Acacia mearnsii de Wild (black wattle) is one of the most important trees planted in Southern Brazil for tannin extraction and charcoal production. The pyrolysis of the black wattle wood used for obtaining charcoal is performed in brick ovens, with the gas fraction being sent directly into the environment. The present study examines the condensable compounds present in the liquor produced from black wattle wood at different thermal degradation conditions, using gas chromatography coupled with mass spectrometry (GC/MS). Branches of black wattle were thermally degraded at controlled ambient and temperature conditions. Overall, a higher variety of compounds were obtained under atmospheric air pressure than under synthetic air pressure. Most of the tentatively identified compounds, such as carboxylic acids, phenols, aldehydes, and low molecular mass lignin fragments, such as guayacol, syringol, and eugenol, were products of lignin thermoconversion. Substituted aromatic compounds, such as vanillin, ethyl vanillin, and 2-methoxy-4-propeny-phenol, were also identified. At temperatures above 200 ºC, furan, 2-acetylfuran, methyl-2-furoate, and furfural, amongst others, were identified as polysaccharide derivatives from cellulose and hemicellulose depolymerization. This study evidences the need for adequate management of the condensable by-products of charcoal production, both for economic reasons and for controlling their potential environmental impact.

Este trabalho reporta um estudo experimental que objetivou a investigação dos efeitos da temperatura, da taxa de aquecimento e do tempo na eficiência e nos parâmetros cinéticos da decomposição da madeira de acácia-negra (Acacia mearnsii De Wild.) plantada no Rio Grande do Sul. O processo da pirólise da acácia-negra foi investigado por análise termogravimétrica (TGA), e os parâmetros cinéticos foram obtidos a partir de ensaios dinâmicos e isotérmicos. Os ensaios dinâmicos foram conduzidos desde a temperatura ambiente até 900 C, sob taxas de aquecimento que variaram de 2 a 50 ºC.min-1. Os ensaios isotérmicos foram realizados entre 250 e 750 ºC, ao aquecer a amostra até a temperatura desejada e mantendo-se nessa temperatura por 2 h. Os dados cinéticos obtidos dinamicamente foram tratados segundo os métodos de Ozawa e Kissinger. Já os parâmetros cinéticos conseguidos isotermicamente foram calculados ao considerar que a reação de pirólise segue uma cinética de primeira ordem em todo o intervalo de tempo e temperatura empregados. Os resultados denotaram a aplicabilidade dos métodos adotados, visto que os valores da energia de ativação do processo de pirólise, além de se aproximarem entre si, isto é, 170-180 kJ.mol-1, segundo modelos dinâmicos, e 140 kJ.mol-1, segundo o método isotérmico, aproximaram-se também dos valores reportados na literatura sobre a pirólise de compostos celulósicos (150-200 kJ.mol-1). Os resultados contribuem para a melhor compreensão dos processos de pirólise da biomassa, em especial da acácia-negra, o que pode levar ao melhoramento das atuais práticas de conversão da biomassa em carvão vegetal.

The present work aimed at investigating the effects of temperature, heating rate and time on the efficiency and kinetics parameters of the pyrolysis process of Acacia mearnsii De Wild. wood. The pyrolysis behavior was experimentally investigated through thermogravimetry (TGA). The kinetics parameters were obtained from dynamic and isothermal runs. Dynamic runs were performed from room temperature to 900 ºC under heating rates ranging from 2 to 50 ºC.min-1. Isothermal experiments were carried out from 250 to 750 ºC, by heating the sample to the desired temperature and keeping at that temperature for 2 hours. The dynamically obtained data were evaluated according to the Ozawa and Kissinger methods. On the other hand, the isothermally obtained ones were treated considering that the pyrolysis reaction follows a first order reaction over the entire range of time and temperature. The results evidenced the applicability of the methods since the activation energy for the pyrolysis process calculated from both methods resulted very similar, i.e., 170- 180 kJ.mol-1 from dynamic models and 140 kJ.mol-1 from the isothermal method, as well as resulted very close to previously reported values for the activation energy of cellulose pyrolysis (150-200 kJ.mol-1). The results contribute to better understand biomass pyrolysis processes, in particular the A. mearnsii pyrolysis, leading to an improvement of the presently applied methods for charcoal biomass conversion.