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.

Phosphorus bearing minerals in iron ores and their possible benefication

Modern electron optical techniques together with X-ray and mineralogical examination have been used to study the occurrence and form of phosphorus bearing minerals in iron ores. Three ores have been studied - Bahariya and Aswan from Egypt and Frodingham ironstone from U.K. The iron in the Bahariya iron ore is mainly as hematite and goethite. The gangue minerals are halite, gypsum, barytes, quartz and calcite. Iron content is between 49.8 to 63.2% and phosphorus 0.14 to 0.34%. The phosphorus occurs as very fine particles of apatite which are distributed throughout the ore. Removal of the phosphorus would require very fine grinding followed by acid leaching. Aswan iron ore is an oolitic iron ore; the iron content between 41-57% and phosphorus content 0.1 to 2.9%. It is mainly hematitic with variable quantities of quartz, apatite and small amount of clay minerals. In the oolitic iron ore beds, apatite occurs in the hematite matrix; filling in the pores of the oolithic surfaces, or as matrix cementing the ooliths with the hematite grains. In sandstone claybeds the distribution of the apatite is mainly in the matrix. It is suggested that the liberation size for the apatite would be -80 m and flotation concentration could be applied for the removal of apatite from Aswan ore. Frodingham ironstone occurs in the lower Jurassic bed of the South Humberside area. The average iron content is 25% and the phosphorus is 0.32%. Seven mineral phases were identified by X-ray; calcite, quartz, chamosite, hematite, siderite, apatite, and chlorite. Apatite occurs as very fine grains in the hematite and chamosite ooliths; as matrix of fine grains intergrown with chamosite and calcite grains; and as anhedral and sub rounded grains in the ooliths (8-28 m). It is suggested that two processes are possible for the dephosphorisation; the Flox process or a reduction roast followed by fine grinding, magnetic separation, and acid leaching.

Phosphorus catalysis in the pyrolysis behaviour of biomass

Phosphorus is a key plant nutrient and as such, is incorporated into growing biomass in small amounts. This paper examines the influence of phosphorus, present in either acid (HPO) or salt ((NH)PO) form, on the pyrolysis behaviour of both Miscanthus × giganteus, and its cell wall components, cellulose, hemicellulose (xylan) and lignin (Organosolv). Pyrolysis-gas chromatography-mass spectrometry (PY-GC-MS) is used to examine the pyrolysis products during thermal degradation, and thermogravimetric analysis (TGA) is used to examine the distribution of char and volatiles. Phosphorus salts are seen to catalyse the pyrolysis and modify the yields of products, resulting in a large increase in char yield for all samples, but particularly for cellulose and Miscanthus. The thermal degradation processes of cellulose, xylan and Miscanthus samples occur in one step and the main pyrolysis step is shifted to lower temperature in the presence of phosphorus. A small impact of phosphorus was observed in the case of lignin char yields and the types of pyrolysis decomposition products produced. Levoglucosan is a major component produced in fast pyrolysis of cellulose. Furfural and levoglucosenone become more dominant products upon P-impregnation pointing to new rearrangement and dehydration routes. The P-catalysed xylan decomposition route leads to a much simpler mixture of products, which are dominated by furfural, 3-methyl-2-cyclopenten-1-one and one other unconfirmed product, possibly 3,4-dihydro-2-methoxy-2H-pyran or 4-hydroxy-5,6-dihydro-(2H)-pyran-2-one. Phosphorus-catalysed lignin decomposition also leads to a modified mixture of tar components and desaspidinol as well as other higher molecular weight component become more dominant relative to the methoxyphenyl phenols, dimethoxy phenols and triethoxy benzene. Comparison of the results for Miscanthus lead to the conclusion that the understanding of the fast pyrolysis of biomass can, for the most part, be gained through the study of the individual cell wall components, provided consideration is given to the presence of catalytic components such as phosphorus.

G-protein-coupled receptor solubilization and purification for biophysical analysis and functional studies, in the total absence of detergent

G-protein coupled receptors (GPCRs) constitute the largest class of membrane proteins and are a major drug target. A serious obstacle to studying GPCR structure/function characteristics is the requirement to extract the receptors from their native environment in the plasma membrane, coupled with the inherent instability of GPCRs in the detergents required for their solubilization. In the present study, we report the first solubilization and purification of a functional GPCR [human adenosine A2A receptor (A2AR)], in the total absence of detergent at any stage, by exploiting spontaneous encapsulation by styrene maleic acid (SMA) co-polymer direct from the membrane into a nanoscale SMA lipid particle (SMALP). Furthermore, the A2AR-SMALP, generated from yeast (Pichia pastoris) or mammalian cells, exhibited increased thermostability (∼5°C) compared with detergent [DDM (n-dodecyl-β-D-maltopyranoside)]-solubilized A2AR controls. The A2AR-SMALP was also stable when stored for prolonged periods at 4°C and was resistant to multiple freeze-thaw cycles, in marked contrast with the detergent-solubilized receptor. These properties establish the potential for using GPCR-SMALP in receptor-based drug discovery assays. Moreover, in contrast with nanodiscs stabilized by scaffold proteins, the non-proteinaceous nature of the SMA polymer allowed unobscured biophysical characterization of the embedded receptor. Consequently, CD spectroscopy was used to relate changes in secondary structure to loss of ligand binding ([³H]ZM241385) capability. SMALP-solubilization of GPCRs, retaining the annular lipid environment, will enable a wide range of therapeutic targets to be prepared in native-like state to aid drug discovery and understanding of GPCR molecular mechanisms.

Impact of potassium and phosphorus in biomass on the properties of fast Pyrolysis bio-oil

This study investigates fast pyrolysis bio-oils produced from alkali-metal-impregnated biomass (beech wood). The impregnation aim is to study the catalytic cracking of the pyrolysis vapors as a result of potassium or phosphorus. It is recognized that potassium and phosphorus in biomass can have a major impact on the thermal conversion processes. When biomass is pyrolyzed in the presence of alkali metal cations, catalytic cracking of the pyrolysis liquids occurs in the vapor phase, reducing the organic liquids produced and increasing yields of water, char, and gas, resulting in a bio-oil that has a lower calorific value and an increased chance of phase separation. Beech wood was impregnated with potassium or phosphorus (K impregnation and P impregnation, respectively) in the range of 0.10-2.00 wt %. Analytical pyrolysis-gas chromatography-mass spectrometry (Py-GC-MS) was used to examine the pyrolysis products during thermal degradation, and thermogravimetric analysis (TGA) was used to examine the distribution of char and volatiles. Both potassium and phosphorus are seen to catalyze the pyrolytic decomposition of biomass and modify the yields of products. 3-Furaldehyde and levoglucosenone become more dominant products upon P impregnation, pointing to rearrangement and dehydration routes during the pyrolysis process. Potassium has a significant influence on cellulose and hemicellulose decomposition, not just on the formation of levoglucosan but also other species, such as 2(5H)-furanone or hydroxymethyl-cyclopentene derivatives. Fast pyrolysis processing has also been undertaken using a laboratory-scale continuously fed bubbling fluidized-bed reactor with a nominal capacity of 1 kg h-1 at the reaction temperature of 525 °C. An increase in the viscosity of the bio-oil during the stability assessment tests was observed with an increasing percentage of impregnation for both additives. This is because bio-oil undergoes polymerization while placed in storage as a result of the inorganic content. The majority of inorganics are concentrated in the char, but small amounts are entrained in the pyrolysis vapors and, therefore, end up in the bio-oil.