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The emissions of heavy metals during incineration of Municipal Solid Waste (MSW) are a major issue to health and the environment. It is then necessary to well quantify these emissions in order to accomplish an adequate control and prevent the heavy metals from leaving the stacks. In this study the kinetic behavior of Cadmium during Fluidized Bed Incineration (FBI) of artificial MSW pellets, for bed temperatures ranging from 923 to 1073 K, was modeled. FLUENT 12.1.4 was used as the modeling framework for the simulations and implemented together with a complete set of user-defined functions (UDFs). The CFD model combines the combustion of a single solid waste particle with heavy metal (HM) vaporization from the burning particle, and it takes also into account both pyrolysis and volatiles' combustion. A kinetic rate law for the Cd release, derived from the CFD thermal analysis of the combusting particle, is proposed. The simulation results are compared with experimental data obtained in a lab-scale fluidized bed incinerator reported in literature, and with the predicted values from a particulate non-isothermal model, formerly developed by the authors. The comparison shows that the proposed CFD model represents very well the evolution of the HM release for the considered range of bed temperature., (Copyright © 2013 Elsevier B.V. All rights reserved.)

The accumulation of toxic metals generated by coal-fired power stations presents a serious threat to the environment. The volatilization behavior of two representative metals (Cd and Zn), and the influence of temperature were investigated during coal combustion. An inductively coupled plasma atomic emission spectrometric (ICP-AES) method was developed to continuously measure the heavy metal concentrations quantitatively in flue gas under combustion conditions in order to track the metal release process. This continuous heavy metal analysis system was implemented by coupling it to two types of high temperature reactors: a bubbling fluidized bed reactor and a fixed bed reactor with diameter of 0.1 m and 0.08 m respectively. For the two metals considered in this study (Cd and Zn), the experimental setup was successfully used to continuously monitor the metal vaporization process during coal combustion independent of reactor design, and at different temperatures. Cd is more easily vaporized than Zn during coal combustion. Temperature significantly influences the metal vaporization process. In general, the higher the temperature, the higher the metal vaporization, although the vaporization is not proportional to temperature. In addition to the experimental study, a thermodynamic calculation was carried out to simulate the heavy metal speciation during coal combustion process. The theoretical volatilization tendency is consistent with the experiment. The thermodynamic calculation identified the formation of binary oxides retarding heavy metal vaporization., (Copyright (c) 2010 Elsevier Ltd. All rights reserved.)

Incineration experiments with MSW, which had been impregnated with heavy metals, were presented to obtain information on the volatilization behavior of the elements cadmium(Cd), lead (Pb), and zinc (Zn) under different conditions. Experiments were carried out in a bubbling fluid bed system connected to a customized inductively coupled plasma optical emission spectroscopy (ICP-OES) for analyzing metals in the flue gas. The results indicated that the combustion temperature, the gas atmosphere, and the chlorine content in the flue gas could affect the volatilization behavior of heavy metals. In the fluidized bed combustion, a large surface area was provided by the bed sand particles, and they may act as absorbents for the gaseous ash-forming compound. Comparer with the metals Cd and Pb, the vaporization of Zn was low. The formation of stable compounds such as ZnO x Al2O3 could greatly decrease the metals volatilization. The presence of chlorine would enhance the volatilization of heavy metals by increasing the formation of metal chlorides. However, when the oxygen content was high, the chlorinating reaction was kinetically hindered, which heavy metals release would be delayed.

Metal vaporization experiments were carried out in an atmospheric fluidized bed to study the influence of operating conditions on the extent of heavy metal (HM) release in fumes from municipal solid waste incinerators. Modelwastes spiked with compounds of Pb, Cd, and Zn were used. The parameters studied were temperature, treatment duration, matrix of the model waste (mineral and organic), HM initial speciation, and gas composition (N2, air, air + HCl, gas mixture simulating the incinerators). The extent of vaporization was measured by solid sample analysis and on-line analysis of the gaseous effluent, after customization of the ICP technique for gas analysis. The results indicate the metal vaporization rate is very high initially and then slows. The results with mineral matrices give the decreasing order of volatility Cd > Pb > Zn, but in industrial incinerators Zn volatilizes slightly more than Pb. Temperature (especially for porous alumina) and mineral matrix have a strong influence on the HM vaporization, but HCl concentration and HM initial speciation do not. The gas composition and the initial metal concentration are significant parameters. The matrix influence clearly denoted the mass transfer limitations in the vaporization process from mineral matrix.

A thermodynamic analysis was performed to determine whether it is suitable to predict the heavy metal (HM) speciation during the Municipal Solid Waste Incineration process. The fate of several selected metals (Cd, Pb, Zn, Cr, Hg, As, Cu, Co, Ni) during incineration was theoretically investigated. The equilibrium analysis predicted the metal partitioning during incineration and determined the impact of operating conditions (temperature and gas composition) on their speciation. The study of the gas composition influence was based on the effects of the contents of oxygen (reducing or oxidising conditions) and chlorine on the HM partitioning. The theoretical HM speciation which was calculated in a complex system representing a burning sample of Municipal Solid Waste can explain the real partitioning (obtained from literature results) of all metals among the various ashes except for Pb. Then, the results of the thermodynamic study were compared with those of characterisation of real incinerator residues, using complementary techniques (chemical extraction series and X-ray micro-analyses). These analysis were performed to determine experimentally the speciation of the three representative metals Cr, Pb, and Zn. The agreement is good for Cr and Zn but not for Pb again, which mainly shows unleachable chemical speciations in the residues. Pb tends to remain in the bottom ash whereas thermodynamics often predicts its complete volatilisation under chlorides, and thus its presence exclusively in fly ash.

This study deals with the fundamental aspects of the volatilisation of heavy metals (HM) during municipal solid waste (MSW) incineration. The thermal treatment of a model waste was theoretically and experimentally studied in a fluid-bed. A mathematical model was developed to predict the fate of metallic species according to the main phenomena controlling the process: heat and mass transfer (transport phenomena), chemical reactions involving HM, and mechanism of vapour metal species sorption inside the porous matrix. The model assumes local thermodynamic equilibrium between the vapour and the metal compound on the substrate in the pores of a particle. This approach permits to predict the extent of HM vaporisation from a mineral porous matrix when its physical properties are known. Experimental data concerning CdCl(2) release from an alumina matrix in a 850 degrees C fluidised bed are in good agreement with theoretical results.

In light of Title I of the Clean Air Act Amendments of 1990, selenium will most probably be considered for regulation in the electric power industry. This has generated interest for removing this element from fossil-fired flue gas. This study deals with coal combustion: selenium volatilization and its speciation in the cooled flue gas were investigated to better understand its chemical behavior to validate the thermodynamic approach to such complex systems and to begin developing emission control strategies. Se volatility is influenced by several factors such as temperature, residence time, fuel type, particle size, and Se speciation of the fuels, as well as the forms of the Se inthe spiked coal/coke. Spiked coke and coal samples were burned in a thermobalance, and atomic Se and its dioxide were identified in the cooled combustion flue gas by X-ray photoelectron spectroscopy (XPS). A thermodynamic calculation was applied to a complex system including 54 elements and 3,200 species that describes the coal combustion. Several theoretical predictions concerning Se behavior, such as its speciation in flue gas, agreed well with experiments, which supports using thermodynamics for predicting trace element chemistry in combustion systems.