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Citronellal was converted to menthol in a one-pot approach using H-Beta zeolite-based Ni catalyst in a batch reactor at 80 °C, under 20 bar of total pressure. The effects of H-Beta acidity (H-Beta-25 with the molar ratio SiO2/Al2O3 = 25 and H-Beta-300 with SiO2/Al2O3 = 300) and Ni loading (5, 10 and 15 wt %) on the catalytic performance were investigated. Ni was impregnated on H-Beta support using the evaporation-impregnation method. The physico-chemical properties of the catalysts were characterized by XRD, SEM, TEM, ICP-OES, N2 physisorption, TPR, and pyridine adsorption–desorption FTIR techniques. Activity and selectivity of catalysts were strongly affected by the Brønsted and Lewis acid sites concentration and strength, Ni loading, its particle size and dispersion. A synergetic effect of appropriate acidity and suitable Ni loading in 15 wt.% Ni/H-Beta-25 catalyst led to the best performance giving 36% yield of menthols and 77% stereoselectivity to (±)-menthol isomer at 93% citronellal conversion. Moreover, the catalyst was successfully regenerated and reused giving similar activity, selectivity and stereoselectivity to the desired (±)-menthol isomer as the fresh one. [ABSTRACT FROM AUTHOR]

In this work, the formation of levulinic acid (LA) as one of the top-twelve chemical building blocks from glucose was studied. In particular, the formulations of heterogeneous acid catalysts based on SBA-15, MCM-41 mesoporous silica was carried out and their performance in catalytic conversion of glucose to LA were assessed and compared with commercial H-Beta-25 (SiO2/Al2O3 = 25) microporous zeolite. The high surface area, suitable porosity, balanced acid sites were considered as the main factors of a proper catalytic performance. Thus, essential modification of mesoporous SBA-15 and MCM-41 materials was carried out by introducing Al in their structures for Lewis acid sites improvement. Alumina was introduced to SBA-15 by post synthesis evaporation impregnation method while it was embedded inside the MCM-41 mesoporous material during the synthesis. In addition, Brønsted acidity was introduced via post-synthesis grafting of sulfonic acid groups. The textural and morphological features and acidity of the materials were investigated using N2 physisorption, SEM, EDX, TEM, XRD and pyridine-FTIR. All catalysts were tested for aqueous glucose conversion in an autoclave at 180 °C. Al-MCM-SO3H has shown the best performance with 54% of LA yield after 4 h reaction. According to Py-FTIR introduction of alumina and sulfonic acid groups improved weak and medium Lewis and Brønsted acid sites. However, the Brønsted to Lewis acid site ratio (B/L) was higher for Al-MCM-SO3H compared to SBA-Al-SO3H leading the reaction pathway to LA. H-Beta-25 zeolite displayed a poor performance because of harsh medium and strong acid sites catalyzing humins formation. [ABSTRACT FROM AUTHOR]

BACKGROUND: The metal–acid bifunctional catalysts are widely used in many industrially significant chemical processes, including hydroisomerization of n‐hexane. Deactivation and regeneration of metal–acid bifunctional extrudates was investigated in continuous n‐hexane hydroisomerization in a fixed‐bed reactor. Four Pt/H‐Beta‐25 catalysts containing 30% Bindzil binder were prepared with the same composition and controlled metal deposition. RESULTS: Different preparation steps led to differences in the mechanical strength, Pt particle size, acidity and strength, metal‐to‐acid site (cPt/cAS) ratio and proximity between two types of active sites. A very slow deactivation and high selectivity to C6 isomers was obtained when Pt was deposited on H‐Beta‐25 zeolite. CONCLUSION: Initial selectivity to the desired products was correlated with the physicochemical properties of the catalysts. Location of the metal has a larger influence on catalyst deactivation of the bifunctional catalysts rather than the metal‐to‐acid site ratio or site proximity. Decline of n‐hexane conversion and selectivity to C6 isomers were correlated with changes in the textural properties and acidity of the deactivated catalyst, respectively. © 2021 The Authors. Journal of Chemical Technology & Biotechnology published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry. [ABSTRACT FROM AUTHOR]

