Transport phenomena in bubble column reactors I: Flow pattern

A new model has been developed for the liquid phase flow pattern in bubble columns. This model satisfies the mass, momentum and energy balances for the gas and liquid phases. Further, it takes into account the variations in the flow pattern due to changes in the physical properties of the liquid phase. The model can be used for batch as well as continuous (co-current and counter-current) modes of operation. A satisfactory agreement is shown between model predictions and experimental observations. A simplified procedure is suggested for quick estimation of the liquid phase velocity profile. The proposed model is expected to be useful for the rational prediction of transfer coefficients for momentum, mass and heat. The prediction and measurement of the pressure drop is discussed in the companion paper.     

Estimation of sodium bicarbonate crystal size distributions in a steady-state bubble column reactor

Sodium bicarbonate is a substance which is produced in the middle stages of the soda ash production process. In this precipitation process, carbon dioxide gas is continuously injected into the bubble column reactor, which contains carbonate and bicarbonate solutions. This work deals with the study of the gas?Cliquid mass transfer, coupled with chemical reactions, and the liquid?Csolid mass transfer, coupled with crystallization. In this mathematical model, a mole balance has been instituted on flows and components through the bubble column, which also utilized a nucleation and growth formula for the solid phase and the Danckwerts?? theory for mass transfer between the gas and liquid phases. The mathematical model can predict the effects of several parameters on the sodium bicarbonate crystal size distributions. We computed the mathematical simulation model results with the experimental results of the bubble column reactor of the Shiraz Petrochemical Complex for validating the model and investigated the effects of different parameters on the sodium bicarbonate crystal size distributions.     

加温加压条件下气液固三相鼓泡塔体积传质系数的测定

气液固三相鼓泡塔反应器被广泛地应用于化工、石油化工、煤化工、化工冶金、环境工程等领域,如石油馏分的加氢、煤的脱硫与脱氮、对二甲苯氧化、费托合成、甲醇合成、二甲醚合成以及含有机物废水的湿式氧化等工业过程[1.2].     

Study of Joule heating effects on temperature gradient in diverging microchannels for isoelectric focusing applications

IEF is a high-resolution separation method taking place in a medium with continuous pH gradients, which can be set up by applying electrical field to the liquid in a diverging microchannel. The axial variation of the channel cross-sectional area will induce nonuniform Joule heating and set up temperature gradient, which will generate pH gradient when proper medium is used. In order to operationally control the thermally generated pH gradients, fundamental understanding of heat transfer phenomena in microfluidic chips with diverging microchannels must be improved. In this paper, two 3-D numerical models are presented to study heat transfer in diverging microchannels, with static and moving liquid, respectively. Through simulation, the temperature distribution for the entire chip has been revealed, including both liquid and solid regions. The model for the static liquid scenario has been compared with published results for validation. Parametric studies have showed that the channel geometry has significant effects on the peak temperature location, and the electrical conductivity of the medium and the wall boundary convection have effects on the generated temperature gradients and thus the generated pH gradients. The solution to the continuous flow model, where the medium convection is considered, shows that liquid convection has significant effects on temperature distribution and the peak temperature location.     

The pressure drop along rectangular microchannels containing bubbles

This paper derives the difference in pressure between the beginning and the end of a rectangular microchannel through which a flowing liquid (water, with or without surfactant, and mixtures of water and glycerol) carries bubbles that contact all four walls of the channel. It uses an indirect method to derive the pressure in the channel. The pressure drop depends predominantly on the number of bubbles in the channel at both low and high concentrations of surfactant. At intermediate concentrations of surfactant, if the channel contains bubbles (of the same or different lengths), the total, aggregated length of the bubbles in the channel is the dominant contributor to the pressure drop. The difference between these two cases stems from increased flow of liquid through the "gutters"-the regions of the system bounded by the curved body of the bubble and the corners of the channel-in the presence of intermediate concentrations of surfactant. This paper presents a systematic and quantitative investigation of the influence of surfactants on the flow of fluids in microchannels containing bubbles. It derives the contributions to the overall pressure drop from three regions of the channel: (i) the slugs of liquid between the bubbles (and separated from the bubbles), in which liquid flows as though no bubbles were present; (ii) the gutters along the corners of the microchannels; and (iii) the curved caps at the ends of the bubble.     

