Statistical models of diffusion and aggregation for coke formation in a catalyst pore

TL;DR

This paper models diffusion and aggregation processes in catalyst pores to understand coke formation, revealing universal deposit features and the transition from uniform to wedge-shaped deposits.

Contribution

It introduces probabilistic models of diffusion and aggregation that capture the transition from uniform to wedge-shaped coke deposits in catalyst pores.

Findings

Deposits initially form uniformly along the pore.

A transition to wedge-shaped deposits occurs after initial uniform deposition.

Average aggregation position decreases as N^{-0.25} with the number of particles.

Abstract

We simulated models of diffusion and aggregation in long pores of small widths in order to represent the basic mechanisms of coke deposition in catalysts' pores. Coke precursors are represented by particles injected at the pore entrance. Knudsen diffusion, which is usually expected inside the pores, is modeled by ballistic motion of those particles. The regime of molecular diffusion is also analyzed via models of lattice random walks biased along the pores. The aggregation at the surface or near previously aggregated particles was modeled by different probabilistic rules, accounting for the possibilities of more compact or more ramified deposits. In the model of Knudsen diffusion and in some cases of molecular diffusion, there is an initial regime of uniform deposition along the pore, after which the deposits acquire an approximately wedge shape, with the pore plugging near its entrance. After the regime of uniform deposition and before that of critical pore plugging, the average aggregation position slowly decreases with the number N of deposited particles approximately as N^{-0.25}. The apparently universal features of deposits generated by microscopic models are compared with those currently adopted in continuum models.