The presence of pharmaceuticals in surface water, drinking water, and wastewater has attracted significant concern because of the non-biodegradability, resistance, and toxicity of pharmaceutical compounds. The catalytic ozonation of an anti-inflammatory pharmaceutical, ibuprofen was investigated in this work. The reaction mixture was analyzed and measured by high-performance liquid chromatography (HPLC). Liquid chromatography-mass spectrometry (LC-MS) was used for the quantification of by-products during the catalytic ozonation process. Ibuprofen was degraded by ozonation under optimized conditions within 1 h. However, some intermediate oxidation products were detected during the ibuprofen ozonation process that were more resistant than the parent compound. To optimize the process, nine heterogeneous catalysts were synthesized using different preparation methods and used with ozone to degrade the ibuprofen dissolved in aqueous solution. The aim of using several catalysts was to reveal the effect of various catalyst preparation methods on the degradation of ibuprofen as well as the formation and elimination of by-products. Furthermore, the goal was to reveal the influence of various support structures and different metals such as Pd-, Fe-, Ni-, metal particle size, and metal dispersion in ozone degradation. Most of the catalysts improved the elimination kinetics of the by-products. Among these catalysts, Cu-H-Beta-150-DP synthesized by the deposition–precipitation process showed the highest decomposition rate. The regenerated Cu-H-Beta-150-DP catalyst preserved the catalytic activity to that of the fresh catalyst. The catalyst characterization methods applied in this work included nitrogen adsorption–desorption, scanning electron microscopy, transmission electron microscopy, and Fourier-transform infrared spectroscopy. The large pore volume and small metal particle size contributed to the improved catalytic activity. [ABSTRACT FROM AUTHOR]

Carbamazepine (CBZ), a widely used pharmaceutical compound, is one of the most detected drugs in surface waters. The purpose of this work was to identify an active and durable catalyst, which, in combination with an ozonation process, could be used to remove CBZ and its degradation products. It was found that the CBZ was completely transformed after ozonation within the first minutes of the treatment. However, the resulting degradation products, 1-(2-benzaldehyde)-4-hydro-(1H,3H)-quinazoline-2-one (BQM) and 1-(2-benzaldehyde)-(1H,3H)-quinazoline-2,4-dione (BQD), were more resistant during the ozonation process. The formation and degradation of these products were studied in more detail and a thorough catalytic screening was conducted to reveal the reaction kinetics of both the CBZ and its degradation products. The work was performed by non-catalytic ozonation and with six different heterogeneous catalysts (Pt-MCM-41-IS, Ru-MCM-41-IS, Pd-H-Y-12-EIM, Pt-H-Y-12-EIM, Pd-H-Beta-300-EIM and Cu-MCM-41-A-EIM) operating at two temperatures 20 °C and 50 °C. The influence of temperature on degradation kinetics of CBZ, BQM and BQD was studied. The results exhibited a notable difference in the catalytic behavior by varying temperature. The higher reactor temperature (50 °C) showed a higher activity of the catalysts but a lower concentration of dissolved ozone. Most of the catalysts exhibited higher removal rate for BQM and BQD compared to non-catalytic experiments in both temperatures. The Pd-H-Y-12-EIM catalyst illustrated a higher degradation rate of by-products at 50 °C compared to other catalysts. [ABSTRACT FROM AUTHOR]

