CFD-PBM coupled modeling of the liquid-liquid dispersion characteristics and structure optimization for Kenics static mixer

Kenics static mixers(KSM)are extensively used in industrial mixing-reaction processes by virtue of high mixing efficiency,low power homogenization and easy continuous production.Resolving liquid droplet size and its distribution and thus revealing the dispersion characteristics are of great significance for structural optimization and process intensification in the KSM.In this work,a computational fluid dynamics-population balance model(CFD-PBM)coupled method is employed to systematically investigate the effects of operating conditions and structural parameters of KSM on droplet size and its distribution,to further reveal the liquid-liquid dispersion characteristics.Results indicate that higher Reynolds numbers or higher dispersed phase volume fractions increase energy dissipation,reducing Sauter mean diameter(SMD)of dispersed phase droplets and with a shift in droplet size distribution(DSD)towards smaller size.Smaller aspect ratios,greater blade twist and assembly angles amplify shear rate,leading to smaller droplet size and a narrower DSD in the smaller range.The degree of impact exerted by the aspect ratio is notably greater.Notably,mixing elements with different spin enhance shear and stretching efficiency.Compared to the same spin,SMD becomes 3.7-5.8 times smaller in the smaller size range with a significantly narrower distribution.Taking into account the pressure drop and efficiency in a comprehensive manner,optimized structural parameters for the mixing element encompass an aspect ratio of 1-1.5,a blade twist angle of 180°,an assembly angle of 90°,and interlaced assembly of adjacent elements with different spin.This work provides vital theoretical underpinning and future reference for enhancing KSM performance.

Numerical simulation of the Liquid-liquid phase separation and microstructure evolution of Al-In immiscible alloys during cooling

A numerical model has been developed to describe the microstructural evolution of Al In immiscible alloys through the miscibility gap. The model considers the common action of nucleation, diffusible growth, Brownian collision and motion collision between the second phase droplets. The simulation results are dynamically visualized and show that the volume fraction, distribution and size of the second phase droplets satisfactorily agree with the experimental results. So the model can be used to predict the microstructural evolution of Al In immiscible alloys during the cooling process.

Novel method for the determination of five carbamate pesticides in water samples by dispersive liquid-liquid microextraction combined with high performance liquid chromatography

A novel method for the determination of five carbamate pesticides （metolcarb, carbofuran, carbaryl, isoprocard and diethofencard） in water samples was developed by dispersive liquid-liquid microextraction （DLLME） coupled with high performance liquid chromatography-diode array detector （HPLC-DAD）. Some experimental parameters that influence the extraction efficiency were studied and optimized to obtain the best extraction results. Under the optimum conditions for the method, the calibration curve was linear in the concentration range from 5 to 1000 ng mL^-1 for all the five carbamate pesticides, with the correlation coefficients （r^2） varying from 0.9984 to 0.9994. Good enrichment factors were achieved ranging from 80 to 177- fold, depending on the compound. The limits of detection （LODs） （S/N = 3） were ranged from 0.1 to 0.5 ng mL^-1. The method has been successfully applied to the analysis of the pesticide residues in environmental water samples.

Ionic liquid based dispersive liquid-liquid microextraction of aromatic amines in water samples

In this work, a new microextraction method termed ionic liquid based dispersive liquid-liquid microextraction （IL-DLLME） was demonstrated for the extraction of 2-methylaniline, 4-chloroaniline, 1-naphthylamine and 4-aminobiphenyl in aqueous matrices. After extraction the ionic liquid （IL） phase was injected directly into the high performance liquid chromatography （HPLC） system for determination. Some parameters that might affect the extraction efficiency were optimized. Under the optimum conditions, good linear relationship, sensitivity and reproducibility were obtained. The limits of detection （LOD, S/N = 3） for the four analytes were in the range of 0.45-2.6 μg L^-1. The relative standard deviations （R.S.D., n = 6） were in the range of 6.2-9.8%. This method was applied for the analysis of the real water samples. The recoveries ranged from 93.4 to 106.4%. The main advantages of the method are high speed, high recovery, good repeatability and volatile organic solvent-free.

