Vl. Cebolla et al., EVALUATION OF THE EFFECT OF A NONPOROUS ULTRAFINE IRON CATALYST ON THE HYDROLIQUEFACTION OF A HIGHLY VOLATILE BITUMINOUS COAL, Energy & fuels, 8(1), 1994, pp. 77-82
The effect of a nonporous ultrafine iron oxide precursor, prepared by
a flame method, was evaluated in the hydroliquefaction of a bituminous
coal in tetralin (350, 400, 430 degrees C) on a laboratory scale, and
compared to that of other aerosols (silica, alumina, SnO2, MoO3, NiMo
/Al2O3). The precursors were sulfided with S during heating, according
to a previously established conditions set. Methods of evaluating cat
alytic activity in hydroliquefaction runs based on extraction yields a
re strongly dependent on the experimental conditions. Special emphasis
has been given here in the application of two alternative parameters
based on electron spin resonance (ESR) data, and on the ratio of hydro
gen consumption from the gas to that from the solvent (H-gas/H-solv).
Our results show that with increasing the temperature, the lower the d
ifferentiation between catalysts measured by extraction conversions. H
owever, H-gas/H-solv and the measurements by ESR of the stable radical
s of the tetrahydrofuran-insoluble fractions are more clearly affected
by the nature of the catalysts and related at a given temperature. Fe
2O3 and MoO3 are the most active catalysts at 30 degrees C. The order
of activity is the same regardless of the method used. The spillover e
ffect can explain the hydroliquefaction mechanism. At 400 degrees C, H
-gas/H-solv permits the dearest differentiation between catalysts. At
this temperature, effects other than spillover can contribute to hydro
gen-transfer mechanisms. Analytical data of the coal-derived liquids (
capillary gas chromatography, size exclusion chromatography, and extro
graphy) show a large temperature effect, independent of the nature of
the catalyst: as the temperature increases from 400 to 430 degrees C,
the percentage, in the oils, of the four or more ringed compounds decr
eases, and the heaviest components of the asphaltenes are degraded. Fu
rthermore, the oils obtained with sulfided Fe2O3 or MoO3 contained sig
nificantly more two-ringed aromatic compounds than the oils obtained w
ith the other catalysts, or with no added catalyst. Possible explanati
ons are discussed in the light of the literature research with model c
ompounds.