[Display omitted] • Prins cyclisation from isovaleraldehyde and isoprenol to tetrahydropyranol. • Zeolites with varying acidity and hierarchical materials as catalysts. • H-Beta-300 zeolite giving 72% selectivity to the desired product at 99% conversion. • The cis/trans ratio of tetrahydropyranols depends on porous structure. • Parallel formation of tetrahydropyranol and dihydropyran confirmed by DFT. In this work, several heterogeneous micro- and mesoporous, acidic catalysts were tested for the selective synthesis of Florol®, an industrial product formed via condensation and rehydration starting from isoprenol and isovaleraldehyde in dimethylcarbonate as a solvent. The results showed that a mildly acidic, microporous H-Beta-300 with SiO 2 /Al 2 O 3 ratio of 300 was the best catalyst, giving 72% selectivity with 99% conversion at 40 °C when using the molar ratio isoprenol to isovaleraldehyde of 1:5. More acidic zeolites gave slightly lower selectivity, while the lowest selectivity (up to 52%) was obtained with mesoporous catalysts exhibiting mild acidity and no strong Brønsted acid sites. Selectivity to pyranols was nearly constant when changing temperature, while a larger excess of isovaleraldehyde promoted formation of tetrahydropyranol. H-Beta-300 catalyst was successfully after calcination at 400 °C. DFT calculations pointed out on the parallel formation of tetrahydro pyranols and dihydropyrans, which are the corresponding dehydration products. [ABSTRACT FROM AUTHOR]

• A clear impact of the precursor on physico-chemical properties of solution impregnated Ni in zeolite 5A and 13X was shown. • Significant differences were also observed in activity and selectivity of the prepared catalysts in CO 2 methanation. • Besides the choice of precursor, the calcination temperature also influenced clearly the performance of the catalysts. • Detailed catalyst characterization was performed. • 13X was concluded to be the superior support and nickel citrate was the best precursor. Zeolite 13X and 5A supported Ni catalysts were synthesized for CO 2 methanation using the evaporation impregnation method. The influence of using different Ni precursors (nitrate, citrate, and acetate) as well as calcination temperatures on the catalyst properties and performance were investigated. XRD, SEM-EDX, TEM, STEM-EDX, N 2 physisorption, H 2- TPR, TPD-NH 3 and TG/DTA were used for detailed characterization of the catalysts. The parent structure of the zeolites did not change during catalyst synthesis. Using nickel citrate and acetate resulted in smaller NiO particle size compared to nitrate. STEM-EDX results showed that all the Ni-precursor complexes entered more efficiently the 13X zeolite structure, which is mainly due to steric hindrance resulting from the smaller pore size of 5A. Methanation experiments revealed that the 13X catalysts synthesized using nickel citrate (5% Ni) displayed clearly higher activity, compared to the catalysts synthesized using nickel nitrate or nickel acetate. A 79% conversion at 320 °C was obtained with 100% selectivity towards CH 4 and the catalyst showed excellent stability during 200 h testing. Overall, it can be concluded that the Ni precursor significantly influences the physico-chemical characteristics and catalytic properties of Ni 13X and Ni 5A zeolite catalysts in CO 2 methanation: complex size and pore size matter. [ABSTRACT FROM AUTHOR]

Partial oxidation of ethanol to acetaldehyde was carried out over gold catalysts supported on various oxides and zeolites by deposition precipitation. The special focus of this work was on the influence of H-Y zeolite surface charge on Au cluster size and loading linking it to activity and selectivity in ethanol oxidation and comparing with other studied catalysts. The catalysts were characterized by nitrogen physisorption, transmission electron microscopy (TEM), scanning electron microscopy/energy dispersive X-ray analysis (SEM/EDXA), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR) and zeta potential measurements. pH of the solution governed the Au NPs size within the range of 5.8–13.2 nm with less negatively charged surfaces leading to formation of smaller clusters. Au loading on H-Y zeolite with silica to alumina ratio of 80 was increased by raising the pH. In fact, H-Y-12 and H-Beta-25 were selective towards diethyl ether while acetaldehyde was the prevalent product on less acidic H-Y-80. The results demonstrated strong dependency of the catalytic activity on the Au cluster size. Namely turn over frequency (TOF) decreased with an increase in metal size from 6.3 to 9.3 nm on H-Y-80. Selectivity towards acetaldehyde and ethyl acetate did not change significantly on H-Y-80 within 6.3–9.3 nm Au particle size range. On Al 2 O 3 support, however, selectivity towards acetaldehyde increased considerably upon diminishing Au average particle size from 3.7 to 2.1 nm. [ABSTRACT FROM AUTHOR]

