In order to better understand the pyrolysis process of cellulose, the decomposition of levoglucosan and glyceraldehyde, which are important intermediate products of cellulose, are simulated by quantum simulation. Ther...In order to better understand the pyrolysis process of cellulose, the decomposition of levoglucosan and glyceraldehyde, which are important intermediate products of cellulose, are simulated by quantum simulation. Thermodynamic analysis of four possible reaction pathways for levoglucosan is conducted by quantum chemistry.The reaction process of glyceraldehyde is checked, and the intermediates and the activation energies of the process are given. The simulation results indicate that the three well-established chemical pathways for levoglucosan in literature can spontaneously occur within the pyrolysis temperature range from 500 to 1 000 K. However, the reaction pathway involving the formation of erythrose cannot be accepted since the free energy ΔG is estimated to be above zero during the pyrolysis process. Through the analysis of glyceraldehyde decomposition by the transition state theory, decarbonylation and dehydration may be the dominant pathways for glyceraldehyde decomposition. The quantum simulation for determining the chemical pathway of glyceraldehyde and levoglucosan can give a conceptual and methodological guide for searching possible chemical pathways of cellulose pyrolysis or other macromolecules in biomass.展开更多
基金The National High Technology Research and Development Program of China(863 Program)(No.2012AA051801)
文摘In order to better understand the pyrolysis process of cellulose, the decomposition of levoglucosan and glyceraldehyde, which are important intermediate products of cellulose, are simulated by quantum simulation. Thermodynamic analysis of four possible reaction pathways for levoglucosan is conducted by quantum chemistry.The reaction process of glyceraldehyde is checked, and the intermediates and the activation energies of the process are given. The simulation results indicate that the three well-established chemical pathways for levoglucosan in literature can spontaneously occur within the pyrolysis temperature range from 500 to 1 000 K. However, the reaction pathway involving the formation of erythrose cannot be accepted since the free energy ΔG is estimated to be above zero during the pyrolysis process. Through the analysis of glyceraldehyde decomposition by the transition state theory, decarbonylation and dehydration may be the dominant pathways for glyceraldehyde decomposition. The quantum simulation for determining the chemical pathway of glyceraldehyde and levoglucosan can give a conceptual and methodological guide for searching possible chemical pathways of cellulose pyrolysis or other macromolecules in biomass.
