An experimental study of immiscible liquid–liquid dispersions in a pump–mixer of mixer–settler

Drop size distribution(DSD) or mean droplet size(d32) and liquid holdup are two key parameters in a liquid–liquid extraction process. Understanding and accurately predicting those parameters are of great importance in the optimal design of extraction columns as well as mixer–settlers. In this paper, the method of built-in endoscopic probe combined with pulse laser was adopted to measure the droplet size in liquid–liquid dispersions with a pump-impeller in a rectangular mixer. The dispersion law of droplets with holdup range 1% to 24% in batch process and larger flow ratio range 1/5 to 5/1 in continuous process was studied. Under the batch operation condition, the DSD abided by log-normal distribution. With the increase of impeller speed or decrease of dispersed phase holdup, the d32 decreased. In addition, a prediction model of d32 of kerosene/deionized system was established as d_(32)/D = 0.13(1 + 5.9φ)We~(-0.6). Under the continuous operation condition, the general model for droplet size prediction of kerosene/water system was presented as d_(32)/D = C_3(1 + C_4φ)We~(-0.6). For the surfactant system and extraction system, the prediction models met a general model as d_(32)/D = bφ~nWe~(-0.6).     

Prediction of liquid–liquid equilibrium from the Peng–Robinson+COSMOSAC equation of state

An approach combining the Peng–Robinson equation of state and novel solvation free energy calculation is developed here to describe the liquid–liquid equilibria for highly nonideal mixtures. This method has been previously shown to provide reliable vapor–liquid equilibria of pure and mixture fluids. The hydrogen-bonding interaction in this model is refined in order to properly describe the variation in the strength of hydrogen bond between different types of species. This method contains only 15 global parameters and 3 element-specific parameters (one atomic radius and two for the dispersion energy), and can be used to predict the miscibility gap of liquid mixtures and its temperature variations without sacrificing its capability in predicting vapor–liquid equilibria. The overall root-mean-square error in the mutual solubility of 68 binary mixtures predicted from PR+COSMOSAC is 0.0689, compared to those from the Modified UNIFAC 0.0822 and UNIFAC-LLE 0.0697, respectively.     

Characteristics of liquid slugs in gas–liquid Taylor flow in microchannels

The hydrodynamics of liquid slugs in gas–liquid Taylor flow in straight and meandering microchannels have been studied using micro Particle Image Velocimetry. The results confirm a recirculation motion in the liquid slug, which is symmetrical about the center line of the channel for the straight geometry and more complex and three-dimensional in the meandering channel. An attempt has also been made to quantify and characterize this recirculation motion in these short liquid slugs (L_s/w<1.5) by evaluating the recirculation rate, velocity and time. The recirculation velocity was found to increase linearly with the two-phase superficial velocity U_TP. The product of the liquid slug residence time and the recirculation rate is independent of U_TP under the studied flow conditions. These results suggest that the amount of heat or mass transferred between a given liquid slug and its surroundings is independent of the total flow rate and determined principally by the characteristics of the liquid slug.     

Predicting the diameters of droplets produced in turbulent liquid–liquid dispersion

The droplet size distribution in liquid–liquid dispersions is a complex convolution of impeller speed, impeller type, fluid properties, and flow conditions. In this work, we present three a priori modeling approaches for predicting the droplet diameter distributions as a function of system operating conditions. In the first approach, called the two-fluid approach, we use high-resolution solutions to the Navier–Stokes equations to directly model the flow of each phase and the corresponding droplet breakup/coalescence events. In the second approach, based on an Eulerian–Lagrangian model, we describe the dispersed fluid as individual spheres undergoing ongoing breakup and coalescence events per user-defined interaction kernels. In the third approach, called the Eulerian–Parcel model, we model a sub-set of the droplets in the Eulerian–Lagrangian model to estimate the overall behavior of the entire droplet population. We discuss output from each model within the context of predictions from first principles turbulence theory and measured data.     

