The present study focuses on the direct chemical adsorption of CO2 onto alkaline hydrothermally activated oil shale fly ash (OSFA). The CO2 chemi­sorption experiments were conducted in a high-pressure reactor at a tem­perature of 150 °C and CO2 partial pressure of 100 bar during a 24-hour period. Original, activated and chemisorbed OSFA samples were charac­terized by means of X-ray diffraction (XRD), field-emission scanning electron microscopy (FESEM) coupled with energy-dispersive X-ray spectroscopy (EDS), specific surface area (BETN2) and high-resolution 29Si magic angle spin­ning nuclear magnetic resonance (MAS-NMR). The results indicated moderate weight increase (max 5 wt%) and according to XRD and MAS-NMR analysis tobermorites had reacted with CO2, leading to calcite forma­tion. The results also show that the alkaline hydrothermally activated OSFA has a potential to be used in industrial processes for direct chemical adsorption of CO2 from flue gases.

The present study focuses on the direct chemical adsorption of CO2 onto alkaline hydrothermally activated oil shale fly ash (OSFA). The CO2 chemisorption experiments were conducted in a high-pressure reactor at a temperature of 150 degrees C and CO2 partial pressure of 100 bar during a 24-hour period. Original, activated and chemisorbed OSFA samples were characterized by means of X-ray diffraction (XRD), field-emission scanning electron microscopy (FESEM) coupled with energy-dispersive X-ray spectroscopy (EDS), specific surface area (BETN2) and high-resolution Si-29 magic angle spinning nuclear magnetic resonance (MAS-NMR). The results indicated moderate weight increase (max 5 wt%) and according to XRD and MAS-NMR analysis tobermorites had reacted with CO2, leading to calcite formation. The results also show that the alkaline hydrothermally activated OSFA has a potential to be used in industrial processes for direct chemical adsorption of CO2 from flue gases.

In this study, a set of nitrogen-doped TiO2-based nanomaterials demonstrating photocatalytic activity was developed by combining the efforts of lattice doping and metal nanoparticle decoration and tested for photo-degradation of methylene blue dye by applying solar simulator irradiation. The surface potential shifts of these TiO2-based photocatalytic nanomaterials measured by Kelvin probe force microscope have been used to study the degree of electron generation of the photocatalysts after irradiation and were well correlated with the photocatalytic activity. The nitrogen-doped TiO2 nanowires decorated with Pt nanoparticles can induce obvious electron accumulation and result in a large shift of surface potential. The analysis shows a clear correlation between the surface potential shift and the photodegradation activity. Furthermore, a thorough comparative photocatalytic activity study combined with X-ray photoelectron spectroscopy analysis of the materials-doped with nitrogen under various conditions-reveals that the photocatalytic efficiency of the catalysts is maintained even if the lattice doping is leached e.g., by thermal treatments after doping.By monitoring the surface potential shifts of various TiO2-based photocatalysts by photo-assisted Kelvin probe force microscopy, we obtain a useful tool for developing novel materials with high photocatalytic activity.

The synthesis of 1-ethyl chloride in the gas-phase mixture of ethanol and hydrochloric acid over ZnCl2/Al2O3 catalysts was studied in a continuous reactor using both commercial and tailor-made supports. The catalytic materials were characterized by the means of structural (XPS, TEM, XRD, and BET) and catalytic activity (selectivity and conversion) measurements. The reaction parameters such as temperature, pressure, and feedstock flow rates were optimized for the conversion of ethanol to ethyl chloride. The new tailor-made highly porous Al2O3-based catalyst outperformed its commercial counterpart by exhibiting high conversion and selectivity (similar to 98%) at the temperature of 325 degrees C. Long-term stability tests (similar to 240 h) confirmed the excellent durability of the tailor-made alumina catalysts. The process demonstrated here poses an efficient and economic "green" large-scale on-site synthesis of this industrially important reactant in industry, where bioethanol is produced and 1-ethyl chloride is necessary, e.g., for ethylation of cellulose and synthetic polymer products. On-site in situ production of ethyl chloride avoids the problems associated with the transportation and storage of toxic and flammable 1-ethyl chloride.