Dispersive liquid-liquid microextraction,an effective tool for the determination of synthetic cannabinoids in oral fluid by liquid chromatography-tandem mass spectrometry

In the present work,dispersive liquid-liquid microextraction(DLLME)was used to extract six synthetic cannabinoids(JWH-018,JWH-019,JWH-073,JWH-200,or WIN 55,225,JWH-250,and AM-694)from oral fluids.A rapid baseline separation of the analytes was achieved on a bidentate octadecyl silica hydride phase(Cogent Bidentate C18;4.6 mm×250 mm,4μm)maintained at 37℃,by eluting in isocratic conditions(water:acetonitrile(25:75,V/V)).Detection was performed using positive electrospray ionization-tandem mass spectrometry.The parameters affecting DLLME(pH and ionic strength of the aqueous phase,type and volume of the extractant and dispersive solvent,vortex and centrifugation time)were optimized for maximizing yields.In particular,using 0.5 mL of oral fluid,acetonitrile(1 mL),was identified as the best option,both as a solvent to precipitate proteins and as a dispersing solvent in the DLLME procedure.To select an extraction solvent,a low transition temperature mixture(LTTM;composed of sesamol and chlorine chloride with a molar ratio of 1:3)and dichloromethane were compared;the latter(100μL)was proved to be a better extractant,with recoveries ranging from 73%to 101%by vortexing for 2 min.The method was validated according to the guidelines of Food and Drug Administration bioanalytical methods:intra-day and inter-day precisions ranged between 4%and 18%depending on the spike level and analyte;limits of detection spanned from 2 to 18 ng/mL;matrixmatched calibration curves were characterized by determination coefficients greater than 0.9914.Finally,the extraction procedure was compared with previous methods and with innovative techniques,presenting superior reliability,rapidity,simplicity,inexpensiveness,and efficiency.

Dispersive Liquid-liquid Microextraction Combined with High-performance Liquid Chromatography for the Determination of Clozapine and Chlorpromazine in Urine

A simple method has been proposed for the determination of clozapine （CLZ） and chlorpromazine （CPZ） in human urine by dispersive liquid-liquid microextraction （DLLME） in combination with high-performance liquid chromatography-ultraviolet detector （HPLC-UV）. All important variables influencing the extraction efficiency, such as pH, types of the extraction solvent and the disperser solvent and their volume, ionic strength and centrifugation time were investigated and optimized. Under the optimal conditions, the limit of detection （LODs） and quantification （LOQs） of the method were 13 and 39 ng/mL for CLZ, and 2 and 6 ng/mL for CPZ, respectively. The relative standard deviations （RSDs） of the targets were less than 5.1% （C=0.100 μg/mL, n=9）. Good linear behaviors over the tested concentration ranges were obtained with the values of R20.999 for the targets. The absolute extraction efficiencies of CLZ and CPZ from the spiked blank urine samples were 98.3% and 97.8%, respectively. The applicability of the technique was validated by analyzing urine samples and the mean recoveries for spiked urine samples ranged from 93.3% to 105.0%. The method was successfully applied for the determination of CLZ and CPZ in real human urine.

Utilization of Dispersive Liquid-Liquid Microextraction Coupled with HPLC-UV as a Sensitive and Efficient Method for the Extraction and Determination of Oleanolic Acid and Ursolic Acid in Chinese Medicinal Herbs

Isomeric triterpenic acids of oleanolic acid (OA) and ursolic acid (UA) both have very low ultraviolet absorption and always exist in the same plant, so the separation and simultaneous determination of them have been a difficult task. In this study, a sensitive method combining dispersive liquid-liquid microextraction (DLLME) with HPLC-UV was developed for the extraction and determination of OA and UA in traditional Chinese medicinal herbs (CMHs). Variables influencing DLLME such as type and volume of extraction solvent, volume of dispersive solvent, ionic strength, aqueous phase pH, extraction time, centrifugation speed and time, and sample volume were investigated and optimized. Under the optimum conditions, both OA and UA attained favorable extraction efficiencies with enrichment factors 1378 and 933, respectively. The linear dynamic ranges of 0.07 - 30.4 μg?mL–1 for OA and 0.08 - 33.6 μg?mL–1 for UA were obtained with square correlation coefficients of 0.9963. The detection limits of OA and UA were both 0.02 μg?mL–1. The method recoveries ranged between 88.2% - 116.2% for OA and 85.7% - 108.2% for UA with the RSDs (n = 5) lower than 8.6%. The proposed method was successfully applied to concentrate and simultaneously determine these two triterpenic acids in Hedyotis diffusa and Eriobotrya japonica samples.