Development of a model for thin-film stability and spreading in solid–liquid–liquid systems

The presence of thin aqueous films and their stability has a profound effect on reservoir rock–fluids interactions involved in spreading and adhesion. The stability of thin wetting aqueous films on rock surfaces is governed by several variables including pH, brine and crude oil compositions, and capillary pressure. These variables govern the wetting states in the solid–liquid–liquid systems. The wetting states influence the residual oil saturation and the oil-water relative permeabilities and, consequently, the oil recovery. The objective of this study was to deduce a functional dependence of thin-film stability on the above parameters by considering intermolecular and surface interactions in rock–crude oil–brine systems. The surface forces are manifested as disjoining pressure in thin films. The disjoining pressure isotherms for the selected solid–liquid–liquid systems have been computed in terms of the bulk properties of the media. The equilibrium contact angles have also been computed from the integration of the Young–Laplace equation, which relates contact angle to the capillary pressure and disjoining pressure isotherm of the system. The contact-angle data obtained from sessile-drop experiments have been compared with the calculated results, as well as with other published results. Adhesion maps, which relate the film stability to brine pH and molarity, have been developed. The rock–fluids systems considered for this study consisted of smooth glass, quartz and Yates reservoir fluids. The DLVO theory has been used to model the intermolecular forces. The structural forces are incorporated to overcome the limitations of the DLVO theory. A charge regulation model has been used to analyze the crude oil–brine and glass–brine interfaces. The effects of multivalent ions have been incorporated using an equivalent molarity concept. The overall computational model developed in this study is aimed at providing a priori prediction capability of rock-fluids interactions in petroleum reservoirs for inclusion in reservoir simulators.     

CFD modelling of liquid–liquid multiphase microstructured reactor: Slug flow generation

Microreactor technology, an important method of process intensification, offers numerous potential benefits for the process industries. Fluid–fluid reactions with mass transfer limitations have already been advantageously carried out in small-scale geometries. In liquid–liquid microstructured reactors (MSR), alternating uniform slugs of the two-phase reaction mixture exhibit well-defined interfacial mass transfer areas and flow patterns. The improved control of highly exothermic and hazardous reactions is also of technical relevance for large-scale production reactors. Two basic mass transfer mechanisms arise: convection within the individual liquid slugs and diffusion between adjacent slugs. The slug size in liquid–liquid MSR defines the interfacial area available for mass transfer and thus the performance of the reactor. There are two possibilities in a slug flow MSR depending on the interaction of the liquids with the solid wall material: a dispersed phase flow in the form of an enclosed slug in the continuous phase (with film—complete wetting of the continuous phase) and an alternate flow of two liquids (without film—partial wetting of the continuous phase). In the present work, a computational fluid dynamics (CFD) methodology is developed to simulate the slug flow in the MSR for both types of flow systems. The results were validated with the experimental results of Tice et al. (J.D. Tice, A.D. Lyon and R.F. Ismagilov, Effects of viscosity on droplet formation and mixing in microfluidic channels, Analytica Chimica Acta507 (1) (2004), pp. 73–77.).     

Mass transfer behavior of liquid–liquid slug flow in circular cross-section microchannel

An alkaline hydrolysis reaction was used as the model reaction to investigate the performance of liquid–liquid slug flow microchannel. The specific interfacial area was determined through the photographic snapshot method physically by means of measuring the lengths of relevant slugs. The overall volumetric mass transfer coefficients were calculated through the Danckwerts’ model chemically. The influences of various operating conditions on the slug length, the overall volumetric extraction rate and the mass transfer coefficient were investigated quantitatively. A decreasing trend of volumetric mass transfer coefficients along the channel length was found. The linear dependence of the volumetric extraction rate on the volumetric mass transfer coefficient indicates that the overall rate of the process is determined by the mass transfer process. In addition, the volumetric mass transfer coefficients were correlated for different channel lengths.     

Modelling and constraint optimisation of an aromatic nitration in liquid–liquid medium

A methodology, which determines the operating conditions simultaneously optimising the chemical yield and considering the safety aspect, has been developed for a chemical reaction which is carried out batch-wise. To illustrate the methodology, the aromatic nitration of toluene by mixed acid has been chosen as a typical exothermic and non-selective reaction. This reaction takes place in a two-phase medium and, therefore, involves simultaneously chemical reaction and mass transfer phenomena. A kinetic model recently proposed for the slow and fast liquid–liquid reaction regimes was integrated to the mass balance. Nitration experiments were carried out in order to compare experimental composition profiles with simulated ones. Afterwards, an optimisation procedure has been used to maximise conversion, by manipulating the operating conditions subject to safety constraints. The p-nitrotoluene yield was chosen as the criterion to be maximised. Experimental validation for the optimisation procedure has been carried out. A monofluid heating–cooling system controlled by a predictive controller was used for the temperature control of the reactor. Simulation and experimental results are presented, discussed and compared.     

