On the thermal stabilization of carbon-supported SiO2 catalysts by phosphorus:evaluation in the oxidative dehydrogenation of ethylbenzene to styrene and a comparison with relevant catalysts

A strategy to enhance the thermal stability of C/SiO2 hybrids for the O2-based oxidative dehydrogenation of ethylbenzene to styrene (ST) by P addition is proposed. The preparation consists of the polymerization of furfuryl alcohol (FA) on a mesoporous precipitated SiO2. The polymerization is catalyzed by oxalic acid (OA) at 160 °C (FA:OA = 250). Phosphorous was added as H3PO4 after the polymerization and before the pyrolysis that was carried out at 700 °C and will extend the overall activation procedure. Estimation of the apparent activation energies reveals that P enhances the thermal stability under air oxidation, which is a good indication for the ODH tests. Catalytic tests show that the P/C/SiO2 hybrids are readily active, selective and indeed stable in the applied reactions conditions for 60 h time on stream. Coke build-up during the reaction attributed to the P-based acidity is substantial, leading to a reduction of the surface area and pore volume. The comparison with a conventional MWCNT evidences that the P/C/SiO2 hybrids are more active and selective at high temperatures (450–475 °C) while the difference becomes negligible at lower temperature. However, the comparison with reference P/SiO2 counterparts shows a very similar yield than the hybrids but more selective to ST. The benefit of the P/C/SiO2 hybrid is the lack of stabilization period, which is observed for the P/SiO2 to create an active coke overlayer. For long term operation, P/SiO2 appears to be a better choice in terms of selectivity, which is crucial for commercialization.

Fe III in a low-spin state in caesium bis[3-ethoxysalicylaldehyde 4-methylthiosemicarbazonato(2–)-κ3O2,N1,S]ferrate(III) methanol monosolvate

The synthesis and crystal structure (at 100K) of the title compound, Cs[Fe(C11H13N3O2S2) 2] CH3OH, is reported. The asymmetric unit consists of an octahedral [FeIII(L)2]- fragment, where L 2- is 3-ethoxysalicylaldehyde 4-methylthiosemicarbazonate(2-) {systematic name: [2-(3-ethoxy-2-oxidobenzylidene)hydrazin-1-ylidene] (methylamino)methanethiolate}, a caesium cation and a methanol solvent molecule. Each L2- ligand binds through the thiolate S, the imine N and the phenolate O atoms as donors, resulting in an FeIIIS2N 2O2 chromophore. The O,N,S-coordinating ligands are orientated in two perpendicular planes, with the O and S atoms in cis positions and the N atoms in trans positions. The FeIII cation is in the low-spin state at 100K. © 2014 International Union of Crystallography.

Bifunctional organorhodium solid acid catalysts for methanol carbonylation

Robust, bifunctional catalysts comprising Rh(CO)(Xantphos) exchanged phosphotungstic acids of general formulas [Rh(CO)(Xantphos)]+n[H3–nPW12O40]n− have been synthesized over silica supports which exhibit tunable activity and selectivity toward direct vapor phase methanol carbonylation. The optimal Rh:acid ratio = 0.5, with higher rhodium concentrations increasing the selectivity to methyl acetate over dimethyl ether at the expense of lower acidity and poor activity. On-stream deactivation above 200 °C reflects Rh decomplexation and reduction to Rh metal, in conjunction with catalyst dehydration and loss of solid acidity because of undesired methyl acetate hydrolysis, but can be alleviated by water addition and lower temperature operation.

Photodeposition as a facile route to tunable Pt photocatalysts for hydrogen production:on the role of methanol

Photodeposition of H2PtCl6 in the presence of methanol promotes the formation of highly dispersed, metallic Pt nanoparticles over titania, likely via capture of photogenerated holes by the alcohol to produce an excess of surface electrons for substrate-mediated transfer to Pt complexes, resulting in a high density of surface nucleation sites for Pt reduction. Photocatalytic hydrogen production from water is proportional to the surface density of Pt metal co-catalyst, and hence photodeposition in the presence of high methanol concentrations affords a facile route to optimising photocatalyst design and highlights the importance of tuning co-catalyst properties in photocatalysis.

Application of staged O2 feeding in the oxidative dehydrogenation of ethylbenzene to styrene over Al2O3 and P2O5/SiO2 catalysts

Drastic improvements in styrene yield and selectivity were achieved in the oxidative dehydrogenation of ethylbenzene by staged feeding of O2. Six isothermal packed bed reactors were used in series with intermediate feeding of O2, while all EB was fed to the first reactor, diluted with helium or CO2 (1:5 molar ratio), resulting in total O2:EB molar feed ratios of 0.2-0.6. The two catalyst samples, γ-Al 2O3 and 5P/SiO2, that were applied both benefitted from this operation mode. The ethylbenzene conversion per stage and the selectivity to styrene were significantly improved. The production of COX was effectively reduced, while the selectivity to other side products remained unchanged. Compared with co-feeding at a total O 2:EB molar feed ratio of 0.6, by staged feeding the EB conversion (+15% points for both catalysts), ST selectivity (+4% points for both samples) and O2 (ST) selectivity (+9% points for γ-Al2O 3 and +17% points for 5P/SiO2) all improved. The ethylbenzene conversion over 5P/SiO2 can be increased from 18% to 70% by increasing the number of reactors from 1 to 6 with each reactor a total amount of O2 of 0.1 without the loss of ST selectivity (93%). For 5P/SiO2 a higher temperature (500 C vs. 450 C for Al 2O3) is required. Essentially more catalyst (5P/SiO 2) was required to achieve full O2 conversion in each reactor. Staged feeding of O2 does not eliminate the existing issues of the catalyst stability both in time-on stream and as a function of the number of catalyst regenerations (5P/SiO2), or the relatively moderate performance (relatively low styrene selectivity for γ-Al2O 3). © 2014 Elsevier B.V.

