Removal of naphthenic acids from high acid crude via esterification with methanol

Refining of high acid crudes (HACs) is seriously limited by extensive corrosion of refinery equipment due to the presence of intrinsic naphthenic acids (NAs). Herein, in the absence of a catalyst or external hydrogen, effective removal of the NAs contained in HACs was achieved using methanol at moderate temperature and moderate pressure. Several process variables, including the temperature, crude concentration, and reaction time are explored to optimize the removal of NAs from HACs. At 250 °C, 6.4 MPa, and 33.3 wt% crude, a very low total acid number (TAN) of 0.08 mg-KOH/g-oil (96.9% reduction efficiency) with a high oil yield (95 wt%) is achieved. During the reduction of the TAN using methanol, some fraction of the resins and asphaltenes in the crude oil crack to form low-molecular-weight aromatic compounds. Compared to deacidification using methanol, pyrolysis (without methanol) results in a much lower TAN reduction efficiency (38.6%). The major deacidification mechanism using methanol is esterification, while that of pyrolysis (without methanol) is decarboxylation.