Flux of gases across the air-water interface studied by reversed-flow gas chromatography.

In the present work the reversed-flow gas chromatographic technique was applied for the study of flux of gases across the air-water interface. The model system was vinyl chloride-water, which is of great significance in food and environmental chemistry. Using suitable mathematical analysis, equations were derived by means of which the following physicochemical quantities were calculated: diffusion coefficient of vinyl chloride (VC) into water, partition coefficient of VC between the water (at the interface and the bulk) and the carrier gas nitrogen, overall mass transfer coefficients of VC in the gas (nitrogen) and the liquid (water), gas and liquid film transfer coefficients of VC, gas and liquid phase resistances for the transfer of VC into the water, and finally the thickness of the stagnant film in the liquid phase, according to the two-film theory of Whitman. From the variation of the above parameters with temperature, as well as the volume and the free surface area of the water, useful conclusions concerning the mechanism for the transfer of VC into water were extracted. These are discussed in comparison with the same parameters calculated from empirical equations or determined experimentally by other techniques.     

Microporous hollow fibers for gas absorption : I. Mass transfer in the liquid

Microporous hollow fiber modules offer a larger area per volume between gas and liquid than that commonly encountered in packed towers. This larger area can be sustained at very low flows, where packed towers will not be loaded, and at very high flows, where packed towers will flood. As a result, the modules offer the potential of faster mass transfer. This potential can be compromised by the resistance to mass transfer of the membrane itself, a resistance which is increased if the liquid wets the membrane. The results presented in this two-part series show when the advantage of the increased area is greater than the disadvantage of the membrane resistance. In this part, a theory for the operation of hollow fiber membrane modules is developed, and mass transfer coefficients in the liquid phase are investigated.     

New insights in the removal of diluted volatile organic compounds from dilute aqueous solution by pervaporation process

The present work aimed the mass transfer investigation in the removal of organic contaminants from water by the pervaporation process. The terpolymer ethene-propene-diene (EPDM) was used as the selective elastomer. Two classes of model organic solutes were chosen: chlorinated hydrocarbons (trichloroethylene, dichloromethane and trichloromethane) and aromatic ones (toluene, phenol and aniline). Pervaporation tests were carried out using dense and composite membranes with different thickness, solute concentrations and feed flow velocities at room temperature. The liquid boundary layer resistance (i.e., concentration polarization phenomenon) was observed for all solutes. The resistance-in-series model was used to determine liquid and polymer phase resistances. The results obtained indicate that the model would be better written considering the chemical potential gradient as driving force, in order to take into account affinity between water and the organic solutes, as well as their interactions with the polymer selective layer. The rational activity coefficients of the solutes in the polymer phase were determined by inverse gas chromatography (IGC) and related to the mass transfer coefficient in the polymer phase.     

浆态床反应器中相含率及粒径分布的研究

以空气－水－石英砂体系为对象，研究了费托合成浆态床反应器中表观气速、平均淤浆浓度、床层轴向位置等因素对气含率、固体浓度轴向分布和粒径分布的影响，并通过实验得出了气含率与操作变量之间的关联式。     

Heterogeneous catalysis on solids of gases diffusing through a liquid layer,studied by inverse gas chromatography

Physicochemical parameters for heterogeneous catalytic reactions when the catalytic bed was under a liquid phase have been determined, using a non-linear adsorption isotherm by the reversed-flow version of inverse gas chromatography (RF-GC). The mathematical analysis developed in heterogeneous catalysis, mass transfer across gas-liquid boundaries, and diffusion coefficients of gases in liquids was associated with a non-linear adsorption isotherm to find the relevant equations pertaining to the problem. These equations were then used to calculate the adsorption/desorption rate constant, the rate constant for the first-order catalytic reaction and the equilibrium constant for the non-linear adsorption isotherm. The diffusion coefficients of the reactant in the liquid and gaseous phases and the partition coefficients for the distribution of the reactant between the gaseous and liquid phase were also determined.     

