The topic of global warming as a result of increased atmospheric CO2 concentration is arguably the most important environmental issue that the world faces today. It is a global problem that will need to be solved on a global level. The link between anthropogenic emissions of CO2 with increased atmospheric CO2 levels and, in turn, with increased global temperatures has been well established and accepted by the world. International organizations such as the United Nations Framework Convention on Climate Change (UNFCCC) and the Intergovernmental Panel on Climate Change (IPCC) have been formed to address this issue. Three options are being explored to stabilize atmospheric levels of greenhouse gases (GHGs) and global temperatures without severely and negatively impacting standard of living: (1) increasing energy efficiency, (2) switching to less carbon-intensive sources of energy, and (3) carbon sequestration. To be successful, all three options must be used in concert. The third option is the subject of this review. Specifically, this review will cover the capture and geologic sequestration of CO2 generated from large point sources, namely fossil-fuel-fired power gasification plants. Sequestration of CO2 in geological formations is necessary to meet the President's Global Climate Change Initiative target of an 18% reduction in GHG intensity by 2012. Further, the best strategy to stabilize the atmospheric concentration of CO2 results from a multifaceted approach where sequestration of CO2 into geological formations is combined with increased efficiency in electric power generation and utilization, increased conservation, increased use of lower carbon-intensity fuels, and increased use of nuclear energy and renewables. This review covers the separation and capture of CO2 from both flue gas and fuel gas using wet scrubbing technologies, dry regenerable sorbents, membranes, cryogenics, pressure and temperature swing adsorption, and other advanced concepts. Existing commercial CO2 capture facilities at electric power-generating stations based on the use of monoethanolamine are described, as is the Rectisol process used by Dakota Gasification to separate and capture CO2 from a coal gasifier. Two technologies for storage of the captured CO2 are reviewed--sequestration in deep unmineable coalbeds with concomitant recovery of CH4 and sequestration in deep saline aquifers. Key issues for both of these techniques include estimating the potential storage capacity, the storage integrity, and the physical and chemical processes that are initiated by injecting CO2 underground. Recent studies using computer modeling as well as laboratory and field experimentation are presented here. In addition, several projects have been initiated in which CO2 is injected into a deep coal seam or saline aquifer. The current status of several such projects is discussed. Included is a commercial-scale project in which a million tons of CO2 are injected annually into an aquifer under the North Sea in Norway. The review makes the case that this can al...

Methods for removing mercury from flue gas have received increased attention because of recent limitations placed on mercury emissions from coal-fired utility boilers by the U. S. Environmental Protection Agency and various states. A promising method for mercury removal is catalytic oxidation of elemental mercury (Hg0) to oxidized mercury (Hg2+), followed by wet flue gas desulfurization (FGD). FGD cannot remove Hg0, but easily removes Hg2+ because of its solubility in water. To date, research has focused on three broad catalyst areas: selective catalytic reduction catalysts, carbon-based materials, and metals and metal oxides. We review published results for each type of catalyst and also present a discussion on the possible reaction mechanisms in each case. One of the major sources of uncertainty in understanding catalytic mercury oxidation is a lack of knowledge of the reaction mechanisms and kinetics. Thus, we propose that future research in this area should focus on two major aspects: determining the reaction mechanism and kinetics and searching for more cost-effective catalyst and support materials.

A laboratory-scale packed-bed reactor system is used to screen sorbents for their capability to remove elemental mercury from various carrier gases. When the carrier gas is argon, an online atomic fluorescence spectrophotometer (AFS), used in a continuous mode, monitors the elemental mercury concentration in the inlet and outlet streams of the packed-bed reactor. The mercury concentration in the reactor inlet gas and the reactor temperature are held constant during a test. For more complex carrier gases, the capacity is determined off-line by analyzing the spent sorbent with either a cold vapor atomic absorption spectrophotometer (CVAAS) or an inductively coupled argon plasma atomic emission spectrophotometer (ICP-AES). The capacities and breakthrough times of several commercially available activated carbons as well as novel sorbents were determined as a function of various parameters. The mechanisms of mercury removal by the sorbents are suggested by combining the results of the packed-bed testing with various analytical results.

Photochemical reactions of mercury with various constituents in flue gas produced by burning coal could be an attractive alternative to dry sorbent- or wet scrubber-based processes for mercury control. The sensitized oxidation of elemental mercury using 253.7-nm ultraviolet radiation has been extensively studied. The photochemistry of elemental mercury in simulated flue gases was examined using quartz flow reactors. Mercury-containing simulated flue gases at temperatures between 80 and 350 °F were irradiated with 253.7-nm ultraviolet light. Results are presented for the photochemical removal of elemental mercury from simulated flue gases, as well as from nitrogen mixtures that contain oxygen, water vapor, or nitrogen oxide. Optimization of the process parameters, including light intensity, is discussed. The implications of photochemical oxidation of mercury with respect to direct ultraviolet irradiation of flue gas for mercury control, analysis of gases for mercury content, and atmospheric reactions are discussed.

Recent field tests of mercury removal with activated carbon injection (ACI) have revealed that mercury capture is limited in flue gases containing high concentrations of sulfur oxides (SOx). In order to gain a more complete understanding of the impact of SOx on ACl, mercury capture was tested under varying conditions of SO2 and SO3 concentrations using a packed bed reactor and simulated flue gas (SFG). The final mercury content of the activated carbons is independent of the SO2 concentration in the SFG, but the presence of SO3 inhibits mercury capture even at the lowest concentration tested (20 ppm). The mercury removal capacity decreases as the sulfur content of the used activated carbons increases from 1 to 10%. In one extreme case, an activated carbon with 10% sulfur, prepared by H2SO4 impregnation, shows almost no mercury capacity. The results suggest that mercury and sulfur oxides are in competition for the same binding sites on the carbon surface.

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The use of noble metals as catalysts for mercury oxidation in flue gas remains an area of active study. To date, field studies have focused on gold and palladium catalysts installed at pilot scale. In this article, we introduce bench-scale experimental results for gold, palladium and platinum catalysts tested in realistic simulated flue gas. Our initial results reveal some intriguing characteristics of catalytic mercury oxidation and provide insight for future research into this potentially important process.

In regard to gasification for power generation, the removal of mercury by sorbents at elevated temperatures preserves the higher thermal efficiency of the integrated gasification combined cycle system. Unfortunately, most sorbents display poor capacity for elemental mercury at elevated temperatures. Previous experience with sorbents in flue gas has allowed for judicious selection of potential high-temperature candidate sorbents. The capacities of many sorbents for elemental mercury from nitrogen, as well as from four different simulated fuel gases at temperatures of 204−371 °C, have been determined. The simulated fuel gas compositions contain varying concentrations of carbon monoxide, hydrogen, carbon dioxide, moisture, and hydrogen sulfide. Promising high-temperature sorbent candidates have been identified. Palladium sorbents seem to be the most promising for high-temperature capture of mercury and other trace elements from fuel gases. A collaborative research and development agreement has been initiated between the Department of Energy's National Energy Technology Laboratory (NETL) and Johnson Matthey for optimization of the sorbents for trace element capture from high-temperature fuel gas. Future directions for mercury sorbent development for fuel gas application will be discussed.