Directional separation of hydrogen-containing gas mixture by hydrate-membrane coupling method

Recovery of hydrogen (H₂) from H₂-containing gas mixtures has great significance for energy conservation, cost reduction and benefit increase. However, the common separation methods have the ubiquitous problem due to phase equilibrium principle and results in the conflict between H₂ concentration and H₂ recovery rate in the product gas. Consequently, an innovative conception of hydrate-membrane coupling approach is proposed in this work. In the separation process, hydration and membrane permeation two separation driving forces coexist to achieve the aim of strengthening mass transfer kinetics. H₂ and non-H₂ components (hydrocarbons) are synchronously and directionally selected by membrane and hydrate to improve different phase compositions. Therefore, the gas in feed side could keep relatively high two separation driving forces (H₂ fugacity and hydrocarbons fugacity). The results show that the coupling method could synchronously increase both the concentration and the recovery rate of H₂ in the product gas. At the same time, the volume and concentration of the hydrocarbons in hydrate both increases effectively. It indicates that hydrate and membrane separation methods support each other in the separation process. The hydrate-membrane coupling method fundamentally solves the issue of the decreasing driving force resulting from single separation method and phase equilibrium relationship.     

In-situ measurement of mineral phase transition and kinetics in roasting process of Bayan Obo mixed rare earth concentrate by sodium carbonate

In this study, the Bayan Obo rare earth concentrates mixed with Na₂CO₃ were used for roasting research. The phase change process of each firing stage was analyzed. The kinetic mechanism model of the continuous heating process was calculated. This study aims to recover valuable elements and optimize the production process to provide a certain theoretical basis. Using X-ray diffraction (XRD), Fourier infrared spectroscopy, scanning electron microscopy with energy dispersive spectrometry, the reaction process and the existence of mineral phases were analyzed. The variable temperature XRD and thermogravimetric method were used to calculate the roasting kinetics. The phase transition results show that carbonate-like substances first decompose into fine mineral particles, and CaO, MgO, and SiO₂ react to form silicates, causing hardening. Further, REPO₄ and NaF can directly generate CeF₃ and CeF₄ at high temperatures, and a part of CeF₄ and NaF forms a solid solution substance Na₃CeF₇. Rare earth oxides calcined at a high temperature of 750 °C were separated to produce Ce_0.6Nd_0.4O_1.8, Ce₄O₇, and LaPrO_3+x. Then, BaSO₄, Na₂CO₃, and Fe₂O₃ react to form barium ferrite BaFe₁₂O₁₉; the kinetic calculation results show that during the continuous heating process, the apparent activation energy E reaches the minimum in the entire reaction stage in the temperature range of 440–524 °C, and the reaction order n reaches the maximum, which indicates that the decomposition product REFO significantly impacts the reaction system and reduces the activation energy. The mechanism function is F(α) = [?ln (1?α)]^1/3. The reaction order n reaches the minimum in the temperature range of 680–757 °C, and the apparent activation energy E is large. The difficulty of the reaction increases during the final stage. The reaction mechanism function is F(α) = [1?(1?α)^1/3]². Observing the entire reaction stage, the step of controlling the reaction rate changes from random nucleation to three-dimensional diffusion (spherical symmetry).     

The kinetics of copper corrosion in nitric acid

The strategy for the permanent disposal of high-level nuclear waste in Canada involves sealing it in a copper-coated steel container and burying it in a deep geologic repository. During the early emplacement period, the container could be exposed to warm humid air, which could result in the condensation of nitric acid, produced by the radiolysis of the humid air, on the copper surface. Previous studies have suggested that both nitrate and oxygen reduction will drive copper corrosion, with the nitrate reduction kinetics being dependent on the concentration of soluble copper(I) produced by the anodic dissolution of copper in the reaction with oxygen. This study focused on determining the kinetics of nitrate and oxygen reduction and elucidating the synergistic relationship between the two processes. This was investigated using corrosion potential and polarization measurements in conjunction with scanning electron microscopy and X-ray photoelectron spectroscopy. Oxygen reduction was shown to be the dominant cathodic reaction with the oxidation of copper(I) to copper(II) by nitrate, promoting the catalytic cycle involving the reaction of copper(II) with copper to reproduce copper(I).     

Kinetic analysis of crystallization of zeolite beta synthesized by direct heating

To quantitatively investigate the initial crystallization of zeolite beta synthesized by direct heating, the extent of the reaction was precisely evaluated by X-ray diffraction measurements and Rietveld structural refinement, and a kinetic analysis of crystallization was performed using the Avrami-Erofe'ev equation. The activation energy for crystallization was lower than that for hydrothermal synthesis. Reaction and synthesis time curves revealed that the initial zeolite beta crystallization consisted of three stages. The first was an induction period with nucleation by the generation of building units and the formation of an initial coordinated structure. The second stage was crystal growth by a diffusion-controlled reaction, and the third stage involved slowing down of crystallization by the limitation of dehydrocondensation. These stages could be analyzed by calculation of the rate constant and Avrami exponent for each stage.     

Helices on Interdomain Interface Couple Catalysis in the ATPPase Domain with Allostery in Plasmodium falciparum GMP Synthetase

GMP synthetase catalyses the conversion of XMP to GMP through a series of reactions that include hydrolysis of Gln to generate ammonia in the glutamine amidotransferase (GATase) domain, activation of XMP to adenyl-XMP intermediate in the ATP pyrophosphatase (ATPPase) domain and reaction of ammonia with the intermediate to generate GMP. The functioning of GMP synthetases entails bidirectional domain crosstalk, which leads to allosteric activation of the GATase domain, synchronization of catalytic events and tunnelling of ammonia. Herein, we have taken recourse to the analysis of structures of GMP synthetases, site-directed mutagenesis and steady-state and transient kinetics on the Plasmodium falciparum enzyme to decipher the molecular basis of catalysis in the ATPPase domain and domain crosstalk. Our results suggest an arrangement at the interdomain interface, of helices with residues that play roles in ATPPase catalysis as well as domain crosstalk enabling the coupling of ATPPase catalysis with GATase activation. Overall, the study enhances our understanding of GMP synthetases, which are drug targets in many infectious pathogens.     