Exact and global rational approximate expressions for resistance coefficients for a colloidal solid sphere moving in a quiescent liquid parallel to a slip gas-liquid interface

In this paper mathematical expressions have been developed to describe the hydrodynamic resistance force on a colloidal particle as it slides along a slip surface of a gas bubble held stationary in a quiescent liquid. The particle size was considered to be sufficiently small relative to the bubble size so that the bubble surface could be locally approximated to a planar interface. The modeling incorporated a bispherical coordinate transformation to solve the equations governing the liquid creeping flow disturbed by the particle. Exact numerical solutions for the resistance coefficients of the particle-shearing motion parallel to the slip bubble surface were obtained as a function of the separation distance from the bubble surface. Finally, simplified analytical rational approximations for the whole range of the separation distance were presented, which were in good agreement with the exact numerical result. Importantly, the approximations for the modeling and simulation of the bubble-particle interactions are mathematically tractable.     

Zero solvent emission process for sulfur dioxide recovery using a membrane contactor and ionic liquids

Selective absorption into a liquid is a widespread method to separate and concentrate sulfur dioxide from gas emissions, reducing air pollution and environmental risks. Process intensification can be performed first by the substitution of the equipment (e.g. scrubbers) for a membrane device to avoid drops dragging, and second by the substitution of the absorption solvent (e.g. N,N-dimethylaniline) for ionic liquids to avoid solvent volatilization. According to this intensification, a zero solvent emission process has been developed.The ionic liquid 1-ethyl-3-methylimidazolium ethylsulfate is used as the absorption solvent and the results are compared to the N,N-dimethylaniline results. A ceramic hollow fibre module is the membrane device where the sulfur dioxide absorption takes place. A gas stream with a typical composition of roasting effluents flows through the shell side and the absorption liquid flows counter currently by the inside of the hollow fibres. The influence of carbon dioxide in the absorption is also evaluated and the overall mass transfer coefficients are calculated. The difference between the estimated mass transfer coefficients and the experimental results for both solvents is discussed assuming partial wetting of the membrane.     

Micromixing of miscible liquids in segmented gas-liquid flow

We present an integrated microfluidic system that achieves efficient mixing between two miscible liquid streams by introducing a gas phase, forming a segmented gas-liquid (slug) flow, and completely separating the mixed liquid and gas streams in a planar capillary separator. The recirculation motion associated with segmented flow enhances advection in straight microchannels without requiring additional fabrication steps. Instantaneous velocity fields are quantified by microscopic particle image velocimetry (muPIV). Velocities in the direction normal to the channel amount to approximately 30% of the bulk liquid velocity inside a liquid segment. This value depends only weakly on the length of a liquid segment. Spatial concentration fields and the extent of mixing (EOM) are obtained from pulsed-laser fluorescence microscopy and confocal scanning microscopy measurements. The mixing length is reduced 2-3-fold in comparison with previously reported chaotic micromixers that use three-dimensional microchannel networks or patterned walls. Segmented gas-liquid microflows allow mixing times to be varied over several orders of magnitude between milliseconds and second time scales.     

Kinetics of hydrate formation using gas bubble suspended in water

An innovative experimental technique, which was devised to study the effects of temperature and pressure on the rate of hydrate formation at the surface of a gas bubble suspended in a stagnant water phase, was adapted in this work. Under such conditions, the hydrate-growth process is free from dynamic mass transfer factors. The rate of hydrate formation of methane and carbon dioxide has been systematically studied. The measured hydrate-growth data were correlated by using the molar Gibbs free energy as driving force. In the course of the experiments, some interesting surface phenomena were observed.     

