BEA Zeolite Research Articles

The Impact of Support and Reduction Temperature on the Catalytic Activity of Bimetallic Nickel-Zirconium Catalysts in the Hydrocracking Reaction of Algal Oil from Spirulina Platensis

The aim of this work was to investigate the hydrocracking of algae oil derived from Spirulina Platensis species catalyzed with bi-component nickel-zirconia catalysts supported onto different carriers (BEA, ZSM-5 and Al2O3) in an autoclave at 320 °C for 2 h with a hydrogen pressure of 75 bar. All catalysts were prepared using the wet co-impregnation method and were characterized by H2-TPR, XRD, NH3-TPD, BET and SEM-EDS. Before reactions, catalysts were calcined at 600 °C for 4 h in a muffle furnace, then reduced with 5%H2-95%Ar reducing mixture at 500 °C, 600 °C or 700 °C for 2 h. The obtained products were analyzed and identified by HPLC and GC-MS techniques. In addition to the investigation of the support effect, the influence of the reduction temperature of catalytic systems on the catalytic activity and selectivity of the products was also examined. The activity results show that Ni-Zr systems supported on zeolites exhibited high conversion of algal oil. A gradual decrease in conversion was observed when increasing the reduction temperature of the catalyst (from 500 °C to 600 °C and 700 °C) for BEA zeolite catalysts. The reaction products contain hydrocarbons from C7 to C33 (for zeolite-supported catalysts) and C36 (for systems on Al2O3). The identified hydrocarbons mainly belong to the gasoil fraction (C14–C22). In the research, the best catalyst for the algal oil hydrocracking reaction was found to be the 5%Ni-5%Zr/BEA system reduced at 600 °C, which exhibited the second highest algal oil conversion (94.0%). The differences in catalytic activity that occur are due to the differences in the specific surface area among the supports and to differences in the acidity of the catalyst surface depending on the reduction temperature.

Effects of Synthesis Method on the Physicochemical Properties and Catalytic Activity of BEA Zeolite in Toluene Disproportionation

Effects of Synthesis Method on the Physicochemical Properties and Catalytic Activity of BEA Zeolite in Toluene Disproportionation

Rational Design of Isolated Tetrahedrally Coordinated Ti(IV) Sites in Zeolite Frameworks for Methyl Oleate Epoxidation.

The rational design of isolated metals containing zeolites is crucial for the catalytic conversion of biomass-derived compounds. Herein, we explored the insertion behavior of the isomorphic substitution of Ti(IV) in different zeolite frameworks, including ZSM-35 (FER), ZSM-5, and BEA. The different aluminium topological densities of each zeolite framework lead to the creation of different degrees of vacant sites for hosting the tetrahedrally coordinated Ti(IV) active sites. These observations show the precise control of the degree of four-coordinated Ti(IV) sites in a zeolite framework, especially in BEA topology, by tuning the degree of unoccupied sites in the host zeolite structure via dealumination. Interestingly, the more vacancies in the host zeolite structure, the more isolated tetrahedrally coordinated Ti(IV) can be increased, eventually enhancing the catalytic performance in methyl oleate (MO) epoxidation for producing methyl-9,10-epoxystearate (EP). The engineered Ti-β exhibits outstanding performances in bulky MO epoxidation with the amount of produced EP per number of Ti sites up to 17.1±1.8 mol mol-1. This observation discloses an alternative strategy for optimizing catalyst efficiency in the rational design of the Ti-embedding zeolite catalyst, endeavoring to reach highly efficient catalytic performance.

Synthesis of aluminosilicate mesoporous material MSU-S from natural resources: Investigating the effects on the structure formation

Zeolite seed-based mesoporous aluminosilicate material MSU-S is normally synthesized from pure chemicals. In the study, MSU-S material was synthesized using natural resources such as rice husk, and kaolin in Vietnam. Here, a systematic investigation is conducted to find the relationship between the synthesis conditions (aging time, hydrothermal time, hydrothermal temperature, pH environment) and the formation of mesoporous structure, as well as the material properties. The sample was characterized by XRD, TEM, N2 adsorption-desorption isotherms, and TGA-DSC. The MSU-S material has been synthesized successfully from rice husk and kaolin. The best conditions are aging time of 24 hours, and hydrothermal conditions at 95 oC during 96 hours with pH=9. The MSU-S has an ordered hexagonal mesoporous structure containing zeolite BEA seed. The pore diameter is concentrated at 2.9 nm. The BET surface area is calculated to be 770 m²/g. Thermal stability is determined to be up to 900 oC.