Desulfurization of liquid hydrocarbon fuels via Cu_2O catalyzed photooxidation coupled with liquid–liquid extraction

By combining the photochemical reaction and liquid–liquid extraction(PODS), we studied desulfurization of model fuel and FCC gasoline. The effects of air flow, illumination time, extractants, volume ratios of extractant/fuel, and catalyst amounts on the desulfurization process of PODS were analyzed in detail. Under the conditions with the air as oxidant(150 ml·min~(-1)), the mixture of DMF–water as extractant(the volume ratio of extractant/oil of 0.5) and photo-irradiation time of 2 h, the sulfur removal rate reached only 42.63% and 39.54% for the model and FCC gasoline, respectively. Under the same conditions, the sulfur removal rate increased significantly up to79% for gasoline in the presence of Cu_2O catalyst(2 g·L~(-1)). The results suggest that the PODS combined with a Cu_2O catalyst seems to be a promising alternative for sulfur removal of gasoline.     

Salting-out-assisted liquid–liquid extraction and reverse-phase high-performance liquid chromatographic monitoring of thiacloprid in fruits and vegetables

Salting-out-assisted liquid–liquid extraction (SALLE) was developed to extract thiacloprid (THI) from fruits and vegetables. SALLE conditions (NaCl/Na₂SO₄, pH, and solvent polarity) were investigated at various levels for the optimal recovery of THI. Meanwhile, reverse-phase high-performance liquid chromatographic (RP-HPLC) conditions were balanced over 1–100 µg/mL of THI. The optimized SALLE-RP-HPLC method offered 78.33–92.00% recovery of standard THI at an acceptable repeatability 1.81–4.30% and reproducibility 1.08–4.74%. The detection and quantification limits were found to be 0.03 and 0.05 µg/mL, respectively. The real-time analysis verifies its suitability and ease of use for the determination of THI in agricultural commodities.     

Evaporative liquid jets in gas–liquid–solid flow system

Some aspects of the fundamental characteristics of evaporative liquid jets in gas–liquid–solid flows are studied and some pertinent literature is reviewed. Specifically, two conditions for the solids concentration in the flow are considered, including the dilute phase condition as in pneumatic convey and the dense phase condition as in bubbling or turbulent fluidized beds. Comparisons of the fundamental behavior are made of the gas–solid flow with dispersed non-evaporative as well as with evaporative liquids.For dilute phase conditions, experiments and analyses are conducted to examine the individual phase motion and boundaries of the evaporative region and the jet. Effects of the solids loading and heat capacity, system temperature, gas flow velocity and liquid injection angle on the jet behavior in gas and gas–solid flows are discussed. For dense phase conditions, experiments are conducted to examine the minimum fluidization velocity and solids distribution across the bed under various gases and liquid flow velocities. The electric capacitance tomography is developed for the first time for three-phase real time imaging of the dense gas–solid flow with evaporative liquid jets. The images reflect significantly varied bubbling phenomenon compared to those in gas–solid fluidized beds without evaporative liquid jets.     

Effect of operating factors on liquid–liquid mass transfer and dispersion pattern of sedimentary liquid in a mechanically stirred vessel

Liquid–liquid dispersion and mass transfer were investigated in mechanically stirred vessels without baffles by changing operation factors such as an impeller rotation speed, off-bottom clearance, volumetric liquid ratio, etc. The dispersion regime was categorized into five groups: the sedimentary liquid was kept at the vessel bottom (I), partially elevated without any collision (II), partially dispersed by colliding with the impeller bottom (III), both liquids were partially dispersed by collisions with impeller blades (III’), and the sedimentary liquid was completely dispersed (IV). The dispersion switched to I → II → III → IV with the increasing rotation speed and decreasing off-bottom clearance. The liquid–liquid mass transfer rate was significantly enhanced with the collision of the sedimentary liquid with the impeller bottom, and subsequently increased with the increasing rotation speed, volumetric liquid ratio, and vessel diameter and with the decreasing off-bottom clearance. A multiple regression analysis method was applied to determine the mass transfer rates of III and III’.     

