Theoretical investigation of solvent effects on the selective hydrogenation of furfural over Pt(111)

It was well known that solvent effect plays a very important role in the catalytic reaction. There are many theoretical studies on the solvent effect in homogeneous catalysis while there are few theoretical studies on the solvent effect in the heterogeneous catalytic reaction and there has been no work to investigate the solvent effect on furfural transformation in heterogeneous catalysis. In the present work, both the density functional calculations and the microkinetic analysis were performed to study the selective hydrogenation of furfural over Pt(111) in the presence of methanol as well as toluene and compared with that in the gas condition. The present results indicated that the methanol can enhance the adsorption strength of furfural and other oxygen-containing reaction species due to its relatively strong polarity properties and this can be a main reason for solvent-induced high activity and selectivity. Another reason is that reaction paths study showed that the presence of methanol solvent makes the dehydrogenation of furfural less thermochemical due to the fact that furfural is more stabilized than that of dehydrogenation species, and methanol also has an inhibition effect on the dehydrogenation of furfural in the kinetic aspect, and further energetic span theory proves highest activity and selectivity for hydrogenation in methanol solvent of vapor, methanol and toluene. Moreover, microkinetic model simulation demonstrated that the activity and selectivity of hydrogenation in methanol is both higher than that in vapor and toluene. The much higher activity in methanol is due to the stabilized adsorbed reactants in the surface, which leads to a higher surface coverage of furfural. It might be proposed based on the present work that a solvent with relatively strong polarity may be favorable for the high selective hydrogenation of furfural.     

Separation of Indium from Acid Sulfate-Containing Solutions by Ion Exchange with Impregnated Resins

Indium separation using ion exchange resins from acidic polymetallic and very diluted solutions are investigated. Since the selectivity of commercial ion exchange resins have proven to be too low for an effective separation from solutions with high content of other metals, Lewatit® TP 208 was impregnated with common extractants to enhance its properties. By resin impregnation with D2EHPA and Cyanex 272, not only the selective indium recovery was reached but also the resin capacity was increased approx. two times. The best loading and elution performance were shown by Cyanex 272-impregnated Lewatit® TP 208, increasing the indium purity in the eluate from 0.75 % to 85 %.     

Solvent Extraction of Copper from Sulfate–Chloride Solutions Using LIX 84-IC and LIX 860-IC

ABSTRACT

The effect of chloride ions on the copper extraction equilibria, the rate of extraction, copper/iron selectivity, and chloride extraction was studied for organic phases containing pure ketoxime (LIX 84-IC) and pure nonylaldoxime (LIX 860N-IC). In these systems, the used aqueous phase contained total chloride concentrations from 0 to 110 g/l. It was determined that the chloride ions in the aqueous solution had a large negative effect on the extraction equilibria for LIX 84-IC and a small effect for LIX 860N-IC. This deleterious effect is attributed to an increase in the hydrogen ion activity coefficient in the presence of chloride ions. The chloride accelerated the rate of copper extraction even though the reaction was fast in all the tested conditions. An increase in the temperature from 25°C to 35°C affected positively the extraction equilibria for LIX 84-IC.     

Improving efficiency of planar hybrid CH3NH3PbI3−xClx perovskite solar cells by isopropanol solvent treatment

Hybrid organic/inorganic perovskite planar heterojunction (PHJ) solar cells are becoming one of the most competitive emerging technologies. Here, the devices (ITO/PEDOT:PSS/CH₃NH₃PbI_3−xCl_x/PC₆₀BM/C₆₀/Al) are fabricated based on solution process. A power conversion efficiency (PCE) up to 13.1% was obtained after isopropanol (IPA) solvent treatment, which was 9% improvement than that of the original devices. Photocurrent hysteresis could be reduced to a certain extent by introducing IPA treatment. Solvent treatment can remove as-grown impurities like CH₃NH₃I and defects formed during the device fabrication. We also demonstrated the electrical and optical properties of perovskite films were improved. The addition of IPA-treated facilitates the formation of a relatively smooth PC₆₀BM films. This work provides a very simple but effective strategy to enhance the power conversion efficiency of perovskite solar cells.     

Influence of solvent characteristics in triaxial electrospun fiber formation

Triaxial electrospinning is a novel method for fabrication of multilayered nano and microsize fibers with desirable features for particular applications. Since the effect of solvent volatilities in each layer and relative polymer molecular weights on uniform encapsulation of the core polymer process is not well understood, we evaluated (i) the role of solvent volatilities, and (ii) molecular weights using cellulose acetate (CA, 30 kDa), polycaprolactone (PCL, 45 kDa and 80 kDa), mineral oil, and polyvinyl alcohol (PVA, 30 kDa and 100 kDa). Different solvent mixtures were evaluated based on the boiling points determined using a simulator. Inner mineral oil was selectively removed to form Hollow fibers. Analysis of chemical compositions using FT-IR and DSC revealed the presence of each component. 24-h viability of human umbilical vein endothelial cells indicated the formed fibers were not toxic. Scanning electron micrographs indicated the formation of triaxial structured fiber of outer hydrophobic PCL/CA/Hollow, PCL/PVA/Hollow and outer hydrophilic CA/PCL/Hollow fibers. Tensile tests (both wet and dry) revealed that PCL/CA/Hollow fibers had increased stiffness and load carrying capacity than CA/PCL/Hollow fibers. Successful fiber formation was dependent on ensuring that the outer shell formed first i.e., the relative solvent volatility of encapsulating core polymer to lower than that of the shell polymer.     

