66 results on '"Pérez‐Ramírez, Javier"'
Search Results
52. Hemicellulose arabinogalactan hydrolytic hydrogenation over Ru-modified H-USY zeolites.
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Murzin, Dmitry Yu., Kusema, Bright, Murzina, Elena V., Aho, Atte, Tokarev, Anton, Boymirzaev, Azamat S., Wärnå, Johan, Dapsens, Pierre Y., Mondelli, Cecilia, Pérez-Ramírez, Javier, and Salmi, Tapio
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HEMICELLULOSE , *ARABINOGALACTAN , *ZEOLITES , *HYDROLYSIS , *HYDROGENATION , *DEPOLYMERIZATION - Abstract
The hydrolytic hydrogenation of hemicellulose arabinogalactan was investigated in the presence of protonic and Ru (1–5 wt.%)-modified USY zeolites (Si/Al ratio = 15 and 30). The use of the purely acidic materials was effective in depolymerizing the macromolecule into free sugars. While the latter partly dehydrated into 5-hydroxymethylfurfural and furfural, the generation of high molecular-weight compounds (aggregates of sugars and humins) was not favored, in contrast to previous evidences over beta zeolites. Application of the bifunctional Ru/USY catalyst, comprising well-dispersed metallic nanoparticles on the aluminosilicate support, resulted in the formation of galactitol and arabitol, in the suppression of dehydration side products, and further inhibition of polymerization reactions, which only yielded low molecular-weight oligomers. Detailed analysis of the reaction pathways as well as kinetic modeling of hydrolytic hydrogenation was performed with an advanced reaction mechanism. [ABSTRACT FROM AUTHOR]
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- 2015
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53. Structuring zeolite bodies for enhanced heat-transfer properties.
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Borchardt, Lars, Michels, Nina-Luisa, Nowak, Torsten, Mitchell, Sharon, and Pérez-Ramírez, Javier
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ZEOLITES , *HEAT transfer , *POROUS materials , *MANUFACTURING processes , *FOCUSED ion beams - Abstract
The predominantly insulating nature of zeolites, as many classes of porous catalysts, can severely impair heat transfer and hence their performance in industrial processes. Strategies developed to engineer the thermophysical properties of technical zeolites for fixed-bed applications comprise the use of conductive secondary phases as structured catalyst supports or as inert diluents. However, the impact of integrating conductive additives into composite zeolite bodies (pellets, extrudates, or granules) has not been widely explored. Here, using a transient hot-plate technique to decouple the distinct contributions of porosity, sample hydration, and temperature, we quantify the impact of metallic (copper), ceramic (silicon carbide, aluminum nitride, boron nitride), and carbonaceous (graphite, carbon nanotubes) phases on the thermal conductivity of shaped zeolites at the body and packed-bed scales. The decisive role of particle morphology, dominating over the intrinsic conductivity of an additive, is corroborated through the three-dimensional reconstruction of data acquired by focused ion beam-scanning electron microscopy and X-ray microtomography coupled with in-situ thermographic studies. In particular, the order-of-magnitude improvement evidenced on application of graphite sheets stems from the extended paths of low thermal resistance created in the millimeter-sized catalyst ensemble. Through the identification of structure-property relations, our approach provides new insights into the rational design of composite porous materials with enhanced heat-transfer properties. [ABSTRACT FROM AUTHOR]
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- 2015
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54. Rediscovering zeolite mechanochemistry – A pathway beyond current synthesis and modification boundaries.
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Majano, Gerardo, Borchardt, Lars, Mitchell, Sharon, Valtchev, Valentin, and Pérez-Ramírez, Javier
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CHEMICAL synthesis , *ZEOLITES , *MECHANICAL chemistry , *SOLVENTS , *ACTIVATION (Chemistry) , *CATALYTIC activity - Abstract
Highlights: [•] Mechanochemical treatment, a versatile tool for zeolite synthesis and modification. [•] Scalable, efficient, and mechanistically-distinct to solvent-intensive routes. [•] Structural transformations classified according to the energy required. [•] Catalytic properties enhanced by mechanochemical activation. [•] Rationalization will facilitate the scale up of future zeolite technologies. [ABSTRACT FROM AUTHOR]
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- 2014
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55. Hydroisomerization and hydrocracking of linear and multibranched long model alkanes on hierarchical Pt/ZSM-22 zeolite.
