Methanol to hydrocarbons conversion: Why dienes and monoenes contribute differently to catalyst deactivation?

The t-plot method is a well-known method for determining the volumes of micro- and/or mesoporous materials and the specific surface area of a sample by comparison with a reference adsorption isotherm of a non-porous material having a similar surface chemical composition. The article describes the applicability of the t-graph method to the analysis of the surface properties of zinc modified samples of zeolite H-ZSM-5 before and after the reactions of methanol transformation into hydrocarbons occur on them. Zeolites are widely used as catalysts in the petrochemical and refining industries. These materials contain active Bronsted acid sites, distributed within the microporous structure of zeolites, which leads to selective catalysis due to the difference in the pore shape of the zeolites used. The size, shape of the zeolite catalyst determines the catalytic performance in terms of both product selectivity and catalyst deactivation. In most zeolite catalyzed hydrocarbon conversion reactions, catalyst activity is lost due to carbon deposition. In this connection, the determination of the surface properties of zeolites is an important task that contributes to the disclosure of the physicochemical essence of the process of deactivation of zeolites. The recalculation of nitrogen adsorption isotherms using the t-plot model made it possible to determine the volume of micro and mesopores. Based on the t-graph data, it can be concluded that during the transformation of methanol into hydrocarbons, carbon accumulates on the surface of the zeolite. In this case, the predominant deposition of carbon on the surface of mesopores, due to the fact that in the process of decontamination, from 61 to 73% of the volume of mesopores is lost. The number of micropores also decreases, but the share of losses is 42–54%, which is 10–15% lower compared to the loss of mesopore volume.

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Effect of Catalyst (de)activation on Reagent Diffusion in ZSM-5/alumina Extruded Pellet for the Methanol-to-hydrocarbons Conversion

International Journal of Chemical Reactor Engineering ◽

10.1515/ijcre-2019-0138 ◽

2019 ◽

Vol 18 (1) ◽

Author(s):

Alexey A. Zhokh

Keyword(s):

Catalyst Deactivation ◽

Diffusion Rate ◽

Micropore Volume ◽

Coke Deposition ◽

Alumina Catalyst ◽

Catalyst Activation ◽

Catalyst Pellet ◽

Methanol To Hydrocarbons ◽

Methanol Transport ◽

Time Decrease

Abstract A pelletized ZSM-5/alumina catalyst was prepared by the extrusion technique. The catalyst was activated by ion-exchange with NH4NO3 aqueous solution. The activated catalyst was trained in the methanol-to-hydrocarbons reaction which caused the catalyst deactivation due to coke deposition (6.5 % wt.). Coke deposition resulted in a two-time decrease in the micropore volume. The methane, benzene, and methanol transport through ZSM-5/alumina pellet were consequently studied prior to activation, after activation, and after catalyst deactivation. A slight decrease in the diffusion rate after catalyst activation is observed. After deactivation, the diffusion rate increases insignificantly. The diffusion regime remains unchanged with respect to either activation or deactivation procedure. Contrary, for the methanol, the diffusion rate through a deactivated catalyst pellet remarkably increases due to micropore blockage by coke deposition. The obtained results reveal that the micropores blockage during the catalyst deactivation enhances the methanol mass transfer.

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New insights into catalyst deactivation and product distribution of zeolites in the methanol-to-hydrocarbons (MTH) reaction with methanol and dimethyl ether feeds

Catalysis Science & Technology ◽

10.1039/c7cy00129k ◽

2017 ◽

Vol 7 (13) ◽

pp. 2700-2716 ◽

Cited By ~ 60

Author(s):

Juan S. Martinez-Espin ◽

Magnus Mortén ◽

Ton V. W. Janssens ◽

Stian Svelle ◽

Pablo Beato ◽

...

Keyword(s):

Dimethyl Ether ◽

Catalyst Deactivation ◽

Product Distribution ◽

Zeolitic Catalyst ◽

Methanol To Hydrocarbons

The ability of a zeolitic catalyst to dehydrate methanol to dimethyl ether affects catalyst deactivation and product distribution during the methanol-to-hydrocarbons (MTH) reaction.

