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Controlling selectivity and stability of zeolite catalysts for methanol to hydrocarbons and ethylene oligomerization

Problem statement

Olefins are commodity chemicals with applications in the production of plastics (petrochemical industry), lubricants, plasticizers, and surfactants, among many others. However, there is an imbalance between their production and demand, which oligomerization-cracking reactions over zeolites could solve. At the same time, zeolites are excellent catalysts for methanol to hydrocarbons (MTH), olefins (MTO), or aromatics (MTA). The processes aim to produce light hydrocarbons like propylene or convert ethylene into higher-value a-olefins, aromatic hydrocarbons (BTX), and jet fuel.

Our focus in this project is to modify, synthesize and develop novel materials of different porosity (engineered at the multiscale): from hierarchical zeolites, nano zeolites, and hollow zeolites to catalytic particles, bodies, spray-dried and extrudates with tuned properties. Additionally, we incorporate different metals (i.e., Ni, Cr, Zn) to adjust the selectivity of desired products.

We use various reactors, such as operando or high-throughput packed-bed and batch reactors.

Goals

  • Develop a quantitative analytical workflow to analyze and interpret these complex reacting environments
  • Explore novel renewable and waste resources to obtain chemicals and fuels
  • Deploy ad-hoc catalysts and process conditions to incorporate these wastes in the refinery (bio- and waste-refinery)
  • Analyze process dynamics and kinetics
OLG2023

Related People

Related Publications

Improving the dehydrogenation function and stability of Zn-modified ZSM-5 catalyst in methanol-to-aromatics reaction by Ca addition

by Vicente, Liu, Gayubo, Castaño, Pidko
Appl. Catal. A: Gen. Year: 2024 DOI: https://doi.org/10.1016/j.apcata.2024.119854

Abstract

Adding Zn to the ZSM-5 zeolite effectively increases the aromatic selectivity in the methanol-to-aromatics (MTA) process. The formation of metal-derived Lewis acid sites promotes the dehydrogenation but at the cost of a rapid deactivation of the catalyst by coke, due to the increased aromatic formation. In this work, we impregnated a Zn-modified catalyst (2 wt%) with variable contents of Ca (0.02 and 0.5 wt%) and evaluated their kinetic behavior in the MTA and ethane dehydrogenation reactions. The results proved the superior performance of the Zn(2)Ca(0.02) catalyst due to a synergistic effect between the two metals. The Ca ions limit coke formation from excessive aromatization, increasing catalyst stability and removing Zn clusters, resulting in a recovery of Brønsted acid sites (BAS) active for the formation of light aromatics. Combining these effects results in a more efficient and viable catalyst for aromatic production from methanol.

Keywords

O2H HCE