Preparation of Hollow Fiber Membranes Based On Poly(4-methyl-1-pentene) for Gas Separation

New hollow fiber gas separation membranes with a non-porous selective layer based on poly(4-methyl-1-pentene) (PMP) granules have been obtained using the solution-free melt spinning process. The influence of the preparation conditions on the geometry of the obtained samples was studied. It was found that a spin head temperature of 280 °C and a specific mass throughput of 103 g mm−2 h−1 are optimal to obtain defect-free, thin-walled hollow fibers in a stable melt spinning process, using the given spinneret geometry and a winding speed of 25 m/min. The gas permeability and separation properties of new fibers were studied using CO2/N2 and CO2/CH4 mixtures, and it was found that the level of gas selectivity characteristic of homogeneous polymer films can be achieved. The features of the gas mixture components permeability below and above the PMP glass transition temperature have been experimentally studied in the range of CO2 concentrations from 10 to 90% vol. The temperature dependences of the permeability of the CO2/CH4/N2 mixture through the obtained HF based on PMP have been investigated, and the values of the apparent activation energies of the permeability have been calculated, which make it possible to predict the properties of membrane modules based on the obtained membranes in a wide temperature range.

Influence of a Prior Oxidation on the Reduction Behavior of Magnetite Iron Ore Ultra-Fines Using Hydrogen

The reduction behavior of raw and prior-oxidized magnetite iron ore ultra-fines with hydrogen was investigated. Reduction tests were conducted with a thermogravimetric analyzer in a temperature range from 873 K to 1098 K at 1.1 bar absolute, using hydrogen as reducing gas. The experimental results show that a prior oxidation of the magnetite has a positive effect on the reduction behavior because of changing morphology. The apparent activation energies show a turnaround to negative values, depending on the prior oxidation and degree of reduction. A multi-step kinetic analysis based on the model developed by Johnson–Mehl–Avrami was used to reveal the limiting mechanism during reduction. At 873 K and 948 K, the reduction at the initial stage is controlled by nucleation and chemical reaction and in the final stage by nucleation only, for both raw and pre-oxidized magnetites. At higher temperatures, 1023 K and 1098 K, the reduction of raw magnetite is mainly controlled by diffusion. This changes for pre-oxidized magnetite to a mixed controlled mechanism at the initial stage. Processing magnetite iron ore ultra-fines with a hydrogen-based direct reduction technology, lower reduction temperatures and a prior oxidation are recommended, whereby a high degree of oxidation is not necessary.

Hydrothermal Treatment of Arsenopyrite Particles with CuSO4 Solution

The nature of the hydrothermal reaction between arsenopyrite particles (FeAsS) and copper sulfate solution (CuSO4) was investigated in this study. The effects of temperature (443–523 K), CuSO4 (0.08–0.96 mol/L) and H2SO4 (0.05–0.6 mol/L) concentrations, reaction time (1–120 min), stirring speed (40–100 rpm) and particle size (10–100 μm) on the FeAsS conversion were studied. The FeAsS conversion was significant at >503 K, and it is suggested that the reaction is characterized by the formation of a thin layer of metallic copper (Cu0) and elemental sulfur (S0) around the unreacted FeAsS core. The shrinking core model (SCM) was applied for describing the process kinetics, and the rate of the overall reaction was found to be controlled by product layer diffusion, while the overall process was divided into two stages: (Stage 1: mixed chemical reaction/product layer diffusion-controlled) interaction of FeAsS with CuSO4 on the mineral’s surface with the formation of Cu1+ and Fe2+ sulfates, arsenous acid, S0, and subsequent diffusion of the reagent (Cu2+) and products (As3+ and Fe2+) through the gradually forming layer of Cu0 and molten S0; (Stage 2: product layer diffusion-controlled) the subsequent interaction of CuSO4 with FeAsS resulted in the formation of a denser and less porous Cu0 and S0 layer, which complicates the countercurrent diffusion of Cu2+, Cu1+, and Fe2+ across the layer to the unreacted FeAsS core. The reaction orders with respect to CuSO4 and H2SO4 were calculated as 0.41 and −0.45 for Stage 1 and 0.35 and −0.5 for Stage 2. The apparent activation energies of 91.67 and 56.69 kJ/mol were obtained for Stages 1 and 2, respectively.

