Glycerol dehydration catalyzed by MWW zeolites and the changes in the catalyst deactivation caused by porosity modification

Increasing worldwide biodiesel production has led to the generation of an important glycerol surplus, which needs to be valorized in order to improve the economic and environmental sustainability of the biodiesel industry. In this context, glycerol dehydration to acrolein by acid catalysis appears to be a potential route of glycerol valorization, since acrolein is an important intermediate for many chemical industries. The main drawback of this catalytic process is catalyst deactivation. Different alternatives have been proposed for overcoming it, such as the use of mesoporous materials in order to facilitate the diffusion of glycerol and reaction products, thus minimizing deactivation. This review compiles the main achievements of the use of mesoporous silica-containing materials that have been deployed either as a catalyst or for support in glycerol dehydration to acrolein. Thus, the effect of mesoporosity on both catalytic performance and deactivation will be discussed, as well as the blocking of pores by coke deposition.

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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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1700615: Kinetic modelling of propane dehydrogenation over a Pt–Sn/hierarchical SAPO-34 zeolite catalyst, including catalyst deactivation-ESI

Progress in Reaction Kinetics and Mechanism ◽

10.3184/146867817x15066861009992 ◽

2017 ◽

Keyword(s):

Zeolite Catalyst ◽

Catalyst Deactivation ◽

Kinetic Modelling ◽

Propane Dehydrogenation

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Identifying and Evading Olefin Isomerization Catalyst Deactivation Pathways Resulting from Ion-Tunable Hemilability

ACS Catalysis ◽

10.1021/acscatal.0c03784 ◽

2020 ◽

Vol 10 (21) ◽

pp. 13019-13030

Author(s):

Henry M. Dodge ◽

Matthew R. Kita ◽

Chun-Hsing Chen ◽

Alexander J. M. Miller

Keyword(s):

Catalyst Deactivation ◽

Olefin Isomerization ◽

Isomerization Catalyst

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Glycerol Hydrogenolysis with In Situ Hydrogen Produced via Methanol Steam Reforming: The Promoting Effect of Pd on a Cu/ZnO/Al2O3 Catalyst

Catalysts ◽

10.3390/catal11010110 ◽

2021 ◽

Vol 11 (1) ◽

pp. 110

Author(s):

Yuanqing Liu ◽

Chau T. Q. Mai ◽

Flora T. T. Ng

Keyword(s):

Steam Reforming ◽

Catalyst Activity ◽

Promoting Effect ◽

Glycerol Conversion ◽

Glycerol Hydrogenolysis ◽

Glycerol Dehydration ◽

Effect Of Pd ◽

Al2o3 Catalyst ◽

Reaction Equilibrium

The glycerol hydrogenolysis to produce 1,2-propanediol without using externally supplied hydrogen was investigated using methanol present in crude glycerol to provide in situ hydrogen via its steam reforming reaction. This paper focuses on the promoting effect of Pd on the reactivity of a Cu/Zn/Al2O3 catalyst. Adding 2 wt% Pd onto a Cu/ZnO/Al2O3 catalyst significantly improved the selectivity to 1,2-propanediol from 63.0% to 82.4% and the glycerol conversion from 70.2% to 99.4%. This enhancement on the catalytic activity by Pd is mainly due to the improved hydrogenation of acetol, which is the intermediate formed during the glycerol dehydration. The rapid hydrogenation of acetol can shift the reaction equilibrium of glycerol dehydration forward resulting in a higher glycerol conversion. The improved reducibility of the catalyst by Pd allows the catalyst to be reduced in situ during the reaction preventing any loss of catalyst activity due to any potential oxidation of the catalyst. The catalyst was slightly deactivated when it was firstly recycled resulting in a 5.4% loss of glycerol conversion due to the aggregation of Cu and the deactivation became less noticeable upon further recycling.

