Since the time of the industrial revolution, the atmospheric CO(2) concentration has risen by nearly 35 % to its current level of 383 ppm. The increased carbon dioxide concentration in the atmosphere has been suggested to be a leading contributor to global climate change. To slow the increase, reductions in anthropogenic CO(2) emissions are necessary. Large emission point sources, such as fossil-fuel-based power generation facilities, are the first targets for these reductions. A benchmark, mature technology for the separation of dilute CO(2) from gas streams is via absorption with aqueous amines. However, the use of solid adsorbents is now being widely considered as an alternative, potentially less-energy-intensive separation technology. This Review describes the CO(2) adsorption behavior of several different classes of solid carbon dioxide adsorbents, including zeolites, activated carbons, calcium oxides, hydrotalcites, organic-inorganic hybrids, and metal-organic frameworks. These adsorbents are evaluated in terms of their equilibrium CO(2) capacities as well as other important parameters such as adsorption-desorption kinetics, operating windows, stability, and regenerability. The scope of currently available CO(2) adsorbents and their critical properties that will ultimately affect their incorporation into large-scale separation processes is presented.

Adsorbent Materials for Carbon Dioxide Capture from Large Anthropogenic Point Sources

. This paper provides an up-to-date assessment of global mercury emissions from anthropogenic and natural sources. On an annual basis, natural sources account for 5207 Mg of mercury released to the global atmosphere, including the contribution from re-emission processes, which are emissions of previously deposited mercury originating from anthropogenic and natural sources, and primary emissions from natural reservoirs. Anthropogenic sources, which include a large number of industrial point sources, are estimated to account for 2320 Mg of mercury emitted annually. The major contributions are from fossil-fuel fired power plants (810 Mg yr−1), artisanal small scale gold mining (400 Mg yr−1), non-ferrous metals manufacturing (310 Mg yr−1), cement production (236 Mg yr−1), waste disposal (187 Mg yr−1) and caustic soda production (163 Mg yr−1). Therefore, our current estimate of global mercury emissions suggests that the overall contribution from natural sources (primary emissions + re-emissions) and anthropogenic sources is nearly 7527 Mg per year, the uncertainty associated with these estimates are related to the typology of emission sources and source regions.

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Global mercury emissions to the atmosphere from anthropogenic and natural sources

M M U Rapid Synthesis of Nitrogen-Doped Porous Carbon Monolith for CO2 Capture N IC By Guang-Ping Hao, Wen-Cui Li, Dan Qian, and An-Hui Lu* A T IO N The development of novel materials and new technologies for CO2 capture and storage has gained great attention over the past decades. The necessity for reducing the concentration of CO2 in the atmosphere is a very important issue, since CO2 is considered as a greenhouse gas causing global warming. In addition, higher concentrations of CO2 are toxic for humans, especially in space-limited chambers like submarines and space ships. Traditional technologies for CO2 capture including absorption and adsorption-coupled membrane separation along with the corresponding sorbents such as aqueous amines, microporous coordination polymers (MCPs), zeolitic imidazolate frameworks (ZIFs), different types of nitrogen-doped zeolite, mesoporous silica, and activated carbons have been widely explored. However, MCPs and ZIFs synthesized with nitrogen-containing organic compounds as the crosslinker often suffer from structural instability and inefficiency for CO2 selectivity in the presence of water and thus are limited in their widespread use. For aminemodified solids, the main drawback is the possible loss of ammonia associated with the temperature needed for regeneration and the energy-intensive nature of the regeneration process. For instance, amine-surface-modified or amineimpregnated porous silica (e.g., MCM-41, MCM-48, SBA-15, SBA-16) and zeolite 13X materials fail to capture CO2 effectively, require high temperature and long regeneration times and lack stability over many cycles. It should be pointed out that amine-modified silica-based solids are usually prepared by a post-treatment, which is a time-consuming and costly procedure and often involves the use of toxic and corrosive reagents. Porous carbon materials have many specific features such as high surface area, thermal and chemical stability, and hydrophobic surface properties. The incorporation of basic nitrogen groups into the carbon framework ensures an improved adsorption/absorption for acidic gases. Up to date, porous carbon materials used for CO2 capture were mostly prepared by post-synthetic amine modification or ammonia treatment, which again leads to materials lacking stability and, in addition, the reagents are corrosive, which brings the same disadvantages as for modified silica and zeolites. Alternatively, nitrogencontaining porous carbons can be prepared directly from

Rapid synthesis of nitrogen-doped porous carbon monolith for CO2 capture.

