Fenton chemistry-based detemplation of an industrially relevant microcrystalline beta zeolite. Optimization and scaling-up studies

A mild template removal of microcrystalline beta zeolite, based on Fenton chemistry, was optimized. Fenton detemplation was studied in terms of applicability conditions window, reaction rate and scale up. TGA and CHN elemental analysis were used to evaluate the detemplation effectiveness, while ICP, XRD, LPHR-Ar physisorption, and 27Al MAS NMR were applied to characterize the structure and texture of the resulting materials. The material properties were compared to calcination. By understanding the interplay of relevant parameters of the Fenton chemistry, the process can be optimized in order to make it industrially attractive for scale-up. The H2O2 utilization can be minimized down to 15 mL H2O2/g (88 °C, 30 ppm Fe), implying a high solid concentration and low consumption of H2O2. When Fe concentration must be minimized, values as low as 5 ppm Fe can be applied (88 °C, 30 mL H2O2/g), to achieve full detemplation. The reaction time to completeness can be reduced to 5 h when combining a Fe-oxalate catalyst with UV radiation. The protocol was scaled up to 100 times larger its original recipe. In terms of the material's properties, the scaled material is structurally comparable to the calcined counterpart (comparable Si/Al and XRD patterns), while it displays benefits in terms of texture and Al-coordination, the latter with full preservation of the tetrahedral A

The Brunauer–Emmett–Teller model on alumino-silicate mesoporous materials. How far is it from the true surface area?

Determining the surface area of porous materials through the Brunauer–Emmett–Teller (BET) model is a common practice. The method is generally applied in commercial software packages, where the assumptions are sometimes accepted by the experimenter whilst they may sometimes require a deeper analysis. One element of debate is the molecular cross-sectional area of the adsorptive. There is not yet agreement about the correctness of the BET model using a certain value for cross-sectional area of N2; the conventionally-used parameter seems to overestimate the surface areas. In this work, a preliminary study of a modified method is presented, which introduces an ‘apparent’ cross-sectional area for N2, which is smaller to the typically-used value. This value was obtained after measuring a number of relevant mesoporous materials in N2 and Ar, using a model that considers an apparent value for the cross-sectional area. The model predicts outcomes very close to the Ar-based measurements in terms of low relative error. Then, we went one step further and looked into the geometrical surface areas, also referred to as true surface areas. By combining prior studies with our work, it was found that the surface area, using N2 and the conventionally-used cross section, can be ca. 50% higher than the geometrical surface area. Therefore, the significance of the BET surface area seems to be far from well understood, though it is widely applied. This approach also allowed to define an ‘effective’ cross section for N2, that relates it to the geometrical surface area. Its value agrees with prior considerations for an epitaxial orientation of the N2 molecule with a hydroxylated silica surface. As a final recommendation, critical thinking is needed about the default settings in standardised calculations, which may not represent a reliable measure of the true surface area.</p

Decoupling hydrolysis and mechanical stress effects on Si-MCM-41 relative to hydrothermal stability

La estabilidad hidrotérmica del Si-MCM-41 ha sido frecuentemente limitada a la hidrólisis de los enlaces Si-O-Si debido al bajo grado de condensación o al espesor de las paredes de dicho material, o a la combinación de ambos. En este estudio se proporcionan evidencias de un factor adicional, efectos físicos que ocurren durante el secado de un material calcinado que se sometió a un tratamiento hidrotérmico, debido a la tensión capilar ejercida sobre el material cuando el secado se lleva a cabo en medio acuoso. Los resultados fueron interesantes ya que la muestra de material después de ser sometida al tratamiento hidrotérmico a diferente temperatura en agua, presentó desorden completo y contracción de la estructura los resultados revelan que la tensión capilar es responsable del orden perdido y la contracción de la estructura del material a temperatura moderada del hidrotratamiento. Los materiales secados en presencia de solvente de baja tensión superficial preservan su estructura hexagonal y son libres de contracción. Los resultados fueron analizados por diferentes técnicas como: SAXS, TGA, Fisisorción de nitrógeno, ²⁹Si-NMR y TEM.MCM-41’s limited hydrothermal stability has been often related to the hydrolysis of Si-O-Si bonds due to the low degree of condensation or its thin walls, or a combination of them. In this study evidence for an additional factor is provided; a physical effect that occurs during the drying of the hydrothermally treated calcined material, due to the intense capillary stress exerted in water. The results were interesting because the samples gets fully disordered and shrunk at all applied hydrothermal temperatures in water. Comparison between water and lowsurface- tension-solvent drying reveals that capillarity is responsible for the loss of ordering (and shrinkage) at moderate hydrothermal temperatures. The material’s structure is maintained hexagonal and shrinkage-free under the low-surface-tension-solvent route. The results were analyzed by different techniques as: SAXS, TGA, Nitrogen physisorption, ²⁹Si-NMR and TEM

