Abstract
The use of thermogravimetric analysis to describe biomass kinetics often uses bench top thermogravimetric analyser (TGA) analysers which are only capable of low heating rates. The aim of this research was to compare experimental fast pyrolysis of Olive kernels in a bespoke laboratory thermogravimetric fluidised bed reactor (TGFBR) characterised by rapid heating rates at high flow rates, compared to a smaller bench scale fixed bed TGA system. The pyrolysis in the TGFBR was analysed by using the isothermal kinetic approach and it was theorised that the pyrolysis decomposition reactions occurred by two mechanisms depending on the temperature, resulting in an activation energy of 67.4 kJ/mol at temperatures below <500 °C and 60.8 kJ/mol at temperatures >500 °C. For comparison, a bench scale TGA was used to look at the thermal behaviour in different fixed bed thermal conditions giving a higher activation energy of 74.4 kJ/mol due to the effect of external particle gas diffusion. The effect of biomass particle size (0.3–4.0 mm) on the conversion of biomass at different temperatures, was investigated between 300 and 660 °C in the TGFBR. The results suggested inhibition of internal gas diffusion was more important at lower temperatures, but in comparison had no significant effect when measured in the fixed bed TGA at lower heating rates. Bench top TGA analysis of pyrolysis is a rapid and valuable method, but is limited by smaller sample sizes and lower heating rates. In comparison, the conditions encountered with the laboratory scale TGFBR are more likely to be relevant to larger scale systems where heat distribution, heat transfer and mass diffusion effects play major roles in the reactivity of biomass.
Highlights
Olive kernels are a co-product residue of agricultural activity in the Mediterranean region
Since the pyrolysis of Olive kernel in the thermogravimetric fluidised bed reactor (TGFBR) is a heterogeneous solid state reaction, the universal kinetics of the thermal decomposition of biomass are expressed by Eq (2) [16], where T is the reaction temperature; t is the reaction time; f(X) is the differential reaction model; X is the conversion; and k(T) is the temperature dependant reaction rate that can be expressed by the Arrhenius Eq (3), where Ea is the activation energy, A is the pre-exponential factor and R is the universal gas constant
The effect of particle size on pyrolysis was investigated for four particle sizes as shown in Fig. 2 and demonstrated that particle size does not have an important influence on the thermogravimetric analyser (TGA) profile of the Olive kernel
Summary
Olive kernels are a co-product residue of agricultural activity in the Mediterranean region. Greece has the third largest Olive oil production industry in the world. About 400,000 tons of Olive kernels are produced annually [1]. Olive kernel is already exploited as a low cost solid biomass fuel (0.046 £/kg), and is mostly utilized for conventional combustion. Olive kernel has not yet utilised its full potential as alternative biofuel [2]. There is limited scientific research concerning the comparison of experimental fast pyrolysis of Olive kernels in fluidised bed and fixed bed systems, experimentation with this kind of biomass is of great interest
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