In the sorption-enhanced hydrogen production process, hydrocarbon reforming, water gas shift, and CO2 separation reactions occur simultaneously in a single reaction step over a reforming catalyst mixed with a CO2 sorbent. Transferring CO2 as it is formed from the gas to the solid phase shifts the normal equilibrium restrictions and allows both the reforming and water gas shift reactions to approach completion. Depending on reaction conditions, the product (dry basis) may contain as much as 98% H2 and only ppmv levels of CO and CO2, thereby minimizing the final H2 purification step or even eliminating it for some applications. A number of CO2 sorbents have been studied including calcium-based oxides, K-promoted hydrotalcite, and mixed metal oxides of lithium and sodium. The sorbent is consumed during H2 production so that the process is intrinsically unsteady state. Process economics requires that the sorbent be regenerable and used in many reaction−regeneration cycles. Regeneration may occur via temperatu...

Sorption-Enhanced Hydrogen Production: A Review

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.

Survey of catalysts for oxidation of mercury in flue gas

New US EPA regulations place caps on the levels of mercury that can be emitted from coal-burning power plants, with targets to hit in 2010 and 2018. To meet these targets, technologies already available to reduce other pollutants, such as SO{sub 2} and NOx, will probably be modified to reduce mercury as a cobenefit. The authors review the effectiveness of these technologies at holding the line on mercury and explore how they can be improved for deeper emission cuts. 19 refs., 3 figs., 1 tab.

Control of mercury emissions from coal-fired electric utility boilers.

Brominated powdered activated carbon sorbents have been shown to be quite effective for mercury capture when injected into the flue gas duct at coal-fired power plants and are especially useful when burning Western low-chlorine subbituminous coals. X-ray absorption spectroscopy (XAS) and X-ray photoelectron spectroscopy (XPS) have been used to determine information about the speciation and binding of mercury on two commercially available brominated activated carbons. The results are compared with similar analysis of a conventional (non-halogenated) and chlorinated activated carbon. Both the XAS and XPS results indicate that the mercury, though introduced as elemental vapor, is consistently bound on the carbon in the oxidized form. The conventional and chlorinated activated carbons appeared to contain mercury bound to chlorinated sites and possibly to sulfate species that have been incorporated onto the carbon from adsorbed SO2. The mercury-containing brominated sorbents appear to contain mercury bound pri...

XAS and XPS Characterization of Mercury Binding on Brominated Activated Carbon

A bench-scale study was conducted on the simultaneous removal of SO2, NOX, and mercury (both Hg0 and Hg2+) from a simulated coal flue gas using a wet calcium carbonate scrubber. The multipollutant capacity of the scrubber was enhanced with the addition of the oxidizing salt, sodium chlorite. The results showed a maximum scrubbing of 100% for SO2 and Hg species and near complete NO oxidation with about 60% scrubbing of the resulting NOX species. The chlorite additive was less effective as an oxidant in the absence of SO2 and NO in the flue gas. Oxidation of NO and mercury were only about 50% and 80%, respectively, in the case of no SO2 in the simulated flue gas. The mercury oxidation was similarly affected by the absence of NO in the flue gas.

Simultaneous Removal of SO2, NOX, and Hg from Coal Flue Gas Using a NaClO2-Enhanced Wet Scrubber

Hydrotalcite-like compounds (HTlcs) are solid sorbents that may potentially be used for high-temperature separation and capture of CO2. The high-temperature adsorption of CO2 on Mg−Al−CO3 HTlc is affected by structural changes that take place upon heating of the material. The structural changes of a synthetic HTlc upon heating to 200 and 400 °C in a vacuum were characterized using various analytical techniques. These structural changes were then related to observed behavior with respect to the physisorption and chemisorption of CO2 at 200 °C. Upon heating to 200 °C, the material retains its layered structure, though the interlayer spacing is decreased by ∼0.6 A due to loss of interlayer water. Chemisorption of CO2 at 200 °C represents more than half of the total adsorption capacity (at 107 kPa) due to increased availability of the framework Mg2+ cation and the subsequent formation of MgCO3. There is no significant increase of surface area or pore volume after heating to 200 °C. Upon heating to 400 °C the ...

Nick D. Hutson

Papers

Control of mercury emissions from coal-fired electric utility boilers.

XAS and XPS Characterization of Mercury Binding on Brominated Activated Carbon

Simultaneous Removal of SO2, NOX, and Hg from Coal Flue Gas Using a NaClO2-Enhanced Wet Scrubber

Structural Effects on the High Temperature Adsorption of CO2 on a Synthetic Hydrotalcite