乙酸丁酯反应精馏过程模拟设计

反应精馏偶合了反应和精馏两种单元操作,通过精馏促进反应,可以提高反应转化率和收率,为可逆反应的化工过程生产提供了新的设计途径。基于严格热力学分析计算,利用计算机模拟和优化手段。提出了乙酸丁酯反应精馏、分离纯化的生产流程。采用UNIQUAC方程表征乙酸-正丁醇-乙酸丁酯-水四元非理想体系的汽液平衡,首先,根据实验数据回归了热力学模型中的交互作用参数,并预测了体系中5个共沸物组成,模型的计算结果与实际数据吻合。基于平衡级模型,提出了由平衡反应器、反应精馏塔、倾析器和纯化塔构成的可行流程,对提出的设计流程进行了模拟、优化,得到了操作工艺参数。模拟结果对工业过程的设计和改造具有一定的指导意义。     

Deoxidation of Ti Melt by Newly Developed Two-Step Plasma Arc Melting Process Using Hydrogen

Metallurgical and Materials Transactions B - A two-step plasma arc melting process, comprising a first step under Ar-30 pct H2 gas flow and the second step under Ar gas flow, has been...     

Corrosion characteristics of reduced activation ferritic steel, JLF-1 (8.92Cr–2W) in molten salts Flibe and Flinak

Static corrosion tests were performed in molten salts, LiF–BeF₂ (Flibe) and LiF–NaF–KF (Flinak), at 500 °C and 600 °C for 1000 h. The purpose is to investigate the corrosion characteristics of reduced activation ferritic steels, JLF-1 (8.92Cr–2W) in the fluids. The concentration of hydrogen fluoride (HF) in the fluids was measured by slurry pH titration method before and after the exposure. The HF concentration determined the fluoridation potential. The corrosion was mainly caused by dissolution of Fe and Cr into the fluids due to fluoridation and/or electrochemical corrosion. Carbon on the surface might be dissolved into the fluids due to the corrosion, and this resulted to the decrease of carbide on the surface. The corrosion depth of the JLF-1 specimen, which was obtained from the weight losses, was 0.637 μm in Flibe at 600 °C and 6.73 μm in Flinak at 600 °C.     

Effect of wall wettability condition on drift-flux parameters in lead–bismuth two-phase flow in circular and annular bubble columns

Lead–bismuth two-phase flow in a cylindrical vessel and annulus was experimentally investigated by varying the surface wettability of the vessel wall. The test section used in this study was a cylindrical stainless vessel with/without inner sleeve to change the hydraulic diameter. Volume-averaged void fraction was measured by varying the surface wettability of the test section, which was enhanced by using a soldering flux. Measured void fraction was compared with existing two-phase flow correlations and with one-dimensional theoretical simulations assuming one-dimensional drift-flux model. From experimental results, measured distribution parameters of the lead–bismuth two-phase flow are much larger than that of ordinary two-phase flow regardless of the surface wettability. In the present work, the one-dimensional analysis was carried out for the cylindrical vessel to reproduce the distribution parameter. From the simulation results, predicted value for the cylindrical vessel showed good agreement with experimental results. However, in annulus, the distribution parameters in annulus were underestimated by the present model. It was suggested that, in case of annulus, steeper void fraction profile might be formed near the inner surface for poor wettability condition.     

All solid-state battery with sulfur electrode and thio-LISICON electrolyte

A high-capacity type of all solid-state battery was developed using sulfur electrode and the thio-LISICON electrolyte. New nano-composite of sulfur and acetylene black (AB) with an average particle size of 1–10 nm was fabricated by gas-phase mixing and showed a reversible capacity of 900 mAh g⁻¹ at a current density of 0.013 mA cm⁻².     

Equilibrium and kinetic studies of selective adsorption and separation for strontium using DtBuCH18C6 loaded resin

A crown ether loaded resin was prepared by successive impregnation and fixing the 4′,4′(5″)-di(tert-butylcyclohexano)-18-crown-6 (DtBuCH18C6) and its molecule modifier, 1-dodecanol, onto the porous silica/polymer composite support (SiO₂-P particles). The characterization of DtBuCH18C6 loaded resin was examined by thermal gravimetry and differential thermal analysis and electron probe microanalysis. The adsorption behavior of Sr(II), Cs(I), Ru(III), Pd(II), La(III), Nd(III), Sm(III), Gd(III), Zr(IV), and Mo(VI) was investigated by the batch method. Furthermore, the column test for Sr (II) was performed. The batch experiments were carried out by varying the shaking times, HNO₃ concentration, and initial concentration of metal ions. A relatively large K _d value above 182 cm³/g for Sr(II) was obtained in the presence of 3 M HNO₃. In contrast, the K _d values of Cs(I), Ru(III), Pd(II), La(III), Nd(III), Sm(III), Gd(III), Zr(IV), and Mo(VI) were considerably lower than 10 cm³/g. The adsorption of Sr(II) was found to be controlled by chemisorption mechanism, and followed a Langmuir-type adsorption equation. The breakthrough curve of Sr(II) had S-shaped profile, and the elution percentage was estimated to be 99.9% by using the eluent of H₂O.     

