Comparison of artificial maturation of lignite in hydrous and nonhydrous conditions

Abstract

The objectives of the study are to compare product compositions and yields generated from lignite artificially matured by open nonhydrous pyrolysis, closed nonhydrous pyrolysis, and hydrous pyrolysis. The pyrolysis products were fractionated into CO2, H2O, CH4, C2-C5, C8-C14, C14+ saturates, C14+ aromatics and NSOs (resins+asphaltenes). All three methods generated high and similar quantities of water during pyrolysis that ranged between 14.6 and 15.2 wt.% of the original lignite. As a result of this high water content generated by the lignite, the experiments with no added water are referred to as nonhydrous rather than anhydrous. Rock-Eval pyrolysis and elemental analyses were conducted on the recovered lignite after solvent extraction to determine their residual hydrocarbon generation potential and to plot their position in a van Krevelen diagram, respectively. Residual lignite from the closed nonhydrous and hydrous experiments showed relationships between vitrinite reflectance (%Ro) values and atomic H/C ratios that occurred within the fields observed for natural maturation of coal. Although no significant differences in the atomic H/C ratios were observed between closed nonhydrous and hydrous pyrolysis, the vitrinite reflectance values were on the average 0.2% Ro lower in the residual lignite from the nonhydrous experiments. The remaining hydrocarbon generation potential as determined by Rock-Eval pyrolysis of the residual lignite showed that the nonhydrous residuals had on the average 16 mg more hydrocarbon potential per gram of original lignite than the hydrous residuals. This suggests there is a better release of the pyrolysis products from the lignite network in the hydrous experiments once generation occurs. For gas generation, at maximum yields, open nonhydrous pyrolysis generates the most hydrocarbon gas (21.0 mg/g original lignite), which is 20% more than closed nonhydrous pyrolysis and 29% more than hydrous pyrolysis. Closed nonhydrous pyrolysis generates on the average 14% more gas than hydrous pyrolysis, but the proportionality of the generated hydrocarbon gases is essentially the same for both pyrolysis methods. At maximum yields, CO2 generation is greatest in hydrous pyrolysis (99.5 mg/g original lignite), with yields being 37 percent higher than closed nonhydrous pyrolysis and 26% higher than open nonhydrous pyrolysis. The maximum yields of C14+ products are highest and similar for open nonhydrous pyrolysis and hydrous pyrolysis (125.6 and 125.9 mg/g lignite, respectively), and are more than 70% higher than closed nonhydrous pyrolysis. This difference in the maximum yields of C14+ products can be explained by differences in the proportionality between either cracking reactions that result in liquid product and char formation or trapping of generated products within the coal network (cross-linking reactions). Maximum yields of C14+ aliphatics from hydrous experiments may not have been attained, but the maximums that were observed and their GC traces are similar for the three pyrolysis systems.