Novel reactivation allows effective reuse of Nafion® super-acid nano-catalyst

An alternative clean regeneration method to calcination on special grade resins, i.e. Nafion, is introduced. The reactivation strategy makes use of advanced oxidation processes (Fenton and non-Fenton) to remove the organic deposits generated from sequential catalytic cycles. Hot water treatment was considered as a control case to evaluate the extraction capacity of water itself at the oxidative conditions. Advanced oxidation processes were effective in reactivating the Nafion SAC-13 resin, which also rendered a cleaner and more sustainable reactivation process. Beta zeolite was studied as model fouled system prior to the Nafion SAC-13. Even though zeolites are considered to be thermally stable, this approach can be used when a full preservation of the acid sites is required. As far as resin Nafion SAC-13 is concerned, organic species deposition was found to be responsible of a selective poisoning of the sulfonic groups in Nafion, with a consequent drop in catalytic activity of the octanoic acid esterification with methanol. The Nafion resin was reactivated either with H2O2 or with Fenton chemistry; the resin remained stable under these oxidative conditions, which is the benefit of the presented non­thermal methodologies as compared to calcination. The optimal method showed full recovery of the initial activity and 90% of the final conversion. This methodology seems attractive for a whole-range of organic catalytic reactions, including those related to biomass valorization, that require the use of highly acidic catalysts, such as acidic resins, in liquid phase reactions

CO2 absorption into aqueous amine blended solutions containing monoethanolamine (MEA), N,N-dimethylethanolamine (DMEA), N,N-diethylethanolamine (DEEA) and 2-amino-2-methyl-1-propanol (AMP) for post-combustion capture processes

Presently monoethanolamine (MEA) remains the industrial standard solvent for CO2 capture processes. Operating issues relating to corrosion and degradation of MEA at high temperatures and concentrations, and in the presence of oxygen, in a traditional PCC process, have introduced the requisite for higher quality and costly stainless steels in the construction of capture equipment and the use of oxygen scavengers and corrosion inhibitors. While capture processes employing MEA have improved significantly in recent times there is a continued attraction towards alternative solvents systems which offer even more improvements. This movement includes aqueous amine blends which are gaining momentum as new generation solvents for CO2 capture processes. Given the exhaustive array of amines available to date endless opportunities exist to tune and tailor a solvent to deliver specific performance and physical properties in line with a desired capture process. The current work is focussed on the rationalisation of CO2 absorption behaviour in a series of aqueous amine blends incorporating monoethanolamine, N,N-dimethylethanolamine (DMEA), N,N-diethylethanolamine (DEEA) and 2-amino-2-methyl-1-propanol (AMP) as solvent components. Mass transfer/kinetic measurements have been performed using a wetted wall column (WWC) contactor at 40°C for a series of blends in which the blend properties including amine concentration, blend ratio, and CO2 loadings from 0.0-0.4 (moles CO2/total moles amine) were systematically varied and assessed. Equilibrium CO2 solubility in each of the blends has been estimated using a software tool developed in Matlab for the prediction of vapour liquid equilibrium using a combination of the known chemical equilibrium reactions and constants for the individual amine components which have been combined into a blend.From the CO2 mass transfer data the largest absorption rates were observed in blends containing 3M MEA/3M Am2 while the selection of the Am2 component had only a marginal impact on mass transfer rates. Overall, CO2 mass transfer in the fastest blends containing 3M MEA/3M Am2 was found to be only slightly lower than a 5M MEA solution at similar temperatures and CO2 loadings. In terms of equilibrium behaviour a slight decrease in the absorption capacity (moles CO2/mole amine) with increasing Am2 concentration in the blends with MEA was observed while cyclic capacity followed the opposite trend. Significant increases in cyclic capacity (26-111%) were observed in all blends when compared to MEA solutions at similar temperatures and total amine concentrations. In view of the reasonable compromise between CO2 absorption rate and capacity a blend containing 3M MEA and 3M AMP as blend components would represent a reasonable alternative in replacement of 5M MEA as a standalone solvent

Improved O2-assisted styrene synthesis by double-function purification of SWCNT catalyst

The catalytic performance of SWCNT was notably improved in the oxidative dehydrogenation of ethylbenzene (EB) to styrene (ST) upon a double-function purification in one step of the raw SWCNT. This consists of lowering the MeOx concentration and generating surface C=O groups after processing it in nitric acid at controlled conditions, while preserving the structure. The textural improvement was ascribed to the cutting of the tubes/bundles by oxidation and to MeOx removal itself (dilution effect). Both EB conversion and ST selectivity increased with a parallel lowering of the undesired COx selectivity. The conversion was interpreted by the enhancement of the intrinsic properties (i.e., more surface ketonic groups) but also to the higher load of SWCNT in the bed upon purification; both factors contribute to a higher number of active sites (C=O) in the bed for styrene formation. The most purified catalyst underperformed in conversion once the purification altered the SWCNT structure notably. Thus, preserving the structure is an important condition to achieve high conversion and yield. The better selectivity was explained in two ways; more styrene-forming sites (C=O) or less COx-forming sites (uncoated MeOx) in the bed, or both. The styrene yield per catalyst volume was improved by an average of ca. 240 % in comparison to the non-purified SWCNT. Deactivation is critical in maximizing the purification effect on the intrinsic and volumetric yields. In practical terms, the purification method proved to enhance the reaction; the selectivity towards the unwanted COx was significantly lowered with a gain towards styrene, achieving comparable selectivity values as in the conventional process, but operated at much lower temperature