THE STRUCTURE AND REACTIVITY OF SOME METALLURGICAL CARBONS

Abstract

The reactivity and micro-structure of three coals and two cokes used in iron and steel manufacture have been studied by a variety of techniques, including gas sorption analysis, thermal analysis and microscopy. Changes in surface areas and porosities of the coals and cokes during combustion have been determined by a gravimetric nitrogen sorption technique at 77K. The cokes and coals have been studied by thermal analysis under isothermal and dynamic conditions in different gas atmospheres. Rates of reaction have been correlated with surface area changes. Attempts have been made to calculate activation energies from Kissinger plots of DTA data. Microstructural changes in the cokes and coals during carbon burn-off have been investigated by electron microscopy. Relative porosities have been estimated by image analysis. Mechanical strengths of the cokes have been measured and correlated with porosity data. Selected metals in the carbons have been determined by flame photometry, atomic absorption spectroscopy and Mossbauer spectroscopy. The composition of residual mineral matter (ash) has been investigated by X-ray diffraction. The chemical compositions of the coal distillates have been characterised by ir/uv spectrosopy, NMR spectroscopy and by GC-MS techniques. Calorific values of the carbons have been determined. Results are discussed in relation to previous work and to applications 1n blast furnace practice. In coal combustion the surface areas increase during the initial stages of carbon burn-off, reaching maximum at about 50% burn-off before decreasing. The increases are considerably higher at 400° and 500° C than at 300° C for all three coals. Hysteresis data from the sorption isotherms show that the coals develop full ranges of mesa-porosity and some micro-porosity during burn-off at the higher temperatures. However, the coal oxidation is only slightly accelerated, since most of the new surface is located in the micro- and meso- pores where access to atmospheric oxygen is restricted by slow diffusion, so that the earlier stages of oxidation are approximately linear with time. This improves our knowledge of current empirical industrial carbon solution tests. There is comparatively little change in surface during the coking of the Coals at 1000° C and only restricted sintering of the coal ashes at 300- 500° C. In the combustion of the cokes in carbon dioxide at 1000° C the maxima in surface areas occur within 25% burn-off. However, one of the cokes shows a second maximum at later stages of burn-off, ascribed to the European component in the parent coal blend. This gives a more uniform rate of burn-off which is advantageous industrially.