Predicting extents of mercury oxidation in coal-derived flue gases

The proposed mercury (Hg) oxidation mechanism consists of a 168-step gas phase mechanism that accounts for interaction among all important flue gas species and a heterogeneous oxidation mechanism on unburned carbon (UBC) particles, similar to established chemistry for dioxin production under comparable conditions. The mechanism was incorporated into a gas cleaning system simulator to predict the proportions of elemental and oxidized Hg species in the flue gases, given relevant coal properties (C/H/O/N/S/Cl/Hg), flue gas composition (O2, H2O, HCl), emissions (NO(X), SO(X), CO), the recovery of fly ash, fly ash loss-on-ignition (LOI), and a thermal history. Predictions are validated without parameter adjustments against datasets from lab-scale and from pilot-scale coal furnaces at 1 and 29 MWt. Collectively, the evaluations cover 16 coals representing ranks from sub-bituminous through high-volatile bituminous, including cases with Cl2 and CaCl2 injection. The predictions are, therefore, validated over virtually the entire domain of Cl-species concentrations and UBC levels of commercial interest. Additional predictions identify the most important operating conditions in the furnace and gas cleaning system, including stoichiometric ratio, NO(X), LOI, and residence time, as well as the most important coal properties, including coal-Cl.     

The impact of wet flue gas desulfurization scrubbing on mercury emissions from coal-fired power stations

This article introduces a predictive capability for Hg retention in any Ca-based wet flue gas desulfurization (FGD) scrubber, given mercury (Hg) speciation at the FGD inlet, the flue gas composition, and the sulphur dioxide (SO2) capture efficiency. A preliminary statistical analysis of data from 17 full-scale wet FGDs connects flue gas compositions, the extents of Hg oxidation at FGD inlets, and Hg retention efficiencies. These connections clearly signal that solution chemistry within the FGD determines Hg retention. A more thorough analysis based on thermochemical equilibrium yields highly accurate predictions for total Hg retention with no parameter adjustments. For the most reliable data, the predictions were within measurement uncertainties for both limestone and Mg/lime systems operating in both forced and natural oxidation mode. With the U.S. Environmental Protection Agency's (EPA) Information Collection Request (ICR) database, the quantitative performance was almost as good for the most modern FGDs, which probably conform to the very high SO2 absorption efficiencies assumed in the calculations. The large discrepancies for older FGDs are tentatively attributed to the unspecified SO2 capture efficiencies and operating temperatures and to the possible elimination of HCl in prescrubbers. The equilibrium calculations suggest that Hg retention is most sensitive to inlet HCl and O2 levels and the FGD temperature; weakly dependent on SO2 capture efficiency; and insensitive to HgCl2, NO, CA:S ratio, slurry dilution level in limestone FGDs, and MgSO3 levels in Mg/lime systems. Consequently, systems with prescrubbers to eliminate HCl probably retain less Hg than fully integrated FGDs. The analysis also predicts re-emission of Hg(O) but only for inlet O2 levels that are much lower than those in full-scale FGDs.     

Multi-component behavior of fixed-bed adsorption of dioxins by activated carbon fiber

The multi-component behavior of fixed-bed adsorption of dioxins (DXNs) was examined through detailed analyses of the concentration profiles of isomers in fixed-bed activated carbon fiber (ACF). Regularities in both adsorption rates and strengths were clarified. (1) The rate of transfer in the adsorption of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCCDs/DFs) tends to increase with decreasing number of chlorine substituents. Axial dispersion also tends to increase with a decreasing number of chlorine substituents under our experimental conditions. (2) Homologues with the same number of chlorine substituents in PCDDs/DFs have similar adsorption strengths. The adsorption strength of PCDD/DF isomers is probably greater than that of co-planar polychlorinated biphenyls (co-PCB) isomers when the number of chlorine substituents is identical. (3) The adsorption strength of isomers depends on their molecular structure. In PCDDs/DFs the toxic isomers, all of which have vicinal chlorine substituents at the 2, 3, 7 and 8 positions, are relatively strong. It is clear, especially in TeCDDs, that isomers with vicinal chlorine substituents are stronger than isomers without. In co-PCBs, isomers without chlorine substituents at ortho positions are stronger than those with, and (4) A close analogy exists between the adsorption strength order for ACF and the elution order in gas chromatography (GC).     

Debromination of hexabromobenzene by its co-grinding with CaO

A hexabromobenzene (HBB, C6Br6) powder was subjected to co-grinding with excess CaO powder in air using a planetary ball mill to investigate mechanochemical debromination of the HBB sample. The reaction proceeds smoothly with an increase in both grinding time and molar ratio of CaO addition. The co-grinding enables us to debrominate HBB, forming CaBr2, C and CaCO3 besides excess CaO in the product. CaBr2 in the product tends to absorb moisture from the atmosphere to form CaBr2 x nH2O. The reaction yield is quantitatively evaluated by measuring the amount of water-soluble bromide through water washing and the amount of unreacted HBB through toluene washing. It is found that almost 100% of debromination is achieved by 6 h grinding with the molar ratio kept constant at 2:1. Radicals are detected in the ground products, possibly due to rupture in the covalent bonds of C-C and C-Br in HBB.     

