Molecular-Level Kinetic Modeling of Methyl Laurate: The Intrinsic Kinetics of Triglyceride Hydroprocessing

Abstract

A molecular-level kinetic model for the hydroprocessing of methyl laurate was constructed. The reaction network was deduced using experimental observations in the context of the delplot method for the discernment of product rank. The resulting 45 species and 83 reactions were used to construct the set of material balances in the kinetic model. Kinetic parameters of the model were determined by minimizing the difference between model outputs and experimental data for methyl laurate hydroprocessing. Differences in reactivity as a result of catalyst metal composition were modeled via the catalyst family concept. The model results show good agreement with the experimental results for a range of process conditions.

Molecular-Level Kinetic Modeling of Triglyceride Hydroprocessing

“…Systematic generation of the reaction network was performed computationally using the Interactive Network Generator (INGen). , INGen iteratively searches for specific reactive subgroups in computational representations of molecules and applies the desired reaction algorithm to generate products. The detailed list of reaction algorithms for the triglyceride hydroprocessing network, represented as matrices in INGen, has been discussed in earlier work . This model used the 13 aforementioned triglycerides along with hydrogen as seeds to the reaction network.…”

“…KME systematically constructs material balances for each component in the reaction network that can be used to define an initial value problem. Details of the model equations and techniques have been explained in previous work . In general, a hydroprocessing unit with a bifunctional catalyst was modeled using Langmuir–Hinshelwood–Hougen–Watson (LHHW) rate laws of the form displayed in eq .…”

“…The adsorption QSRRs have been shown to work well for hydroprocessing systems As an initial evaluation, an extrapolation from the kinetic parameters of the catalyst in previous work was used in the current work based on the catalyst family concept. In the catalyst family concept, the changes in reactivity between different but similar catalysts are modeled as constants.…”

“…This present work builds upon previous modeling work on methyl laurate, a model compound for coconut oil, to develop a molecular-level kinetic model for triglycerides based on recently published experimental data , on coconut oil and soybean oil hydroprocessing. The experimental work used alumina-supported NiMo and CoMo catalysts to hydroprocess vegetable oils at different temperatures, pressures, and liquid hourly space velocities (LHSVs). , Using an in-house software suite, the Kinetic Modeler’s Toolbox (KMT), , a reaction network for the triglycerides present in vegetable oils was constructed and used to make a kinetic model.…”

“…These molecule-to-molecule variations for differ- ent isomers illustrate the importance of modeling the specific molecules of the paraffinic product from triglyceride hydroprocessing to better predict the properties of commercial interest. This present work builds upon previous modeling work 17 on methyl laurate, a model compound for coconut oil, to develop a molecular-level kinetic model for triglycerides based on recently published experimental data 18,19 on coconut oil and soybean oil hydroprocessing. The experimental work used alumina-supported NiMo and CoMo catalysts to hydroprocess vegetable oils at different temperatures, pressures, and liquid hourly space velocities (LHSVs).…”