Coal-fired power plants are a major anthropogenic source of worldwide mercury (Hg) emissions. Since mercury is considered to be one of the most toxic metals found in the environment, Hg emissions from coal-fired power plants is of major environmental concern. Mercury in coal is vaporized into its gaseous elemental form throughout the coal combustion process. Elemental Hg can be oxidized in subsequent reactions with other gaseous components (homogeneous) and solid materials (heterogeneous) in coal-fired flue gases. While oxidized Hg in coal-fired flue gases is readily controlled by its adsorption onto fly ash and/or its dissolution into existing solution-based sulfur dioxide (SO2) scrubbers, elemental Hg is not controlled. The extent of elemental Hg formed during coal combustion is difficult to predict since it is dependent on the type of coal burned, combustion conditions, and existing control technologies installed. Therefore, it is important to understand heterogeneous Hg reaction mechanisms to predict the speciation of Hg emissions from coal-fired power plants to design and effectively determine the best applicable control technologies. In this work, theoretical and experimental investigations have been performed to investigate the adsorption and in some cases the oxidation, of Hg on solid surfaces, e.g., calcium oxide (CaO), noble metals and activated carbon (AC). The objective of this research is to identify potential materials that can be used as multi-pollutant sorbents in power plants by carrying out both high-level density functional theory (DFT) electronic structure calculations and experiments to understand heterogeneous chemical pathways of Hg. This research uses a fundamental science-based approach to understand the environmental problems caused by coal-fired energy production and provides solutions to the power generation industry for emissions reductions. Understanding the mechanism associated with Hg and SO2 adsorption on CaO will help to optimize the conditions or material to limit Hg emissions from the flue gas desulfurization process. Plane-wave DFT calculations were used to investigate the binding mechanism of Hg species and SO2 on the CaO(100) surface. The binding strengths on the high-symmetry CaO adsorption sites have been investigated for elemental Hg, SO2, mercury chlorides (HgCl and HgCl2) and mercuric oxide (HgO). It has been discovered that HgCl, HgCl2, and SO2 chemisorb on the CaO(100) surface at 0.125 ML coverage. Binding energies of elemental Hg are minimal indicating a physisorption mechanism. Noble metals such as palladium (Pd), gold (Au), silver (Ag), and copper (Cu) have been proposed to capture elemental Hg. Plane-wave DFT calculations have been carried out to investigate the mercury interactions with Pd binary alloys and overlays in addition to pure Pd, Au, Ag, and Cu surfaces. It has been determined that Pd has the highest mercury binding energy in comparison to other noble metals. In addition, Pd is found to be the primary surface atom responsible for increasing the adsorption of Hg with the surface in both Pd binary alloys and overlays. Deposition of Pd overlays on Au and Ag has been found to enhance the reactivity of the surface by shifting the d-states of surface atoms up in energy. The possible binding mechanisms of elemental Hg onto virgin, brominated and sulfonated AC fiber and brominated powder AC sorbents have been investigated through packed-bed experiments in a stream of air and simulated flue gas conditions, including SO2, hydrogen chloride (HCl), nitrogen oxide (NO) nitrogen dioxide (NO2). A combination of spectroscopy and plane-wave DFT calculations was used to characterize the sorption process. X-ray photoelectron spectroscopy (XPS) and x-ray absorption fine structure (XAFS) spectroscopy were used to analyze the surface and bulk chemical compositions of brominated AC sorbents reacted with Hg0. Through XPS surface characterization studies it was found that Hg adsorption is primarily associated with halogens on the surface. Elemental Hg is oxidized on AC surfaces and the oxidation state of adsorbed Hg is found to be Hg2+. Though plane-wave DFT and density of states (DOS) calculations indicate that Hg is more stable when it is bound to the edge carbon atom interacting with a single bromine bound atop of Hg, a model that includes an interaction between the Hg and an additional Br atom matches best with experimental data obtained from extended x-ray absorption fine structure (EXAFS) spectroscopy. The flue gas species such as HCl and bromine (Br2) enhance the Hg adsorption, while SO2 is found to decrease the Hg adsorption significantly by poisoning the active sites on the AC surface. The AC sorbents represent the most market-ready technology for Hg capture and therefore have been investigated by both theory and experiment in this work. Future work will include similar characterization and bench-scale experiments to test the metal-based materials for the sorbent and oxidation performance.

