Effect of alkali and alkaline metals on gas formation behavior and kinetics during pyrolysis of pine wood

This study examines the acid and alkaline treatment of pine wood to help understand the effect of alkali and alkaline earth metals (AAEMs) content on the pyrolysis behavior at different temperatures. Acid and alkali pretreatment of pine wood were conducted to modify AAEMs content by ion-exchanging method. Thermal kinetic behavior of the pretreated samples was first conducted by a thermogravimetric analyzer (TGA) at different heating rates that provided activation energies of pyrolysis. Gas formation behavior of the samples for different extents of conversion was carried out in a fixed-bed reactor at two different temperatures of 823 K and 1073 K. Evolutionary behavior of the gas components during pyrolysis, including flow rate, and yield and their energy content were measured and compared. Results showed that the values of activation energies increased with the extent of conversion for all the pretreated samples examined. The effect of AAEMs on pyrolysis behavior of biomass varied with the extent of conversion. The presence of AAEMs in biomass decreased the decomposition energy at low conversion while it greatly improved under high conversion. Besides, alkali treated sample with higher AAEM content enhanced the gas and char yield while it reduced the bio-oil production at low temperature with low conversion. However, at high temperature the opposite trend was observed. Presence of AAEMs was favorable for the generation of H2, CO, CO2 and CnHm at low temperature, while it showed an inhibition effect on CO and CnHm yield and syngas energy at high temperature. The catalytic mechanism of AAEMs on the pyrolysis behavior at different temperatures was discussed based on activation energy and gaseous formation. Results revealed decomposition of carboxylate at low temperature and formation of stable biomass-Na (BM-Na) structure at high temperature that led to the variation of activation energy and changed gaseous products yield and syngas energy. Acid washing pretreatment was found to be effective to enhance bio-oil yield at low temperature and increase syngas energy at high temperature. Syngas yield of acid pretreated sample was 19.6% higher than that raw sample, while alkali pretreatment was favorable for enhanced char yield. These results help to achieve the desired yield of gas or solid using AAEM modification.