Polymeric liquid precursor of multi-component ZrC–SiC ceramic

Polymeric liquid ceramic precursors for the production of multi-component ZrC–SiC ceramics were prepared by reactive blending of polyzirconoxanesal, phenylacetylene-terminated polysilane and bisphenol-A type benzoxazine. The polymeric liquid precursors of ZrC–SiC ceramic have the processing capability of Precursor-Infiltration-and-Pyrolysis technique in ceramic composites fabrication. The thermal cure reactions included by the catalytic polymerisation of ethynyl groups, the ring opening polymerisation of benzoxazine rings, and the condensation of zirconate with phenolic hydroxyl and Si–H at 200–350°C. The monolithic ceramics were formed upon pyrolysis at 1000, 1200 and 1600°C in a yield of 65, 62 and 40%, respectively. X-ray diffraction and SEM–EDS results revealed that almost pure, elemental, uniformly distributed ZrC–SiC multi-component ceramic monolith was obtained through pyrolysis at 1600°C via carbothermal reduction of ZrO₂.     

Numerical simulation of micro-mixing in gas–liquid and solid–liquid stirred tanks with the coupled CFD-E-model

The coupled CFD-E-model for multiphase micro-mixing was developed, and used to predict the micro-mixing effects on the parallel competing chemical reactions in semi-batch gas–liquid and solid–liquid stirred tanks. Based on the multiphase macro-flow field, the key parameters of the micro-mixing E-model were obtained with solving the Reynolds-averaged transport equations of mixture fraction and its variance at low computational costs. Compared with experimental data, the multiphase numerical method shows the satisfactory predicting ability. For the gas–liquid system, the segregated reaction zone is mainly near the feed point, and shrinks to the exit of feed-pipe when the feed position is closer to the impeller. Besides, surface feed requires more time to completely exhaust the added H⁺ solution than that of impeller region feed at the same operating condition. For the solid–liquid system, when the solid suspension cloud is formed at high solid holdups, the flow velocity in the clear liquid layer above the cloud is notably reduced and the reactions proceed slowly in this almost stagnant zone. Therefore, the segregation index in this case is larger than that in the dilute solid–liquid system.     

Experimental study and hydrodynamic modeling of countercurrent liquid–solid system with batch liquid

It is known that a transient effluent outlet concentration is obtained with a batch of adsorbent solids in any operation. A preferred steady state outlet concentration can be achieved with a continuous flow of solids. In the present work, information on pressure profiles, the total pressure drop across the column and holdup of solids are experimentally obtained for various solid flow rates, particle sizes and densities in a countercurrent liquid–solid system. These experimental results are compared with the prediction obtained using a phenomenological model containing continuity and momentum balance equations. The dominant drag force term was expressed in terms of various drag equations. The drag expression developed by Foscolo et al. (1983 Foscolo, P. U., Gibilaro, L. G., and Waldram, S. P. (1983). A unified model for particulate expansion of fluidized beds and flow in fixed porous media, Chem. Eng. Sci., 38(8), 1251–1260.[Crossref], [Web of Science ®] , [Google Scholar]) could predict the axial profiles of pressure drop and holdup, and the effect of various parameters on total pressure drop and solid holdup most satisfactorily.     

On the effect of phase fraction on drop size distribution of liquid–liquid dispersions in agitated vessels

The theory of Kolmogorov–Hinze is the base for many studies that have been done on mean drop size and drop size distribution of liquid–liquid dispersions in agitated vessels. Although this theory has been used extensively in the literature, but it does not always give a satisfactory result in the studies and therefore needs to be modified. This paper addresses the effect of phase fraction on drop size distribution in agitated vessels and on the proportionality coefficient and Weber number exponent in the relation d₃₂/D ∝ We^m. The experimental data that were taken from Pacek et al. (1998) and Desnoyer et al. (2003) have been applied to this relation to investigate the effect of phase ratio. It is shown that even at low phase fractions, the Kolmogorov–Hinze theory necessarily does not give the best result with the −0.6 exponent for the Weber number. Furthermore, for the non-coalescing system, a range of exponent for the Weber number typically from −0.6 to −0.43 can be considered where the system may be approximated as a pseudo-coalescing system at Φ = 0.4 in which the obtained results are in good agreement with the results of Pacek et al. (1998).     