In this paper, both sulfite and sulfate (kraft) celluloses from Nordic pulp mills were used as raw materials in the catalytic one-pot synthesis of green platform chemicals, levulinic and formic acids, respectively. The catalyst of choice was a macro-porous, cationic ion-exchange resin, Amberlyst 70. The optimal reaction conditions were determined and the influence of various gas atmospheres was investigated. The maximum yields of 53% formic acid and 57% of levulinic acid were separately obtained in a straight-forward conversion system only containing cellulose, water and the heterogeneous catalyst. The concept introduces a one-pot procedure providing a feasible route to green platform chemicals obtained via conversion of coniferous soft wood pulp to levulinic and formic acids, respectively.

Mesostructured siliceous SBA-15 was synthesized via direct hydrothermal crystallization from acidic solution of poly-(ethylene glycol)-block-poly(propylene glycol)-block poly(ethylene glycol)-copolymer and tetraethyl orthosilicate. The amorphous surface of the calcined Si-SBA-15 was modified with 20wt.% of TiO2 by chemical grafting method using titanium isopropoxide as the titanium source in ethanol solution. Various metal nanoparticles Au, Au–M (M=Co, Ni, Cu and Zn) were supported on TiO2/SBA-15 by deposition–precipitation method (DP) using urea as the precipitating agent. The structural features of the synthesized materials were characterized by various physico-chemical techniques such as X-ray diffraction, nitrogen physisorption (BET), XPS and HR-TEM. BET results of Si-SBA-15 revealed the formation of mesoporous structure with an average pore size of 5.9nm, pore volume of 1.12cm3/g and the specific surface area of 846m2/g. HR-TEM results demonstrated that metal nanoparticles were highly dispersed over TiO2/SBA-15 and long range ordering of hexagonal mesopores of Si-SBA-15 was well retained after loading of 20wt.% TiO2 and 3wt.% of bimetallic nanoparticles. The catalytic performances of the prepared catalysts were studied on dehydroisomerization of α-pinene under gas phase conditions using hydrogen atmosphere. The stability and catalytic activity of Au–M–TiO2/SBA-15 (DP) catalysts upon conversion of α-pinene into p-cymene was explored in comparison with the catalysts prepared by conventional method. AuNi–TiO2/SBA-15 catalysts prepared via DP method were found to be stable upon longer reaction time as well as superior in terms of conversion and selective towards the formation of p-cymene.

The aim of this work was to study the how various heterogeneous catalysts perform upon lignosulfonate decomposition reactions. The main target of the study was to obtain extractable phenolic compounds as potential renewable chemicals for the production of fuel components and chemicals. The nature of the heterogeneous catalyst was found to have a great impact on the obtained product yields and the composition of the product mixture. Initially, a nickel–tungsten on alumina (NiW/Al2O3) reference catalyst was applied upon screening the influence of catalyst particle size and various reaction parameters. Significantly increasing product yields with decreasing catalyst particle size indicated that the lignosulfonate transformation takes place on the external catalyst surface due to large macromolecular structure of the feedstock. The contact time (space time velocity) and catalyst particle size were the most important factors influencing the selectivity profiles towards various products as well as the yields observed. The highest conversion to phenolics was obtained over in-house-prepared NiO/Al2O3 and NiMo/Al2O3 catalysts with various NiO and MoO3 loadings.

The effective dispersion of active metal species on mesoporous Si-SBA-15 is acquired by means of deposition-precipitation method. In order to achieve this, the surface of Si-SBA-15 was first modif ...

