From modification to mechanism: Supercritical hydrothermal synthesis of nano-zirconia

Nano-zirconia has been widely applied due to its excellent physical and chemical properties (e.g., high strength, corrosion resistance, oxygen ion conductivity). Existing preparation methods of nano-zirconia tend to require long reaction time, and the sizes of final particles are large with uneven distributions. Sub-/supercritical hydrothermal synthesis of nanoparticles is favored by researchers owing to controllable reaction process, uniform particle size distribution, good reproducibility, short reaction time, high conversion rate and harmlessness to environment. In this paper, the characteristics and mechanisms of dissolution, crystallization and growth of nano-zirconia during sub-/supercritical hydrothermal synthesis are systematically reviewed. The influences of process and material parameters on the size and purity of particles are analyzed. Then, the reaction mechanism and product phase transition mechanism during hydrothermal synthesis of zirconia are summarized to provide a theoretical reference for the oriented preparation. Finally, the improvement and commercialization of sub-/supercritical hydrothermal synthesis technology are evaluated, and the future research topics are proposed.     

Hydrogen production by supercritical water gasification of lignin over CuO–ZnO catalyst synthesized with different methods

In this study, lignin was gasified in supercritical water with catalysis of CuO–ZnO synthesized by deposition precipitation, co-precipitation and sol-gel methods. Sol-gel synthesized CuO–ZnO showed the highest catalytic performance, and the gasification efficiency was increased by 37.92% with it. The XRD, SEM-EDS and N₂ adsorption/desorption analysis showed that the priority of the sol-gel catalyst was the smallest crystallite size, largest specific surface area and high dispersion. For sol-gel synthesized CuO–ZnO, the increase of CuO/ZnO ratio improved the gasification efficiency but reduced H₂ selectivity. And the catalytic activity was reduced with the calcination temperature above 600 °C due to enlarged crystallites and reduced pores. During sol-gel preparation, both the addition of ethanol and PEG in the solvent reduced the agglomeration and improved the catalytic activity. With CuO–ZnO prepared with 1 g PEG + water as the solvent, the highest H₂ yield of 6.86 mol/kg was obtained, which was over 1.5 times of that without catalyst.     

Prediction of Flooding in Packed Liquid-Liquid and High-Pressure Extraction Columns Using a Gaussian Process

Reliable prediction of flooding conditions is needed for sizing and operating packed extraction columns. Due to the complex interplay of physicochemical properties, operational parameters and the packing-specific properties, it is challenging to develop accurate semi-empirical or rigorous models with a high validity range. State of the art models may therefore fail to predict flooding accurately. To overcome this problem, a data-driven model based on Gaussian processes is developed to predict flooding for packed liquid-liquid and high-pressure extraction columns. The optimized Gaussian process for the liquid-liquid extraction column results in an average absolute relative error (AARE) of 15.23 %, whereas the algorithm for the high-pressure extraction column results in an AARE of 13.68 %. Both algorithms can predict flooding curves for different packing geometries and chemical systems precisely.     

Catalytic supercritical water oxidation of tri-n-butyl phosphate: Process optimization by response surface methodology and cytotoxicity assessment

Catalytic supercritical water oxidation (SCWO) of an organophosphate flame retardant, namely tri-n-butyl phosphate (TNBP) was studied. Firstly, copper oxide nanoparticles (NPs) were synthesized in SCW and their properties were characterized by various analyses. Afterwards, their catalytic performance was investigated under different conditions including reaction temperature (400–500 °C), TNBP volume percentage in the feed (1–4%), oxidant ratio (0–2) and reaction time (50–150 min) based on response surface methodology (RSM). The synthesized CuO NPs had an average particle size of 30 nm with a narrow distribution. According to RSM analysis, the reaction temperature and time are the most significant factors; whereas, the impact of the other factors, especially TNBP volume percentage in the feed, was found to be negligible. Overall, excellent performance was achieved under optimal conditions found by the RSM, which was reaction temperature of 500 °C, TNBP volume percentage of 4%, oxidant ratio of 1.5, and reaction time of 90 min. The TOC removal efficiency as an indicator of TNBP degradation was about 99%. Finally, in vitro cell viability assays for the cytotoxicity evaluation of fresh and SCW-treated solution were applied. The results of MTT showed that SCWO converts TNBP into by-product that did not induce any cytotoxicity.     

