Molecular-level heavy petroleum hydrotreating modeling and comparison with high-resolution mass spectrometry

The establishment of a molecular-level process model is critical for heavy petroleum hydrotreating optimization. This paper focuses on constructing a heavy petroleum compositional model and hydrotreating process model with a more accurate molecular detail. Besides the bulk property data, the detail molecular characterization data from high-resolution mass spectrometry was used to guide the compositional and kinetic model development. Under the framework of structural unit and bond-electron matrix (SU-BEM), more than 12,000 representative molecules were constructed to form a heavy petroleum molecular structure library. The probability density functions (PDFs) were combined to constrain the molecular composition of the heavy petroleum. The optimal molecular composition was obtained by optimizing the PDFs parameters. 18 reaction rules were formulated to express the heavy petroleum molecular conversion pathways. The reaction network was generated automatically and transformed mathematically into a micro-kinetic model. The total numbers of involved reactions and molecules were - 25,000 and - 17,000, respectively. The model parameters were globally optimized according to experimental data. The model results show good agreement with the bulk property data. Moreover, the predicted molecular distribution and molecular conversion regulations are consistent with the high-resolution mass spectrometry data.

Automated summary

This paper focuses on constructing a heavy petroleum compositional model and hydrotreating process model with a more accurate molecular detail using high-resolution mass spectrometry data. Over 12,000 representative molecules were constructed to form a heavy petroleum molecular structure library, and 18 reaction rules were formulated to express the molecular conversion pathways. The model parameters were globally optimized according to experimental data, showing good agreement with bulk property data and high-resolution mass spectrometry data.