Determination of Cobalt in Food, Environmental and Water Samples with Preconcentration by Dispersive Liquid-Liquid Microextraction

A new method for the determination of cobalt was developed by dispersive liquid-liquid microextraction preconcentra-tion and flame atomic absorption spectrometry. In the proposed approach, 1,5-bis(di-2-pyridyl) methylene thiocarbohydrazide (DPTH) was used as a chelating agent, and chloroform and ethanol were selected as extraction and dispersive solvents. Some factors influencing the extraction efficiency of cobalt and its subsequent determination, including extraction and dispersive solvent type and volume, pH of sample solution, concentration of the chelating agent, and extraction time, were studied and optimized. Under the optimum conditions, a preconcentration factor of 8 was reached. The detection limit for cobalt was 12.4 ng?mL–1, and the relative standard deviation (RSD) was 3.42% (n = 7, c = 100 ng?mL–1). The method was successfully applied to the determination of cobalt in food, environmental and water samples.

Evaluation of Response Surface Methodology in Dispersive Liquid-Liquid Microextraction for Lead Determination Using Ionic Liquids

This paper describes a dispersive liquid–liquid microextraction (DLLME) procedure using room temperature ionic liquids (RTILs) coupled with flame atomic absorption spectrometry detection with microsample intro-duction system capable of quantifying trace amounts of lead. In the proposed approach, ammonium pyr-rolidine dithiocarbamate (APDC) was used as a chelating agent and 1-hexyl-3-methylimmidazolium bis (trifluormethylsulfonyl)imid as an extraction solvent was dissolved in acetone as the disperser solvent. The binary solution was then rapidly injected by a syringe into the water sample containing Pb2+ complex. Some factors influencing the extraction efficiency of Pb2+ and its subsequent determination, including extraction and dispersive solvent type, pH of sample solution, concentration of the chelating agent and salt effect were inspected by a full factorial design to identify important parameters and their interactions. Next, a central composite design was applied to obtain the optimum points of the important parameters. Under the optimum conditions, the limit of detection (LOD) was 0.2 μg/L. The relative standard deviation (R.S.D) was 1.4% for 5 μg/L of Pb2+ (n = 7). The relative recovery of lead in seawater, blood, tomato and black tea samples was measured.

Determination of organochlorine pesticides from juice samples using magnetic biochar-based dispersive micro-solid phase extraction in combination with dispersive liquid-liquid microextraction

Analysis of pesticide residue levels in juice beverages is important to ensure safe consumption and avoid global trade concerns associated to pesticide contaminations.A simple,inexpensive and effective method was developed for the determination of organochlorine pesticides(OCPs)in bottled juice drinks using GC-MS.Sample pretreatment was performed using dispersive solid-phase microextraction(D-μ-SPE)for matrix desorption and dispersive liquid-liquid microextraction(DLLME)for analyte enrichment.In this study,an affordable and effective sorbent for the adsorption of OCPs from juice samples was synthesized from avocado seeds mixed with magnetic precursors for D-μSPE.The ground avocado seeds combined with a magnetic precursor nanocomposite were characterized using various instruments including scanning electron microscopy(SEM),X-ray diffraction(XRD),Fourier transform infrared spectroscopy(FTIR),and Brunauer-Emmett-Teller(BET)analysis.The solution obtained from D-μ-SPE desorption was used as a dispersant for the subsequent DLLME,which made the combination of D-μ-SPE with DLLME much easier.The effectiveness of the method was enhanced by optimizing the influential parameters in both D-μ-SPE and DLLME.Then after,the optimal values were determined for the real sample analysis.Accordingly,there was good linear dynamic range with a coefficient of determination(r2)≥0.9989.The limit of detection and quantification were 0.02–0.69 and 0.06–2.10 ng/L respectively.The method showed high enrichment factors ranging from 96 to 313 with recoveries of 87–100%.Intraday and interday precisions were≤4%.Compared with other reported methods,this method is a one-step,simple,cheap,fast,and environmentally friendly alternative and straightforward method for adsorbing organochlorine pesticides from sample solutions.These results demonstrates the high potential of the proposed method for the extraction and cleanup of contaminants in selected juices and other related samples.