H/D Exchange of Isobutane on In-Modified BEA Zeolite Investigated by 1H MAS NMR

H/D Exchange of Isobutane on In-Modified BEA Zeolite Investigated by ¹H MAS NMR

Insights into Si/Al ratios for enhanced performance of β-zeolites in thermocatalytic cracking of crude oil to light olefins

The escalating demand for key petrochemicals, particularly ethylene and propylene, underscores the critical need for proficient catalysts in crude oil conversion processes. Attaining high propylene selectivity necessitates catalysts with superior adsorption capacity, thermal stability, moderate surface acidity, and pores large enough to facilitate the diffusion of larger crude oil molecules. In the present study, three different BEA Zeolites (β-zeolite) catalysts were successfully synthesized by hydrothermal method and used for catalytic cracking of Arabian Light crude oil to produce valuable petrochemical products, such as propylene, ethylene, and naphtha. The catalysts were characterized using 27Al and 29Si NMR, NH3-TPD, BET, XRD, TGA, FTIR, XRF, and FE-SEM. The thermocatalytic cracking of Arabian Light crude oil was evaluated in a fixed-bed microactivity test (MAT) unit between 550 and 600 °C. The as-prepared β-zeolite with a Si/Al ratio of 50 exhibited better catalytic activity in the catalytic cracking of Arabian Light crude oil compared to counterparts with Si/Al ratios of 35 and 65, This superiority can be attributed to its optimal combination of surface acid site distribution, textural properties, surface morphology, and high adsorption capacity. The highest feed conversion (83.4 %) and selectivity to propylene (16.11 %) were attained using β-zeolite with a Si/Al ratio of 50 at 600 °C. Importantly, our findings suggest that these catalysts hold significant potential, rivalling primary MFI catalysts like ZSM-5 commonly employed in similar reactions. This underscores their promise as catalysts of choice in the realm of catalytic cracking processes, paving the way for advancements in petrochemical production.

The Rôle of Iron in Zeolite Beta for deNOx Catalysis

Selective catalytic reduction with ammonia (NH3-SCR) is a widely used deNOx process, employing zeolitic catalysts. Here, we examine framework substituted and extra-framework exchanged transition metal zeolite catalysts, in the extensively studied Fe – zeolite Beta focusing on the influence of the transition metal cation on the NH3-SCR reaction, and aiming to unravel the underlying mechanisms and their impact on catalytic performance. We use hybrid multiscale density functional theory (DFT)/molecular mechanics to investigate the NH3-SCR at various Fe-BEA active sites including systems with both framework and extra-framework Fe cations. The catalytically active sites under investigation include Fe-FeF-BEA, Fe-AlF-BEA, and Cu-FeF-BEA, (where the subscript F indicates framework species) on which the formation and consumption of key intermediates of both oxidation and reduction half cycles species are analysed. We show the distinctive ability of framework Fe sites to promote the formation of key nitrate and nitrosamine intermediates. Furthermore, we find a strong binding affinity of NH3 with framework Fe systems including Cu(II)-FeF-BEA, Fe(III)-FeF-BEA, and H-FeF-BEA compared to framework Al systems (Fe(III)-AlF-BEA). We explore the reduction potential of the framework Fe3+/Fe2+ in BEA zeolite and establish its feasibility in the presence of a Brønsted acid site. Our calculations clearly predict the bimetallic Cu-FeF system to be the best catalyst which supports a recent experimental report by Yue et al. (Chem. Eng. J. 2020, 398, 125515) for a related FeCu-SSZ-13 (CHA) zeolite. We provide a new understanding of the reactivity of Fe-BEA zeolites, suggesting the advantages of framework Fe over Al sites in NH3-SCR reactions, and establishing a foundation for interpretation of the rôle of framework cations in metal-exchanged zeolites.

Zeolites and their composites as novel remediation agent for antibiotics: A review

Antibiotic residues in aquatic environments pose significant challenges when exceeding permissible limits. Zeolites, particularly aluminosilicate zeolites, have emerged as effective adsorption materials and solid substrates for semiconductor photocatalysts, facilitating the removal of antibiotics from wastewater. This review highlights the versatility of zeolites and their composites in antibiotic remediation, showcasing recent advancements in adsorption and photocatalytic degradation. Noteworthy examples include Fe (III)-modified synthetic zeolite 13X, exhibiting a maximum tetracycline adsorption capacity of approximately 200 mg/g, and MoS2@Zeolite achieving a remarkable efficiency of 396.70 mg/g for tetracycline removal. Additionally, zeolite-based photocatalysts like Fe-TiO2/BEA zeolite and exceptional CdS/CaFe2O4-clinoptilolite demonstrate high removal percentages, reaching 100% for tetracycline and 86% for cefazolin, respectively. The discussion encompasses an introduction to zeolites, including synthetic and natural zeolites, as well as techniques for modifying natural zeolites. It further delves into the production of synthetic zeolites as well as the fabrication of zeolite-based composite materials. These findings underscore the potential of zeolites and their composites as novel remediation agents for tackling antibiotic contamination in aquatic ecosystems, paving the way for sustainable wastewater treatment strategies. It highlights key elements, distinct qualities, and areas needing further research, paving the way for future studies.

