Kinetic study on a commercial amorphous hydrocracking catalyst by weighted lumping strategy

Abstract

Hydrocracking is an important upgrading process in the petroleum refinery, and it is generally used to process feedstocks ranging from vacuum gas oil (VGO) to vacuum residue. In this work, hydrocracking of VGO using a dual functional amorphous catalyst was carried out at a pilot scale unit under the following reaction conditions: liquid hourly space velocity (LHSV) from 1 to 1.5 hr-1 and reaction temperatures of 360-440°C at the constant pressure and hydrogen to oil, 156 bar and 1780 Nm3/m3, respectively. The effluent of the reactor was characterized to dry gas, naphtha, kerosene, diesel and unconverted VGO or residue. The pilot tests demonstrated that performing experiments beyond the temperature, recommended by catalyst vendor, lead the process to unstable hydrocracking. To describe the yield of hydrocracking products a five-lump discrete lumping approach with ten reactions was proposed. At first, the kinetic model contained twenty kinetic constants which were estimated by using the conventional objective function. The estimated parameters showed that the tendency of the catalyst to convert VGO to gas and naphtha was negligible whilst rate constants for hydrocracking of VGO to middle distillates were considerably high which was compatible with the nature of amorphous hydrocracking catalysts. After evaluating the magnitude of reaction rates and eliminating the ignorable constants, the network was reduced to six reactions in which only nine parameters were needed. The predictions indicated that the latter network could fit the yield of products more acceptable as if the average absolute deviation between experimental and calculated yields was descended from 16.25% to 12.6%. Then, to have a better prediction, a weighted objective function was used in which weight factors were calculated by a proposed weighted least square expression. The results confirmed that this approach could reduce average absolute deviation of model to 10.75%, and it created a fairly even distribution of deviation between hydrocracking products.