(241e) A Strategy for Developing Structure-Based Kinetic Model for Hydrodesulfurization Reactor Under Petroleomics Concept

In petroleum refining industry, modeling of reaction kinetics is critically important for the design and simulation, control and operation of reactors. The conventional modeling method, which groups all the components in the feedstock into lumps based on boiling ranges, has capability of predicting product yields. As it cannot provide structure-based information of product mixtures, it cannot be used to produce new high-value and environmentally friendly products.

Petroleomics has emerged as a result of the increasing need of compositional characterization of petroleum crude oils and derived product slates and the advancement of molecular analytical techniques and instrumentation. Within the concept of petroleomics, all components of petroleum are characterized and their properties and reactivity are correlated with the composition data. The application of petroleomics opens variety of opportunities to noble and efficient use of both conventional and unconventional crude oils, elimination of control and operation problems, reduction of production cost, etc. To capture the wealth of available information of molecular based characterization, chemical properties and reactivity provided by petroleomics, a new kinetic model at molecular level needs to be developed.

In this study, we present a strategy for developing a structure-based kinetic lumping model for design and simulation of refinery reactors. The applicability of the proposed strategy is demonstrated through a case study on petroleum residue hydrodesulfurization (RDS). Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (FT-ICR MS) is used to characterize the basis core structures of substances included in the feed. On the basis of this, Kinetic Modeler’s Toolbox (KMT) is utilized to generate a detailed kinetic model consisting of more than 1200 substances and 2100 elementary reactions. By applying the proposed strategy, a much simpler structure-based kinetic model including only 14 lumps and 16 lump-based reactions was developed and examined for its prediction capability. On the basis of the flow rate profiles of the structure-based lumps described by the developed kinetic model, suitable operation conditions such as reaction temperatures, residence time and catalysts for RDS can be proposed. Overcoming the limitations of the conventional model, the developed model can provide basic insights into the structure-based composition of the product mixture, which are essential information for the design of ultrahigh efficient refinery reactor and optimization and control of product slates.

This work was supported by Ministry of Economy, Trade and Industry (METI) and Japan Petroleum Energy Center (JPEC).