Metal-acid synergistic catalysis accelerates the hydrogen borrowing amination of alcohols by confining Ru sites in Beta zeolite

Direct hydrogen transfer amination of alcohols with amines is an environmentally friendly and atom-economical route for the synthesis of N-alkylamines. Noble metal species are highly catalytic active sites, but the exorbitant price makes the urgency to boost the atom efficiency with stable recyclability. Herein, we demonstrated that encapsulation of Ru nanoparticles (NPs) within BEA zeolite through direct hydrothermal approach greatly promoted the catalytic efficiency in the N-alkylation of aromatic alcohols and amines under additive- and solvent-free conditions, resulting in the high yield (∼93 %), maximum turnover number (TON) of 12,822 and turnover frequency (TOF) of 9012 h−1, with stable recyclability and extendable substrate scope. The kinetic studies and in-situ characterizations revealed that the synergy of confined Ru NPs and adjacent acid sites of BEA zeolite significantly promoted the C–H bond activation in the rate-determining step of alcohol dehydrogenation into aldehydes. Besides, the acid sites also accelerated the condensation of aldehyde intermediates and anilines to promote the kinetic equilibrium, while the moderate strength of the Ru–H bond resulting from the confined Ru NPs is advantageous to balance the dehydrogenation and hydrogenation steps to reach the fascinating H-transfer process.

An optimal combination of Na+ and H+ co-ions for high-performance Cu-impregnated *BEA zeolites: Unravelling the trade-off between the cold-start hydrocarbon trap activity and hydrothermal stability

A Cu-impregnated *BEA (denoted as BEA) type zeolite can serve as an effective hydrocarbon (HC) trap, but its long-term hydrothermal stability should be improved for real uses. However, designing robust high-performance HC traps, which is closely related to the confined environment that accommodates active Cu species and strengthens the zeolite structure, remains elusive. In this study, to the best of our knowledge, we, for the first time, systematically varied the Na content in the BEA zeolite prior to Cu impregnation. Intriguingly, we found a trade-off between the cold-start test (CST) activity (a simplified trap test for simulated HC emissions) and hydrothermal stability of the Cu-impregnated BEA zeolites. Specifically, increasing Na content decreased the CST performance monotonically, whereas it increased the hydrothermal stability. The decreased CST performance could be attributed to the less formation of the active Cu species (both Cu cations inside for preferred HC adsorption and CuO particles outside for facile HC oxidation). In addition, the improved hydrothermal stability benefited from dual features: Na+ ions could alleviate the zeolite structural collapse/damage during hydrothermal treatment (HT) at 800 °C by reducing the amount of most easily hydrolyzed Si-O(H)-Al bonds and avoid the formation of large CuO particles, which are known to destroy the zeolite structure during HT. As a net, we revealed that the Cu-impregnated BEA zeolite with an optimal Na/Al ratio of ca. 0.7 was key to achieving marked CST efficiencies in the HT state (22 %) in contrast to the H-form-based counterpart that exhibited extremely poor performance (i.e., nil).

Effects of Synthesis Method on the Localization of Aluminum Atoms and on Catalytic Performance of BEA Zeolite in Toluene Disproportionation

Effects of Synthesis Method on the Localization of Aluminum Atoms and on Catalytic Performance of BEA Zeolite in Toluene Disproportionation

Biodiesel Production via Transesterification Reaction over Mono- and Bimetallic Copper-Noble Metal (Pt, Ru) Catalysts Supported on BEA Zeolite

This work focuses on the study of biodiesel production from commercial rapeseed oil and methanol via transesterification reactions on monometallic copper and bimetallic copper–noble metal (platinum, ruthenium) catalysts supported on BEA zeolite. The catalysts were prepared by wet impregnation method on the hydrogen form of BEA zeolite. As part of the study, the physicochemical and catalytic properties of the prepared catalytic materials were determined. The catalytic activity tests were carried out in the transesterification reaction over prepared catalysts at 220 °C for 2 h in an autoclave. The physicochemical properties of the obtained catalysts were investigated by X-ray diffraction (XRD), specific surface area and porosity (BET), a scanning electron microscope equipped with an energy dispersive spectrometer (SEM–EDS) and temperature-programmed desorption of ammonia (TPD-NH3) method. The results of the catalytic activity showed the promotional effect of the noble metal on the TG conversion and FAME efficiency of copper catalysts in the biodiesel production process. The most active catalyst turned out to be the calcined 5%Cu–1%Ru/BEA catalyst, which showed the highest TG conversion of 85.7% and the second highest FAME efficiency of 58.4%. The high activity of this system is explained by its surface acidity and large specific surface area.

