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The effect of the timing of adding 1 wt% decalin as a hydrogen donor on heavy oil visbreaking was studied. Experiments show that either premixing decalin with heavy oil or adding decalin during the reaction accelerates the formation of light distillates and improves the efficiency of viscosity reduction. Premixing with heavy oil is an appropriate way to add decalin. After 10 min of reaction at 400 ℃, the viscosity reduction rate of the product reaches 90% and the asphaltene content of the product is 1.8 wt% lower than that of the raw heavy oil. According to theoretical calculations, the active hydrogens of decalin preferentially saturate the aromatic C radicals that are critical for condensation. The equilibrium constant of the H-donation reaches the order of 105, while the activation energy of the reaction is only about 26 kJ/mol. The thermal cracking of decalin itself releases active and small-sized radicals, which accelerate visbreaking by participating in the dealkylation network of heavy oil molecules. • Decalin cracking releases radicals with high activity and diffusivity. • Addition of decalin in visbreaking greatly accelerates viscosity reduction. • Decalin selectively saturates aromatic C radicals vital for condensation. • Premixing decalin with heavy oil inhibits condensation in early reaction stage. • Premixing decalin as a hydrogen donor with heavy oil in visbreaking is recommended. [ABSTRACT FROM AUTHOR]

The strategy of adding tetralin as a H-donor in the thermal processing of heavy oil was investigated by experimental characterization and theoretical calculations. According to the experiments, the timing of adding 1 wt% of tetralin has a great influence on the visbreaking performance of heavy oil. Calculations based on density functional theory showed that benzyl radicals released from the thermal cracking of tetralin accelerate the dealkylation that determines the heavy oil upgrading. Meanwhile, H α provided by tetralin is able to selectively saturate aromatic C radicals which are essential for condensation. Compared with the conventional H-donor addition, i.e., pre-mixing of tetralin with heavy oil, a similar viscosity reduction rate of about 98% can be obtained during the visbreaking with delayed tetralin addition. Furthermore, the addition of tetralin before the significant occurrence of condensation further increases the conversion of vacuum residue fraction by 3.4% and reduces the asphaltene content of the product by 2.6 wt%. [Display omitted] • Tetralin cracking releases benzyl radicals which accelerate heavy oil upgrading. • H α provided by tetralin selectively saturates aromatic C radicals. • Pre-mixing of tetralin with heavy oil affects sufficient condensation inhibition. • In visbreaking tetralin should be added before apparent occurrence of condensation. • In delayed coking the addition of tetralin is not recommended. [ABSTRACT FROM AUTHOR]

The performance of introducing a free radical initiator into dealkylation-based visbreaking of heavy oil in the N 2 or supercritical benzene (SC benzene) medium was investigated. Calculations based on density functional theory show that the introduction of di-tert-butyl peroxide (DTBP) into heavy oil visbreaking results in the formation of alkyl C radicals similar to those naturally formed in high temperature initiation. The visbreaking in SC benzene environment is sensitive to the introduction of DTBP, which is different from the visbreaking in N 2 environment. According to reaction kinetics analysis, the presence of SC benzene solvent and the introduction of DTBP greatly accelerate the dealkylation related lumped reactions. Benefiting from improved diffusion environment, the superimposed radicals resulting from DTBP introduction effectively participate in visbreaking and selectively accelerate dealkylation. After only 10–20 min of reaction at 380 °C, visbreaking products with satisfactory viscosity reduction, reduced asphaltene content and improved light component yield can be obtained. • Initiator-introduced heavy oil visbreaking in supercritical benzene was examined. • DTBP introduction results in rapid superposition of alkyl C radicals. • The presence of supercritical benzene accelerates visbreaking. • Superimposed radicals effectively participate in visbreaking in SC benzene. • Best upgrading is obtained in DTBP-introduced visbreaking in SC benzene. [ABSTRACT FROM AUTHOR]