Coal-fired power plants are a major anthropogenic source of worldwide mercury (Hg) emissions. Since mercury is considered to be one of the most toxic metals found in the environment, Hg emissions from coal-fired power plants is of major environmental concern. Mercury in coal is vaporized into its gaseous elemental form throughout the coal combustion process. Elemental Hg can be oxidized in subsequent reactions with other gaseous components (homogeneous) and solid materials (heterogeneous) in coal-fired flue gases. While oxidized Hg in coal-fired flue gases is readily controlled by its adsorption onto fly ash and/or its dissolution into existing solution-based sulfur dioxide (SO2) scrubbers, elemental Hg is not controlled. The extent of elemental Hg formed during coal combustion is difficult to predict since it is dependent on the type of coal burned, combustion conditions, and existing control technologies installed. Therefore, it is important to understand heterogeneous Hg reaction mechanisms to predict the speciation of Hg emissions from coal-fired power plants to design and effectively determine the best applicable control technologies. In this work, theoretical and experimental investigations have been performed to investigate the adsorption and in some cases the oxidation, of Hg on solid surfaces, e.g., calcium oxide (CaO), noble metals and activated carbon (AC). The objective of this research is to identify potential materials that can be used as multi-pollutant sorbents in power plants by carrying out both high-level density functional theory (DFT) electronic structure calculations and experiments to understand heterogeneous chemical pathways of Hg. This research uses a fundamental science-based approach to understand the environmental problems caused by coal-fired energy production and provides solutions to the power generation industry for emissions reductions. Understanding the mechanism associated with Hg and SO2 adsorption on CaO will help to optimize the conditions or material to limit Hg emissions from the flue gas desulfurization process. Plane-wave DFT calculations were used to investigate the binding mechanism of Hg species and SO2 on the CaO(100) surface. The binding strengths on the high-symmetry CaO adsorption sites have been investigated for elemental Hg, SO2, mercury chlorides (HgCl and HgCl2) and mercuric oxide (HgO). It has been discovered that HgCl, HgCl2, and SO2 chemisorb on the CaO(100) surface at 0.125 ML coverage. Binding energies of elemental Hg are minimal indicating a physisorption mechanism. Noble metals such as palladium (Pd), gold (Au), silver (Ag), and copper (Cu) have been proposed to capture elemental Hg. Plane-wave DFT calculations have been carried out to investigate the mercury interactions with Pd binary alloys and overlays in addition to pure Pd, Au, Ag, and Cu surfaces. It has been determined that Pd has the highest mercury binding energy in comparison to other noble metals. In addition, Pd is found to be the primary surface atom responsible for increasing the adsorption of Hg with the surface in both Pd binary alloys and overlays. Deposition of Pd overlays on Au and Ag has been found to enhance the reactivity of the surface by shifting the d-states of surface atoms up in energy. The possible binding mechanisms of elemental Hg onto virgin, brominated and sulfonated AC fiber and brominated powder AC sorbents have been investigated through packed-bed experiments in a stream of air and simulated flue gas conditions, including SO2, hydrogen chloride (HCl), nitrogen oxide (NO) nitrogen dioxide (NO2). A combination of spectroscopy and plane-wave DFT calculations was used to characterize the sorption process. X-ray photoelectron spectroscopy (XPS) and x-ray absorption fine structure (XAFS) spectroscopy were used to analyze the surface and bulk chemical compositions of brominated AC sorbents reacted with Hg0. Through XPS surface characterization studies it was found that Hg adsorption is primarily associated with halogens on the surface. Elemental Hg is oxidized on AC surfaces and the oxidation state of adsorbed Hg is found to be Hg2+. Though plane-wave DFT and density of states (DOS) calculations indicate that Hg is more stable when it is bound to the edge carbon atom interacting with a single bromine bound atop of Hg, a model that includes an interaction between the Hg and an additional Br atom matches best with experimental data obtained from extended x-ray absorption fine structure (EXAFS) spectroscopy. The flue gas species such as HCl and bromine (Br2) enhance the Hg adsorption, while SO2 is found to decrease the Hg adsorption significantly by poisoning the active sites on the AC surface. The AC sorbents represent the most market-ready technology for Hg capture and therefore have been investigated by both theory and experiment in this work. Future work will include similar characterization and bench-scale experiments to test the metal-based materials for the sorbent and oxidation performance.

