Total Acid Number Reduction of Naphthenic Acid Using Subcritical Methanol: A Kinetic Study

The aim of this study is to explore the capability of subcritical methanol to reduce the acidity of naphthenic acids and to determine reaction kinetics for large-scale reactor design. The experiments were carried out in a 25 mL autoclave reactor (China) at temperatures of 70-120oC, Methanol Partial Pressures (MPPs) of 0.1-1.5 MPa, and reaction times of 0-60 min. The total acid number content of the samples was analyzed using ASTM D 974 techniques. Experimental results reveal that total acid number reduction of naphthenic acids increased with increasing reaction temperature, MPP, and reaction time. Approximately 74.20% total acid number was reduced at a temperature of 120oC, a MPP of 1 MPa, and a reaction time of 60 min. Experimental data revealed that total acid number removal reaction kinetics followed second-order kinetics with an activation energy of 11.27 kcal/mol. Therefore, subcritical methanol is able to reduce the total acid number of naphthenic acids without the addition of any catalyst.