Enhanced hydrogen desorption kinetics and cycle durability of amorphous TiMgVNi3-doped MgH2

MgH₂ is considered as a promising hydrogen storage material for on-board applications. In order to improve hydrogen storage properties of MgH₂, the amorphous TiMgVNi₃-doped MgH₂ is prepared by ball milling under hydrogen atmosphere. It is found that the catalytic (Ti,V)H₂ and Mg₂NiH₄ nanoparticles are in situ formed after activation. As a result, the amorphous TiMgVNi₃-doped MgH₂ exhibits enhanced dehydrogenation kinetics (the activation energy for hydrogen desorption is 94.4 kJ mol^?1 H₂) and superior cycle durability (the capacity retention rate is up to 92% after 50 cycles). These results demonstrate that the in situ formation of highly dispersed catalytic nanoparticles from an amorphous phase is an effective pathway to enhance hydrogen storage properties of MgH₂.     

Molecular dynamics study on growth of carbon dioxide and methane hydrate from a seed crystal

In the current work, molecular dynamics simulation is employed to understand the intrinsic growth of carbon dioxide and methane hydrate starting from a seed crystal of methane and carbon dioxide respectively. This comparison was carried out because it has relevance to the recovery of methane gas from natural gas hydrate reservoirs by simultaneously sequestering a greenhouse gas like CO₂. The seed crystal of carbon dioxide and methane hydrate was allowed to grow from a super-saturated mixture of carbon dioxide or methane molecules in water respectively. Two different concentrations (1:6 and 1:8.5) of CO₂/CH₄ molecules per water molecule were chosen based on gas–water composition in hydrate phase. The molecular level growth as a function of time was investigated by all atomistic molecular dynamics simulation under suitable temperature and pressure range which was well above the hydrate stability zone to ensure significantly faster growth kinetics. The concentration of CO₂ molecules in water played a significant role in growth kinetics, and it was observed that maximizing the CO₂ concentration in the aqueous phase may not result in faster growth of CO₂ hydrate. On the contrary, methane hydrate growth was independent of methane molecule concentration in the aqueous phase. We have validated our results by performing experimental work on carbon dioxide hydrate where it was seen that under conditions appropriate for liquid CO₂, the growth for carbon dioxide hydrate was very slow in the beginning.     

Chitosan-catalyzed n-butyraldehyde self-condensation reaction mechanism and kinetics

The chitosan was found to possess an excellent catalytic performance in n-butyraldehyde selfcondensation to 2E2H. Under suitable conditions, the conversion of n-butyraldehyde, the yield and selectivity of 2E2H separately attained 96.0%, 86.0% and 89.6%. The chitosan catalyst could be recovered and used for 5 times without a significant deactivation after being treated with ammonium hydroxide. In order to elucidate the reaction mechanism, the adsorption and desorption of n-butyraldehyde on the surface of chitosan were studied using in situ FT-IR spectroscopy analysis. The result showed that n-butyraldehyde interacts with-NH₂ group of chitosan to form an intermediate species with an enamine structure. Then the reaction process of n-butyraldehyde self-condensation was monitored by React-IR technique and it was found that n-butyraldehyde self-condensation to 2-ethyl-3-hydroxyhexanal followed by a dehydration reaction to 2-ethyl-2-hexenal. On this basis, chitosan-catalyzed n-butyraldehyde self-condensation reaction mechanism was speculated and its reaction kinetics was investigated. The self-condensation reaction follows auto-catalytic reaction characteristics and then the corresponding kinetic model was established.     

Adsorption of anionic dye on eco-friendly synthesised reduced graphene oxide anchored with lanthanum aluminate: Isotherms,kinetics and statistical error analysis

In the present study we made an effort to deploy eco-friendly synthesized reduced graphene oxide/Lanthanum Alluminate nanocomposites (RGO-LaAlO₃) and Lanthanum Alluminate (LaAlO₃) as adsorbents to remove dye from the synthetic media. XRD, SEM, BET surface area and EDX have been used to characterize the above-mentioned adsorbents. The impacts of different factors like adsorbent dosage, the concentration of adsorbate and PH on adsorption were studied. The best fit linear and nonlinear equations for the adsorption isotherms and kinetic models had been examined. The sum of the normalized errors and the coefficient of determination were used to determine the best fit model. The experimental data were more aptly fitted for nonlinear forms of isotherms and kinetic equations. Pseudo-second-order and Freundlich isotherm model fits the equilibrium data satisfactorily. Methyl orange (MO) has been used as model dye pollutant and maximum adsorption capacity was found to be 469.7 and 702.2 mg g^?1 for LaAlO₃ and RGO-LaAlO₃, respectively.     

Reaction behavior of quartz in gibbsite-boehmite bauxite in Bayer digestion and its effect on caustic consumption and alumina recovery

A high content of quartz is usually present in Australian gibbsite-boehmite bauxite. The reaction between quartz and sodium aluminate solution at high temperatures in the Bayer process can lead to loss of alumina and sodium oxide. Therefore, to improve alumina recovery, the reaction of quartz needs to be avoided. The digestion behavior of Australian gibbsite-boehmite bauxite and pure quartz in the Bayer process at 230–250 °C was systematically studied in this paper. The mineral composition and morphology of the reaction products were characterized and the kinetics of the quartz dissolution process was studied in detail. It was shown that boehmite in gibbsite-boehmite bauxite can be completely digested at high temperature (250 °C) with a short digestion time (5 min). A short digestion time results in a low reaction rate of quartz in bauxite, and is ideal for alumina recovery at high temperatures. The quartz reaction rate rapidly increases with longer digestion times. The apparent activation energy of the dissolution of quartz in bauxite in the caustic solution is 151.9 kJ mol^?1, and the rate-controlling step of this reaction process is the interfacial chemical reaction. By controlling the particle size of bauxite, the digestion temperature, and the digestion time, the reaction rate of quartz in bauxite can be inhibited, which is beneficial for improving alumina recovery and reducing caustic consumption. Therefore, based on the above theoretical research, a process for digesting gibbsite-boehmite bauxite is proposed using high digestion temperature (250 °C), short digestion time (5 min) and large mineral size. An economic benefit of about US$101.9 million for a refinery with the annual output of 2 million tons of alumina can be created by the proposed process.     