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What catalysis needs from the electron microscopist

Proceedings, annual meeting, Electron Microscopy Society of America ◽

10.1017/s0424820100105539 ◽

1988 ◽

Vol 46 ◽

pp. 694-695

Author(s):

Alexis T. Bell

Keyword(s):

Active Sites ◽

Heterogeneous Catalysts ◽

Catalyst Deactivation ◽

Surface Composition ◽

Internal Surface ◽

Active Phase ◽

Atomic Scale ◽

Metal Catalyst ◽

Internal Surface Area ◽

Porous Support

Heterogeneous catalysts, used in industry for the production of fuels and chemicals, are microporous solids characterized by a high internal surface area. The catalyticly active sites may occur at the surface of the bulk solid or of small crystallites deposited on a porous support. An example of the former case would be a zeolite, and of the latter, a supported metal catalyst. Since the activity and selectivity of a catalyst are known to be a function of surface composition and structure, it is highly desirable to characterize catalyst surfaces with atomic scale resolution. Where the active phase is dispersed on a support, it is also important to know the dispersion of the deposited phase, as well as its structural and compositional uniformity, the latter characteristics being particularly important in the case of multicomponent catalysts. Knowledge of the pore size and shape is also important, since these can influence the transport of reactants and products through a catalyst and the dynamics of catalyst deactivation.

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Analytical Electron Microscopy study of two vehicle-aged automotive exhaust catalysts having dissimilar activities

Proceedings, annual meeting, Electron Microscopy Society of America ◽

10.1017/s0424820100153336 ◽

1989 ◽

Vol 47 ◽

pp. 272-273

Author(s):

Sooho Kim ◽

M. J. D’Aniello

Keyword(s):

Electron Microscopy ◽

Particle Size ◽

Noble Metal ◽

Catalyst Deactivation ◽

Analytical Electron Microscopy ◽

Microscopy Study ◽

Metal Particles ◽

Automotive Exhaust ◽

Exhaust Catalysts ◽

Analytical Electron

Automotive catalysts generally lose-agtivity during vehicle operation due to several well-known deactivation mechanisms. To gain a more fundamental understanding of catalyst deactivation, the microscopic details of fresh and vehicle-aged commercial pelleted automotive exhaust catalysts containing Pt, Pd and Rh were studied by employing Analytical Electron Microscopy (AEM). Two different vehicle-aged samples containing similar poison levels but having different catalytic activities (denoted better and poorer) were selected for this study.The general microstructure of the supports and the noble metal particles of the two catalysts looks similar; the noble metal particles were generally found to be spherical and often faceted. However, the average noble metal particle size on the poorer catalyst (21 nm) was larger than that on the better catalyst (16 nm). These sizes represent a significant increase over that found on the fresh catalyst (8 nm). The activity of these catalysts decreases as the observed particle size increases.

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An analytical microscopic study of metals in fluidized catalytic cracking catalyst

Proceedings, annual meeting, Electron Microscopy Society of America ◽

10.1017/s0424820100145613 ◽

1986 ◽

Vol 44 ◽

pp. 854-855

Author(s):

Clifford S. Rainey

Keyword(s):

Electron Microscopy ◽

Spatial Distribution ◽

Catalytic Cracking ◽

Catalyst Deactivation ◽

Coke Formation ◽

Acid Sites ◽

Y Zeolite ◽

Fcc Catalyst ◽

Fluidized Catalytic Cracking ◽

High Regeneration

The spatial distribution of V and Ni deposited within fluidized catalytic cracking (FCC) catalyst is studied because these metals contribute to catalyst deactivation. Y zeolite in FCC microspheres are high SiO2 aluminosilicates with molecular-sized channels that contain a mixture of lanthanoids. They must withstand high regeneration temperatures and retain acid sites needed for cracking of hydrocarbons, a process essential for efficient gasoline production. Zeolite in combination with V to form vanadates, or less diffusion in the channels due to coke formation, may deactivate catalyst. Other factors such as metal "skins", microsphere sintering, and attrition may also be involved. SEM of FCC fracture surfaces, AEM of Y zeolite, and electron microscopy of this work are developed to better understand and minimize catalyst deactivation.

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