Towards Diastereomeric Pure Salts with Antisolvent Methods

Chiral molecules, especially enantiomers and diastereomers of purity > 99 %, present a significant market share within the chemical, pharmaceutical, and flavor industries. Antisolvent precipitations, both batch and semicontinuous operations to serve the current trends in flow chemistry were demonstrated to be environmentally benign and efficient tools in achieving high optical purities. Although salts are known to be insoluble in supercritical CO₂, instabilities of the nascent salts were detected and applied for increasing efficiency. Diastereomeric excess values of the crystalline products exceeded 99 % in maximum of three consecutive steps both by repeated resolution with half molar equivalent of the amine to the acid and by direct recrystallization of the salts.     

600MW超临界CFB机组深度调峰运行技术

经通过分析超临界CFB机组在深度调峰方面的优势,结合600MW超临界CFB机组的实际运行工况,提出机组在深度调峰前应开展的试验工作。研究600MW超临界CFB机组的深度调峰过程,从汽机、锅炉、电气等方面提出有效的技术措施,解决深度调峰可能带来的锅炉流化不良、环保参数控制困难等问题。通过在600MW超临界CFB机组上应用,机组在30%负荷深度调峰运行,工况稳定,各项参数正常,取得了较好效果。     

High areal capacitance of FeOOH-carbon nanotube negative electrodes for asymmetric supercapacitors

The relatively low capacitance of negative electrodes, as compared to the capacitance of advanced positive electrodes, poses a serious problem, since this limits the development of asymmetric supercapacitor (SC) devices with a large voltage window and enhanced power-energy characteristics. We fabricate negative SC electrodes with a high capacitance that match the capacitance of advanced positive electrodes at similar active mass loadings, as high as 37?mg?cm^?2. Cyclic voltammetry, impedance spectroscopy, galvanostatic charge-discharge data and the power-energy characteristics of the asymmetric SC device exhibit good electrochemical performance for a voltage window of 1.6?V. Our approach involves the development and application of particle extraction through liquid-liquid interface (PELLI) methods, new extraction mechanisms and efficient extractors to synthesize α-FeOOH and β-FeOOH electrode materials. The use of PELLI allows agglomerate-free processing of powders, which facilitates their efficient mixing with multiwalled carbon nanotubes (MWCNT) and allows improved electrolyte access to the particle surface. Experiments to determine the properties of FeOOH-MWCNT composites provided insight into the influence of the electrode material and the structure of extractor molecules on the composite properties. The highest capacitance of 5.86?F?cm^?2 for negative electrodes and low impedance were achieved using α-FeOOH-MWCNT composites and a 16-phosphonohexadecanoic acid (PHDA) extractor. This extractor allows adsorption on particles, not only at the liquid-liquid interface, but also in the bulk aqueous phase and can potentially be used as a capping agent for particle synthesis and as an extractor in the PELLI method.     

抽采孔液态CO2预裂效果显微CT实验研究

为研究液态CO2预裂爆破后,煤体内裂隙发育情况,采用高精度微焦点显微CT系统,对预裂后不同区域的煤样进行CT扫描,并利用Photoshop进行孔裂隙占比统计学分析。研究结果显示,距预裂孔4 m处的煤体裂隙发育明显,孔裂隙占比增加了一倍,而在5 m处的煤体裂隙则发育较弱。表明抽采孔内采取液态C2预裂技术后,4 m范围内的煤体裂隙得到了充分发育,为瓦斯抽采提供了有利条件。     

吉林大情字井油田低阻油层的识别方法研究

吉林大情字井油田是一个具有多套含油层系的大型油田。由于本区构造幅度低、岩性细、地层水矿化度变化大以及钻井液滤液侵入等因素的影响，使得该区流体识别的难度大。通过分析油水层与测井曲线的典型对应关系，提出了适合本区的流体识别方法：微差识图法、电阻率增大法、油藏综合分析法。     

WAVE INTERACTION WITH PERFORATED CAISSON BREAKWATERS

The reflection coefficient of perforated caissons and the total horizontal forces acting on them were experimentally and numerically analyzed and discussed when wave propagates normally. To consider the viscosity effect of fluid and nonlinear action of waves on structures, the VOF (Volume Of Fluid) method combined with the k-ε turbulence model was used to simulate the interaction between waves and structures. Governing equations were solved with the finite difference method. Through 2D experimental study in the wave flume, the empirical relationship between the reflection coefficient of perforated caissons and the main affecting factors were obtained from the experimental data using the least square method. Also the correlation between the ratio of the total horizontal force acting on perforated caisson and the force acting on solid caisson and the main affecting factors were regressed from the experimental data.