Corrosion of phosphate added high-chrome refractory materials in an entrained-flow gasifier

Durability of the refractory liner located in an entrained-flow gasifier is one of the main factors affecting the efficiency and cost of gasification process. This study investigates the corrosion mechanism of phosphate added high-chrome refractories in a commercial entrained-flow gasifier and the effect of phosphate additives on the improvement of service life combining thermodynamic simulation calculations. The microstructures, chemical compositions, and mineral phases of the corroded samples were analyzed by scanning electron microscopy (SEM and EDS) and X-ray powder diffraction (XRD). The results demonstrated that chemical corrosion mainly occurred at the slag-matrix interface and the junction of aggregates and matrix regions. Complex spinel solid solutions were formed at the slag-refractory interface. Phosphate additives decomposed into gaseous products (such as O₂, P₂O₃) and diffused into the interior of refractories at or close to the slag-refractory interface, not only causing an oxidizing environment but also increasing the phosphate contents in the interior of refractories. Phosphate additives in the infiltration layer occupied the gaps between crystal grains of (Cr, Al)₂O₃ solid solutions, reduced the infiltration of silicate phases, and absorbed Ca and Na in the slag, which subsequently increased the viscosity of the slag.     

磷矿山开采系统对黄柏河东支的影响研究

从黄柏河东支流域磷矿山绿色开发要求出发，基于地表水环境系统和矿业开采的耦合影响作用，开展了磷矿山开采对黄柏河东支的水环境的影响研究。通过定量和定性分析，在磷矿山开采过程中对黄柏河东支的各种影响因素中，矿井涌水(占比为43.19%)、尾渣淋溶水(占比为15.51%)、矿废石淋溶水(占比为14.64%)和生产废水(占比为10.84%)为磷矿山开采对黄柏河东支水环境的主要影响因素，尤其是矿井涌水携带的总污染物量大，影响占比接近50%。该研究影响分析为黄柏河东支水环境的治理提供有力指引支撑。     

Non-linear dissolution mechanisms of sodium calcium phosphate glasses as a function of pH in various aqueous media

Phosphate glasses for bioresorbable implants display dissolution rates that vary significantly with composition, however currently their mechanisms of dissolution are not well understood. Based on this systematic study we present new insights into these mechanisms. Two-stage dissolution was observed, with time dependence initially parabolic and later linear, and a two-stage model was developed to describe this behaviour. Dissolution was accelerated by lower Ca concentration in the glass, and lower pH in the dissolution medium. A new dissolution mechanism is proposed, involving an initial stage where diffusion-controlled formation of a conversion layer occurs. Once the conversion layer is stabilised, layer dissolution reactions become rate-limiting. Under this mechanism the transition time is sensitive to the nature of the conversion layer and solution conditions. These results reveal the dependence of P₂O₅–CaO–Na₂O glass dissolution on solution pH, and provide new insight into the dissolution mechanisms, particularly regarding the transition between the two dissolution stages.     

Co3xCu3-3x(PO4)2 microspheres,a novel non-precious metal catalyst with superior catalytic activity in hydrolysis of ammonia borane for hydrogen production

Development of robust and cheap catalyst for fast hydrogen evolution from ammonia borane (AB) aqueous solution is an interesting and important topic in the field of hydrogen energy. Herein, a novel non-precious Co_3xCu_3-3x(PO₄)₂ catalyst possessing high reactivity in AB hydrolysis has been developed for the first time. By tuning the molar ratio of Co and Cu, a series of Co_3xCu_3-3x(PO₄)₂ with different x were synthesized and the catalytic behavior in AB hydrolysis was examined. At the optimal x of 0.8, an ultrahigh turnover frequency of 72.6 min⁻¹ was achieved. Additionally, the synergistic effect between Cu₃(PO₄)₂ and Co₃(PO₄)₂ was experimentally confirmed, and the reaction kinetics of AB hydrolysis catalyzed by Co_2.4Cu_0.6(PO₄)₂ were investigated. This work provides a simple route and some new insights for the fabrication of a cheap P-containing catalyst with robust catalytic performance.     

Prediction of sediment,particulate nutrient and dissolved nutrient concentrations in a dry tropical river to provide input to a mechanistic coastal water quality model

A Generalised Additive Modelling (GAM) approach is applied to prediction of both particulate and dissolved nutrient concentrations in a wet-tropical river (the Fitzroy River, Queensland, Australia). In addition to covariant terms considered in previous work (i.e. flow, discounted flow and a rising-falling limb term), we considered several new potential covariates: meteorological and hydrological variables that are routinely monitored, available in near-real time, and were considered to have potential predictive power. Of the additional terms considered, only flows from three tributaries of the Fitzroy River (namely, the Nogoa, Comet and Isaac Rivers) were found to significantly improve the model. Inclusion of one or more of these additional flow terms greatly improved results for dissolved nitrogen and dissolved phosphorus concentrations, which were not otherwise amenable to prediction. In particular, the Nogoa sub-catchment, dominated by pasture for cattle, was found to be important in determining dissolved inorganic nitrogen and phosphorus concentrations reaching the river mouth. This insight may direct further research, including future refinement of processed-based catchment models. The GAMs described here are used to provide near real-time river boundary conditions for a complex coupled hydrodynamic and biogeochemical model of the Great Barrier Reef Lagoon, and can be coupled with a forecasting hydrological model to allow integrated forecasting simulations of the catchment to coast system.     

