Department of Chemistry, Center for Scientific Computation, Center for Drug Discovery, Design, and Delivery (CD4), Southern Methodist University, Dallas, TX, 75275, USA.
Exploring free energy profile of petroleum thermal cracking mechanisms
Understanding the mechanisms of petroleum thermal cracking is critical to develop more efficient and eco-friendly petroleum cracking processes. Asphaltenes are the main component of petroleum subjected to cracking processes. Thermal cracking mechanisms of petroleum were explored by computational methods using 1,2-diphenylethane (DPE) as a model molecule in this study. The overall mechanisms were divided into four steps including initiation, H-transfer reaction, H-ipso reaction, and termination represented by seven reactions. We carried out extensive quantum chemistry calculations at high levels of theory to accurately explore the minimum energy pathways as the mechanisms of the proposed reactions. The reaction energy and barriers in terms of enthalpy and free energy and their temperature dependence were calculated in the vacuum and in both polar and nonpolar solvents using the polarizable continuum model (PCM) method. The temperature dependence of the target reaction barriers are characterized in different environments and provides computational guidance for future development for petroleum thermal cracking. As the first reported systematic investigation of petroleum cracking mechanisms, this study provided a comprehensive theoretical description of petroleum cracking processes with valuable information about temperature and solvent dependence.
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