Acid-washing-alkali-fusion pretreated red mud for fabricating Cu-based BEA zeolite for NH3-SCR

The utilization of red mud as a solid waste to fabricate high-value-added products was a critical approach to reduce its storage. This research successfully synthesized a series of Cu-based BEA zeolite NH3-SCR catalysts with the acid-washing-alkali-fusion pretreated red mud as the Al source. XRF, XRD and N2 adsorption–desorption characterized the textual information of all samples. The H2-TPR, XPS, and UV–Vis DRS characterized the electronic structure of Cu. The highest Cu2+ content was obtained in Cu-BA0.5-H among all samples. The Cu-BA0.5-H processed the excellent low-temperature NO removal performance of ca. 99 % in 200 °C ∼ 300 °C when NH3/NO was 1. Finally, the in-situ DRIFTS analysis was carried out regarding the NH3 adsorption, NO + O2 adsorption, and co-adsorption to evaluate the possible reaction route. It was confirmed that the SCR reduction over Cu-BA0.5-H in SCR reactions followed the E-R mechanism, but different critical intermediate species depended on the reaction temperatures. It was deduced that the acid-washing-alkali-fusion pretreatment made the non-water-soluble components containing Si and Al into soluble components and further affected NO removal performance of the fabricated catalysts. Our research provided a novel approach for converting red mud into high-value products and unravelled the possible mechanism for NH3-SCR.

Brønsted Acid-Site Density Controls the Mechanistic Cycle and Product Selectivity in the Methanol-to-Hydrocarbons Reaction in BEA Zeolite

Brønsted Acid-Site Density Controls the Mechanistic Cycle and Product Selectivity in the Methanol-to-Hydrocarbons Reaction in BEA Zeolite

Biodiesel Production by Methanolysis of Rapeseed Oil-Influence of SiO2/Al2O3 Ratio in BEA Zeolite Structure on Physicochemical and Catalytic Properties of Zeolite Systems with Alkaline Earth Oxides (MgO, CaO, SrO).

Alkaline earth metal oxide (MgO, CaO, SrO) catalysts supported on BEA zeolite were prepared by a wet impregnation method and tested in the transesterification reaction of rapeseed oil with methanol towards the formation of biodiesel (FAMEs-fatty acid methyl esters). To assess the influence of the SiO2/Al2O3 ratio on the catalytic activity in the tested reaction, a BEA zeolite carrier material with different Si/Al ratios was used. The prepared catalysts were tested in the transesterification reaction at temperatures of 180 °C and 220 °C using a molar ratio of methanol/oil reagents of 9:1. The transesterification process was carried out for 2 h with the catalyst mass of 0.5 g. The oil conversion value and efficiency towards FAME formation were determined using the HPLC technique. The physicochemical properties of the catalysts were determined using the following research techniques: CO2-TPD, XRD, BET, FTIR, and SEM-EDS. The results of the catalytic activity showed that higher activity in the tested process was confirmed for the catalysts supported on the BEA zeolite characterized by the highest silica/alumina ratio for the reaction carried out at a temperature of 220 °C. The most active zeolite catalyst was the 10% CaO/BEA system (Si/Al = 300), which showed the highest triglyceride (TG) conversion of 90.5% and the second highest FAME yield of 94.6% in the transesterification reaction carried out at 220 °C. The high activity of this system is associated with its alkalinity, high value of the specific surface area, the size of the active phase crystallites, and its characteristic sorption properties in relation to methanol.

Effect of Surface Acidity/Basicity of Cr/Zn−BEA Zeolite Catalysts on Performance in CO2‐PDH Process

AbstractThe influence of adding Cr(III) compounds into Zn−BEA zeolite samples (with silicate modulus Si/Al=17, 100, and 1000) on the redox and acid–base characteristics of Cr/Zn−BEA zeolites were studied, and their catalytic properties in propane dehydrogenation with CO2 to propylene. It was established (based on the XRD, low–temperature (77 K) ad/desorption of N2, TPR−H2, TPD−MSC−NH3(CO2), C3H8(C3H6), FTIR−Py data) that the acid–base characteristics of the surface of bifunctional Cr/Zn−BEA catalysts, namely the amount, strength, and nature (Lewis and Brønsted sites), determine their activity/selectivity, and operation stability in the process of CO2−PDH. This indicates that over Cr/Zn−BEA catalysts, the process runs along the route of direct propane dehydrogenation combined with the reverse water gas shift reaction.

