Multiscale kinetic modeling in catalysis ⇒ from microkinetics to computational fluid dynamics and process simulations

Problem statement

We envision multiscale modeling as critical enablers of reaction understanding, catalyst and reactor design, scale-up, and process optimization. The framework includes predicting the molecular reaction mechanism at the molecular level to the process optimization stage. As catalytic processes occur at the multiscale, we address these issues individually and collectively.

At the microkinetic level, our models resolve the rates of the individual elementary steps, rate-determining step (RDS), adsorption, and desorption mechanisms. We use quantum chemical calculations (density functional theory, DFT) to support our assumed kinetic pathways, original parameter estimations, and adsorption-desorption energies.

We incorporate thermodynamic constraints into our models. Once developed, the microkinetic model could guide the catalyst and reactor design. We also have experience developing Langmuir-Hinshelwood and Eley-Rideal types of kinetic models.

At the macrokineitc level, we develop lump-based and empirical models which, in some cases, are very robust and, together with other models, can be used to extract information such as mechanism change, optimize conditions, or for reactor pre-design.

We couple hydrodynamics, heat transfer, and reaction kinetics at the reactor level in computational fluid dynamic (CFD) simulations. Together with optimization algorithms, we aim to improve operating scenarios, develop innovative reactor prototypes, and predict process behaviors at the industrial scale.

Goals

  • Microkinetics I ⇒ key thermodynamic relationships
  • Microkinetics II ⇒ fitting, training, and optimization
  • Microkinetics III ⇒ ab initio kinetic modeling
  • Macrokinetics ⇒ complex reaction networks and population balances
  • CPFD ⇒ reactor modeling and scale-up
  • CFD ⇒ reactor modeling and optimization
  • CFD II ⇒ modeling operando reactors
  • Process system engineering ⇒ gPROMS

Related People

Related Publications

Modeling-aided coupling of catalysts, conditions, membranes, and reactors for efficient hydrogen production from ammonia

by Realpe, Kulkarni, Cerrillo, Morlanes, Lezcano, Kekalainen, Paglieri, Rakib, Solami, Gascon, Castaño
React. Chem. Eng. Year: 2023 DOI: https://doi.org/10.1039/D2RE00408A

Abstract

The production of high-purity, pressurized hydrogen from ammonia decomposition in a membrane catalytic reactor is a feasible technology. However, because of the multiple coupled parameters involved in the design of this technology, there are extensive opportunities for its intensification. We investigated the coupling between the type of catalyst, process conditions, type of membrane, and reactor operation (isothermal and non-isothermal) in the catalytic decomposition of ammonia. First, we developed an agnostic dimensionless model and calculated the kinetic parameters for a set of lab-made Ru- and Co-based catalysts and the permeation parameters of a Pd–Au membrane. The non-isothermal model for the Pd–Au membrane reactor was validated with the experiments using Co-based catalysts. Finally, we analyzed the coupling conditions based on the model predictions, results obtained in the literature and our experimental results, including several case studies. The thorough analysis led us to identify optimized combinations of catalyst–conditions–membrane–reactor that yield similar or improved results compared to the ones of Ru-based catalyst in a non-membrane reactor. Our results indicate that optimizing a single factor, such as the catalyst, may not lead to the desired outcome and a more holistic approach is necessary to produce pressurized and pure hydrogen efficiently.

Keywords

AMD MKM