Melt-Fluid and Fluid-Fluid Immiscibility in a Na_(2)SO_(4)-SiO_(2)-H_(2)O System and Implications for the Formation of Rare Earth Deposits

Liquid-liquid immiscibility has crucial influences on geological processes,such as magma degassing and formation of ore deposits.Sulfate,as an important component,associates with many kinds of deposits.Two types of immiscibility,including(i)fluid-melt immiscibility between an aqueous solution and a sulfate melt,and(ii)fluid-fluid immiscibility between two aqueous fluids with different sulfate concentrations,have been identified for sulfate-water systems.In this study,we investigated the immiscibility behaviors of a sulfate-and quartz-saturated Na_(2)SO_(4)-SiO_(2)-H_(2)O system at elevated temperature,to explore the phase relationships involving both types of immiscibility.The fluid-melt immiscibility appeared first when the Na_(2)SO_(4)-SiO_(2)-H_(2)O sample was heated to~270℃,and then fluid-fluid immiscibility emerged while the sample was further heated to~450℃.At this stage,the coexistence of one water-saturated sulfate melt and two aqueous fluids with distinct sulfate concentrations was observed.The three immiscible phases remain stable over a wide pressure-temperature range,and the appearance temperature of the fluid-fluid immiscibility increases with the increased pressure.Considering that sulfate components occur extensively in carbonatite-related deposits,the fluid-fluid immiscibility can result in significant sulfate fractionation and provides implications for understanding the formation of carbonatite-related rare earth deposits.

Determination of Vanadyl Porphyrins by Liquid-liquid Microextraction and Nano-baskets of p-tert-Calix[4]arene Bearing Di-[N-(X)sulfonye Carboxamide] and Di-(1-propoxy) in Ortho-cone Conformation

Dispersive liquid-liquid microextraction technique was introducd to remove the centrifuging step and conduct inclusion microextraction of charged porphyrins by nano-baskets. For nano-baskets of p-tert-calix[4]arene bearing di-[N-（X）sulfonyl carboxamide] and di-（1-propoxy） in ortho-cone conformation was synthesized and used. The related parameters including ligand concentration, the volume of water disperser, salt effect, and extraction time were optimized. The linear range, detection limit（S/N=3） and precision（RSD, n=6） were determined to be 0.2―50, 0.07 μg/L and 5.3%, respectively. The results reveal that the new approach is competitive analytical tool and an alternative of the traditional methods in the crude oil and related systems.

Behavior of Liquid-Liquid Dispersions in a Stirred Vessel——Part 2: Phase Inversion Delay Time

A delay time was observed for both W/O inversion to O/W and the opposite inversion process. The delay time decreased with increasing stirring speed. For O/W inversion to W/O, the delay time was very sensitive to the oil volume fraction and the initial stirring speed. Increased oil volume fraction and increased initial stirring speed both reduced the delay time. Inversion from W/O to O/W was a gradual process. But inversion from O/W to W/O had two stages: the preparation stage and the phase inversion stage. The time needed in the first stage was the delay time.

Investigation of Phase Inversion of Liquid-Liquid Dispersions in Agitated Vessels

In this paper we report results from on-going theoretical and experimental studies carried out jointly at Imperial College London and University College London. Laser-induced fluorescence （LIF） is used to investigate liquid-liquid phase inversion experimentally and to observe in detail phenomena that accompany the inversion process, such as secondary dispersions and drop coalescence and breakup. Theoretically, a two-region model together with a criterion based on a dynamic balance between drop coalescence and breakup is employed to predict phase inversion. The concept of a radial distribution function for hard spheres was also utilized in order to better model the interaction of drops at high dispersed phase holdup, The modeling work is capable of predicting the existence of ambivalent ranges which are in good agreement with experimental observations.

Behavior of Liquid-Liquid Dispersions in a Stirred Vessel——Part 1: Uniformity Property

The conductivity of liquid-liquid dispersions in a stirred vessel was measured at different sampling positions inside the vessel. The results showed that both O/W dispersions and W/O dispersions are not spatially uniform inside the vessel, especially the W/O dispersions. The results provide further understanding of the properties of the liquid-liquid dispersions.

