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.


  • 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

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Streamlining the estimation of kinetic parameters using periodic reaction conditions: The methanol-to-hydrocarbon reaction as a case study

by Vicente, Gayubo, Aguayo, Castaño
Chem. Eng. J. Year: 2022 DOI: https://doi.org/10.1016/j.cej.2022.134800


Reducing the experimental time required to obtain a robust kinetic model with reliable kinetic parameters has been a long-standing objective in reaction engineering. In the present study, we compare the kinetic modeling of two sets of data obtained using periodic reaction conditions (PRC) and stationary reaction conditions (SRC). As a case study, we use the well-known methanol-to-hydrocarbon reaction on HZSM-5 zeolite. The SRC experiments are conducted with a temperature of 425–475 °C, a total pressure of 2.5 bar, a partial pressure for methanol of 1.125 bar, a space time of 0.1–1.5 gcat h molC−1, a initial molar ratio water:methanol of 0–0.66 and 16 h on stream. The PRC experiments involve sinusoidal variation in the methanol and water flowrates of 135 ± 88 µL min−1 and 20 ± 20 µL min−1, respectively, with a period of 16 h or sinusoidal variation in the temperature of 450 ± 25 °C with periods of 8 and 16 h. Several strategies are then used in fitting the kinetic parameters of five models. We obtain relatively similar results in terms of model discrimination, the parameters, and confidence intervals with a cumulative experimental time of 64 h on stream under the PRC compared with 192 h on stream under the SRC, a reduction of 67% in the experimental time.