The Catalytic Effect of Iron and Alkali and Alkaline Earth Metal Sulfates Loading Series on the Conversion of Cellulose-Derived Hydrochars and Chars.

The catalytic effect of minerals on biomass conversion was studied focusing on Fe as well as alkali and alkaline earth metals as the metallic inorganic elements typically present in minerals found in biomass. A mineral-free reference hydrochar and an analogous char material based on cellulose were systematically doped with sulfates of the different metallic inorganic elements in various amounts via impregnation, thereby excluding differences originating from the counterion and the carbon matrix. Thermogravimetric reactivity measurements were performed in diluted O2 and CO2, and the derivative thermogravimetry curves were fitted using the random pore model. This procedure enabled a quantification of the apparent activation energy decrease due to doping as well as the influence of doping on the carbon structural parameter. Fe sulfate was always among the most active minerals, and alkali metal sulfates were typically more active than alkaline earth metal sulfates. The only exception was the high activity of very small Ca sulfate loadings during gasification. A saturation behavior of the kinetic parameter upon increasing the mineral loading was observed. The Langmuir-type modeling of this dependence further revealed that catalytically influenced devolatilization results in a char with higher oxidation reactivity, whereas for gasification, thermal annealing dominates. The systematically derived parameters provide a comprehensive description of catalytic effects, taking into account the type of mineral, the applied loading, the used atmosphere, and the fuel morphology. The derived activation energies can be used to include catalytic effects into combustion models.

Thermicity of the Decomposition of Oxygen Functional Groups on Cellulose-Derived Chars.

The evolution of oxygen functional groups (OFGs) and the associated thermic effects upon heat treatment up to 800 °C were investigated experimentally as well as by theoretical calculations. A synthetic carbon with a carbonaceous structure close to that of natural chars, yet mineral-free, was derived from cellulose and oxidized by HNO3 vapor at different temperatures and for varied durations in order to generate char samples with different concentrations and distributions of OFGs. The functionalized samples were subjected to calorimetric temperature-programmed desorption measurements in correlation with an extensive effluent gas analysis, thereby focusing on the specific heat effects of individual OFG evolution. Interpretation of the experimental results was aided by density functional theory (DFT) calculations which allowed one to infer the thermal stability of different OFGs and the reaction energy associated with their evolution upon heating. Results showed that, with increasing temperature, H2O was released due to the loss of physisorbed water, the decomposition of clusters bound to carboxylic acids, and condensation reactions. The associated heat uptake amounted to about 100 kJ mol-1. Contrarily, the release of CO2, attributed to the decomposition of condensed acids, carboxylic acids, anhydrides, and lactones, resulted in a heat release of about 40 kJ mol-1. The most strongly pronounced thermic effects were detected for the release of CO, comprising highly exothermic effects due to the decomposition of condensed acids and carbonyls/quinones as well as endothermic effects attributed to anhydrides and phenols/ethers. Notably, anhydrides can be formed during the oxidative treatment as well as during heating by condensation of adjacent carboxylic acids. In the latter case, the two-step decomposition is overall highly exothermic, indicating the associated occurrence of pronounced carbon matrix rearrangements. DFT investigations suggest that these rearrangements not only affect the immediate OFG proximity but also involve several carbon sheets.