Catalytic synthesis of a dioxinol compound, (2 S ,4a R ,8 R ,8a R )-4,4,7-trimethyl-2-phenyl-4a,5,8,8a-tetrahydro-4 H -benzo[d][1,3]dioxin-8-ol, exhibiting analgesic activity was demonstrated over Fe-modified beta zeolite. During interactions between cis-verbenol oxide and benzaldehyde, two main reactions occurred. In the first reaction, namely isomerization of verbenol oxide both cyclopentenic hydroxyketone, oxetane as well as a cyclohexyl compound, (1 R ,2 R ,6 S )-3-methyl-6-(prop-1-en-2-yl)cyclohex-3-ene-1,2-diol were formed. In the second parallel reaction the target compound was generated. The highest yield of the target compound was achieved in the reaction between verbenol oxide and benzaldehyde at their molar ratio of 1:133 with the bifunctional iron modified Fe-H-Beta-150 catalyst at 70 °C giving a much higher yield than reported earlier in the literature, being 46 mol-% at complete conversion of verbenol oxide. [ABSTRACT FROM AUTHOR]

• Heterogeneous catalysts for ethene and diethyl ether formation from ethanol were screened. • The role of active sites in the product distribution was revealed. • Very precise kinetic data were produced in a microreactor device. • It was demonstrated that microreactors are strong tools in the study of gas-phase kinetics and catalyst stability. Dehydration and etherification of bio-ethanol was studied in a microreactor using γ-alumina, H-Beta-38 and Sn-Beta-38 as catalysts. An extensive series of kinetic experiments was carried out in the microreactor device operating at ambient pressure and temperatures 225–325 °C. The H-Beta-38 catalyst coated microplates exhibited the highest production rate of ethene. While the fresh H-Beta-38 catalyst allowed complete conversion of ethanol and 98% selectivity towards ethene, the catalyst deactivated significantly with time-on-stream. Diethyl ether was the dominating co-product, whereas trace amounts of acetaldehyde were detected in the experiments. Based on the kinetic studies, thermodynamic analysis and catalyst characterization results obtained with SEM-EDX, TEM, nitrogen physisorption, FTIR-Pyridine and white light confocal microscopy, a surface reaction mechanism was proposed. The fundamental hypothesis of the reaction mechanism was the co-existence of two kinds of active sites on the catalyst surface, namely the Brønsted sites promoting dehydration and the Lewis sites responsible for etherification. The Brønsted sites deactivate, whereas the Lewis sites are more stable, which leads to a shift of the product distribution during long-term experiments, from ethene to diethyl ether. The rate equations were implemented in the microreactor model. The kinetic and adsorption parameters included in the model were estimated by non-linear regression analysis. The experimental data were satisfactorily described by the proposed mechanism. The work demonstrated that microreactors are strong tools in the determination of catalytic kinetics and catalyst durability. [ABSTRACT FROM AUTHOR]

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]

[Display omitted] • Hydrocracking of hexadecane to jet fuel components H- proton and metal Beta zeolites with different acidity. • Extensive catalyst characterization by physico-chemical methods. • Mildly acidic 2.5 wt% Ru-H-Beta-300 afforded 24% yield of the jet fuel components and 89% liquid mass balance closure. Hydrocracking of hexadecane to produce jet fuel components was investigated over proton and metal modified Beta zeolites with different acidity. They were characterized by a range of physico-chemical methods. The initial catalyst screening was performed at 210 °C under 40 bar hydrogen showing that the most promising catalysts were 2.5 wt% Pt-H-Beta-25 and 2.5 wt% Ru-H-Beta-300, which were also tested at 240 °C under 45 bar hydrogen. The results revealed that the yield of jet fuel components was maximally 27% over 2.5 wt% Pt-H-Beta-25. This catalyst gave, however, only 55% mass balance closure to the liquid phase products, while a mildly acidic 2.5 wt% Ru-H-Beta-300 afforded 24% yield of the jet fuel components and 89% liquid mass balance closure. [ABSTRACT FROM AUTHOR]