Combustion properties of Illinois coal-char blends
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A carbon catalyst, prepared either by oxidizing activated carbon with air at 500-700??C or by oxidizing activated carbon with boiling nitric acid followed by heating it to 500-700??C, is the subject of this paper. This catalyst, designated OAC500-700, catalyzes the removal of hydrogen chloride from alkyl halides. Because OAC500-700 retains adsorptive properties of an activated carbon it can be used both to adsorb pollutants from liquid or gaseous streams and to convert them to recyclable products. A highly-developed micropore structure is not required for all uses of activated carbon or a catalyst produced from it. A comparatively inexpensive ($325/ton projected) low surface area (<300 m2/g) carbon has been developed at the Illinois State Geological Survey (ISGS) for cleaning incinerator flue gas. This grade of activated carbon is widely used in Europe for flue gas cleaning and for other applications. Activated carbon adsorbers of some type are required by recently passed U.S. Environmental Protection Agency (EPA) regulations for municipal waste combustors to control emission of cadmium, mercury, lead, dioxins, furans and acid gases (U.S. EPA, 1995). Similar regulations are expected for hospital and hazardous waste incinerators. The marketing of less costly activated carbons of the type used widely in Europe is expected in the United States. Low cost OAC500-700 made from less expensive grades of activated carbon may become available for large scale adsorbent/catalyst systems designed to both remove and decompose toxic pollutants found in liquid and gaseous streams, chlorinated organic compounds in particular.
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Utilities burning Illinois coals currently do not consider trace elements in their flue gas emissions. After the US EPA completes an investigation on trace elements, however, this may change and flue gas emission standards may be established. The mode of occurrence of a trace element may determine its cleanability and Hue gas emission potential. X-ray Absorption Fine Structure (XAFS) is a spectroscopic technique that can differentiate the mode of occurrence of an element, even at the low concentrations that trace elements are found in coal. This is principally accomplished by comparing the XAFS spectra of a coal to a database of reference sample spectra. This study evaluated the technique as a potential tool to examine six trace elements in an Illinois #6 coal. For the elements As and Zn, the present database provides a definitive interpretation on their mode of occurrence. For the elements Ti, V, Cr, and Mn the database of XAFS spectra of trace elements in coal was still too limited to allow a definitive interpretation. The data obtained on these elements, however, was sufficient to rule out several of the mineralogical possibilities that have been suggested previously. The results indicate that XAFS is a promising technique for the study of trace elements in coal.
Test specimens of methane hydrate were grown under static conditions by combining cold, pressurized CH4 gas with H2O ice grains, then warming the system to promote the reaction CH4 (g) + 6H2O (s???l) ??? CH4??6H2O. Hydrate formation evidently occurs at the nascent ice/liquid water interface, and complete reaction was achieved by warming the system above 271.5 K and up to 289 K, at 25-30 MPa, for approximately 8 hours. The resulting material is pure methane hydrate with controlled grain size and random texture. Fabrication conditions placed the H2O ice well above its melting temperature before reaction completed, yet samples and run records showed no evidence for bulk melting of the ice grains. Control experiments using Ne, a non-hydrate-forming gas, verified that under otherwise identical conditions, the pressure reduction and latent heat associated with ice melting is easily detectable in our fabrication apparatus. These results suggest that under hydrate-forming conditions, H2O ice can persist metastably at temperatures well above its melting point. Methane hydrate samples were then tested in constant-strain-rate deformation experiments at T= 140-200 K, Pc= 50-100 MPa, and ????= 10-4-10-6 s-1. Measurements in both the brittle and ductile fields showed that methane hydrate has measurably different strength than H2O ice, and work hardens to a higher degree compared to other ices as well as to most metals and ceramics at high homologous temperatures. This work hardening may be related to a changing stoichiometry under pressure during plastic deformation; x-ray analyses showed that methane hydrate undergoes a process of solid-state disproportionation or exsolution during deformation at conditions well within its conventional stability field.
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The distribution of Cr and other trace metals of environmental interest in a range of widely used U.S. coals was investigated using the Stanford-USGS SHRIMP-RG ion microprobe . Using the oxygen ion source, concentrations of Cr (11 to 176 ppm), V (23 to 248 ppm), Mn (2 to 149 ppm), Ni (2 to 30 ppm), and 13 other elements were determined in illite/smectite, a group of clay minerals commonly present in coal. The results confirm previous indirect or semi-quantitative determinations indicating illite/smectite to be an important host of these metals. Calibration was achieved using doped aluminosilicate-glass synthetic standards and glasses prepared from USGS rock standards. Grains for analysis were identified optically, and confirmed by 1) precursory electron microprobe analysis and wavelength-dispersive compositional mapping, and 2) SHRIMP-RG major element data obtained concurrently with trace element results. Follow-up investigations will focus on the distribution of As and other elements that are more effectively ionized with the cesium primary beam currently being tested.
The speciation of arsenic in an Ohio bituminous coal and a North Dakota lignite has been examined by the complementary methods of arsenic XAFS spectroscopy and sequential extraction by aqueous solutions of ammonium acetate, HCl, HF, and HNO3. In order to facilitate a more direct comparison of the two methods, the arsenic XAFS spectra were obtained from aliquots of the coal prepared after each stage of the leaching procedure. For the aliquots, approximately linear correlations (r2 > 0.98 for the Ohio coal, > 0.90 for the ND lignite) were observed between the height of the edge-step in the XAFS analysis and the concentration of arsenic measured by instrumental neutron activation analysis. Results from the leaching sequence indicate that there are two major arsenic forms present in both coals; one is removed by leaching with HCl and the other by HNO3. Whereas the XAFS spectral signatures of the arsenic leached by HCl are compatible with arsenate for both coals, the arsenic leached by HNO3 is identified as arsenic associated with pyrite for the Ohio coal and as an As3+ species for the North Dakota lignite. Minor arsenate forms persist in both coals after the final leaching with nitric acid. The arsenate forms extracted in HCl are believed to be oxidation products derived from the other major arsenic forms upon exposure of the pulverized coals to air.
The properties of tire-derived carbon adsorbents (TDCA) produced from select tire chars were compared with those derived from an Illinois coal and pistachio nut shells. Chemical analyses of the TDCA indicated that these materials contain metallic elements not present in coal-and nut shell-derived carbons. These metals, introduced during the production of tire rubber, potentially catalyze steam gasification reactions of tire char. TDCA carbons contained larger meso-and macopore volumes than their counterparts derived from coal and nut shell (on the moisture-and ash-free-basis). Adsorptive properties of the tire-derived adsorbent carbons for air separation, gas storage, and gas clean up were also evaluated and compared with those of the coal-and nut shell derived carbons as well as a commercial activated carbon. The results revealed that TDCA carbons are suitable adsorbents for removing vapor-phase mercury from combustion flue gases and hazardous organic compounds from industrial gas streams.