Physico-Chemical Characteristics of Spodumene Concentrate and Its Thermal Transformations

Spodumene concentrate from the Pilbara region in Western Australia was characterized by X-ray diffraction (XRD), Scanning Electron Microscope Energy Dispersive Spectroscopy (SEM-EDS) and Mineral Liberation Analysis (MLA) to identify and quantify major minerals in the concentrate. Particle diameters ranged from 10 to 200 microns and the degree of liberation of major minerals was found to be more than 90%. The thermal behavior of spodumene and the concentration of its polymorphs were studied by heat treatments in the range of 900 to 1050 °C. All three polymorphs of the mineral (α, γ and β) were identified. Full transformation of the α-phase was achieved at 975 °C and 1000 °C after 240 and 60 min treatments, respectively. SEM images of thermally treated concentrate revealed fracturing of spodumene grains, producing minor cracks initially which became more prominent with increasing temperature. Material disintegration, melting and agglomeration with gangue minerals were also observed at higher temperatures. The metastable γ-phase achieved a peak concentration of 23% after 120 min at 975 °C. We suggest 1050 °C to be the threshold temperature for the process where even a short residence time causes appreciable transformation, however, 1000 °C may be the ideal temperature for processing the concentrate due to the degree of material disintegration and α-phase transformation observed. The application of a first-order kinetic model yields kinetic parameters which fit the experimental data well. The resultant apparent activation energies of 655 and 731 kJ mol−1 obtained for α- and γ-decay, respectively, confirm the strong temperature dependence for the spodumene polymorph transformations.

5-Nitrotetrazol and 1,2,4-Oxadiazole Methylene-Bridged Energetic Compounds: Synthesis, Crystal Structures and Performances

A new structural type for melt cast materials was designed by linking nitrotetrazole ring with 1,2,4-oxadiazole through a N-CH2-C bridge for the first time. Three N-CH2-C linkage bridged energetic compounds, including 3-((5-nitro-2H-tetrazol-2-yl) methyl)-1,2,4-oxadiazole (NTOM), 3-((5-nitro-2H-tetrazol-2-yl)methyl)-5-(trifluoromethyl)-1,2,4 -oxadiazole (NTOF) and 3-((5-nitro-2H-tetrazol-2-yl)methyl)-5-amine-1,2,4-oxadiazole (NTOA), were designed and synthesized through a two-step reaction by using 2-(5-nitro-2H-tetrazole -2-yl)acetonitrile as the starting material. The synthesized compounds were fully characterized by NMR (1H, 13C), IR spectroscopy and elemental analysis. The single crystals of NTOM, NTOF and NTOA were successfully obtained and investigated by single-crystal X-ray diffraction. The thermal stabilities of these compounds were evaluated by DSC-TG measurements, and their apparent activation energies were calculated by Kissinger and Ozawa methods. The crystal densities of the three compounds were between 1.66 g/cm3 (NTOA) and 1.87 g/cm3 (NTOF). The impact and friction sensitivities were measured by standard BAM fall-hammer techniques, and their detonation performances were computed using the EXPLO 5 (v. 6.04) program. The detonation velocities of the three compounds are between 7271 m/s (NTOF) and 7909 m/s (NTOM). The impact sensitivities are >40 J, and the friction sensitivities are >360 N. NTOM, NTOF and NTOA are thermally stable, with decomposition points > 240 °C. The melting points of NTOM and NTOF are 82.6 °C and 71.7 °C, respectively. Hence, they possess potential to be used as melt cast materials with good thermal stabilities and better detonation performances than TNT.

Chemical Feedstock Recovery via the Pyrolysis of Electronically Heated Tobacco Wastes

The pyrolysis of waste electronically heated tobacco (EHT), consisting of tobacco leaves (TL), a poly-lactic acid (PLA) filter, and a cellulose acetate (CA) filter, was investigated using thermogravimetric (TG) and pyrolyzer–gas chromatography/mass spectrometry (Py-GC/MS) analysis. The pyrolytic properties of waste EHT obtained after smoking were comparable to those of fresh EHT. Although the maximum decomposition temperatures (TmaxS) of waste TL and CA were similar to those of fresh EHT components, the Tmax of waste PLA was slightly higher than that of fresh PLA due to smoldering. The Tmaxs of PLA and CA were lowered when they were co-pyrolyzed with TL due to interactions between pyrolysis intermediates. The apparent activation energies for the non-isothermal pyrolysis of waste EHT components were higher than those of fresh EHT components. Py-GC/MS analysis results indicated that considerable amounts of chemical feedstocks, such as nicotine and limonene from TL, caprolactone and lactide from PLA, and acetic acid and triacetin from CA, can be recovered by simple pyrolysis of EHT. Co-pyrolysis of TL, PLA, and CA revealed that the experimental amount of lactide was much larger than the calculated value, suggesting its synergistic formation.