Nordic sulphite and sulphate (Kraft) cellulose originating from Nordic pulp mills were used as raw materials in the catalytic synthesis of green platform chemicals, levulinic and formic acids, respectively. The catalyst of choice used in this study was a macro-porous, cationic ion-exchange resin Amberlyst 70 for which the optimal reaction conditions leading to best yields were determined. For this system, maximum yields of 53 mol-% and 57 mol-% were obtained for formic and levulinic acid, respectively. The reaction network of the various chemical species involved was investigated and a simple mechanistic approach involving first order reaction kinetics was developed. The prototype model was able to describe the behaviour of the system in a satisfactory manner.

Environmentally friendly product, calcium-silica-aluminum hydrate, was synthesized from oil shale fly ash, which is rendered so far partly as an industrial waste. Reaction conditions were: temperature 130 and 160 degrees C, NaOH concentrations 1, 3, 5 and 8 M and synthesis time 24 h. Optimal conditions were found to be 5 M at 130 degrees C at given parameter range. Original and activated ash samples were characterized by XRD, XRF, SEM, EFTEM, Si-29 MAS-NMR, BET and TGA. Semi-quantitative XRD and MAS-NMR showed that mainly tobermorites and katoite are formed during alkaline hydrothermal treatment. Physical adsorption of CO2 on the surface of the original and activated ash samples was measured with thermo-gravimetric analysis. TGA showed that the physical adsorption of CO2 on the oil shale fly ash sample increases from 0.06 to 3-4 mass% after alkaline hydrothermal activation with NaOH. The activated product has a potential to be used in industrial processes for physical adsorption of CO2 emissions. (C) 2011 Elsevier B.V. All rights reserved.

We report the synthesis of N-doped TiO(2) nanofibers and high photocatalytic efficiency in generating hydrogen from ethanol-water mixtures under UV-A and UV-B irradiation. Titanate nanofibers synthesized by hydrothermal method are annealed in air and/or ammonia to achieve N-doped anatase fibers. Depending on the synthesis route, either interstitial N atoms or new N-Ti bonds appear in the lattice, resulting in slight lattice expansion as shown by XPS and HR-TEM analysis, respectively. These nanofibers were then used as support for Pd and Pt nanoparticles deposited with wet impregnation followed by calcination and reduction. In the hydrogen generation tests, the N-doped samples were clearly outperforming their undoped counterparts, showing remarkable efficiency not only under UV-B but also with UV-A illumination. When 100 mg of catalyst (N-doped TiO(2) nanofiber decorated with Pt nanoparticles) was applied to 1 L of water-ethanol mixture, the H(2) evolution rates were as high as 700 μmol/h (UV-A) and 2250 μmol/h (UV-B) corresponding to photo energy conversion percentages of ∼3.6 and ∼12.3%, respectively.

Background/purpose: Near-infrared (NIR) spectroscopy and skin impedance (IMP) measurements are useful techniques for objective diagnostics of various skin diseases. Here, we present a combined probe head for simultaneous, time-saving NIR spectroscopy and skin impedance measurements. The probe also ensures that both measurements are performed under equal conditions and at the same skin location.Methods: Finite element method simulations were performed for evaluation of the impedance. In vivo skin measurements were performed and combined NIR and impedance spectra were analysed by means of multivariate methods with respect to body location, age and gender. The classification rate was determined by a planar discriminant analysis. Reproducibility was investigated by calculation of scatter values and statistical significance between overlapping groups was assessed by the calculation of intra-model distances, q.Results: The novel probe yielded rapid reproducible results and was easy to manage. Significant differences between skin locations and to a lesser extent age groups and gender were demonstrated.Conclusion: With the novel probe, statistically significant differences between overlapping classes in score plots can be confirmed by calculating intra-model distances. The influence of molecular differences in the skin at different body locations is larger than the influence of gender or age and therefore relevant reference measurements are discussed.

