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In the present work we studied the hydrogenation/hydrogenolysis of d -glucose over Pt and Ru catalysts supported on activated micro/mesoporous carbon (AC), under low hydrogen pressure (1.6 MPa) and relatively high reaction temperature, i.e. 180 °C. We also studied the effect of metal content (1–5 wt.%), method of metal pre-treatment/reduction (H 2 at 350 °C or NaBH 4 ) and reaction time (1–12 h). All the Ru and Pt/AC catalysts were very active (conversion ≥97%) with the Pt/AC catalysts being also very selective toward sorbitol (sel. ≥90%) irrespective of metal content, method of reduction and reaction time (up to 12 h). On the other hand, the Ru/AC catalysts exhibited a wide range of sorbitol selectivity values (55–93%) having various C 3 –C 6 sugar alcohols (1,2,5,6-hexanetetrol, arabinitol, threitol, glycerol and 1,2-propanediol) as main by-products. The formation of by-products was dependent on the crystalline/amorphous nature of Ru and Ru(O) x δ + nanoparticles which were in turn affected by the Ru content and the method of reduction.

Supported Ir, Pd, Rh and Ru catalysts were examined for the conversion of glucose and cellulose in water in the presence of hydrogen. The catalysts were prepared by incipient wetness impregnation of a BEA zeolite (SiO2/Al2O3 = 21.6, Ssp = 739 m2/g) with acetylacetonate metal precursors. Among these catalysts, Ru-BEA was found to be the most active for the conversion of cellulose, while Ir-BEA was found to be the most selective for the formation of sorbitol. Thus, the highest yield to sorbitol was found in the presence of 3 wt%Ru/BEA catalyst irrespective of the raw material nature (glucose or cellulose). It corresponded to a value of 22% for the conversion of the commercial cellulose, and of 72.8% for the conversion of glucose. The Ru-BEA catalyst was followed by the 3 wt%Ir-BEA that led to a yield of 55.3% for glucose and 22% for cellulose but to a much higher selectivity, i.e. over 99.9% for glucose and 89.2% for cellulose. While the high selectivity of Ir to sorbitol was correlated with the d-band width of the metal, the high activity of Ru for the cellulose conversion was assigned to the generation of H+ and [Ru(H2O)5OH]2+ as Bronsted acids by Ru species in water. Finally, the addition of pure nanoscopic hydroxylated SnF4 to the 3 wt%Ir-BEA catalyst led to a conversion of cellulose of almost 99% after only 3 h with a selectivity to sorbitol of 72.5%.

The development of novel catalytic processes for the upgrading of F–T waxes towards the production of clean transportation fuels as well as other valuable gaseous alkenes in the overall Biomass-to-Liquid (BTL) process would increase the sustainability of this growing technology significantly. Recent studies have shown that an alternative to the classical hydrocracking process for the upgrading of heavy waxy hydrocarbons could be the Fluid Catalytic Cracking (FCC) process, which aims mainly to the production of gasoline and gaseous (C3, C4) alkenes. In the present work, we have used “model” zeolitic and mesoporous aluminosilicate catalytic materials that exhibit different acidic and porosity characteristics, in order to elucidate the reaction mechanism of F–T wax cracking and to identify the effects of these catalyst properties on conversion and product yields. In addition, the effect of moderating the acidity of zeolites via steaming (in analogy to commercial FCC equilibrated catalysts) or by using alkaline metals that block the acid sites and the effect of using specific metals with dehydrogenation activity, have also been studied. It was shown that the Bronsted zeolitic acid sites, mainly the ones of higher strength, are responsible for the high cracking activity of the heavy paraffinic feed, while the Lewis acid sites contributed to a lesser extent. Furthermore, the different micropore structure/size of zeolites Y, ZSM-5 and Beta had a significant effect on conversion and product yields (C2–C4 gases, gasoline, LCO, coke), as well as on gasoline composition (PIONA) and octane number (RON/MON). The mildly acidic amorphous mesoporous aluminosilicates exhibited moderate conversion and different product yields and gasoline composition, compared to zeolites. The catalytic results of the present study were rationalized on the basis of well-established reaction mechanisms for n-paraffins cracking on zeolites, and can be utilized for the design of new cracking catalysts with tailored catalytic properties in F–T wax upgrading.

The main objective of the present work was the study of the effect of hydrothermal pretreatment of lignocellulosic biomass (beech wood) on the product yields and bio-oil composition produced from biomass flash pyrolysis as well as from the catalytic upgrading of the biomass pyrolysis vapours. The hydrothermal pretreatment of lignocellulosic biomass was performed at a severity factor (Ro) of 3.55 leading to ∼35 wt.% loss of solids, mainly due to solubilization and removal of hemicellulose. The production of sugars (mainly levoglucosan) was significantly increased by the use of the hydrothermally pretreated biomass instead of the untreated biomass in the non-catalytic flash pyrolysis experiments. On the other hand, the concentration of carboxylic acids, ketones and phenols was decreased in the bio-oil derived from the pretreated biomass. The catalysts tested in the upgrading of the biomass pyrolysis vapours were the strongly acidic zeolites H-ZSM-5 and silicalite (with very low number of acid sites) and the mildly acidic mesoporous aluminosilicate Al-MCM-41. The effect of catalysts on product yields and composition of bio-oil in the upgrading of pyrolysis vapours, was similar for both the pretreated and untreated biomass. The use of zeolite H-ZSM-5 decreased the total liquid yield (bio-oil) via decreasing the organic phase of bio-oil and increasing its water content, accompanied by increase of gases and moderate formation of coke on the catalyst. The zeolite silicalite and the Al-MCM-41 induced similar effects with those of H-ZSM-5 but to a less extent, except of the significantly higher coke that was deposited on Al-MCM-41. With regard to the composition of the bio-oil, all the catalysts and mostly the strongly acidic H-ZSM-5 zeolite reduced the oxygen content of the organic fraction, mainly by decreasing the concentration of acids, ketones and phenols in the untreated biomass pyrolysis oil or the concentration of sugars in the pretreated biomass pyrolysis oil. Aromatics and polycyclic aromatic hydrocarbons (PAHs) were significantly increased by the use of all catalysts, for both types of biomass feed. A substantial increase in the concentration of phenols was observed in the upgraded bio-oil derived by the hydrothermally pretreated biomass, using the less acidic silicalite and Al-MCM-41 catalysts.