Genetic structure of green turtle (Chelonia mydas) peripheral populations nesting in the northwestern Pacific rookeries: evidence for northern refugia and postglacial colonization

Several green turtle (Chelonia mydas) nesting populations have been reported in the northwestern Pacific region, the northernmost limit of its distribution range. However, the population history in this region as a whole is not well understood. To clarify how the green turtle nesting populations have evolved in the northwestern Pacific region, the genetic composition of mitochondrial DNA control region sequences in the northwestern Pacific was compared with that of the other Pacific populations. We analyzed 302 samples from the northwestern Pacific rookeries, including 78 newly collected samples from rookeries in the Ryukyu Archipelago, Japan (from 24.27°N, 123.76°E to 28.45°N, 129.61°E). Our results revealed that the northwestern Pacific populations consisted of one highly endemic lineage (Clade IV) in the northwestern Pacific rookeries and two other lineages (Clades I and V) which were widely observed in other Pacific populations. We concluded that the highly endemic lineage indicated that a refugial population existed in this region during the Last Glacial Maximum, and the other two lineages indicated that colonization from populations at lower latitudes occurred during interglacial periods. The green turtle nesting populations in the present periphery of their distribution range had been thought to have their origin in colonization from lower latitudes, which served as refugia during glacial periods. However, the present results indicated that the northwestern Pacific peripheral populations have been maintained on the evolutionary timescale of this species and should be treated as long-term conservation resources.     

Activity and emission inventory of open waste burning at the household level in developing countries: a case study of Semarang City

Journal of Material Cycles and Waste Management - In this study, total burned household waste and the potential emissions released from waste burning in Semarang City, Indonesia, were estimated....     

Cracking styrene derivative polymers in decalin solvent with metal-supported carbon catalysts

The cracking of styrene derivative polymers dissolved in decalin was conducted with metal-supported carbon catalysts under an inert gas atmosphere to recover monosubstituted styrene or monosubstituted ethylbenzene in higher yields than is obtained by pyrolysis, and to elucidate the detailed reaction mechanisms in the solvent. Poly-(4-methylstyrene), poly-(4-t-butylstyrene), poly-(α-methylstyrene), and polystyrene were used. In decalin without a catalyst, each polymer was decomposed into the monomer, dimer, and trimer derived from the corresponding polymer except for poly-(α-methylstyrene), which was decomposed into the monomer and styrene. By using metal-supported carbon, the olefinic compounds derived from the corresponding polymer were thoroughly hydrogenated to the saturated form in a nitrogen atmosphere by a hydrogen transfer reaction from decalin, which was simultaneously dehydrogenated to tetralin and naphthalene with the evolution of hydrogen gas. In comparison with metal species, Pd- and Ru-supported carbon catalysts maintained the hydrogenation activity for a longer time and with a lower evolution of hydrogen than Pt or Rh. The dehydrogenation of decalin was mainly observed not on the metal surfaces, but on the carbon surfaces over Pd-supported carbon. Stabilization of the monomers will be able to suppress the coking which occurs with repolymerization in long running process. Received: July 19, 2000 / Accepted: March 16, 2001     

Evaluation of an electrolysis apparatus for inactivating antineoplastics in clinical wastewater

We recently reported a system for inactivating antineoplastics in which sodium hypochlorite is supplied by the electrolysis of sodium chloride solution. In this study, we designed an electrolysis apparatus for inactivating the cytotoxicity of antineoplastics in clinical wastewater using the system. The apparatus consists of an electrolysis cell with platinum-iridium electrodes, a pool tank, a circulating system for wastewater, a safety system for explosive gas and overflow, and an exhaust duct. The free chlorine concentration increased linearly up to 6500 mg l(-1), and pH also increased to 9.0-10.0 within 2h, when 0.9% sodium chloride solution was electrolyzed. We examined its efficacy with model and clinical wastewaters. The reciprocal of dilution factor for disappearance of cytotoxicity using Molt-4 cells was compared before and after electrolysis. In the model wastewater, that was 9.10 x 10(4) before electrolysis, and 3.56 x 10(2) after 2h of electrolysis. In the clinical wastewater (n=26), that was 6.90 x 10(3)-1.02 x 10(6) before electrolysis, and 1.08 x 10(2)-1.45 x 10(4) after 2h of electrolysis. Poisonous and explosive gases released by the electrolysis were measured; however, they were found to be negligible in terms of safety. The environmental load was evaluated by carbon dioxide generation as an index and it was found that the carbon dioxide generated by the electrolysis method was 1/70 lower than that by the dilution method with tap water. Moreover, the cost of the electrolysis method was 1/170 lower than that of the dilution method. This method was found to be both effective and economically valuable.