Mass transfer coefficients in reactive extraction of lactic acid from fermentation broths in hollow-fibre membranes

Mass transfer of lactic acid was investigated during its extractive recovery from fermentation broths in a hydrophobic hollow-fibre membrane module. The solvent and the aqueous phases were continuously recycled through the hollow-fibre module into their respective reservoirs, and the mass transfer rate was calculated from the measurements of concentration of lactic acid in solvent phase. Mainly, the tubeside resistance controlled the mass transfer rate. A mathematical analysis was conducted for the mass transfer process in the membrane module and values of the overall mass transfer coefficient were estimated at different flow rates.     

中空纤维更新液膜传质性能的研究

研究了中空纤维更新液膜(HFRLM)技术的传质性能.以CuCl2水溶液-10%P204 煤油-盐酸为实验体系,研究结果表明,中空纤维更新液膜技术可以实现同级萃取-反萃,且总传质系数随料液相流速的增大而增大,在实验条件下,总传质系数受反萃相流速的影响较小.实验研究探讨了混合方式(料液与萃取剂混合和反萃剂与萃取剂混合)和体系分配系数对传质性能的影响.实验结果表明,由于相间分配系数的不同,总传质系数受混合方式的影响较大,以分配系数较大的一相与萃取相混合流经管程的方式对传质过程有利.     

New liquid membrane technology for simultaneous extraction and stripping of copper(II) from wastewater

In this paper, a new liquid membrane technique, hollow fiber renewal liquid membrane (HFRLM), is presented, which is based on the surface renewal theory, and integrates the advantages of fiber membrane extraction, liquid film permeation and other liquid membrane processes. The results from the system of CuSO₄+D2EHPA in kerosene+HCl show that the HFRLM process is very stable. The liquid membrane is renewed constantly during the process, the direct contact of organic droplets and aqueous phase provides large mass transfer area. These effects can significantly reduce the mass transfer resistance in the lumen side. Then the mixture of feed phase and organic phase flowing through the lumen side gives a higher mass transfer rate than that of stripping phase and organic phase, because the aqueous layer diffusion of feed phase is the rate-controlling step. The overall mass transfer coefficient increases with increasing flow rates and D2EHPA concentration in the organic phase, and with decreasing initial copper concentration in the feed phase. The overall mass transfer coefficient also increases with increasing pH in the feed phase, and reaches a maximum value at pH of 4.44, then decreases. Also, there is a favorable w/o volume ratio of 20:1 to 30:1 for this process. Compared with hollow fiber supported liquid membrane and hollow fiber membrane extraction processes, HFRLM process has a high mass transfer rate. Mathematical model for the HFRLM process based on the surface renewal theory is developed. The calculated results are in good agreement with experimental results under the conditions studied.     

Performance of hollow fiber supported liquid membrane on the extraction of mercury(II) ions

The extraction and recovery or stripping of mercury ions from chloride media using microporous hydrophobic hollow fiber supported liquid membranes (HFSLM) has been studied. Tri-n-octylamine (TOA) dissolved in kerosene was used as an extractant. Sodium hydroxide was used as a stripping solution. The transport system was studied as a function of several variables: the concentration of hydrochloric acid in the feed solution, the concentration of TOA in the liquid membrane, the concentration of sodium hydroxide in the stripping solution, the concentration of mercury ions in the feed solution and the flow rates of both feed and stripping solutions. The results indicated that the maximum percentages of the extraction and recovery of mercury ions of 100% and 97% were achieved at the concentration of hydrochloric acid in the feed solution of 0.1 mol/l, the concentration of TOA at 3% v/v, the concentration of sodium hydroxide at 0.5 mol/l and the flow rates of the feed and stripping solutions of 100 ml/min. However, the concentration of mercury ions from 1–100 ppm in the feed solution had no effect on the percentages of extraction and recovery of mercury ions. Thus, these results have identified that the hollow fiber supported liquid membrane process has high efficiency on both the extraction and recovery of mercury (II) ions. Moreover, the mass transfer coefficients of the aqueous phase (k _i ) and membrane or organic phase (k _m ) were calculated. The mass transfer coefficients of the aqueous phase and organic phase are 0.42 and 1.67 cm/s, respectively. The mass transfer coefficient of the organic phase is higher than that of the aqueous phase. Therefore, the mass transfer controlling step is the diffusion of the mercury ions through the film layer between the feed solution and the liquid membrane.     