Mercury (Hg) is one of the most toxic heavy metals, harmful to both the environment and human health. Hg is released into the atmosphere from natural and anthropogenic sources and its emission control has caused much concern. This book introduces readers to Hg pollution from natural and anthropogenic sources and systematically describes coal-fired flue gas mercury emission control in industry, especially from coal-fired power stations. Mercury emission control theory and experimental research are demonstrated, including how elemental mercury is oxidized into oxidized mercury and the effect of flue gas contents on the mercury speciation transformation process. Mercury emission control methods, such as existing APCDs (air pollution control devices) at power stations, sorbent injection, additives in coal combustion and photo-catalytic methods are introduced in detail. Lab-scale, pilot-scale and full-scale experimental studies of sorbent injection conducted by the authors are presented systematically, helping researchers and engineers to understand how this approach reduces the mercury emissions in flue gas and to apply the methods in mercury emission control at coal-fired power stations. Readers will arrive at a comprehensive understanding of various mercury emission control methods that are suitable for industrial applications. The book is intended for scientists, researchers, engineers and graduate students in the fields of energy science and technology, environmental science and technology and chemical engineering.

This essential handbook and ready reference offers a detailed overview of the existing and currently researched technologies available for the control of mercury in coal-derived gas streams and that are viable for meeting the strict standards set by environmental protection agencies. Written by an internationally acclaimed author team from government agencies, academia and industry, it details US, EU, Asia-Pacific and other international perspectives, regulations and guidelines.

Carbon dioxide and mercury from anthropogenic emissions pose a significant threat to our environment and human health. Removal from their major source -- coal-fired power plants -- is one of the most effective approaches to control their emissions. Thermodynamics and kinetics are critical to the studies of the removal technologies as they provide fundamental knowledge of the capture process. In this work, the thermodynamics and kinetics of CO2 and Hg capture through absorption using aqueous amines solutions and adsorption using supported ionic liquid sorbents were investigated. A vapor-liquid equilibrium (VLE) data reduction method that simplifies experimental measurements while maintaining accuracy was applied for the first time to the thermodynamic study of CO2 absorption in aqueous amine systems. The method eliminates the measurements of speciation in liquid phase and vapor phase by applying a layer of mass balance iteration in the correlation. Incorporating the electrolyte non-random two liquid (eNRTL) model and the Soave-Redlich-Kwong (SRK) model, the data reduction method was used to correlate VLE and heat of absorption data collected in a modified batch calorimeter for ethanolamine (MEA) - H2O - CO2 system and piperazine (PZ) - H2O - CO2 systems. The optimized model with the best-fit eNRTL model parameters was used to predict vapor pressures under the conditions reported in the literature; the predicted values were consistent with the independent literature results, indicating successful application of the Barker data reduction method and the mathematical model in the thermodynamic study of CO2-aqueous amine systems. With the current technologies, capture of CO2 and Hg from coal combustion flue gas requires additional air pollution control devices that can only do a single task . To reduce the cost, a new approach to capture both CO2 and Hg from coal combustion flue gas in an integrated adsorbent system was discovered. In this approach, a task-specific amino acid ionic liquid is supported on silica gel particles with high surface area and pore volume. The CO2 capacity for was found to be 0.4 mol of CO2/ mol of ionic liquid. The ionic liquid loading was optimal for CO2 capture at 40 wt%. Mass transfer in fixed-bed trials was slow at high ionic liquid loadings due to the decreasing in contact surface area. Hg capture performance was assessed for the same material under a nitrogen environment. These sorbent systems had a total Hg uptake of more than 14 mg/g. Slipstream testing of the sorbents, along with other novel Hg sorbents developed previously, using coal combustion flue gas showed promising and competitive results in Hg removal rate and Hg capacity. When both CO2 and Hg are present in the gas phase, it is expected that Hg accumulates and fixes in the sorbent via strong chemical bonding over an extended time, while CO2 can reversibly be adsorbed and desorbed on the sorbent. This hypothesis was validated by the experimental evidence that the present of CO2 has limited effect on the capture of elemental Hg vapor and the theoretical evidence that oxidized Hg has a stronger bonding with the ionic liquid than CO2.