Electrophoretic partitioning of proteins in two-phase microflows

This work reports on protein transport phenomena discovered in partitioning experiments with a novel setup for continuous-flow two-phase electrophoresis consisting of a microchannel in which a phase boundary is formed in flow direction. Proteins can be partitioned exploiting their affinity to different aqueous phases in two-phase systems. This separation process may be enhanced or extended by applying an electric field perpendicular to the phase boundary. In this context, microsystems offer new possibilities, as interfacial forces usually dominate over volume forces, thus allowing a superior control of the formation and arrangement of liquid/liquid phase boundaries. The two immiscible phases which are injected separately into the microchannel are taken from a polyethylene glycol (PEG)-dextran system. The side walls of the channel are partially made of gel material which serves as an ion conductor and decouples the channel from the electrodes, thus preventing bubble generation inside the separation channel. The experiments show that the electrophoretic transport of proteins between the laminated liquid phases is characterized by a strong asymmetry. When bovine serum albumin (BSA) is introduced into the PEG-rich phase, it can easily be transferred into the dextran-rich phase via an applied electric field of low strength or just by diffusion. In the reverse case, up to a certain field strength the transfer to the opposing phase is strongly inhibited. Only if the field strength is further increased will the BSA molecules leave the dextran-rich phase almost completely.     

基于整体材料的微流控芯片反相液相色谱-串联质谱平台用于蛋白质分析

微流控芯片高效液相色谱-串联质谱系统具有高通量、高灵敏度等优点,已成为生物样品分析的热点领域之一。本文在玻璃芯片上以甲基丙烯酸十二酯(LMA)和三羟甲基丙烷三甲基丙烯酸酯(TMPTMA)为单体,制备了以聚丙烯酸酯整体材料为固定相的捕集柱和分离柱。通过在芯片通道末端连接细内径的毛细管作为芯片-质谱接口,并以常规的液相色谱泵和微阀控制流体,构建了芯片反相液相色谱-电喷雾串联质谱(RPLC-ESI-MS/MS)平台,并将其用于分析牛血清白蛋白(BSA)的酶解产物。经过3次平行分析,BSA的序列覆盖率分别为39.37%、37.89%和34.10%(相对标准偏差为7.3%)。采用不同批次制作的芯片构建RPLC-ESI-MS/MS平台,对BSA酶解产物进行分析,其序列覆盖率相当。上述结果表明,该平台具有灵敏度高和重现性好等优点,有望用于蛋白质样品的快速分离和高灵敏度鉴定。     

Dissolution of polycyclic aromatic hydrocarbons from a non-aqueous phase liquid into a surfactant solution using a rotating disk apparatus

The mass transfer of two polycyclic aromatic hydrocarbons (PAHs), naphthalene and phenanthrene from a multicomponent non-aqueous phase liquid (NAPL) into a nonionic surfactant solution, Brij 35 was investigated using a rotating apparatus. Few experimental methods have been applied to the study of solubilization kinetics in organic liquids because in those systems, the interfacial area during mixing is more difficult to maintain and measure. This challenge was overcome by permeating the NAPL through a membrane. Mass transfer experiments were conducted in the absence and presence of surfactant, and the concentrations of naphthalene and phenanthrene in the bulk aqueous phase were determined in samples collected at different time intervals from the time of initial contact of the NAPL phase with the aqueous solution phase. Experiments in pure water demonstrated that the rotating apparatus behaves as in much the same way as the Levich's rotating disk. The mass transfer coefficients and the dissolution of PAHs into the surfactant solution were measured at different doses of Brij 35. As the surfactant concentration increased, the mass transfer coefficients for both PAHs from the NAPL decreased.     

Mass transfer,mixing and heat transfer phenomena in low viscosity bubble column reactors

Bubble columns are widely used in chemical and biotechnological process industries. The important reasons for this wide usage are the simple construction, without moving parts, and the high energy efficiency for mass transfer. It is not surprising therefore that much research on this subject has been published, yet selecting material of practical use is rather difficult. To overcome this problem, in this review, attempts are made to extract formulae and guidelines as simply as possible on the basis of currently available material.The starting point is the mechanisms occurring in bubble columns, i.e. bubble formation, bubble rise and resulting circulation patterns. Once these phenomena are understood, mixing and heat and mass transfer are much easier to deal with. Bubble formation is largely dependent on the sparger type, which can be divided into three groups: single orifices, porous discs and two-phase injectors. The original bubble diameter together with the superficial velocity and liquid properties determine the bubble diameter, holdup and circulation patterns in the bubble column. Gas holdup, bubble diameter control k_LA and circulation patterns determine mixing and heat transfer. Simple relations are derived for model systems. By means of a mechanistic approach, guidelines are given for more complex liquids.