Co-pirólise e avaliação termoquímica de misturas com serragem e coque verde de petróleo verificando a eficiência energética
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2023-12-16
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Universidade Estadual Paulista (Unesp)
Resumo
O progresso industrial, tecnológico e econômico exige que seja revista a matriz energética de forma local e global visando o suprimento de energia mitigando os riscos ambientais. Para tanto utilizou-se o processo de co-pirólise, com diferentes correlações mássicas de misturas das matérias-primas, provenientes de resíduos do setor madeireiro e da indústria do petróleo. O objetivo deste trabalho foram caracterizações químicas e tratamentos térmicos comparativos, para as substâncias resultantes, de poder calorífico, teor de carbono fixo, porcentagem de voláteis e cinzas, teor de enxofre, análise elementar bem como análise térmica e cinética com o propósito de avaliar o efeito sinergético entre os compostos utilizados. O coque verde de petróleo apresentou valores superiores de PCS (35,73 MJ kg-1) e de teor de CF (88,15%) em comparação a serragem (PCI=19,29 MJ kg-1 e CF=19,88%). Para as misturas co-pirolisadas obteve-se maiores valores de PCS nas condições reacionais efetuadas à 3500C (PCS25SE:75CVP=30,10 MJ kg-1, PCS50SE:50CVP=28,82 MJ kg-1 e PCS75SE:25CVP=26,81 MJ kg-1). Através da técnica EDX, os principais elementos químicos identificados em todos os compostos analisados foram carbono, alumínio, silício e enxofre. Pela análise de MEV observou-se que o CVP apresentou uma estrutura em camadas com arranjo irregular e textura densa em função de ser originado da fração pesada de petróleo. Como o CVP apresenta grande estabilidade térmica não se observou modificações na microestrutura do composto in natura e após os processos de pirólise. Enquanto para a SE, observou-se que as superfícies morfológicas modificaram após os processos de pirólise. Em relação aos estudos cinéticos observou-se que as amostras estudadas sofreram decomposição térmica em várias etapas e que os valores da energia de ativação sofreram redução após o processo de pirólise. A mistura que apresentou efeito sinergético promissor, semelhança nos resultados obtidos através dos modelos (KAS, Friedman e OFW) e menor valor na energia de ativação foi a 25SE:75CVP co-pirolisada à 450°C (valores médios de Ea em kJ mol-1: KAS=.56,6; Friedman=58,0 e OFW=72,7).
Industrial, technological and economic progress requires that the energy matrix be reviewed locally and globally in order to supply energy while mitigating environmental risks. For this purpose, the co-pyrolysis process was used, with different mass correlations of mixtures of the raw materials, from residues from the wood sector and the oil industry. The objective of this work was chemical characterizations and comparative heat treatments, for the resulting substances, of calorific value, fixed carbon content, percentage of volatiles and ash, sulfur content, elemental analysis as well as thermal and kinetic analysis in order to evaluate the synergistic effect between the compounds used. Green petroleum coke showed higher values of PCS (35.73 MJ kg-1) and CF content (88.15%) compared to sawdust (PCI=19.29 MJ kg-1 and CF=19.88%). For the co-pyrolysed mixtures, higher PCS values were obtained under the reaction conditions performed at 350ºC (PCS25SE:75CVP =30.10 MJ kg-1, PCS50SE:50CVP =28.82 MJ kg-1 and PCS75SE:25CVP=26.81 MJ kg-1). Through the EDX technique, the main chemical elements identified in all compounds analyzed were carbon, aluminum, silicon and sulfur. The SEM analysis showed that the CVP presented a layered structure with irregular arrangement and dense texture due to being originated from the heavy fraction of oil. As CVP has great thermal stability, no changes were observed in the microstructure of the compound in natura and after the pyrolysis processes. While for SE, it was observed that the morphological surfaces changed after the pyrolysis processes. Regarding the kinetic studies, it was observed that the samples studied underwent thermal decomposition in several steps and that the activation energy values were reduced after the pyrolysis process. The mixture that showed a promising synergistic effect, similarity in the results obtained through the models (KAS, Friedman and OFW) and lower value in the activation energy was 25SE: 75CVP co-pyrolyzed at 450°C (mean values of Ea in kJ mol-1: KAS= .56.6; Friedman=58.0 and OFW=72.7).
Industrial, technological and economic progress requires that the energy matrix be reviewed locally and globally in order to supply energy while mitigating environmental risks. For this purpose, the co-pyrolysis process was used, with different mass correlations of mixtures of the raw materials, from residues from the wood sector and the oil industry. The objective of this work was chemical characterizations and comparative heat treatments, for the resulting substances, of calorific value, fixed carbon content, percentage of volatiles and ash, sulfur content, elemental analysis as well as thermal and kinetic analysis in order to evaluate the synergistic effect between the compounds used. Green petroleum coke showed higher values of PCS (35.73 MJ kg-1) and CF content (88.15%) compared to sawdust (PCI=19.29 MJ kg-1 and CF=19.88%). For the co-pyrolysed mixtures, higher PCS values were obtained under the reaction conditions performed at 350ºC (PCS25SE:75CVP =30.10 MJ kg-1, PCS50SE:50CVP =28.82 MJ kg-1 and PCS75SE:25CVP=26.81 MJ kg-1). Through the EDX technique, the main chemical elements identified in all compounds analyzed were carbon, aluminum, silicon and sulfur. The SEM analysis showed that the CVP presented a layered structure with irregular arrangement and dense texture due to being originated from the heavy fraction of oil. As CVP has great thermal stability, no changes were observed in the microstructure of the compound in natura and after the pyrolysis processes. While for SE, it was observed that the morphological surfaces changed after the pyrolysis processes. Regarding the kinetic studies, it was observed that the samples studied underwent thermal decomposition in several steps and that the activation energy values were reduced after the pyrolysis process. The mixture that showed a promising synergistic effect, similarity in the results obtained through the models (KAS, Friedman and OFW) and lower value in the activation energy was 25SE: 75CVP co-pyrolyzed at 450°C (mean values of Ea in kJ mol-1: KAS= .56.6; Friedman=58.0 and OFW=72.7).
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Co-pirólise, Coque verde de petróleo, Resíduos de madeira, Bioenergia, Co-pyrolysis, Green petroleum coke, Wood waste, Bioenergy
Como citar
GUERTA, A. C. Co-pirólise e avaliação termoquímica de misturas com resíduos da indústria madeireira e coque verde de petróleo verificando a eficiência energética. 2023. 180 f. Tese (Doutorado em Ciências Ambientais) – Instituto de Ciência e Tecnologia, Universidade Estadual Paulista, Sorocaba, 2023.