Determining Stability Constants Using the AKUFVE Technique

ABSTRACT

The AKUFVE techniques were developed by Rydberg and co-workers in the 1960s. The main aim was to be able to perform a series of liquid-liquid extraction data varying one or more parameters and at the same time achieve very pure phases. As such, this technique was later used for short-lived isotope studies in the SISAK system, but also as a standalone unit for a large number of thermodynamic studies of extraction systems both for fundamental understanding as well as more applied investigations. In this paper, the apparatus with modifications made over the decades is described. In addition, studies with stability constant determinations for the zirconium-water-acetylacetone system as well as lanthanide extraction using bromodecanoic acid are exemplified to demonstrate the potential use of the technique. The results shown clearly demonstrate the versatility and ability of the AKUFVE system.     

Experimental Investigation and Thermodynamic Modeling of Glycerin/Methanol/Organic Solvent Systems

Glycerin is an important by‐product in biodiesel production. To increase its quality to be suitable for use it in other operations, e.g., the pharmaceutical industry, it needs to be purified. Therefore, the purification of glycerin by liquid‐liquid extraction of methanol using different solvents was investigated. It was shown that, in terms of separation, petroleum ether was more effective than toluene and toluene was more effective than n‐butanol. In addition to the experimental investigations, the NRTL and UNIQUAC thermodynamic models were used to predict the compositions of ternary mixtures of glycerin + methanol + organic solvent in glycerin‐rich and organic solvent‐rich phases. The results showed the high accuracy of the presented models and their consistency with the measured data.     

The control of paracetamol particle size and surface morphology through crystallisation in a spray dryer

The parameters governing the crystallisation of paracetamol using various conventional techniques has been extensively studied, however the factors influencing the drug crystallisation using spray drying is not as well understood. The aim of this work was to investigate the crystallisation of an active pharmaceutical ingredient through evaporative crystallisation using a spray dryer to study the physicochemical properties of the drug and to use semi-empirical equations to gain insight into the morphology and particle size of the dried powder. Paracetamol solutions were spray dried at various inlet temperatures ranging from 60 °C to 120 °C and also from a series of inlet feed solvent compositions ranging from 50/50% v/v ethanol/water to 100% ethanol and solid-state characterisation was done. The size and morphology of the dried materials were altered with a change in spray drying parameters, with an increase in inlet temperature leading to an increase in particle Sauter mean diameter (from 3.0 to 4.4 µm) and a decrease in the particle size with an increase in ethanol concentration in the feed (from 4.6 to 4.4 µm) as a result of changes in particle density and atomised droplet size. The morphology of the dried particles consisted of agglomerates of individual crystallites bound together into larger semi-spherical agglomerates with a higher tendency for particles having crystalline ridges to form at higher ethanol concentrations of the feed.     

Particle size reduction of RDX by sequential application of solvent–antisolvent recrystallization and mechanical methods

ABSTRACT

Solvent–antisolvent recrystallization produced ~8 µm average size RDX particles (UF-RDX) that were subsequently subjected to mechanical methods of ultrasonication and ball-milling to find further achievable reduction in particle size. Long duration ultrasonication for 20 h and 300 rpm ball milling for 4 h of UF-RDX decreased its average particle size to ~2 µm. RDX produced by all the three processes (solvent–antisolvent recrystallization, ultrasonication and ball-milling) was similar to coarser RDX in structure and thermal decomposition behavior. However, UF-RDX produced by solvent–antisolvent recrystallization was significantly less impact sensitive than that produced by ball-milling and ultrasonication. The issues of residual solvent and the metal contamination during RDX processing were addressed by process parameter optimization. Solvent–antisolvent recrystallization and mechanical methods even when used sequentially could not bring average particle size of RDX to nano-scale.     

Concept for a Hydrometallurgical Processing of a Copper-Cobalt-Nickel Alloy Made from Manganese Nodules

The processing of manganese nodules for the production of raw materials has been a subject of research for many decades. The nodules contain many valuable metals like copper, cobalt and nickel. In recent years, the German Federal Institute for Geoscience and Natural Resources developed a process for the processing of manganese nodules based on a combined pyro- and a hydrometallurgical route. Clausthal University of Technology was assigned to develop the hydrometallurgical process for the treatment of a FeNiCuCo alloy. The developed process consists of pressurized sulfuric acid leaching with the suppression of hydrogen gas formation, precipitation and solvent extraction.