Description of the thermodynamic properties and fluid-phase behavior of aqueous solutions of linear,branched, and cyclic amines

The SAFT-γ Mie group-contribution equation of state is used to represent the fluid-phase behavior of aqueous solutions of a variety of linear, branched, and cyclic amines. New group interactions are developed in order to model the mixtures of interest, including the like and unlike interactions between alkyl primary, secondary, and tertiary amine groups (NH₂, NH, N), cyclic secondary and tertiary amine groups (cNH, cN), and cyclic methine-amine groups (cCHNH, cCHN) with water (H₂O). The group-interaction parameters are estimated from appropriate experimental thermodynamic data for pure amines and selected mixtures. By taking advantage of the group-contribution nature of the method, one can describe the fluid-phase behavior of mixtures of molecules comprising those groups over broad ranges of temperature, pressure, and composition. A number of aqueous solutions of amines are studied including linear, branched aliphatic, and cyclic amines. Liquid–liquid equilibria (LLE) bounded by lower critical solution temperatures (LCSTs) have been reported experimentally and are reproduced here with the SAFT-γ Mie approach. The main feature of the approach is the ability not only to represent accurately the experimental data employed in the parameter estimation, but also to predict the vapor–liquid, liquid–liquid, and vapor–liquid–liquid equilibria, and LCSTs with the same set of parameters. Pure compound and binary phase diagrams of diverse types of amines and their aqueous solutions are assessed in order to demonstrate the main features of the thermodynamic and fluid-phase behavior.     

Influence of α′‐/α‐crystal polymorphism on properties of poly(l‐lactic acid)

Poly(l ‐lactic acid) (PLLA) is a biodegradable and biocompatible thermoplastic polyester produced from renewable sources, widely used for biomedical devices, in food packaging and in agriculture. It is a semicrystalline polymer, and as such its properties are strongly affected by the developed semicrystalline morphology. As a function of the crystallization temperature, PLLA can form different crystal modifications, namely α′‐crystals below about 120 °C and α‐crystals at higher temperatures. The α′ modification is therefore of special importance as it may be the preferred polymorph developing at processing‐relevant conditions. It is a metastable modification which typically transforms into the more stable α‐crystals on annealing at elevated temperature. The structure, kinetics of formation and thermodynamics of α′‐ and α‐crystals of PLLA are reviewed in this contribution, together with the effect of α′‐/α‐crystal polymorphism on the properties of PLLA. © 2018 Society of Chemical Industry     

Upgrading of low-grade manganese ore based on reduction roasting and magnetic separation technique

The selective reduction of low-grade manganese ore followed by magnetic separation was proposed to produce rich-manganese ore. The optimized parameters include a roasting temperature of 1050°C, a roasting time of 6 h, a manganese ore size of 8–13 mm, and an FC/O ratio of 2.5. The reduction roasting products of low-grade manganese ore, mainly comprising of MnO, metallic iron, and residual gangue, could be separated effectively to obtain rich-manganese ore and magnetic product. The RMn, RFe, and TMn can reach the peak values of 71.00%, 93.60%, and 56.20wt%, respectively, at a rational magnetic field strength of 100 mT. In particular, the Mn/Fe ratio is up to 10.85, which meets the requirements of ferromanganese alloy smelting.     

Macromolecular Crowding Tunes Protein Stability by Manipulating Solvent Accessibility

In all intracellular processes, protein structure and dynamics are subject to the influence of macromolecular crowding (MC). Here, the impact of MC agents of different types and sizes on the model protein Bacillus subtilis Cold shock protein B (BsCspB) during both thermal and chemical denaturation have been comprehensively investigated. We consistently reveal a distinct stabilization of BsCspB in a manner dependent on the MC concentration but not on viscosity, polarity, or size of the MC agent used. This general stabilization has been decoded by use of NMR spectroscopy, through monitoring of chemical shift (CS) perturbations and the intramolecular hydrogen-bonding networks, as well as local protection of amide protons against exchange with solvent protons. Whereas CSs and hydrogen-bonding networks are not systematically affected in the presence of MC, we detected a pronounced reduction in exchange in loop regions of BsCspB. We conclude that this reduced accessibility of solvent protons is a key parameter for the increases in protein stability seen under MC.     

Kinetic,thermodynamic parameters and in vitro digestion of tannase from Aspergillus tamarii URM 7115

Tannase is an enzyme used in various industries and produced by a large number of microorganisms. The aim of this study was to evaluate tannase production to determine the biochemical, kinetic, and thermodynamic properties and to simulate tannase in vitro digestion. The tannase-producing fungal strain was isolated from “jamun” leaves and identified as Aspergillus tamarii. Temperature at 26°C for 67?h was the best combination for maximum tannase activity (6.35-fold; initial activity in Plackett–Burman design—15.53?U/mL and average final activity in Doehlert design—98.68?U/mL). The crude extract of tannase was optimally active at 40°C, pH 5.5 and 6.5. Moreover, tannase was stimulated by Na⁺, Ca²⁺, Mg²⁺, and Mn²⁺. The half-life at 40°C lasted 247.55?min. The free energy of Gibbs, enthalpy, and entropy, at 40°C, was 81.47, 16.85, and ?0.21?kJ/mol?·?K, respectively. After total digestion, 123.95% of the original activity was retained. Results suggested that tannase from A. tamarii URM 7115 is an enzyme of interest for industrial applications, such as gallic acid production, additive for feed industry, and for beverage manufacturing, due to its catalytic and thermodynamic properties.     