Protective properties of cataphoretic epoxy coating on aluminium alloy AA6060 modified with electrodeposited Ce-based coatings: Effect of post-treatment

Ce-based conversion coatings (CeCCs) are a promising alternative to toxic chromate coatings on the metal substrates. In this work the CeCCs were electrodeposited on aluminium alloy AA6060 from aqueous solution of Ce(NO₃)₃ at different potentials (−0.95 V, −1.2 V and −1.4 V). Effect of deposition potential and post-treatment in the phosphate solution on morphology and protective properties of CeCCs with top cataphoretic epoxy coating was studied. To assess the differences between the protective systems, originating from the different CeCCs pre-treatments, electrochemical impedance spectroscopy (EIS), polarization measurements, AFM and SEM/EDS analysis were used. The EIS study was undertaken to follow the evolution of corrosion behaviour of epoxy coating/CeCCs protective systems over prolonged time of exposure to the chloride environment (3 wt.% NaCl). Results suggest significantly improved corrosion stability of epoxy coating on AA6060 with as-deposited CeCCs sub-layers with respect to the same epoxy coatings with phosphate post-treated CeCCs. The far best protective properties, i.e., the greatest value of pore resistance and the lowest value of corrosion current density were provided by the epoxy coating/CeCC protective system with CeCC deposited at −1.2 V and without post-treatment.     

Importance of finding the proper ratio of alkaline earth oxide in a lithium-bismuthate-phosphate glass in order to enhance the tailoring of structural and electrical properties

Structural features of the glass family xLi₂O- yMgO (4.8 Bi₂O₃ 47.6 P₂O₅) obtained by melt quenching technique were studied taking into account the density, FTIR and UV–vis spectra and also the electrical response observed by impedance spectroscopy. In this work it becomes clarified how the alkaline earth oxides stabilize the glassy matrix and also, the fundamental importance of determining the optimal proportion in order to obtain a flabby easily polarizable matrix to enhance the electrical behavior due to a boosted cation mobility. It is evidenced that when the glass composition becomes complex it is needed to take into account a larger number of structural parameters to understand, to predict or to design the resulting physical properties.     

A mixed collector system for phosphate flotation

Flotation has been used in industry for more than a half century as the primary technique for upgrading phosphate. While the flotation of phosphate was inefficient when oleic acid was used alone as a collector, therefore a mixed collector of oleic acid (HOl), linoleic acid (LA) and linolenic acid (LNA) was employed to improve the recovery of phosphate flotation. The batch flotation results showed that the optimal composition of the mixed collector was 54 wt.% HOl, 36 wt.% LA and 10 wt.% LNA. Additionally, the effect of pH on the mixed collector application was studied while considering the surface tension, contact angle and micro-flotation. The results showed that the mixed collector should be used at a pH of 9.5. Above a pH of 9.5, the adsorption of fatty acids dimers on the apatite surface hindered phosphate flotation. The influence of the mixed collector assembly on apatite flotation was also investigated. It was demonstrated that due to its low critical micelle concentration, a sufficiently hydrophobic apatite surface could be generated at a collector concentration of 60 mg/L. In addition, zeta potential experiments suggested that collector adsorption was governed by chemisorption. FTIR and XPS spectra studies further indicated that the chemical reaction involved the carboxyl groups of fatty acids and Ca species at the apatite surface for each fatty acid in the mixed collector.     

海州式磷矿低温浮选的研究

对棉油皂脚复配改性获得低温浮选捕收剂OT-8，在矿浆温度3℃下，海州式磷矿的低温浮选获得了较好的选矿指标。     

Microbially mediated phosphine emission

There is still a lot of controversy in literature concerning the question whether a biochemical system exists enabling micro-organisms to reduce phosphate to phosphine gas. The search for so-called 'de novo synthesised' phosphine is complicated by the fact that soils, slurries, sludges, etc., which are often used as inocula, usually contain matrix bound phosphine (MBP). Matrix bound phosphine is a general term used to indicate non-gaseous reduced phosphorus compounds that are transformed into phosphine gas upon reaction with bases or acids. A study was carried out to compare the different digestion methods, used to transform matrix bound phosphine into phosphine gas. It was demonstrated that caustic and acidic digestion methods should be used to measure the matrix bound phosphine of the inoculum prior to inoculation to avoid false positive results concerning de novo synthesis. This is especially true if anthropogenically influenced inocula possibly containing minute steel or aluminium particles are used. The comparative study on different digestion methods also revealed that the fraction of phosphorus in mild steel, converted to phosphine during acid corrosion depended on the temperature. Following these preliminary studies, anaerobic growth experiments were set up using different inocula and media to study the emission of phosphine gas. Phosphine was detected in the headspace gases and its quantity and timeframe of emission depended on the medium composition, suggesting microbially mediated formation of the gas. The amount of phosphine emitted during the growth experiments never exceeded the bound phosphine present in inocula, prior to inoculation. Hence, de novo synthesis of phosphine from phosphate could not be demonstrated. Yet, microbially mediated conversion to phosphine of hitherto unknown reduced phosphorus compounds in the inoculum was evidenced.