On the stability of conventional and nano-structured carbon-based catalysts in the oxidative dehydrogenation of ethylbenzene under industrially relevant conditions

Relevant carbon-based materials, home-made carbon-silica hybrids, commercial activated carbon, and nanostructured multi-walled carbon nanotubes (MWCNT) were tested in the oxidative dehydrogenation of ethylbenzene (EB). Special attention was given to the reaction conditions, using a relatively concentrated EB feed (10 vol.% EB), and limited excess of O2 (O 2:EB = 0.6) in order to work at full oxygen conversion and consequently avoid O2 in the downstream processing and recycle streams. The temperature was varied between 425 and 475 °C, that is about 150-200 °C lower than that of the commercial steam dehydrogenation process. The stability was evaluated from runs of 60 h time on stream. Under the applied reactions conditions, all the carbon-based materials are apparently stable in the first 15 h time on stream. The effect of the gasification/burning was significantly visible only after this period where most of them fully decomposes. The carbon of the hybrids decomposes completely rendering the silica matrix and the activated carbon bed is fully consumed. Nano structured MWCNT is the most stable; the structure resists the demanding reaction conditions showing an EB conversion of ∼30% (but deactivating) with a steady selectivity of ∼80%. The catalyst stability under the ODH reaction conditions is predicted from the combustion apparent activation energies. © 2014 Elsevier Ltd. All rights reserved.

Coke formation in the oxidative dehydrogenation of ethylbenzene to styrene by TEOM

A packed bed microbalance reactor setup (TEOM-GC) is used to investigate the formation of coke as a function of time-on-stream on γ-Al2O3 and 3P/SiO2 catalyst samples under different conditions for the ODH reaction of ethylbenzene to styrene. All samples show a linear correlation of the styrene selectivity and yield with the initial coverage of coke. The COX production increases with the coverage of coke. On the 3 wt% P/SiO2 sample, the initial coke build-up is slow and the coke deposition rate increases with time. On alumina-based catalyst samples, a fast initial coke build-up takes place, decreasing with time-on-stream, but the amount of coke does not stabilize. A higher O2 : EB feed ratio results in more coke, and a higher temperature results in less coke. This coking behaviour of Al2O3 can be described by existing "monolayer-multilayer" models. Further, the coverage of coke on the catalyst varies with the position in the bed. For maximal styrene selectivity, the optimal coverage of coke should be sufficient to convert all O2, but as low as possible to prevent selectivity loss by COX production. This is in favour of high temperature and low O2 : EB feed ratios. The optimal coke coverage depends in a complex way on all the parameters: temperature, the O2 : EB feed ratio, reactant concentrations, and the type of starting material. This journal is

Making coke a more efficient catalyst in the oxidative dehydrogenation of ethylbenzene using wide-pore transitional aluminas

The thermal activation of a silica-stabilized γ-Alumina impacts positively on the oxidative dehydrogenation of ethylbenzene (EB) to styrene (ST). A systematic thermal study reveals that the transition from γ-alumina into transitional phases at 1050C leads to an optimal enhancement of both conversion and selectivity under pseudo-steady state conditions; where active and selective coke have been deposited. The effect is observed in the reaction temperature range of 450-475C at given operation conditions resulting in the highest ST yield, while at 425C this effect is lost due to incomplete O2 conversion. The conversion increase is ascribed to the ST selectivity improvement that makes more O2 available for the main ODH reaction. The fresh aluminas and catalytically active carbon deposits on the spent catalysts were characterized by gas adsorption (N 2 and Ar), acidity evaluation by NH3-TPD and pyridine adsorption monitored by FTIR, thermal and elemental analyses, solubility in CH2Cl2 and MALDI-TOF to correlate the properties of both phases with the ST selectivity enhancement. Such an increase in selectivity was interpreted by the lower reactivity of the carbon deposits that diminished the COx formation. The site requirements of the optimal catalyst to create the more selective coke is related to the higher density of Lewis sites per surface area, no mixed Si-Al Brønsted sites are formed while the acid strength of the formed Lewis sites is relatively weaker than those of the bare alumina. © 2013 Elsevier B.V. All rights reserved.

Oxidative dehydrogenation of ethylbenzene to styrene over alumina:effect of calcination

Commercially available γ-Al2O3 was calcined at temperatures between 500 and 1200 °C and tested for its performance in the oxidative ethylbenzene dehydrogenation (ODH) over a wide range of industrially-relevant conditions. The original γ-Al2O 3, as well as η- and α-Al2O3, were tested. A calcination temperature around 1000/1050 °C turned out to be optimal for the ODH performance. Upon calcination the number of acid sites (from 637 to 436 μmol g-1) and surface area (from 272 to 119 m 2 g-1) decrease, whereas the acid site density increases (from 1.4 to 2.4 sites per nm2). Less coke, being the active catalyst, is formed during ODH on the Al-1000 sample compared to γ-Al 2O3 (30.8 wt% vs. 21.6 wt%), but the coke surface coverage increases. Compared with γ-Al2O3, the EB conversion increased from 36% to 42% and the ST selectivity increased from 83% to 87%. For an optimal ST selectivity the catalyst should contain enough coke to attain full conversion of the limiting reactant oxygen. The reactivity of the coke is changed due to the higher density and strength of the Lewis acid sites that are formed by the high temperature calcination. The Al-1000 sample and all other investigated catalysts lost ODH activity with time on stream. The loss of selectivity towards more COX formation is directly correlated with the amount of coke. © The Royal Society of Chemistry 2013.