Mitigation of gaseous mercury emissions from waste-to-energy facilities: Homogeneous and heterogeneous Hg-oxidation pathways in presence of fly ashes.

This study describes the main mechanisms that take part in the mercury homogeneous oxidation pathway in presence of some of the main reactive compounds formed during waste incineration processes (O2, HCl, SO2 and NO). Series of model, synthetic dry flue gases were used to elucidate the effects of HCl, SO2, NO and their proportions in the gas on mercury behaviour. Three samples of fly ash collected from a MSWI facility were characterized and evaluated both for Hg heterogeneous oxidation and Hg removal in a laboratory scale device. The results obtained in this study showed that homogeneous mercury oxidation in the models MSWI and coal combustion flue gas atmospheres was 52 ± 5% and 25%, respectively. SO2, NO and HCl have a synergetic effect in Hg oxidation in presence of oxygen, but the main differences found are mainly caused by the strong influence of HCl and the likely inhibitory oxidation effects of SO2. Surface area together with carbon and chloride content of the fly ashes were correlated with their capacity for Hg-heterogeneous oxidation and adsorption. The sample of fly ash with relatively high content of unburnt carbon and chlorine, and with BET surface (2.42 m2/g) was able to remove up to 100% of Hg0 (g) during 300 min. The results obtained in this study provide a complete overview of the behaviour of mercury during MSWI processes and may help to clarify the fate/behaviour of mercury in a filter (e.g. electrostatic precipitator) providing a deeper knowledge about the impacts of fly ash properties on mercury fate in waste incineration.

Mercury removal from MSW incineration flue gas by mineral-based sorbents.

Three samples of commercially available mineral-based sorbents (zeolite, bentonite and diatomaceous earth) were selected and evaluated for Hg capture under conditions of simulated dry flue gas atmosphere typical in Municipal Solid Waste Incineration (MSWI). The experiments were carried out in a lab-scale fixed-bed device at temperatures between 120 and 200 °C. Two samples of activated carbons (AC) (raw-AC and sulphur impregnated AC) were tested under the same conditions. The mineral-based sorbents were chemically promoted by sulphur, FeCl3 and CaBr2, achieving an improvement in the overall reduction percentage of Hg0out (g) up to 85%, which was comparable to that obtained using a commercial activated carbon for Hg capture (sulphur impregnated AC). The study demonstrates that sorbents with a matrix relatively richer in TiO2, Fe2O3 and Al2O3, as bentonite, favour Hg heterogeneous oxidation. The best Hg capture capacity was achieved with a zeolite sorbent sample characterized by high specific surface (132 m2/g) and impregnated with elemental sulphur. The final form of mercury retained in this sorbent was HgS with proved long-term stability in disposal and landfilling. The higher the temperature, the lower the efficiency of Hg capture being the optimum temperature for Hg-capture in the range of 120-150 °C. This study provides a basis for the development of new efficient non-carbon sorbents for mercury removal in the air pollution control lines of MSWI facilities considering the non-hazardous final form of mercury and its long-term landfilling/sequestration.

An assessment of the environmental fate of mercury species in highly polluted brownfields by means of thermal desorption.

High contents of mercury (Hg) have been found in old mining-metallurgy sites occurring a widespread contamination and degradation of the land. The ability to identify the Hg species present in these areas is essential to clarify fate of Hg and its bioavailability and additionally, to be able to parameterize remediation techniques based on thermal desorption in order to carry out a full-scale decontamination of the land. This study has proven the usefulness of a thermal programmed desorption procedure (Hg-TPD) for identifying Hg species in contaminated samples related to mining-metallurgy activities. Hg bound to organic matter (Hg-OM) and to pyrite (Hg-FeS2), HgS red, HgCl2, Hg0 and HgO were identified in most of waste samples. The absence of mobile Hg species in soils and sediments showed both its re-emission to the atmosphere (Hg0) or of its oxidation and lixiviation (HgO and HgCl2) over the years. The results have demonstrated that most of these polluted solids can be remediated by thermal treatment at temperatures ranging between 150 and 600°C. The study evidence that Hg-TPD is useful either for parameterizing a thermal remediation or for identifying the evolution pathways of Hg species in different environmental compartments and in general, for any environmental remediation treatment.

A comparison of devices using thermal desorption for mercury speciation in solids.

The goal of this work is to emphasize the reliability of the thermal desorption technique in identifying mercury species. The analysis of mercury species in solids is essential for assessing the risk of disposal or re-use of mercury-contaminated materials. This study evaluates the accuracy and reliability of thermal desorption as a technique for identifying mercury species by means of different thermo-desorption devices. For this purpose, mercury species present in samples related with coal utilization processes were identified. Three devices were compared for analyzing samples free of carbon or with a low carbon content (fly ashes, gypsums and soils), and a new equipment was developed to analyze samples with a high carbon content (coal). In spite of the fact that the first three devices employ different experimental conditions (i.e., heating rate, gas flow and carrier gas), the mercury species identified in the samples were comparable in all cases. The need for new equipment for mercury speciation in materials containing carbon was a consequence of interferences produced from the pyrolysis products of the organic matter. The new device consists of two furnaces and two gas inlets to allow thermal oxidation of organic pyrolysis products and the identification of mercury species in carbonaceous samples. This new approach offers the application of thermal desorption to mercury speciation in all types of materials contaminated with mercury.

Application of thermal desorption for the identification of mercury species in solids derived from coal utilization.

The speciation of mercury is currently attracting widespread interest because the emission, transport, deposition and behaviour of toxic mercury species depend on its chemical form. The identification of these species in low concentrations is no easy task and it is even more complex in coal combustion products due to the fact that these products contain organic and mineral matter that give rise to broad peaks and make it difficult to carry out qualitative and quantitative analysis. In this work, a solution to this problem is proposed using a method based on thermal desorption. A sequential extraction procedure was employed for the comparison and validation of the method developed. Samples of fly ashes and soils were analyzed by both of these methods, and thermal desorption was found to be an appropriate technique for mercury speciation. Even in the case of low mercury contents, recovery percentages were close to 100%. The main mercury species identified in the samples studied were HgS and, to a lesser extent, HgO and HgSO4. In addition, although the presence of mercury complexes cannot be demonstrated, the desorption behaviour and sequential extraction results suggest that this element might be associated with the mineral matrix or with carbon particles in some of the solids.

Mercury compounds characterization by thermal desorption.

The ability to accurately determine metal mercury content and identify different mercury species in solid samples is essential for developing remediation and control strategies. The aim of the present study is to characterize mercury compounds based on thermal desorption. For this purpose a series of samples was prepared and the operational parameters-heating velocity, carrier gas-were optimized. Fifteen commercial mercury compounds were analyzed for use as fingerprints. The results of the study show that the identification of mercury species by the method of thermal desorption is possible. The temperature of desorption increased according to the following order HgI2