Efficient Self-Condensation of Cyclohexanone into Biojet Fuel Precursors over Sulfonic Acid-Modified Silicas: Insights on the Effect of Pore Size and Structure.

Mesoporous silica materials with different pore structures and sizes have been used for supporting aryl sulfonic acid catalytic sites via a postsynthetic grafting approach. The synthesized materials have been evaluated in the solventless acid-catalyzed self-condensation of cyclohexanone (CHO) to obtain the corresponding C12 adducts. These compounds display great potential as oxygenated fuel precursors as they can be transformed into jet fuel range alkanes in a subsequent hydrodeoxygenation process. In this work, the synthesized catalysts have displayed high selectivity values toward monocondensed compounds (>95%), thus limiting the formation of undesired heavier condensation products, together with CHO conversion values in the range 20-40% after 2 h of reaction at 100 °C. The structural and textural properties of the supports play an important role in the catalytic performance. Moreover, the activity per acid center is correlated with the textural properties of the supports, indicating that a lower surface density of the anchored aryl sulfonic groups affords an improvement in their specific activity. Finally, the benefit of using supports with large pore sizes and open structures, which limit the fouling of the catalysts by organic deposits, is demonstrated in a stability and reusability test.

Xylose isomerization with zeolites in a two-step alcohol-water process.

Isomerization of xylose to xylulose was efficiently catalyzed by large-pore zeolites in a two-step methanol-water process that enhanced the product yield significantly. The reaction pathway involves xylose isomerization to xylulose, which, in part, subsequently reacts with methanol to form methyl xyluloside (step 1) followed by hydrolysis after water addition to form additional xylulose (step 2). NMR spectroscopy studies performed with (13) C-labeled xylose confirmed the proposed reaction pathway. The most active catalyst examined was zeolite Y, which proved more active than zeolite beta, ZSM-5, and mordenite. The yield of xylulose obtained over H-USY (Si/Al=6) after 1 h of reaction at 100 °C was 39%. After water hydrolysis in the second reaction step, the yield increased to 47%. Results obtained from pyridine adsorption studies confirm that H-USY (6) is a catalyst that combines Brønsted and Lewis acid sites, and isomerizes xylose in alcohol media to form xylulose at low temperature. The applied zeolites are commercially available; do not contain any auxiliary tetravalent metals, for example, tin, titanium, or zirconium; isomerize xylose efficiently; are easy to regenerate; and are prone to recycling.

Conformal sulfated zirconia monolayer catalysts for the one-pot synthesis of ethyl levulinate from glucose.

Here we describe a simple route to creating conformal sulphated zirconia monolayers throughout an SBA-15 architecture that confers efficient acid-catalysed one-pot conversion of glucose to ethyl levulinate.

Efficient isomerization of glucose to fructose over zeolites in consecutive reactions in alcohol and aqueous media.

Isomerization reactions of glucose were catalyzed by different types of commercial zeolites in methanol and water in two reaction steps. The most active catalyst was zeolite Y, which was found to be more active than the zeolites beta, ZSM-5, and mordenite. The novel reaction pathway involves glucose isomerization to fructose and subsequent reaction with methanol to form methyl fructoside (step 1), followed by hydrolysis to re-form fructose after water addition (step 2). NMR analysis with (13)C-labeled sugars confirmed this reaction pathway. Conversion of glucose for 1 h at 120 °C with H-USY (Si/Al = 6) gave a remarkable 55% yield of fructose after the second reaction step. A main advantage of applying alcohol media and a catalyst that combines Brønsted and Lewis acid sites is that glucose is isomerized to fructose at low temperatures, while direct conversion to industrially important chemicals like alkyl levulinates is viable at higher temperatures.

Etherification of biodiesel-derived glycerol with ethanol for fuel formulation over sulfonic modified catalysts.