Spray and mixing characteristics of liquid jet in a tubular gas–liquid atomization mixer

For the design and optimization of a tubular gas–liquid atomization mixer,the atomization and mixing characteristics of liquid jet breakup in the limited tube space is a key problem.In this study,the primary breakup process of liquid jet column was analyzed by high-speed camera,then the droplet size and velocity distribution of atomized droplets were measured by Phase-Doppler anemometry (PDA).The hydrodynamic characteristics of gas flow in tubular gas–liquid atomization mixer were analyzed by computational fluid dynamics (CFD) numerical simulation.The results indicate that the liquid flow rate has little effect on the atomization droplet size and atomization pressure drop,and the gas flow rate is the main influence parameter.Under all experimental gas flow conditions,the liquid jet column undergoes a primary breakup process,forming larger liquid blocks and droplets.When the gas flow rate (Q_g) is less than 127 m~3·h~(-1),the secondary breakup of large liquid blocks and droplets does not occur in venturi throat region.The Sauter mean diameter (SMD) of droplets measured at the outlet is more than 140μm,and the distribution is uneven.When Q_g127 m~3·h~(-1),the large liquid blocks and droplets have secondary breakup process at the throat region.The SMD of droplets measured at the outlet is less than 140μm,and the distribution is uniform.When 127Q_g162 m~3·h~(-1),the secondary breakup mode of droplets is bag breakup or pouch breakup.When 181Q_g216 m~3·h~(-1),the secondary breakup mode of droplets is shear breakup or catastrophic breakup.In order to ensure efficient atomization and mixing,the throat gas velocity of the tubular atomization mixer should be designed to be about 51 m·s~(-1)under the lowest operating flow rate.The pressure drop of the tubular atomization mixer increases linearly with the square of gas velocity,and the resistance coefficient is about 2.55 in single-phase flow condition and 2.73 in gas–liquid atomization condition.     

The effect of scale and interfacial tension on liquid–liquid dispersion in in-line Silverson rotor–stator mixers

The effect of scale, processing conditions, interfacial tension and viscosity of the dispersed phase on power draw and drop size distributions in three in-line Silverson rotor–stator mixers was investigated with the aim to determine the most appropriate scaling up parameter. The largest mixer was a factory scale device, whilst the smallest was a laboratory scale mixer. All the mixers were geometrically similar and were fitted with double rotors and standard double emulsor stators. 1 wt.% silicone oils with viscosities of 9.4 mPa s and 339 mPa s in aqueous solutions of surfactant or ethanol were emulsified in single and multiple pass modes. The effect of rotor speed, flow rate, dispersed phase viscosity, interfacial tension and scale on drop size distributions was investigated.     

Hydrodynemics of a cocurrent upflow liquid–liquid reciprocating plate reactor for homogeneously base-catalyzed methanolysis of vegetable oils

Hydrodynamics of a continuous cocurrent two-phase upflow reciprocating plate reactor (RPR) for homogeneously base-catalyzed methanolysis of sunflower oil was studied. Here, methanol constituted the dispersed phase and sunflower oil was the continuous phase. The measurements were performed in both the non-reactive (methanol–sunflower oil) and reactive (sunflower oil–methanol–KOH) systems. The main goal was to define the effects of the vibration intensity and the important reaction operating conditions on the pressure fluctuation at the reactor bottom, the power consumption, the dispersed phase holdup, the Sauter-mean drop diameter and the specific interfacial area. The power consumption under batch, single- and two-phase flow was proved to depend on the vibration intensity. The Sauter-mean drop diameter was found to depend on the specific power consumption in accordance with the turbulent model due to the turbulent energy dissipation in well-mixed regions around perforated plates. The simplified correlation of Kumar and Hartland could be used for estimating the Sauter-mean drop diameter. The energy dissipation due to reciprocating plate motion and the superficial dispersed phase velocity affected the dispersed phase holdup and the specific interfacial area. The present results are crucial for designing RPRs for application in continuous base-catalyzed methanolysis of vegetable oils.     

Observations of solid–liquid systems in anchor agitated vessels

Although process development is often done in well agitated vessels (e.g. with a retreat curve, pitched blade turbine etc.), there are a sizeable number of contract manufacturers’ still deploying a significant number of anchor agitated process units. For the purpose of observing the Zwietering constant value ‘S’ and few industrially important solid–liquid systems, we conducted extensive suspension experiments with anchor agitated vessels for varying D/T ratios (0.74 and 0.73). In this study, Zwietering's N_js (just suspension speed) and the corresponding ‘S’ factor were obtained for each system over a range of solid loadings. We found that the Zwietering constant was strongly dependent on the nature of the solid–liquid system; i.e. different systems had different ‘S’ values for the same geometrical configuration.