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Martens, Johan A., Verboekend, Danny, Thomas, Karine, Vanbutsele, Gina, Pérez-Ramírez, Javier, and Gilson, Jean-Pierre
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ISOMERIZATION , *HYDROCRACKING , *ALKANES , *ZEOLITES , *PLATINUM , *ACIDITY , *MOLECULAR probes - Abstract
Highlights: [•] Hierarchization of ZSM-22 favors hydroisomerization and limits hydrocracking [•] Hierarchical ZSM-22 has lower acidity in micropores and higher acidity in pore mouths [•] Branching occurs in pore mouths; hydrocracking in pore mouths and micropores [•] Hierarchization is a unique tool to design superior hydroisomerization catalysts [•] Pristane is a convenient model molecule for probing pore mouth catalysis [Copyright &y& Elsevier]
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- 2013
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56. Hierarchical Zeolites by Desilication: Occurrenceand Catalytic Impact of Recrystallization and Restructuring.
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Verboekend, Danny, Milina, Maria, Mitchell, Sharon, and Pérez-Ramírez, Javier
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ZEOLITES , *CATALYSIS , *RECRYSTALLIZATION (Metallurgy) , *SILICATES , *FOURIER transform infrared spectroscopy , *TRANSMISSION electron microscopy - Abstract
The manifestation of zeolite recrystallizationand the formationof amorphous aluminosilicate species during desilication are examinedto better understand the properties of alkaline-treated hierarchicalzeolites and their catalytic performance. This is achieved using asystematic experimental strategy, starting from treating the filtrateof alkaline-treated silicalite-1 in the presence of various externaladditives. No recrystallization is evidenced upon addition of tetrapropylammonium(TPA+) and/or aluminum hydroxide ions [Al(OH)4–], confirming the low probability of zeolite nucleationand/or growth during desilication. Conversely, ordered mesoporousmaterials (OMMs) form upon addition of cetyltrimethylammonium (CTA+) to the filtrate. By using other silicon sources, i.e., tetramethylorthosilicate or the organosilane dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium,we verify the facile formation of amorphous materials during alkalinetreatment of USY zeolites in the presence of hydrophobic micelle-formingalkyl moieties. A systematic characterization by X-ray diffraction,transmission electron microscopy, N2and Ar adsorption,inductively coupled plasma optical emission spectroscopy, and Fouriertransform infrared spectroscopy of pyridine adsorbed, demonstratesthat zeolites exposed to base solutions containing CTA+display weaker zeolitic properties, compared to those prepared usingTPA+, and should be considered as hierarchical zeolite/OMMcomposites. Catalytic tests in the alkylation of toluene with isopropylalcohol or benzyl alcohol evidence that CTA+-derived compositesdo not outperform the conventional USY zeolite. Only the hierarchicalUSY zeolite prepared by alkaline treatment in the presence of TPA+yielded a superior catalytic performance. [ABSTRACT FROM AUTHOR]
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- 2013
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57. HierarchyBrings Function: Mesoporous Clinoptiloliteand L Zeolite Catalysts Synthesized by Tandem Acid–Base Treatments.
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Verboekend, Danny, Keller, TobiasC., Milina, Maria, Hauert, Roland, and Pérez-Ramírez, Javier
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MESOPOROUS materials , *ZEOLITES , *CATALYSTS , *ACID-base chemistry , *CLINOPTILOLITE , *CHEMICAL synthesis - Abstract
Hierarchical clinoptilolite and Lzeolites are prepared using optimizedtandem dealumination–desilication treatments. The main challengein the postsynthetic modification of these zeolites is the high Alcontent, requiring a tailored dealumination prior to the desilicationstep. For natural clinoptilolite, sequential acid treatments usingaqueous HCl solutions were applied, while for L a controlled dealuminationusing ammonium hexafluorosilicate is required. Subsequent desilicationby NaOH treatment yields mesopore surfaces of up to 4-fold (clinoptilolite,64 m2g–1; L, 135 m2g–1) relative to the parent zeolite (clinoptilolite,15 m2g–1; L, 45 m2g–1). A thorough characterization sheds light on thecomposition, crystallinity, porosity, morphology, coordination, andacidity of the modified clinoptilolite and L zeolites. It is elaboratedthat, besides the degree of dealumination, the resulting Al distributionis a critical precondition for the following mesopore formation bydesilication. Adsorption experiments of Cu2+and methyleneblue from aqueous solutions and the catalytic evaluation in alkylationsand Knoevenagel condensation evidence the superiority of the hierarchicalzeolites, as compared to their purely microporous counterparts. Finally,the postsynthetic routes for clinoptilolite and L are generalizedwith other recently reported modification strategies, and presentedin a comprehensive overview. [ABSTRACT FROM AUTHOR]