The ion transfer of the basic dye rhodamine B across the liquid-liquid interface of two immiscible solvents

The ion transfer of the basic dye rhodamine B at the interface between water and nitro- benzene,water and 1,2-dichloroethane,as well as water and nitrobenzene-chlorobenzene mixtures has been studied by cyclic voltammetry and chronopotentiometry with linear current scanning.A transfer mechanism of rhodamine B is proposed in terms of its electrochemical behavior,dissociation and distribution equilibria,and is ascribed as diffusion-controlled reversible process of rhodamine B.The ex- perimental data obtained for the relationship between interfacial half-wave potential ° and pH are in agreement with the theoretical equation based on the mechanism,and the standard interracial potential differences °and standard Gibbs energies G°are calculated by extrapolation.The effect of the nature of solvent on the transfer behavior and the stability of the interface have been dis- cussed.

流场下不相容聚合物共混物分散相形态的研究进展

介绍了流场下不相容聚合物共混物分散相形态及演变研究进展,并指出这是获得性能优异共混材料的关键。在流场下,不相容共混物分散相尺寸由破碎和凝聚等动力学过程决定。鉴于模型的理想化,早期研究主要针对牛顿流体,且分散相的变形、破碎和凝聚等理论均发源于此。对于聚合物共混物,其在本质上与牛顿流体有很多相似之处,然而,独特黏弹性质却是影响其相形态的重要因素。最后,对一些预测分散相尺寸的理论模型进行了总结,并重点讨论了分散相浓度、聚合物弹性、增容和填料等因素对流场下分散相形态的影响。

不溶混聚合物共混体系相态尺寸的研究进展

阐述了不溶混聚合物共混体系相态的形成与发展过程 ,对影响共混体系相态尺寸的因素进行了分析 ,通过对目前建立的各种分散相粒径大小及其聚结概率计算公式的介绍与分析 。

分散液液微萃取-反相液液微萃取-扫集-胶束电动色谱法测定红酒中的3种氯酚类物质

建立了分散液液微萃取（DLLME）-反相液液微萃取（RP-LLME）-扫集-胶束电动色谱富集模型，并用于红酒中五氯酚（PCP）、2，4，6-三氯酚（TCP）和2，4-二氯酚（DCP）3种氯酚的测定。实验考察了两步微萃取的萃取参数对氯酚萃取率的影响和样品分离富集的电泳条件。最佳萃取条件 DLLME 为：3.5 mL 红酒（ pH 3.0，120 g / L NaCl），300μL 正己烷（萃取剂）；RP-LLME 为：25μL 0.16 mol / L NaOH（萃取剂）。最佳电泳条件：25 mmol / L NaH2 PO4，100 mmol / L 十二烷基硫酸钠（ SDS），30％（ v / v）乙腈，pH 2.3；分离电压-15 kV；样品基质为80 mmol / L NaH2 PO4；压力进样20 s×20.67 kPa（3 psi）。PCP 和 TCP 的线性范围为0.5～100μg / L（ r≥0.9910）， DCP 的线性范围为1.5～80μg / L（r =0.9851）。3种分析物的检出限（ S / N =3）为0.035～0.114μg / L，加标回收率为75.2％～104.7％，相对标准偏差≤6.17％。该方法富集倍数高、灵敏度高、重现性好、分析速度快，可为不同样品基质中痕量氯酚污染物及某些弱酸性有机污染物测定提供参考。

双相不混溶流体饱和裂缝——孔隙岩石依赖频率的地震响应数值分析

裂缝—孔隙岩石中流体类型及其分布特征是影响弹性参数的重要因素,实际储层中流体大多不是单一流体,且在数值模拟过程中很少考虑流体间饱和状态的影响。为此,基于Chapman模型,针对饱含双相不混溶流体的裂缝—孔隙岩石,研讨了饱和度和毛细压力参数变化对砂岩储层频散衰减和地震响应的影响。数值分析结果表明:随着油气饱和度的增加,特征频率(不同于于单一流体介质情形)呈先减后增趋势,且在中间频段的变化最明显,地震响应存在时间延迟和波形畸变现象;当双相流体中存在气体时,频散衰减和地震响应对饱和度的变化更敏感;随着衡量流体间毛细压力的参数q值的增加,双相流体间由"斑块饱和"趋向"均匀饱和"状态,特征频率向着"高频低饱"方向移动。该数值模拟结果为储层流体识别提供了有效依据。