The structural characteristics and the performance of vanadia catalysts (0.7–8 wt.% V) supported on mesoporous (MCM-41, HMS, MCF, SBA-15), microporous (silicalite) and non-porous (SiO 2 ) silicas in oxidative dehydrogenation of propane were investigated. The structure of vanadia species, the redox and the acidic properties of the catalysts were studied using in situ Raman spectroscopy, TPD- NH 3 and H 2 -TPR. The only vanadia species detected on the surface of HMS and MCM-41 for V loadings up to 8 wt.% were isolated monovanadates indicating high vanadia dispersion. Additional bands ascribed to V 2 O 5 nanoparticles were evidenced in the case of SBA-15 and MCF supported catalysts while these bands were the only ones identified on the surface of the catalysts supported on silicalite and non-porous silica. The catalysts supported on mesoporous HMS and MCM-41 materials showed the best performance achieving high propane conversions (35–40%) with relatively high propene selectivities (35–47%). Lower activity due to the lower degree of vanadia dispersion, caused by the partial destruction of the pore structure was observed for the SBA-15 and MCF supported catalysts. The degree of dispersion of the V species on the catalyst surface and not the pore size and structure of the mesoporous support or the acidity/reducibility characteristics mainly determine the catalytic activity towards propene production. In addition, it was shown that the pore structure and size of the mesoporous supports did not have any significant effect in the turnover rates (TOF values) of propane conversion (and propene formation at low propane conversion, below ca. 10%). However, the highest propene yield (up to 19%) and stable catalytic behavior was attained for catalysts supported on HMS mesoporous silica, and especially for those combining framework mesoporosity and textural porosity (voids between primary nanoparticles).

Well defined layered-double hydroxides (LDH: Mg3Al–NO3/CO3, Mg3Ga–NO3/CO3, Zn2Al–NO3/CO3 and Zn2Ga–NO3/CO3) were prepared using typical procedures starting from Mg(NO3)2·6H2O, Zn(NO3)2·6H2O, Al(NO3)3·9H2O and Ga(NO3)3·H2O. Rh-TPPTS complex was prepared by simple complexation of a Rh precursor [Rh(cod)Cl]2 and TPPTS (3,3′,3″-phosphanetriyl benzenesulfonic acid) in water. The heterogeneization of the Rh-TPPTS complex was performed by anionic exchange between Rh-complex and LDH supports. The catalysts’ structures and the chemical composition were confirmed by chemical analysis, XRD patterns, XP, FTIR and DRIFT spectroscopy. LDH-substituted Rh-TPPTS heterogeneous catalysts showed good catalytic activity in the 1,4-addition of arylboronic acid to 2-cyclohexen-1-one.

The ethylene epoxidation activity of Ag catalysts supported on non-porous SiO 2 , microporous silicalite zeolite and mesoporous MCM-41 and HMS silicates was investigated in the present study in comparison to conventional low surface area α-Al 2 O 3 based catalysts. The MCM-41 and HMS based catalysts exhibited similar ethylene conversion activity and ethylene oxide (EO) selectivity with the SiO 2 and α-Al 2 O 3 based catalysts at relatively lower temperatures (up to ∼230 °C), whereas their activity and selectivity decreased significantly at higher temperatures (≥300 °C). The silicalite based catalyst was highly active for a wide temperature range, similar to the SiO 2 and α-Al 2 O 3 based catalysts, but it was the less selective amongst all catalysts tested. High loadings of Ag particles (up to ca. 40 wt.%) with medium crystallites size (∼20–55 nm) could be achieved on the mesoporous materials resulting in very active epoxidation catalysts. The HMS-type silicate with the 3D network of wormhole-like framework mesopores (with average diameter of ∼3.5 nm), in combination with a high-textural (interparticle) porosity, appeared to be the most promising mesoporous support.

Aluminosilicate mesostructures (MSU-S BEA ) assembled from zeolite Beta (BEA) seeds exhibited relatively high hydrothermal stability and were significantly more active in the cracking of gas–oil compared to MCM-41 after severe steaming pretreatment. The MSU-S BEA mesoporous materials with wormhole framework structure and those having morphology of solid nanoparticles with high interparticle mesoporosity were more steam-stable and more active after severe steaming than those with hexagonal pore structure. Differences in acid sites strength between the MSU-S BEA materials and MCM-41 could not be probed by the complex reaction system of the large hydrocarbon molecules of gas–oil.