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Insight into Active Centers and Anti-Coke Behavior of Niobium-Containing SBA-15 for Glycerol Dehydration

Catalysts ◽

10.3390/catal11040488 ◽

2021 ◽

Vol 11 (4) ◽

pp. 488

Author(s):

Katarzyna Stawicka ◽

Maciej Trejda ◽

Maria Ziolek

Keyword(s):

Coke Formation ◽

Catalytic Performance ◽

Acid Sites ◽

Silica Matrix ◽

High Concentration ◽

Active Centers ◽

Acidic Sites ◽

Glycerol Dehydration ◽

Adsorption Desorption ◽

Insight Into

Niobium containing SBA-15 was prepared by two methods: impregnation with different amounts of ammonium niobate(V) oxalate (Nb-15/SBA-15 and Nb-25/SBA-15 containing 15 wt.% and 25 wt.% of Nb, respectively) and mixing of mesoporous silica with Nb2O5 followed by heating at 500 °C (Nb2O5/SBA-15). The use of these two procedures allowed obtaining materials with different textural/surface properties determined by N2 adsorption/desorption isotherms, XRD, UV-Vis, pyridine, and NO adsorption combined with FTIR spectroscopy. Nb2O5/SBA-15 contained exclusively crystalline Nb2O5 on the SBA-15 surface, whereas the materials prepared by impregnation had both metal oxide and niobium incorporated into the silica matrix. The niobium species localized in silica framework generated Brønsted (BAS) and Lewis (LAS) acid sites. The inclusion of niobium into SBA-15 skeleton was crucial for the achievement of high catalytic performance. The strongest BAS were on Nb-25/SBA-15, whereas the highest concentration of BAS and LAS was on Nb-15/SBA-15 surface. Nb2O5/SBA-15 material possessed only weak LAS and BAS. The presence of the strongest BAS (Nb-25/SBA-15) resulted in the highest dehydration activity, whereas a high concentration of BAS was unfavorable. Silylation of niobium catalysts prepared by impregnation reduced the number of acidic sites and significantly increased acrolein yield and selectivity (from ca. 43% selectivity for Nb-25/SBA-15 to ca. 61% for silylated sample). This was accompanied by a considerable decrease in coke formation (from 47% selectivity for Nb-25/SBA-15 to 27% for silylated material).

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Ordered Mesoporous Carbon as a Support for Palladium-Based Hydrodechlorination Catalysts

Catalysts ◽

10.3390/catal11010023 ◽

2020 ◽

Vol 11 (1) ◽

pp. 23

Author(s):

Farzeen Sakina ◽

Carlos Fernandez-Ruiz ◽

Jorge Bedia ◽

Luisa Gomez-Sainero ◽

Richard Baker

Keyword(s):

Photoelectron Spectroscopy ◽

Mesoporous Carbon ◽

Catalyst Deactivation ◽

Average Diameter ◽

Pd Nanoparticles ◽

Ordered Mesoporous Carbon ◽

Catalyst Composition ◽

Ordered Mesoporous ◽

Higher Hydrocarbons ◽

Carbon Catalysts

Ordered mesoporous carbon (OMC) was employed as a support for palladium nanoparticles in catalysts for the gas phase hydrodechlorination (HDC) of trichloromethane (TCM). 1 wt% palladium was incorporated using three methods: incipient wetness (IW); a dilute solution (DS) method; and a solid-liquid (SL) method. The effect of the preparation method on catalyst structure and activity was investigated. Catalyst composition and nanostructure were studied using gas physisorption, high specification transmission electron microscopy and X-ray photoelectron spectroscopy. Catalytic conversion and product selectivities were determined in steady-state activity tests at temperatures between 70 and 300 °C. Two of the catalysts (IW and DS) showed excellent dispersion of fine Pd nanoparticles of average diameter ~2 nm. These materials showed excellent activity for HDC of TCM which compares favourably with the performance reported for Pd on amorphous carbon catalysts. In addition, they showed relatively high selectivities to the more valuable higher hydrocarbons. However, the SL method gave rise to catalysts with larger particles (~3 nm) and a less uniform palladium distribution. This resulted in lower conversion and lower selectivities to higher hydrocarbons and in more severe catalyst deactivation at the highest reaction temperatures.

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