Simulation Study on Hydrogen-Heating-Power Poly-Generation System based on Solar Driven Supercritical Water Biomass Gasification with Compressed Gas Products as an Energy Storage System

Supercritical water gasification driven by solar energy is a promising way for clean utilization of biomass with high moisture content, but direct discharge of liquid residual causes energy waste and decreases energy efficiency. To reduce energy waste, a poly-generation system for hydrogen-rich gas production coupling heat supply and power generation based on supercritical water gasification of biomass driven by concentrated solar energy was established in this paper, which also provided a novel energy storage method to overcome the shortcomings of solar discontinuity. Thermodynamic model of the system was proposed and life cycle assessment(LCA) of the system was conducted. Influence of different parameters(temperature of 600℃ to 800℃, outlet temperature of heat exchanger of 42℃ to 56℃, biomass slurry concentration of 5% to 6.5%) on the gasification performance, energy and exergy efficiency, energy distribution and global warming potential(GWP) was discussed. The results indicated that hydrogen yield increased as gasification temperature increased since free radical reaction was enhanced which gas production reaction was classified into. Molar fraction of hydrogen increased as gasification temperature increased and reached 65.6% at 750℃. Energy and exergy efficiency of the system reached 74.84% and 34.87% at 700℃ and 600℃ respectively and that of gas production was 18.15% at 650℃, which was the highest. Increasing reaction temperature and decreasing biomass slurry concentration were effective ways to decrease GWP. Optimal operating parameter was reaction temperature of 650℃, outlet temperature of heat exchanger of 50℃ and biomass concentration of 5%.     

火灾条件下拱顶油罐弱连接结构的失效分析

拱顶油罐受外部火焰烘烤发生失效爆炸，易造成严重人员伤亡和巨大经济损失。为对火灾条件下拱顶油罐的失效爆炸进行预警，通过高温材料力学性能实验平台对拱顶油罐弱连接结构进行破坏测试，得出不同火灾温度条件下弱连接结构失效的拉断力和应力值。实验结果表明，当温度高于300℃时，拉断力和失效应力值变化显著，其中450℃为变化峰值温度。在此基础上，构建了拱顶油罐失效压力计算模型，推导出了不同容积拱顶油罐在不同火灾温度下的失效压力。所得结果可作为拱顶油罐失效的判定依据，为油罐的爆炸预警提供数据支撑。     

Biosorption of chromium (VI) from aqueous solution by seed powder of prickly pear (Opuntia ficus indica L.) fruits

ABSTRACT

The solid residue of the cold press oil extraction from prickly pear (Opuntia ficus indica L.) fruit seeds was evaluated as a low-cost biosorbent for biosorption of Cr(VI) from aqueous solutions. Batch experiments were conducted as a function of initial pH, contact time, biosorbent dose, initial Cr(VI) concentration, and temperature. Biosorption was highly pH-dependent and found to be maximum at pH 1.0. Langmuir and Freundlich equations fitted very well with experimental data. The maximum monolayer adsorption capacity was 19.61 mg/g at 298 K and pH 1.0. Biosorption kinetics was controlled by the pseudo-second-order model. Thermodynamic parameters indicated that biosorption of Cr(VI) was a spontaneous, favorable and endothermic process. The activation energy was found to be 40.68 kJ.mol^?1.     

等温滴定量热法探索酪蛋白磷酸肽单体与不同钙盐的相互作用

本研究探讨了在模拟小肠末端环境下酪蛋白磷酸肽（β-casein phosphopeptides(1-25)，简称CPP）与不同钙盐的相互作用情况。实验以等温滴定量热仪为方法，以热力学参数、化学计量数及亲和力常数为指标，评价不同钙盐与CPP的相互作用情况。结果表明，CPP与不同钙盐两两相互作用，且均为由熵驱动的自发反应（pH 8.0，37 ℃），该反应的主要推动力为离子相互作用力。不同钙盐与CPP反应时，焓变，熵变及自由能无明显差别（p>0.05），而化学计量数和亲和力常数存在显著性差异（p<0.05）。CPP与葡萄糖酸钙，乳酸钙和氯化钙相互作用时，化学计量数较高（3~4 mol/mol），而与天冬氨酸钙结合的化学计量数较低（2~3 mol/mol）。此外，相比其他钙盐，乳酸钙与CPP结合的亲和力常数最低。多肽与钙盐结合数高且亲和力较低时有利于小肠对钙的吸收。因此，相对于其他钙盐，CPP与乳酸钙结合可能更有利于小肠对钙的吸收。本研究为更好地了解CPP与不同钙盐溶液在模拟小肠末端环境下的热力学变化及结合情况奠定坚实的基础。     

离子液体的溶液热力学模型研究进展

离子液体是近年来发展起来的一种绿色介质，在化工反应和分离过程中具有广泛的应用前景。离子液体的溶液热力学性质和相平衡数据是其相关工艺过程设计的基础。本文从如下几个方面综述了离子液体溶液热力学模型的研究进展，即溶液热力学研究方法、溶液热力学模型的构建、离子液体的结构和分子间作用力、离子液体的溶液热力学模型及其在相平衡计算中的应用。重点分析了适用于离子液体溶液热力学性质计算的状态方程模型和过量Gibbs自由能模型或活度系数模型，离子液体的电解质和非电解质溶液模型，以及这些模型对ILs结构、氢键和静电作用的处理方法。分析了这些模型的优缺点，并对今后离子液体的溶液热力学研究提出了建议。