Impact of varied zeolite materials on nickel catalysts in CO2 methanation

Ni catalysts supported on 4A, 5A, 13X, ZSM-5, and BEA zeolites were prepared using the vacuum-heating method for CO2 methanation. These support materials play a pivotal role in shaping the catalysts' properties and their catalytic performance. High-resolution high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) and energy-dispersive X-ray spectroscopy (EDS) mappings suggest a significant concentration of Ni nanoparticles situated on the external surfaces of catalysts with low Si/Al ratios zeolites (Ni-4A, Ni-5A, and Ni-13X). These Ni nanoparticles exhibit characteristics of weaker metal-support interaction, lower metal reduction temperatures, and moderate H2 adsorption activity. Moreover, these low Si/Al ratio zeolites demonstrate robust CO2 adsorption activity. These properties endow Ni-5A and Ni-13X catalysts with heightened CO2 conversion (70.4–70.9%) and methane selectivity (92.4–96.4%). In contrast, high Si/Al ratio zeolite-based catalysts (Ni-ZSM-5 and Ni-BEA) exhibit smaller Ni particles, strong metal-support interaction and weaker CO2 adsorption activity, resulting in reduced CO2 methanation activity and decreased methane selectivity (71.2–73.4%). The normalized CO2 conversion rate presents a correlation with the average Ni particle size.

Experimental and simulation investigation on the different iron content beta zeolite for controlling the cold-start hydrocarbon emission from a gasoline vehicle

In this work, cold start experiments results showed that the HC catcher coated with 1% iron content is more effective than that with 3% iron content, the peak HC emission is reduced from 0.0029 g to 0.0018 g. To further reveal the reasons for the effects of BEA zeolite molecular sieves with different iron contents on HC adsorption, the measured HC emission components (butene, propene, ethene, acetaldehyde, and acetylene) were used as HC simulation molecules for molecular simulation experiments, the simulation results showed that, for single-component adsorption, the adsorption effect of beta zeolite molecular sieves with high iron content was better; for multi-component adsorption, acetaldehyde and butene maintained higher adsorption amounts, and the adsorption of acetaldehyde increased with the increase of the iron content in the beta zeolite molecular sieves; in the presence of water and CO2, the effect of water is greater than that of carbon dioxide, and its effect increases with the increase of iron content in beta zeolite molecular sieves. The maximum adsorption capacity of water can reach 4.5mmol/zeolite, which seriously affected the adsorption of HC molecules. Properly reducing the iron content of BEA zeolite molecular sieve is useful for enhancing its adsorption effect on the main HC simulated molecules.

Modification of Hierarchical Pore Zeolite BEA and its Application in the Purification of Ink Wastewater

Modification of Hierarchical Pore Zeolite BEA and its Application in the Purification of Ink Wastewater

A Deep Insight into Perfluorooctanoic Acid Photodegradation Using Metal Ion-Exchanged Zeolites.

Treating perfluorooctanoic acid (PFOA) in an aqueous environment is problematic due to its low concentration and its high resistance to biological and chemical degradation. To tackle this challenge, combinations of pre-enrichment and photodegradation processes are promising solutions. In this work, we investigated metal ion-exchanged zeolites as adsorbents and photocatalysts for PFOA treatment. Among various transition metal ion-exchanged BEA zeolites, Fe-exchanged BEA (Fe-BEA) zeolites showed significant activity for the photodegradation of PFOA. The isolated iron species in Fe-BEA zeolite are responsible for PFOA photodegradation, whereas other iron species present from excess iron loading in the zeolite will lower its photocatalytic activity. Furthermore, it was proved via size exclusion tests using branched PFOA isomers that the photodegradation of PFOA took place on the internal surface rather than the external surface of Fe-BEA zeolite. Photodegradation of PFOA was also tested to be effective with Fe-exchanged BEA-type zeolites having various SiO2/Al2O3 ratios, but ineffective with FAU-type zeolites. The optimal Fe-BEA zeolite showed a sorption coefficient Kd of 6.0 × 105 L kg-1 at an aqueous phase PFOA concentration of 0.7 μg L-1 and a PFOA half-life of 1.8 h under UV-A irradiation. The presented study offers a deeper understanding of the use of metal ion-exchanged zeolites for photodegradation of PFOA.