng·kg⁻¹,远低于填埋标准中二恶英排放限值,说明该中试系统能够满足飞灰处理要求。该研究结果可为热等离子体熔融飞灰中试系统的工业应用提供参考。     

Experimental and statistical determination of indicator parameters for the evaluation of fly ash and boiler ash PCDD/PCDF concentration from municipal solid waste incinerators

On-line detectable indicator parameters in the flue gas of municipal solid waste incinerators (MSWI) such as chlorinated benzenes (PCBz) are well known surrogate compounds for gas-phase PCDD/PCDF concentration. In the here presented work derivation of indicators is broadened to the detection of fly and boiler ash fractions with increased PCDD/PCDF content. Subsequently these fractions could be subject to further treatment such as recirculation in the combustion chamber to destroy their PCDD/PCDF and other organic pollutants' content. Aim of this work was to detect suitable on-line detectable indicator parameters in the gas phase, which are well correlated to PCDD/PCDF concentration in the solid residues. For this, solid residues and gas-phase samples were taken at three MSWI plants in Bavaria. Analysis of the ash content from different plants yielded a broad variation range of PCDD/PCDF concentrations especially after disturbed combustion conditions. Even during normal operation conditions significantly increased PCDD/PCDF concentrations may occur after unanticipated disturbances. Statistical evaluation of gas phase and ash measurements was carried out by means of principal component analysis, uni- and multivariate correlation analysis. Surprisingly, well known indicators for gas-phase PCDD/PCDF concentration such as polychlorinated benzenes and phenols proved to be insufficiently correlated to PCDD/PCDF content of the solid residues. Moreover, no single parameter alone was found appropriate to describe the PCDD/PCDF content of fly and boiler ashes. On the other hand, multivariate fitting of three or four parameters yielded convenient correlation coefficients of at least r=0.8 for every investigated case. Thereby, comprehension of plant operation parameters such as temperatures and air flow alongside concentrations of inorganic compounds in the gas phase (HCl, CO, SO2, NOx) gave the best results. However, the suitable set of parameters suited best for estimation of PCDD/PCDF concentration in solid residues has to be derived anew for each individual plant and type of ash.     

水热法外加硅铝添加剂稳定垃圾焚烧飞灰中的重金属

研究了在碱性水热条件下添加粉煤灰、膨润土、高岭土等以提供硅铝元素稳定生活垃圾焚烧飞灰中的重金属。实验结果表明,水热反应中添加粉煤灰、膨润土合成了雪硅钙石和水钙铝榴石,添加高岭土合成了雪硅钙石和加藤石。水热反应中添加粉煤灰、膨润土、高岭土对降低飞灰中Pb、Zn等重金属的浸出毒性均具有显著效果,水热产物中Pb、Zn和Cu的浸出浓度与飞灰相比分别降低了87%~96%、87%~94%和57%~78%。硅铝添加剂还能抑制飞灰中Pb、Zn等在碱性水热条件下向液相的转移,使重金属稳定在固相中。     

The toxicity and toxic potential of fly ash from municipal incinerators assessed by means of a fish early life stage test

The toxicity and toxic potential of fly ash were assessed, using rainbow trout yolk sac fry. In contrast to fly ash itself, extracts of fly ash were extremely toxic, producing typical toxicopathological features of TCDD-intoxication. By comparison with earlier experiments using pure 2,3,7,8-TCDD, the toxic potential of fly ash was roughly estimated to be 75–125 ng.g^?1 toxic aequivalents TCDD. Obviously, this toxic potential is attributable for a minor part to 2,3,7,8-TCDD and for the greater part to the other chlorinated dioxin congeners and the dibenzofurans, present in fly ash.     

Microbe-induced changes in metal extractability from fly ash

A low cost and eco-friendly technology to bioremediate toxic metals associated with fly ash dumps that contaminate ground and surface water in and around fly ash settling ponds, was investigated. The impact of augmentation of fly ash tolerant bacterial strains, isolated from Typha latifolia growing naturally on fly ash dumps, was studied for metal extractability. It was observed that most of the bacterial strains either induced the bioavailability of Fe, Zn and Ni or immobilized Pb, Cr, Cu, Cd in the fly ash. However, there were few exceptions also. In case of Ni, eight strains enhanced metal mobility, while others caused metal immobilization. The findings also suggest that metal solublization and immobilization are specific to bacterial strains. While induced bioavailability of metals by bacteria may be used to accelerate the phytoextraction of metals from fly ash by hyper accumulator plants, immobilization of metals can check their migration to water reservoirs and reduce the human suffering in affected areas. Thus, bacteria serve the dual purpose and may result in the microbe- assisted phytoremediation of contaminated sites.     

The effects of temperature and oxygen content on the PCDD/PCDFs formation in MSW fly ash

In this study, the effects of the temperature, oxygen content in the gas stream and carbon content in ash particles on PCDD/Fs formation on the fly ash surface were investigated. The optimum temperatures for dioxin formation were found at 350 degrees C for boiler ash, 300 degrees C for cyclone ash and 250 degrees C for ESP ash, respectively. Preliminary results indicate that the optimum temperature will decrease as the particle size decreases. When the O2 concentration is varied between 0% and 100%, the optimum oxygen content for PCDD/Fs formation is found to be at 7.5% for cyclone ash, and the PCDD/PCDF ratio increases with the increase of oxygen content. Dioxin formation is observed even for the gas containing no oxygen passed through the fly ash. Hence, other reacted routes that do not need O2 for dioxin formation take place on fly ash. The carbon content in fly ash is varied between 0% and 20% in this study, and the results have indicated that the maximum dioxin formation is to be found at 5%. The precursors are not injected into the fly ash or gas stream in all formation experiments, however, dioxin is still formed in fly ash. Consequently, other chlorinated routes besides Deacon reactions may take place on the fly ash surface.