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- 2013
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58. Influence of crystal size and probe molecule on diffusion in hierarchical ZSM-5 zeolites prepared by desilication
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Meunier, Frederic C., Verboekend, Danny, Gilson, Jean-Pierre, Groen, Johan C., and Pérez-Ramírez, Javier
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MOLECULAR probes , *DIFFUSION , *ZEOLITES , *SILICATES , *TRANSPORT theory , *DESORPTION , *FOURIER transform infrared spectroscopy , *POROUS materials - Abstract
Abstract: The improvement of molecular transport properties of hierarchical H-ZSM-5 obtained by desilication was evidenced by studying the desorption of o-xylene and isooctane by in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). This technique enabled monitoring simultaneously bands associated with the molecular probes and the zeolite, using powdered sample masses as low as 1mg. Two H-ZSM-5 samples with markedly different crystal sizes were investigated. The first sample was commercial and consisted of small crystallites (ca. 250nm). The second sample were laboratory-made large crystals with coffin-like shape (ca. 17×4×4μm3). The hierarchical derivatives of the small and large zeolite crystals displayed 250 and 120m2 g−1 of mesopore surface area, respectively, in contrast to the 62 and 5m2 g−1 of the parent counterparts. The data based on o-xylene desorption were partly disguised by site-desorption limitations. Desorption experiments using isooctane evidenced a 4-fold reduction in the characteristic diffusion path length on both mesoporous small and large zeolites with respect to their purely microporous analogues. These results confirm the substantial potential for improvement of commercial nanocrystalline zeolites in diffusion-limited reactions upon the introduction of intra-crystalline mesoporosity by post-synthesis modification. [Copyright &y& Elsevier]
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- 2012
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59. Spray deposition method for the synthesis of supported catalysts with superior metal dispersion
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Santiago, Marta, Restuccia, Alberto, Gramm, Fabian, and Pérez-Ramírez, Javier
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NANOPARTICLES , *CATALYSTS , *SPRAYING , *SOLVENTS , *PARTICLE size distribution , *AEROSOLS , *ZEOLITES , *PALLADIUM - Abstract
Abstract: We introduce a novel ‘spray deposition’ method as a continuous, reproducible, versatile, simple, and scalable method for the preparation of highly-dispersed, uniformly-sized, and sintering-resistant supported metal nanoparticles on porous supports. Instant drying of aqueous aerosol droplets containing the metal precursor (e.g. palladium nitrate) and the support (e.g. ferrierite zeolite) in a commercial bench-scale spray drier proves the key for maximizing the metal dispersion. In contrast, the much lower rates of solvent removal characteristic of dry and wet impregnation methods using classical drying or even freeze drying led to broad particle size distributions. The spray-dried Pd/ferrierite catalyst exhibited high alkene selectivity in the gas-phase hydrogenation of propyne. These results demonstrate that spray drying is not only a highly suited unit operation to prepare catalyst supports but also functional catalysts in one step. The method offers attractive opportunities for large-scale catalyst manufacture and as well as for preparation of well-defined systems for academic studies. [Copyright &y& Elsevier]
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- 2011
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60. Acidity and accessibility studies on mesoporous ITQ-4 zeolite
- Author
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Verboekend, Danny, Villaescusa, Luis A., Thomas, Karine, Stan, Irina, and Pérez-Ramírez, Javier
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MESOPOROUS materials , *ZEOLITES , *SODIUM hydroxide , *SOLUTION (Chemistry) , *MOLECULAR structure , *ACID-base chemistry , *NITROGEN absorption & adsorption , *X-ray diffraction - Abstract