The present study is focused on the etherification of biodiesel-derived glycerol with anhydrous ethanol over arenesulfonic acid-functionalized mesostructured silicas to produce ethyl ethers of glycerol that can be used as gasoline or diesel fuel biocomponents. Within the studied range, the best conditions to maximize glycerol conversion and yield towards ethyl-glycerols are: T=200 °C, ethanol/glycerol molar ratio=15/1, and catalyst loading=19 wt%. Under these reaction conditions, 74% glycerol conversion and 42% yield to ethyl ethers have been achieved after 4 h of reaction but with a significant presence of glycerol by-products. In contrast, lower reaction temperatures (T=160 °C) and moderate catalyst loading (14 wt%) in presence of a high ethanol concentration (ethanol/glycerol molar ratio=15/1) are necessary to avoid the formation of glycerol by-products and maximize ethyl-glycerols selectivity. Interestingly, a close catalytic performance to that achieved using high purity glycerol has been obtained with low-grade water-containing glycerol.

Low-grade oils and fats: effect of several impurities on biodiesel production over sulfonic acid heterogeneous catalysts.

Different lipidic wastes and low-grade oils and fats have been characterized and evaluated as feedstocks for the acid-catalyzed production of FAME. The characterization of these materials has revealed significant contents of free fatty acids, Na, K, Ca, Mg, P, unsaponifiable matter and humidity. Arenesulfonic acid-functionalized SBA-15 silica catalyst has provided yields to FAME close to 80% in the simultaneous esterification-transesterification of the different feedstocks, regardless of their nature and properties, using methanol under the following reaction conditions: 160 °C, 2 h, methanol to oil molar ratio of 30, 8 wt.% catalyst loading, and 2000 rpm stirring rate. Nevertheless, reutilization of the catalyst is compromised by high levels of impurities, especially because of deactivation by strong interaction of unsaponifiable matter with the catalytic sites. The conditioning of these materials by aqueous washing in the presence of cationic-exchange resin Amberlyst-15, followed by a drying step, resulted in a lower deactivation of the catalyst.

Heterogeneous photo-Fenton treatment for the reduction of pharmaceutical contamination in Madrid rivers and ecotoxicological evaluation by a miniaturized fern spores bioassay.

Fifty-six pharmaceuticals of various chemical groups, such as anti-inflammatory, antibacterial and cardiovascular drugs, were detected in four selected river waters receiving sewage effluents in the Community of Madrid (Spain). A promising approach for the degradation of those residues is the application of a photo-Fenton treatment. Several new bioassays using fern spores were employed for the evaluation of acute and chronic toxicity based on mitochondrial activity, DNA and chlorophyll quantifications of as-received river water and photo-Fenton-treated samples. photo-Fenton treatment provided a high degree of total organic carbon mineralization with up to 70% reduction for river water samples. In addition, the elimination of most of the studied pharmaceutical compounds was confirmed. A few compounds, however (salicylic acid, ofloxacin, caffeine, cotinine and nicotine), seemed more resistant, with after-treatment concentrations between 4 and 44ngL(-1). Nicotine showed the most refractory behaviour with concentrations ranging from 29 to 224ngL(-1) for treated samples. Photo-Fenton treatment yielded a significant decrease in acute and chronic toxicity, even though some residual toxicity remained after treatment. This fact seemed to be related to the presence of toxicants in the water matrix, probably of inorganic nature, rather than the toxic effect of the studied pharmaceutical compounds, as revealed by the effective removal of these compounds and high TOC mineralization of photo-Fenton treatments.

Mechanism of CIT-6 and VPI-8 crystallization from zincosilicate gels.

The crystallisation of CIT-6, a large-pore zincosilicate with the framework topology of zeolite Beta and synthesised from clear hydrogels that contain, tetraethylammonium (TEA+), Li+ and Zn2+ cations, proceeds initially through the formation of an amorphous solid that incorporates all the initial Zn species. Nucleation of the *BEA phase is effected by reorganisation of the amorphous phase, whereas crystal growth involves the incorporation of soluble species also. A highly crystalline CIT-6 material is obtained after 164 h of synthesis at 140 degrees C. Scanning electron microscopy (SEM) shows that this sample exhibits two different types of crystals: well-defined pseudo-cubic crystals and rounded crystals. The latter has a broad crystal-size distribution. If crystallisation is continued with longer synthesis times, the VPI-8 crystalline phase appears, and a new population of needle-shaped crystals is detected in the SEM images. This new crystalline phase is nucleated on the surface of the rounded CIT-6 crystals, which disappear as the crystallisation progresses, while no changes are observed in the population of pseudo-cubic CIT-6 crystals. At higher crystallisation temperatures these phase transformations are accelerated, and the formation of VPI-8 is favoured over that of CIT-6.