Short communication: In vitro rumen gas production and starch degradation of starch-based feeds depend on mean particle size

Our objective was to model the effect of mean particle size (mPS) on in vitro rumen starch degradation (IVSD) and the kinetics of gas production for different starch-based feeds. For each feed, 2 batches of the same grains were separately processed through 2 different mills (cutter or rotor speed mills), with or without different screens to achieve a wide range of mPS (0.32 to 3.31 mm for corn meals; 0.19 to 2.81 mm for barley meals; 0.16 to 2.13 mm for wheat meals; 0.28 to 2.32 mm for oat meals; 0.21 to 2.36 mm for rye meals; 0.40 to 1.79 for sorghum meals; 0.26 to 4.71 mm for pea meals; and 0.25 to 4.53 mm for faba meals). The IVSD data and gas production kinetics, obtained by fitting to a single-pool exponential model, were analyzed using a completely randomized design, in which the main tested effect was mPS (n = 6 for all tested meals, except n = 7 for corn meals and n = 5 for sorghum meals). Rumen inocula were collected from 2 fistulated Holstein dairy cows that were fed a total mixed ration consisting of 16.2% crude protein, 28.5% starch, and 35.0% neutral detergent fiber on a dry matter basis. The IVSD, evaluated after 7 h of rumen incubation, decreased linearly with increasing mPS for corn, barley, wheat, rye, pea, and faba meals, and decreased quadratically with increasing mPS for the other meals. The y-axis intercept for 7-h IVSD was below 90% starch for corn, barley, and rye feeds and greater than 90% for the other tested feeds. The mPS adjustment factors for the rate of rumen starch degradation varied widely among the different tested feeds. We found a linear decrease in starch degradation with increasing mPS for barley, wheat, rye, and pea meals, whereas we noted a quadratic decrease in starch degradation for the other tested meals. Further, we observed a linear decrease in the rate of gas production with increasing mPS in each tested feed, except for pea meal, which had a quadratic relationship. For each 1 mm increase in mPS, the gas production was adjusted by ?0.009 h^?1 for corn, ?0.011 h^?1 for barley, ?0.008 h^?1 for wheat, and ?0.006 h^?1 for faba, whereas numerically greater adjustments were needed for oat (?0.022 h^?1), rye (?0.017 h^?1), and sorghum (?0.014 h^?1). These mPS adjustment factors could be used to modify the starch-based feed energy values as a function of mean particle size, although in vivo validation is required.     

南方山葡萄酒的氧化褐变动力学研究

为深入了解红葡萄酒的氧化机制,利用加速氧化的方法,通过分析2种南方山葡萄酒氧化褐变过程中,褐变程度、红色色调、游离SO2、氧化还原电位以及氧化前、后主要理化指标的变化,研究南方山葡萄酒的氧化褐变动力学、主要影响因素及对葡萄酒品质的影响。试验结果表明:南方山葡萄酒的氧化褐变动力学符合0级动力学模型方程,桂葡1号葡萄酒耐氧化能力高于刺葡萄酒,然而其红色色调的保持力要低于刺葡萄酒。在加速氧化过程中,葡萄酒的游离SO2快速下降,氧化-还原电位加速上升,且二者呈显著的负相关关系。加速氧化30 d后,2种葡萄酒的总酸、挥发酸升高,其pH值和主要的抗氧化物质(原花青素、游离花色苷、总酚)均显著下降。     

Time-Resolved Structural Kinetics of an Organic Mixed Ionic–Electronic Conductor

The structure and packing of organic mixed ionic–electronic conductors have an especially significant effect on transport properties. In operating devices, this structure is not fixed but is responsive to changes in electrochemical potential, ion intercalation, and solvent swelling. Toward this end, the steady-state and transient structure of the model organic mixed conductor, poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS), is characterized using multimodal time-resolved operando techniques. Steady-state operando X-ray scattering reveals a doping-induced lamellar expansion of 1.6 Å followed by 0.4 Å relaxation at high doping levels. Time-resolved operando X-ray scattering reveals asymmetric rates of lamellar structural change during doping and dedoping that do not directly depend on potential or charging transients. Time-resolved spectroscopy establishes a link between structural transients and the complex kinetics of electronic charge carrier subpopulations, in particular the polaron–bipolaron equilibrium. These findings provide insight into the factors limiting the response time of organic mixed-conductor-based devices, and present the first real-time observation of the structural changes during doping and dedoping of a conjugated polymer system via X-ray scattering.     

两相区配分时间对IQ&P钢组织与性能的影响

以含Cu低碳钢为研究对象,利用SEM、EPMA和拉伸试验研究了两相区配分时间对其组织演变、元素配分以及经IQ&P处理后力学性能的影响,并利用Dictra软件对元素配分行为进行了动力学计算。结果表明,IQ处理后试验钢中的块状马氏体形成于原铁素体区域;随两相区配分时间延长,粒状马氏体数量减少,板条状马氏体之间的间距减小。检测和计算结果的对比显示,C、Mn、Cu 3种元素的相对配分速率与计算结果一致,但实际配分速率低于各自的计算结果。随两相区配分时间延长,经IQ&P处理后试验钢的抗拉强度先增加后减小,而伸长率持续减小;在600 s时达到较好的强塑性匹配,强塑积为16 963.24 MPa·%。