Abstract: Desilication of ITQ-4 (IFR code, 1-dimensional 12-MR channel system of 0.62nm×0.72nm) in aqueous NaOH solutions was practiced in order to produce the zeolite in the hierarchical form, i.e. combining the native micropores with a secondary network of intracrystalline mesopores. The parent material (Si/Al=32) was synthesized using benzylquinuclidinium as the structure-directing agent in the presence of fluoride anions. The samples were characterized by ICP-OES, XRD, TEM, N2 adsorption, and FTIR spectroscopy. In a representative treatment, the mesopore surface area of the ITQ-4 experienced a sevenfold increase (from 29 to 206m2 g−1) upon optimized NaOH post-treatment, whereas the microporosity was reduced by 70% (from 0.20 to 0.06cm3 g−1). Chemical analysis and infrared spectroscopy of adsorbed pyridine showed that after alkaline treatment the amount of Brønsted acid sites remains practically constant whereas a significant increase in Lewis acid sites was obtained. Infrared studies with adsorbed 2,4,6-collidine concluded that the accessibility of acid sites in the hierarchical zeolite increased substantially due to an increase in the available active sites at the pore mouths of the hierarchical zeolite. [Copyright &y& Elsevier]
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- 2010
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61. Mesoporous metallosilicate zeolites by desilication: On the generic pore-inducing role of framework trivalent heteroatoms
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Groen, Johan C., Caicedo-Realpe, Rosario, Abelló, Sònia, and Pérez-Ramírez, Javier
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POROUS silicon , *SILICATES , *ZEOLITES , *ATOMS , *CRYSTALS , *HYDROLYSIS - Abstract
Abstract: Desilication in alkaline medium is demonstrated as a general route to synthesize hierarchical metallosilicate zeolite crystals with preserved crystallinity. The lattice trivalent cation (not only Al3+ but also Ga3+, Fe3+, and B3+) regulates the alkaline-assisted hydrolysis of silicon towards controlled mesoporosity development. This finding widens the family of modified zeolite compositions that integrate in a single crystalline material micropores and mesopores and enables better accessibility in catalytic applications compared to the purely microporous counterparts. [Copyright &y& Elsevier]
- Published
- 2009
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62. Quantification of enhanced acid site accessibility in hierarchical zeolites – The accessibility index
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Thibault-Starzyk, Frédéric, Stan, Irina, Abelló, Sònia, Bonilla, Adriana, Thomas, Karine, Fernandez, Christian, Gilson, Jean-Pierre, and Pérez-Ramírez, Javier
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EXTRACTION (Chemistry) , *SILICON , *ZEOLITES , *CATALYSTS , *PYRIDINE , *INFRARED spectroscopy , *CRYSTALS , *MESOPOROUS materials - Abstract
An accessibility index (ACI) was derived from infrared spectroscopy of substituted alkylpyridines with different size (pyridine: 0.57nm, 2,6-lutidine: 0.67nm, and 2,4,6-collidine: 0.74nm) over hierarchical porous ZSM-5 crystals. The samples were prepared by selective silicon extraction of a commercial sample in NaOH (desilication), and they contained different degrees of intracrystalline mesoporosity. Our results demonstrate the enhanced accessibility of Brønsted acid sites in the hierarchical zeolites. For example, a relatively bulky molecule such as collidine, which probes practically no acid site of the parent medium-pore MFI structure, can access up to 40% of the acid sites in the mesoporous sample. The ACI is a powerful tool to standardize acid site accessibility in zeolites, and can be used to rank the effectiveness of synthetic strategies to prepare hierarchical zeolites. [Copyright &y& Elsevier]
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- 2009
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63. Mesoporous beta zeolite obtained by desilication
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Groen, Johan C., Abelló, Sònia, Villaescusa, Luis A., and Pérez-Ramírez, Javier
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ZEOLITES , *FLUORIDES , *SCANNING electron microscopy , *X-ray diffraction - Abstract
Abstract: Zeolite beta crystals (Si/Al=35) synthesized in fluoride medium were treated in aqueous 0.2M NaOH solution for mesopore formation by selective extraction of framework silicon. A 16 parallel-batch reactor was used to study the influence of the treatment time and temperature on the physico-chemical properties of the zeolites, which were characterized by ICP-OES, XRD, N2 adsorption at 77K, SEM, TEM, DRIFTS, and in situ ATR-IR. Alkaline treatment of H-beta within the optimal window of Si/Al ratios identified for other zeolite families leads to extensive silicon extraction at mild treatment conditions. This originates substantial mesoporosity and presumably improved transport, but negatively impacts on the microporous and acidic properties of the resulting sample. Consequently, the alkaline-treated beta zeolites show lower catalytic activity in the acid-catalyzed liquid-phase benzene alkylation than the purely microporous parent material. The relatively low stability of framework aluminum in BEA, compared to MFI and MOR, is detrimental for the controlled mesopore formation by Si dissolution, since aluminum cannot optimally exert its pore-directing role. [Copyright &y& Elsevier]
