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.     

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.     

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.     

双河油田注入水适应性及注水井酸化解堵研究

考察了双河油田双河联、江河联注入水堵塞地层的因素;膨胀性黏土，悬浮固体颗粒。细菌及悬浮污油。含膨胀性黏土的双河南、双河北及不含膨胀性黏土的双江岩心粉，在注入水中相对于地层水中的体积膨胀度分别为14．5％、11．1％及0．02％；注入100PV不含悬浮颗粒的等体积比地层水、注入水混合水使双河、双江岩心渗透率分别下降7％和4％、9％和7％。注入水中悬浮颗粒引起岩心渗透率下降，粒径越大、颗粒浓度越大、注入量越大，则渗透率越低。在粒径2．1μm或颗粒浓度3mg／L前后下降幅度变化较大。注入水中硫酸盐还原菌引起岩心渗透率下降，含菌量越大则渗透率开始下降时的注水量越小，注入含菌50个／L的水100PV使岩心渗透率下降7％。岩心对注水合油量敏感，注入含油量20mg／L的水50PV使岩心渗透率下降20％。在岩心注水实验中渗透率下降最严重的是双河南岩心，其次是双河北岩心．江河岩心较轻，注入精细过滤水的双河北岩心渗透率下降大大减少．说明悬浮固体是造成注水堵塞的主要因素。为了解除双河油田注水井的堵塞，研制了含黏土稳定剂、缓蚀剂、铁离子稳定剂、互溶剂的土酸液，与南阳油田使用的低伤害酸液一起，用于1口注水井的解堵，效果良好。图7表4参5。     

Experimental and modeling approaches of MR behaviors under large step strains

Rheological properties of MR fluids under large step strain shear are presented in this paper. The experiments were carried out using a rheometer with parallel-plate geometry. Under the large step strain shear, MR fluids behave as nonlinear viscoelastic properties, where the stress relaxation modulus, G(t, γ), shows a decreasing trend with step strain. The experimental results indicate that G(t, γ) obeys time-strain separability. Thus, a mathematical form based on finite exponential serials is proposed to predict MR behavior. In this model, G(t, γ) is represented as the product of a linear stress relaxation, G(t), and the damping function, h(γ), i.e. G(t, γ)=G(t) h(γ). G(t) is simply represented as a three-parameter exponential serial and h(γ) has a sigmoidal form with two parameters. The parameters are identified by adopting an efficient optimization method proposed by Stango et al. The comparison between the experimental results and the model-predicted values indicates that this mathematical model can accurately predict MR behavior.     

MEG钻井液在吐哈油田小井眼侧钻井中的应用

吐哈油田小井眼开窗侧钻井主要采用混原油钻井液,不利于环境保护。从研究MEG单体的作用机理入手,以钻井液润滑性、抑制防塌性为主要评价指标,对MEG钻井液配方进行了优选,并对优选配方钻井液性能进行了评价。该钻井液在4口小井眼开窗侧钻井进行了试验应用。结果表明:应用井无阻、卡现象,平均钻井周期缩短了7.2d;在未混原油的情况下钻井液润滑系数比乳化原油(15%~20%)钻井液降低了34.6%;油层保护效果好,其中温5-41C井日产油14.4t,同比温五区块平均产量提高了128.4%,神218C井是神229区块目前唯一的自喷井。表明优选出的MEG钻井液具有优良的润滑性、抑制防塌性及良好的储层保护效果,特别适合强水敏地层及大斜度井和水平井等特殊复杂工艺井的钻进。