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.     

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.     

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.     

Kinetic analysis of magnesium aluminate spinel formation: Effect of MgO:Al2O3 ratio and titania dopant

The mechanistic pathway of MgO-Al₂O₃ reaction in solid state to form MgAl₂O₄ spinel was investigated to correlate the kinetic parameters with ratio of reactants (MgO:Al₂O₃) and with the presence of a doping agent, TiO₂. The time-temperature-expansion data of oxide compacts was analyzed using several model free analyses and model based (linear and non-linear) kinetic algorithms. These indicated that spinel formation process can be best described by single step with n-dimensional Avrami equation for every MgO:Al₂O₃ ratio, irrespective of titania dopant. The activation energy (E_a) of the process was proportional to % spinel formed in each system and validated with quantitative XRD analysis. The higher value of Avrami coefficient (n) in 90 wt% Al₂O₃ compositions has been explained with geometric considerations of powder packing. Incorporations of 1% TiO₂ in the MgO: Al₂O₃ oxide compact did not markedly affect the reaction model, frequency factor and Activation energy.     

Study on the hydrogen storage properties of a TiZrNbTa high entropy alloy

High-entropy alloys (HEAs), as a new class of metallic materials, have received more and more attention due to its excellent mechanical properties. In this study, the hydrogen absorption properties, such as hydrogen absorption capacity, thermodynamics, kinetics and cyclic properties, as well as the hydride structure of a newly designed TiZrNbTa HEA were investigated. The results showed that multiple hydrides including ε-ZrH₂, ε-TiH₂ and β-(Nb,Ta)H were found in the TiZrNbTa HEA after hydrogenation. With the increase of temperature from 293 K to 493 K, the maximum hydrogen absorption capacity decreased from 1.67 wt% to 1.25 wt% and the plateau pressure related with β-(Nb,Ta)H hydrides increased from 1.6 kPa to 14.8 kPa. The formation enthalpy of β-(Nb,Ta)H hydride was determined to be −6.4 kJ/mol, which was less stable than that of NbH and TaH hydrides. The results also showed that the TiZrNbTa HEA exhibited a rapid hydrogen absorption kinetic even at the room temperature with a short incubation time, and the hydrogen absorption mechanism was determined to be the nucleation and growth mechanism. Moreover, the hydrogen absorption capacity at 293 K decreased slowly with the cycle numbers, and remained 86% capacity after 10 cycles. Cracking occurred after hydrogen absorption and became worse with cycles.     

Enzymolysis kinetics of garlic powder with single frequency countercurrent ultrasound pretreatment

This research was to describe the enzymolysis process of garlic powder which was pretreated by single frequency countercurrent ultrasound. The kinetic constants for ultrasonic pretreated and traditional enzymolysis have been determined. Results showed the value of K_M in ultrasonic pretreated enzymolysis decreased by 12.7% over the traditional enzymolysis, which indicates a fast reaction speed induced by ultrasound pretreatment. Degrees of hydrolysis (DH) in the enzymolysis of garlic powder were determined and kinetics of the reaction was considered in detail in relation to substrate concentration, enzyme concentration, reaction time and DH. Our results suggested a general kinetic equation for the enzymolysis model of ultrasonic pretreated garlic powder. For the model system, the calculated values agree well with the experimental data with average relative error of 4.42%. The proposed kinetic equation can be used to model the bio-reaction process of protein enzymatic hydrolysis and optimize the operation parameters for bioreactor design.