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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.

    OLG-O2H

    Goals

    • Control structure–selectivity: Tune zeolite porosity and acidity to maximize propylene and α-olefin yields.
    • Metal modulation: Use Ni, Cr, Zn to bias reaction pathways and improve selectivity to target hydrocarbons.
    • Deactivation control: Reduce coke formation and extend catalyst lifetime with regeneration strategies.
    • Reactor optimization: Shape catalysts into bodies/extrudates and validate 100 h continuous stable operation.

    Related People

    Hend Omar Mohamed
    Kiruthika Jayaseelan

    Related Publications

    Deactivating Species in the Transformation of Crude Bio-Oil with Methanol into Hydrocarbons on a HZSM-5 Catalyst

    by Valle, Castaño, Olazar, Bilbao, Gayubo
    J. Catal. Year: 2012

    Abstract

    A study has been carried out by using different techniques (TPO, FTIR, Raman, 13C NMR, GC/MS of the coke dissolved in CH2Cl2) on the nature of the coke deposited on a HZSM-5 catalyst modified with Ni in the transformation of the crude bio-oil obtained by flash pyrolysis of lignocellulosic biomass (pine sawdust) into hydrocarbons. The reaction system has two steps in-line. In the first one, the components of crude bio-oil derived from the pyrolysis of biomass lignin are polymerized at 400 °C. In the second one, the remaining volatile oxygenates are transformed into hydrocarbons in a fluidized bed catalytic reactor at 450 °C. The reaction has been carried out with different bio-oil/methanol mass ratios in the feed (from 100/0 to 0/100). Co-feeding methanol significantly attenuates coke deposition, and the nature of the coke components varies according to the bio-oil/methanol ratio in the feed. When bio-oil is co-fed, the coke deposited on the catalyst has a significant content of oxygenates and oxo-aromatics and consists of two fractions, identified by temperature programmed oxidation, corresponding to external and internal coke in the zeolite crystals. The fraction of external coke is soluble in CH2Cl2, with a high content of oxygenates and oxo-aromatics, and is generated by polymerization of products derived from biomass lignin pyrolysis activated by the zeolite acid sites. The fraction of coke retained within the zeolite crystals is partially insoluble and is formed by several routes: from the intermediates in the transformation of both methanol and bio-oil oxygenates into hydrocarbons; by evolution of the other coke fraction; from the hydrocarbons (with high aromatics content) in the reaction medium.

    Keywords

    O2H FCC W2C ANW