- Published
- 2008
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64. Mechanistic origin of the different activity of Rh-ZSM-5 and Fe-ZSM-5 in N2O decomposition
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Kondratenko, Evgenii V., Kondratenko, Vita A., Santiago, Marta, and Pérez-Ramírez, Javier
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NITROUS oxide , *ZEOLITES , *CHEMICAL reactors , *CATALYSTS , *ADSORPTION (Chemistry) , *CHEMICAL decomposition - Abstract
A temporal analysis of products (TAP) reactor was used to study relationships between the mechanism of direct N2O decomposition over metal-loaded zeolites and their resulting activity. Rh-ZSM-5 (prepared by incipient wetness) and Fe-ZSM-5 (prepared by liquid-ion exchange) were chosen as prototypic catalysts displaying low (<550 K) and high (>650 K) temperature activity, respectively. Transient studies at the same contact time revealed the higher activity of Rh-ZSM-5 below 623 K and significantly stronger N2O adsorption over Rh species than over Fe species in the zeolites. Several microkinetic models were applied for simultaneous fitting the transient responses of N2O, N2, and O2. Classical reaction schemes failed to describe the experimental data. The preferred models of N2O decomposition over Rh-ZSM-5 and Fe-ZSM-5 differ in the reaction pathways of O2 formation. For both catalysts, free active metal sites (*) and those occupied by monoatomic oxygen species (*-O) from N2O participate in the decomposition of gas-phase N2O. Gas-phase O2 is formed directly on N2O interaction with *-O over Rh-ZSM-5, whereas the latter reaction over Fe-ZSM-5 leads to a surface bi-atomic oxygen species (O-*-O), followed by its transformation to *-O2. The latter species desorbs as molecular oxygen. Comparison of ion-exchanged and steam-activated Fe-ZSM-5 [J. Phys. Chem. B 110 (2006) 22586] revealed that the reaction mechanism is independent of the iron constitution induced by the preparation and activation routes, despite important differences in catalytic activity. Our quantitative microkinetic analysis demonstrated that both the stronger reversible N2O adsorption and, most importantly, the faster desorption of O2 are distinctive mechanistic features of Rh-ZSM-5, likely indicating its high de-N2O activity. [Copyright &y& Elsevier]
- Published
- 2008
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65. Alkaline-mediated mesoporous mordenite zeolites for acid-catalyzed conversions
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Groen, Johan C., Sano, Tsuneji, Moulijn, Jacob A., and Pérez-Ramírez, Javier
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PETROLEUM refining , *ZEOLITES , *CHEMICAL reactions , *SURFACE chemistry - Abstract
Abstract: The preparation of mesoporous mordenite zeolite and its subsequent application in the liquid-phase alkylation of benzene with ethylene is discussed. Mesoporous mordenite was obtained by controlled silicon extraction on alkaline treatment of successfully synthesized high-silica mordenite zeolites with molar Si/Al ratios in the range of 20–30. Besides substantial mesoporosity development, the combined microporous and mesoporous zeolites show preserved Brønsted acidic properties, which are highly attractive when acid-catalyzed reactions are targeted. Catalytic testing of the mesoporous mordenite found superior performance in benzene alkylation due to the unique interplay between improved physical transport in the shortened micropores and the preserved high density of acid sites. [Copyright &y& Elsevier]
- Published
- 2007
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66. Hydrocracking of hexadecane to jet fuel components over hierarchical Ru-modified faujasite zeolite.
- Author
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Azkaar, Muhammad, Vajglová, Zuzana, Mäki-Arvela, Päivi, Aho, Atte, Kumar, Narendra, Palonen, Heikki, Eränen, Kari, Peurla, Markus, Kulikov, Leonid A., Maximov, Anton L., Mondelli, Cecilia, Pérez-Ramírez, Javier, and Murzin, Dmitry Yu.
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HYDROCRACKING , *JET fuel , *BATCH reactors , *SODIUM hydroxide , *ZEOLITES , *RUTHENIUM catalysts - Abstract
Hexadecane hydrocracking was investigated over bifunctional Ru-containing micro- and mesoporous USY zeolites at 250°C under 45 bar in the presence of hydrogen in a batch reactor. A comparative study was performed using the Ru-free zeolites in the protonic form. The highest yield of jet-fuel products, C 9 - C 15 , being 26% at 71% conversion, was obtained with 2.5 wt% Ru deposited on a hierarchical micro-mesoporous USY zeolite, e.g. a material possessing secondary porosity, where a superior combination of acidity and mesoporosity was created by treatment of the parent zeolite with aqueous sodium hydroxide and tetrapropylammonium hydroxide. [ABSTRACT FROM AUTHOR]
- Published
- 2020
- Full Text
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