CONSOL Energy Inc., Research & Development (CONSOL), with support from the U.S. Department of Energy, National Energy Technology Laboratory (DOE) and the Electric Power Research Institute (EPRI), is evaluating the effects of selective catalytic reduction (SCR) on mercury (Hg) capture in coal-fired plants equipped with an electrostatic precipitator (ESP)--wet flue gas desulfurization (FGD) combination or a spray dryer absorber--fabric filter (SDA-FF) combination. In this program CONSOL is determining mercury speciation and removal at 10 coal-fired facilities. The objectives are (1) to evaluate the effect of SCR on mercury capture in the ESP-FGD and SDA-FF combinations at coal-fired power plants, (2) evaluate the effect of catalyst degradation on mercury capture; (3) evaluate the effect of low load operation on mercury capture in an SCR-FGD system, and (4) collect data that could provide the basis for fundamental scientific insights into the nature of mercury chemistry in flue gas, the catalytic effect of SCR systems on mercury speciation and the efficacy of different FGD technologies for mercury capture. This document, the seventh in a series of topical reports, describes the results and analysis of mercury sampling performed on a 1,300 MW unit burning a bituminous coal containing three percent sulfur. The unit was equipped with an ESP and a limestone-based wet FGD to control particulate and SO2 emissions, respectively. At the time of sampling an SCR was not installed on this unit. Four sampling tests were performed in September 2003. Flue gas mercury speciation and concentrations were determined at the ESP outlet (FGD inlet), and at the stack (FGD outlet) using the Ontario Hydro method. Process stream samples for a mercury balance were collected to coincide with the flue gas measurements. The results show that the FGD inlet flue gas oxidized:elemental mercury ratio was roughly 2:1, with 66% oxidized mercury and 34% elemental mercury. Mercury removal, on a coal-to-stack basis, was 53%. The average Hg concentration in the stack flue gas was 4.09 [mu]g/m3. The average stack mercury emission was 3.47 Ib/TBtu. The mercury material balance closures ranged from 87% to 108%, with an average of 97%. A sampling program similar to this one was performed on a similar unit (at the same plant) that was equipped with an SCR for NOx control. Comparison of the results from the two units show that the SCR increases the percentage of mercury that is in the oxidized form, which, in turn, lends to more of the total mercury being removed in the wet scrubber. The principal purpose of this work is to develop a better understanding of the potential mercury removal ''co-benefits'' achieved by NOx, and SO2 control technologies. It is expected that this data will provide the basis for fundamental scientific insights into the nature of mercury chemistry in flue gas, the catalytic effect of SCR systems on mercury speciation and the efficacy of different FGD technologies for mercury capture. Ultimately, this insight could help to design and operate SCR and FGD systems to maximize mercury removal.