Highly active and selective bimetallic catalysts supported on transition metal oxides for the oxidation of α-pinene using molecular oxygen

Formamide (FA), N-methylformamide (NMF), and dimethylformamide (DMF), were evaluated as solvents for coulometric Karl Fischer (KF) reagents in combination with several amine bases. Except for the effect of the iodine species (iodine or triiodide), the pH of the reagent and the position of the sulfur dioxide/hydrogen sulfite equilibrium were found to be the main factors explaining the large difference in the observed reaction rates between water and the KF reagent in these solvents. Acid–base titrations showed that hydrogen sulfite is the main sulfur reactant in these media. The results will be of great importance in finding suitable combinations of base and solvent with respect to stoichiometry, side reactions caused by active carbonyl compounds, and reagent stability.

A non-alcoholic coulometric reagent based on N-methylformamide (NMF) was shown to eliminate the severe interference effect caused by the alcohol component of the conventional Karl Fischer (KF) reagent on the battery electrolyte lithium bis(oxalato)borate (LiBOB). For sample amounts up to 240 μg of water, the stoichiometry of the KF reaction deviated only slightly from the ideal 1:1 ratio for the best reagent composition. Both solid and dissolved (in acetonitrile, tetrahydrofuran (THF), and ethylene carbonate/ethyl methyl carbonate) LiBOB were titrated successfully using a Metrohm 756 KF Coulometer with a diaphragm cell. The detection limit was estimated to be 0.5–1 μg of water using 100 ml of reagent in this system.

Factors influencing the accuracy and precision for diaphragm-free Karl Fischer coulometric determinations of low mug-amounts of water have been studied using the Metrohm 756 (pulsed current) coulometer and eight different types of commercial coulometric reagents and some modifications of these. As in the case of diaphragm-free coulometric titration of large amounts of water, the positive errors, due to the formation of oxidizable reduction products (of sulfur dioxide) in the cathode reaction (besides hydrogen), were found to be minimized by the use of highest possible pulse current (in the range 100-400mA) in combination with the fastest possible titration rate. Most accurate (102-103%) and precise results (typical relative standard deviation 1.8%) were obtained for reagents containing very large concentrations of imidazole in combination with the presence of modifiers like hexanol, chloroform and propylene glycol (i.e. the HYDRA-POINT reagents). Similar results were obtained when this type of reagent was mixed 60/40 with xylene according to the ASTM recommendation for water determinations in petroleum products like crude and lubricating oils. Addition of decanol to this type of reagent mixture was found to reduce the influence from the oxidative reduction products significantly. A reduction of the error from 3.6% relative to 1.6% was achieved by addition of 9% (v/v) of decanol to a 60/40 reagent mixture of HYDRA-POINT Coulometric Gen (containing hexanol as modifier) and xylene. For larger concentrations of decanol the pulse current had to be lowered to 100mA and this might explain why no further improvement was observed. An additional attempt to minimize the interference by lowering the concentration of sulfur dioxide in the reagents gave no significant effect. However, by means of a home-built computer-controlled coulometric instrumentation based on continuous instead of pulsed current (including a large cathodic current density) it was possible to achieve recovery rates close to 100% for the best reagents investigated. The reason for this improvement is discussed.

The efficiency of azeotropic techniques for trace determination of water in oils has recently been questioned by the National Institute of Standards and Technology (NIST), on the basis of measurements of the residual water found after the extraction step. The results were obtained by volumetric Karl Fischer (KF) titration in a medium containing a large excess of chloroform (greater than or equal to65%), a proposed prerequisite to ensure complete release of water from the oil matrix. In this work, the extent of this residual water was studied by means of a direct zero-current potentiometric technique using a KF medium containing more than 80% chloroform, which is well above the concentration recommended by NIST. A procedure is described that makes it possible to correct the results for dilution errors as well as for chemical interference effects caused by the oil matrix. The corrected values were found to be in the range of 0.6-1.5 ppm, which should be compared with the 12-34 ppm (uncorrected values) reported by NIST for the same oils. From this, it is concluded that the volumetric KF method used by NIST gives results that are much too high.