the coking properties of coal at elevated pressures. - Argonne ...
the coking properties of coal at elevated pressures. - Argonne ... the coking properties of coal at elevated pressures. - Argonne ...
variations, indicated by the number of counts per second during ESCA analysis, are attributed to chemical variations in coal surfaces. The differences in carbon peak positions were of interest especially in sample no. 8, for which the C 1s peak posi- tion is indicative of graphitic carbon and this scan also contains the largest F 1s signal. Recently, an examination of raw coal macerals by XPS indicates that fisinite displays characteristics (C 1s binding energy 284.4 eV) essentially identical to pure graphite. It was also observed that the vitrinite fraction of a western Canadian coal sample was greatly enriched (> 1 wt. percentage) in an organically found fluorine species, ~(CFZ)~ type. In the ESCA scans of ashed coals (Table 4) many more elements (Na, Mg, Ti and Fe) a peared and the F 1s and S 2s peaks are enhanced. S appearing both as SO:and S8- is likely associated with Fe as iron sulphide (pyrite), the outer shell oxidized to sulphate by combustion. The concentrations of Al, Ca, Ti and Fe in NBS reference ash (1633a) measured by ESCA (using the Si 2s peak as a reference) agree well with recommended values. In the ash, F and S surface concentrations are much greater than those observed in the bulk samples, and this could be evidence for preferential siting of these elements on ash surfaces. C1 was not detected on the ash surfaces by ESCA, in contrast to the high signals noted on raw coal surfaces, and C1 may be removed in the volatile phase during combustion. CONCLUSION The combined use of SSMS and ESCA results was successful in part in overcoming the unique analytical difficulties presented by the heterogeneous chemical and physical distribution of intimately combined inorganic and organic species in coal. These techniques and modifications of them are applicable to the study of the combustion chemistry of coal as well as to the assessment of the environmental impact of coal uti1 ization. REFERENCES Babu, S.P. (Ed.) 1975. Trace elements in fuels. Adv. Chem. Ser. 141. Am. Chem. SOC., Washington, D.C. 214 pp. Bancroft, G.M., Brown, J.R., and Fyfe, W.S. 1979. Advances in, and applications of, x-ray photoelectron spectroscopy (ESCA) in mineralogy and geochemistry. 25, 227-243. Chem. Geol. Brown, J.R. 1979. Adsorption of metal ions by calcite and iron sulphides: A quantitative XPS study. 220 pp. Ph.D. thesis, University of Western Ontario, London, Ontario, Brown, J.R., Kronberg, B.I., and Fyfe, W.S. 1981,a. Semi-quantitative ESCA examina- tion of coal ash surfaces. FUEL 60: 439-446. Brown, J.R., Kronberg, B.I., and Fyfe, W.S. 1981,b. An ESCA examination of coal and coal ash surfaces, In: Proceedings "Coal: Phoenix of the '80's" (ed. A.M. A1 Taweel), 64th Canadian Chemical Conference, Halifax, N.S. Chapelle, F.H. 1980. A proposed model for predicting trace metal composition of fly-ash leachates. Environ. Geol. 3(3): 117-122. Oegens, E.T. 1958. Geochemische Untersuchungen zur Faziesbestimung im Ruhrkarbon und im Saarkarbon. Gluckauf, Jg. 94, Essen. 118
I I Fairbridge, R.W. (ed.) 1972, Encyclopedia of geochemistry and environmental earth \ sciences series, Vol. IVA, Van Nostrand Reinhold, New York, 1321 pp. I Flanagan, F.J. 1973. 1972 values for international geochemical reference samples. ' Geochim. Cosmochim Acta 37: 1189-1200. Goldberg, E.D., Hodge, V.F., Griffin, J.J., Koide, M. and Edgington, D.N. 1981. \ Impact offossil fuel combustion on the sediments of Lake Michigan. Envir. SCi. & Tech. 15 (4): 466-471. Goldschmidt, V.M. 1954. Geochemistry, Claredon press, Oxford 730 pp. Kennedy, J.F., 1979. Transition-metal oxide chelates of carbohydrate-directed macro- ' molecules. Chem. SOC. Rev. 8 (2) 221-257. Kronberg, B.I., Brown, J.R., Fyfe, W.S., Peirce, M. and Winder, C.G. 1981. Distri- btuions of trace elements in western Canadian coal ashes. FUEL 60: 59-63. Taylor, S.R. 1965. Geochemical analysis by spark sourc-mass spectrography. Geochim. Cosmochim. Acta 29: 1234-1261. Taylor, L.T., Hausler, D.W. and Squires, A.M. 1981. Organically bound metals in a solvent-refined coal : metallograms for a Wyoming subbituminous coal. 644-646. Science, 213, Wedepohl, K.H. 1969. Handbook of Geochemistry. Springer-verlag, Berlin. 119
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I<br />
I<br />
Fairbridge, R.W. (ed.) 1972, Encyclopedia <strong>of</strong> geochemistry and environmental earth<br />
\ sciences series, Vol. IVA, Van Nostrand Reinhold, New York, 1321 pp.<br />
I Flanagan, F.J. 1973.<br />
1972 values for intern<strong>at</strong>ional geochemical reference samples.<br />
' Geochim. Cosmochim Acta 37: 1189-1200.<br />
Goldberg, E.D., Hodge, V.F., Griffin, J.J., Koide, M. and Edgington, D.N. 1981.<br />
\ Impact <strong>of</strong>fossil fuel combustion on <strong>the</strong> sediments <strong>of</strong> Lake Michigan. Envir. SCi. &<br />
Tech. 15 (4): 466-471.<br />
Goldschmidt, V.M. 1954.<br />
Geochemistry, Claredon press, Oxford 730 pp.<br />
Kennedy, J.F., 1979. Transition-metal oxide chel<strong>at</strong>es <strong>of</strong> carbohydr<strong>at</strong>e-directed macro-<br />
' molecules. Chem. SOC. Rev. 8 (2) 221-257.<br />
Kronberg, B.I., Brown, J.R., Fyfe, W.S., Peirce, M. and Winder, C.G. 1981. Distri-<br />
btuions <strong>of</strong> trace elements in western Canadian <strong>coal</strong> ashes. FUEL 60: 59-63.<br />
Taylor, S.R. 1965. Geochemical analysis by spark sourc-mass spectrography. Geochim.<br />
Cosmochim. Acta 29: 1234-1261.<br />
Taylor, L.T., Hausler, D.W. and Squires, A.M. 1981. Organically bound metals in a<br />
solvent-refined <strong>coal</strong> : metallograms for a Wyoming subbituminous <strong>coal</strong>.<br />
644-646.<br />
Science, 213,<br />
Wedepohl, K.H. 1969. Handbook <strong>of</strong> Geochemistry. Springer-verlag, Berlin.<br />
119
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