Thermal degradation of corn starch based biodegradable plastic plates and determination of kinetic parameters by isoconversional methods using thermogravimetric analyzer

Oil shortage and awareness of environment pollution leads to the extensive use of biodegradable starch-based materials against synthetic plastics. The accumulated wastes of these plastics takes more time for natural recycling and the process is complex. Therefore the best option of recycling would be to convert these polymers into a source of energy by pyrolysis. So to understand the pyrolytic behaviour, kinetics of such waste plastics is studied by using thermogravimetric analysis at different heating rates of 10 °C, 20 °C, 40 °C, 60 °C, 80 °C and 100 °C in nitrogen atmosphere followed by characterization of the pyrolysis products. The kinetic parameters are obtained for two major stages of decomposition in two different temperature ranges 250–620 °C and 620–855 °C by iso-conversional methods such as Friedman, Coats-Redfern, FWO and Kissinger methods. The regression coefficient data (>0.9) of kinetic plots obtained for different methods best fits to the kinetic equation. Empirical formula of the compound is determined by ultimate analysis is CH_2.214S_0.0018O_0.6910. Proximate analysis gives the idea of volatile component which is74.33%. The range of average value of activation energy is 120.7013 kJ/mol to 140.7707 kJ/mol for the biodegradable plastic plate with different conversion (0.1–0.6) and (0.1–0.3) respectively at two different temperatures. The pyrolysis products obtained using a semi-batch reactor are characterized to know their composition and other properties.     

Experimental investigation on gasification characteristics of polycarbonate (PC) microplastics in supercritical water

In order to solve the problem of marine microplastics and realize the harmless resource utilization of plastics, the gasification experiments of polycarbonate (PC) microplastics were carried out in supercritical water and a novel seawater gasification of microplastic experiment was investigated. In this paper, the effects of different operating conditions (temperature, time, feedstock concentration, pressure) on gasification performance were discussed. The gasification kinetic of microplastics in supercritical water was calculated. The experimental results showed that the increase in gasification temperature and time enhanced the cracking reaction and free radical reaction of the microplastics to increase the gasification efficiency, while the reduction in feedstock concentration improved the gasification efficiency by increasing the gasification level of unit feedstock. The change in pressure had no significant effect on gasification due to the fact that the properties of the supercritical water were not significantly changed. It was found that the valuable results that all alkali metal salts in seawater promote hydrogen conversion, while in terms of carbon conversion, only KCl, CaCl₂, NaHCO₃ and seawater had a significant catalytic effect on the gasification. Seawater gasification of microplastics was a potential resource utilization method. Finally, it was considered that the PC plastic gasification conformed to the random nucleation and subsequent growth model (n = 3), and the reaction activation energy was 230.45 kJ/mol, which was smaller than that of traditional pyrolysis.     

Catalytic dehydrogenation of formic acid-triethanolamine mixture using copper nanoparticles

In a bid to complement the lost reserves from fossils, recent advances in research are tailored towards producing hydrogen as an alternative source of fuel which is aimed at fostering a globally sustainable and reliable energy-economy. In this work, hydrogen was produced from formic acid (FA) using a new technology that involves the use of copper nanoparticles (CuNPs) supported on triethanolamine. The CuNP-catalysts of variant concentrations (i.e. 0.6–1.2 M) were synthesized using the conventional chemical deposition method. Also, a novel approach that bothers on the application of the Differential Method of Analysis (DMA) was used in determining the kinetic parameters for the FA-dehydrogenation. Based on the results, the volume of H₂ produced varied with time, pH, concentration and catalyst-size. At 6 h, the 1 M CuNPs gave the highest volume (815 mL) of hydrogen with corresponding pH, particle size and approximate conversion of 3.19, 1.5 nm and 100% respectively, whereas, over extended periods i.e. over 6 h, the approximate volume-conversions of FA increased insignificantly for all catalysts. According to the investigation, the optimum CuNP-catalyst concentration required to produce 815 mL H₂ in 6 h is 1 M. The decomposition was a first-order-type with a rate constant (k-value) of 1.0041 s⁻¹.     

Lab-Scale Microreactor Plant for the Study of Methylations with Liquid Chloromethane

Chloromethane is an important reagent for methylations in the process industry. However, as a gas suspected of causing cancer, it is rarely used at laboratory scale. Therefore, a setup is presented here for studies in a laboratory under safe and reproducible conditions. The use of a microreactor guarantees high heat transfer rates and a low holdup of the reagent. As a proof-of-concept, the reaction of chloromethane with the secondary amine morpholine in aqueous solution is investigated. By applying elevated pressures, a liquid-liquid system with enhanced solubility of chloromethane in the aqueous phase is accessible.     

Materialwissenschaftliche Analyse des Abbindeverhaltens von Holzklebstoffen am Beispiel von 1K-PUR

The curing of wood adhesives has so far been evaluated on a basis of parameters, which offer process optimization only to a small degree. However, the curing becomes analyzable in detail by using oscillation measurements and a test setup adapted to the bonding process. With time sweep measurements, the adhesion process can be divided into characteristic ranges of molecular and structural processes. This method is presented and analyzed using a polyurethane prepolymer for joining wood-based materials.