Influence of mass transfer on thermogravimetric analysis of combustion and gasification reactivity of coke

Non-isothermal TG/DTG measurements are widely used to determine kinetic parameters of oxidation and gasification of carbons, e.g. by multi-heating rate methods. Thereby it is important to avoid spurious effects due to diffusion limitations. In this work, TG/DTG experiments with activated carbon were conducted under isothermal and non-isothermal conditions. The agreement of the experimental results with results of simulations based on the intrinsic kinetics, pore diffusion and external diffusion in/to the sample (crucible) is very good. The simulations show that mass transfer has an unwanted influence on TG measurements, if the concentration of the gaseous reactant (O₂ and CO₂) is too low and/or the heating rate is too high. Based on literature data, the simulation was extended to blast furnace coke with a very low reactivity and to highly reactive coke from pyrolysis of miscanthussinensis. The simulations and theoretical considerations lead to a criterion to exclude the influence of mass transfer on TG measurements a priori. This criterion is valid for combustion as well as for gasification with steam or carbon dioxide.