Experimental determination of walnut shell pyrolysis kinetics in N2 and CO2 via thermogravimetric analysis, fluidized bed and drop tube reactors

Abstract

A thermogravimetric analyzer (TGA), a fluidized bed reactor (FBR) and a drop tube reactor (DTR) are used to study the effect of reactor type, heating rate and temperature on the pyrolysis of pulverized walnut shell particles in N2 and in CO2. These setups cover a temperature range of 400–1300 K with heating rates of 10−1 to 105 K s−1. The single first-order model in combination with an Arrhenius approach is used to describe the pyrolysis reaction. Derived activation energies for all setups show similar values (Ea,TGA = 71.96 kJ mol−1, Ea,FBR = 68.60 kJ mol−1 and Ea,DTR = 60.83 kJ mol−1), while an increase in the reactor temperature tend to lower the activation energy. Pyrolysis gas compositions in FBR and DTR reveal consistent trends towards lower H2O and higher CO contents with increasing reactor temperature. To evaluate the impact of CO2 on the solid conversion, TGA measurements in CO2 are used to determine gasification kinetics (Ea,g = 214.1 kJ mol−1, Ag = 71.96 s−1). CFD simulations using these kinetics in CO2 drop tube experiments let assume that the changed thermophysical properties of the gas and not the gasification reaction lead to the observed stronger conversion in CO2 compared to N2.