Kinetic Study on Microwave-Assisted Oligomerization of 1-Decene over a HY Catalyst

A promising production route for a high-quality base stock for lubricants is the oligomerization of high molecular-weight olefins in a high energy efficiency system. Oligomerization of 1-decene (C10) was conducted in a microwave-assisted system over a HY zeolite catalyst at different reaction temperatures and times. Higher reaction temperature resulted in increasing formation of dimers and trimers. The oligomerization reaction yielded 80% conversion, 54.2% dimer product, 22.3% trimer product and 3.4% heavier product at 483 K for a reaction time of 3 h. The best fit kinetic model for the dimerization reaction was formulated from an assumption of no vacant reaction sites. For the trimerization reaction, a molecule of dimer (C20) formed on the active site, interacted with a molecule of 1-decene in the bulk solution to form a molecule of trimer (C30). Apparent activation energies for the dimerization and trimerization reactions were 70.8 ± 0.8 and 83.6 ± 0.9 kJ/mol, respectively. The C13-NMR spectrum indicated that the oligomer product contained a significant portion of highly branched hydrocarbons, causing a substantial reduction in the viscosity index compared to conventional poly-alpha olefin lubricant (PAO).

Effect of Reduction Rate on the Recrystallization Behavior in AA3003 Aluminum Alloy Fabricated by DC Casting

The recrystallization behavior of the cold-rolled AA3003 aluminum alloy with the reduction rate of 20%, 50% and 90% during annealing at the temperature ranging from 300°C to 400°C was investigated. As increasing reduction rate, the cold rolled specimens exhibit deformation bands with elongated grain microstructure consisting of straight grain boundary parallel to rolling direction. Therefore, large density of nucleation sites for recrystallization would be expected with increase of strain energy. The grain size of the cold-rolled specimens decreased with increase of reduction rate, c.f., as the rolling reduction increased to 90%, grain size along the direction normal to the sheet decreased to about 8μm in thick. When the sample annealed at 350°C for 5s, the first recrystallized grains were observed in the vicinity of the grain boundary. The relaxation and recrystallization kinetics under different annealing conditions were characterized in terms of the Johnson–Mehl–Avrami–Kolmogorov (JMAK) model. The apparent activation energies of recrystallization for the cold-rolled specimens with reduction rate of 20%, 50% and 90% were determined as 332 kJ/mol, 239 kJ/mol and 115 kJ/mol, respectively. XRD analysis by using modified Williamson–Hall plots revealed that the tendency of the change in dislocation density is varied depending on reduction rate. These results indicate that the apparent activation energy for recrystallization and the crystallites size decrease with increase of the reduction rate, which leads to a decrease in the size of the recrystallized grains.

Calculations of activation energy and frequency factors for corn leafs pyrolysis using excel solver: new concept

Thermal degradations of biomass corn leaves were studied for kinetic modeling. Thermogravimetric-differential analyzer runs at 5, 10, 20, and 30 °C min−1 heating rates were employed. Apparent activation energy and frequency factor values were calculated for first-order kinetics using several procedures. The procedure of Coats and Redfern showed 28.89 to 31.78 kJ mol−1 apparent activation energy and 15.5 to 157.12 min−1 frequency factor, respectively. Calculation of the apparent activation energy and frequency factor using Kissinger–Akahira–Sunose procedure gave 229.9–364.2 kJ/mol and 8.567 × 1023 and 1.13 × 1031 (min−1), respectively as the conversion increased from 0.1 to 0.9. The newly introduced excel solver procedure indicates a distribution activation energy over the entire range of conversion. For first-order reaction kinetics, the calculated apparent activation energy magnitudes ranged between 5.0 kJ mol−1 with frequency factor equals to 0.239 and 196.2 kJ mol−1 with frequency factor 2.89 × 1012 in the studied range. The low or high magnitudes of the calculated activation energy are not associated with a particular value of the conversion. The calculated apparent activation energies are related to the direct solution of the simultaneous equations that constitute the basis of the excel solver.

Systematic Incorporation of Gold Nanoparticles onto Mesoporous Titanium Oxide Particles for Green Catalysts

This report describes the systematic incorporation of gold nanoparticles (AuNPs) onto mesoporous TiO2 (MPT) particles without strong attractive forces to efficiently serve as reactive and recyclable catalysts in the homocoupling of arylboronic acid in green reaction conditions. Unlike using nonporous TiO2 particles and conventional SiO2 particles as supporting materials, the employment of MPT particles significantly improves the loading efficiency of AuNPs. The incorporated AuNPs are less than 10 nm in diameter, regardless of the amount of applied gold ions, and their surfaces, free from any modifiers, act as highly reactive catalytic sites to notably improve the yields in the homocoupling reaction. The overall physical properties of the AuNPs integrated onto the MPT particles are thoroughly examined as functions of the gold content, and their catalytic functions, including the rate of reaction, activation energy, and recyclability, are also evaluated. While the rate of reaction slightly increases with the improved loading efficiency of AuNPs, the apparent activation energies do not clearly show any correlation with the size or distribution of the AuNPs under our reaction conditions. Understanding the formation of these types of composite particles and their catalytic functions could lead to the development of highly practical, quasi-homogeneous catalysts in environmentally friendly reaction conditions.