Multiresidue method for pesticides and veterinary drugs in bovine milk using GC/MS and LC/MS/MS

A simple, sensitive and selective method with gas chromatography/mass spectrometry (GC/MS) and liquid chromatography/tandem mass spectrometry (LC/MS/MS) has been developed to detect 342 pesticides and veterinary drugs contaminating bovine milk at the maximum residue limits (MRLs) defined in the "positive list system". Sample preparation was performed by extracting the analytes with acetonitrile, followed by salting-out with sodium chloride. For some pesticides, the extract was further cleaned up by n-hexane partitioning and PSA cartridge column chromatography. GC/MS-EI or -NCI was used to determine pesticide residues, while LC/MS/MS-ESI was applicable to the determination of pesticide and veterinary drug residues. The variation of the recoveries of these drugs at MRL was relatively wide; however the relative standard deviations of the recovery of each drug were within 28%, suggesting that the present method is good enough for use as a screening test for contaminants at the MRLs. These results show that this method is useful for multiresidue analysis of numerous pesticides and veterinary drugs in bovine milk.     

Carbon Nitride Loaded with an Ultrafine,Monodisperse, Metallic Platinum-Cluster Cocatalyst for the Photocatalytic Hydrogen-Evolution Reaction

For the realization of a next-generation energy society, further improvement in the activity of water-splitting photocatalysts is essential. Platinum (Pt) is predicted to be the most effective cocatalyst for hydrogen evolution from water. However, when the number of active sites is increased by decreasing the particle size, the Pt cocatalyst is easily oxidized and thereby loses its activity. In this study, a method to load ultrafine, monodisperse, metallic Pt nanoclusters (NCs) on graphitic carbon nitride is developed, which is a promising visible-light-driven photocatalyst. In this photocatalyst, a part of the surface of the Pt NCs is protected by sulfur atoms, preventing oxidation. Consequently, the hydrogen-evolution activity per loading weight of Pt cocatalyst is significantly improved, 53 times, compared with that of a Pt-cocatalyst loaded photocatalyst by the conventional method. The developed method is also effective to enhance the overall water-splitting activity of other advanced photocatalysts such as SrTiO₃ and BaLa₄Ti₄O₁₅.     

Association and physical gelation of ABA triblock copolymer in selective solvent

Association behavior and physical gelation mechanism of ABA triblock copolymer dissolved in B-selective solvent have been studied systematically from dilute to moderately concentrated solutions. Static and dynamic light scattering and nuclear magnetic resonance measurements for dilute solutions of poly(methyl methacrylate)-block-poly(tert-butyl acrylate)-block-poly(methyl methacrylate) (PMMA-PtBuA-PMMA) in 1-butanol (PtBuA selective solvent) indicated that PMMA-PtBuA-PMMA chains are molecularly dissolved above 50 °C. With decreasing temperature, the triblock copolymers form associated micelles consisting PMMA associated core and PtBuA shell. Linear dynamic viscoelastic measurements for solutions with moderate concentration (3.9-12.0 wt%) revealed that the system was viscous sol state at 60 °C. Drastic increase of shear storage modulus (G′) occurred with decreasing temperature, and at 25 °C, G′ showed rubbery plateau with weak frequency dependency, means the formation of elastic physical gel. The consistency between the temperature for micelle formation and that at the increase in G′ indicates that the physical gelation is owing to the network formation as the result of the association of PMMA chains and the bridging PtBuA chains connecting the PMMA cores. Master curves for the dynamic moduli were derived by time-temperature superposition along the frequency axis. Just above sol-gel transition concentration (C_gel), the master curves suggest the existence of fairy amount of aggregate that is not incorporated in the macroscopic network. With the increase in polymer concentration, the master curves become to reveal Maxwell-type viscoelasticity with narrow relaxation time distribution, suggesting the formation of transient network with easily generation and destruction of crosslinks. Concentration dependency of the plateau modulus is stronger than the theoretically expected, means the macroscopic transient network grows with polymer concentration by increasing the fraction of elastically effective bridging PtBuA chain above C_gel.