磷酸三丁酯/煤油支撑液膜体系中苯酚的传质分离

研究了苯酚在以多孔聚丙烯平板膜(Celgard2500)为支撑体、磷酸三丁酯(TBP)为膜载体和煤油为膜溶剂的支撑液膜体系中的传质过程;用传统萃取法测定了TBP/煤油体系中苯酚络合物摩尔比为1∶1,同时得到25.0℃萃取平衡常数为96.72;考察了原料相pH值、初始质量浓度、膜二侧转速、载体浓度和反萃取相碱浓度对苯酚传质的影响,确定了该体系分离苯酚的最佳条件:原料相pH<9,苯酚初始质量浓度<1 000 mg/L,膜二侧转速>300 r/m in,载体浓度为0.55 mol/L,反萃取相碱浓度0.10 mol/L;根据双膜理论提出苯酚的传质动力学方程,采用直线斜率法计算了苯酚在TBP/煤油支撑液膜体系中的扩散层厚度和膜内扩散系数,计算结果表明动力学方程计算值能较好地与实验值吻合,平均相对误差在2%以内。     

Extraction of penicillin G from aqueous solutions: Analysis of reaction equilibrium and mass transfer

Analysis of the reaction equilibrium and mass transfer in the extraction of penicillin G (Pen G) into an organic phase is an important research area to develop a cost-effective process for its separation from an aqueous fermentation media. In order to evaluate this, equilibrium experiments were first carried out to select the organic phase (composed of the carrier and solvent) that gives good values for the distribution of penicillin G between the aqueous and organic phases. An organic phase of Amberlite LA-2 in any of the solvents (Shellsol TK/butyl acetate/tributyl phosphate) gave high distribution coefficient and the stoichiometry of the reaction has been shown to follow a simple ratio of 2:2. The performance of the organic phases was evaluated in a membrane contactor and very high percentage extraction was achieved. The extraction was performed by contacting a “feed” solution containing penicillin G (flowing in the fiber side) with an “organic phase” of Amberlite LA-2 in one of the solvents (flowing on the shell side) of the contactor. The antibiotic solutes formed complex with the Amberlite LA-2 molecules which were transported across the fiber wall to the shell side and extracted in the organic phase. The extraction in once-through mode was low and the feed/organic solutions need to be recycled to increase the percentage extraction. In the recycle mode operated at flow rates of 3.6–4.4 mL/s, an extraction of 90–98% was achieved. A simple mathematical model and its semi-analytical solution presented here can be used to determine the overall mass transfer coefficient using the experimental values of the distribution coefficient, operating parameters and the dimensions of the membrane module.     

萃取凝胶膜过程工艺条件对镍离子传质效率及稳定性增进

利用交联反应在PVDF超滤膜表面创新性的构建含有萃取剂磷酸二异辛酯的聚二甲基硅氧烷-正硅酸乙酯体系萃取凝胶膜（EGM）;并对其基本物理化学性质进行了表征。研究了EGM过程中料液相循环方式、料液相及反萃相浓度与流量、水相温度、组件装填密度等工艺条件对镍离子传质性能及EGM运行稳定性的影响规律。9 h实验结果表明在室温水相温度为22℃条件下,当工艺运行条件为料液相流量1900 ml·min^-1、反萃相流量93 ml·min^-1、组件装填密度14%、料液相循环于壳程时,EGM对镍离子的萃取性能及稳定性达到最佳值。在此基础上,对该系统进行了60 h稳定性实验,并与传统支撑液膜进行了对比。结果显示传统支撑液膜持续运行35 h后通量降为0,衰减率为100%;而EGM持续运行60 h后通量衰减率仅为27.1%;同时EGM初始传质通量相比于传统支撑液膜提高了6.8倍,体现了EGM过程在传质通量大幅提升和长期运行稳定性显著增进方面具有双重优势。     

液-液微尺度混合体系的传质模型

针对微尺度液-液混合体系,考察了流量对膜分散萃取过程的影响,并根据传质过程方程,计算了各种条件下的传质系数和传质速率;采用现有的传质模型分别计算分散相和连续相的分传质系数,然后根据传质阻力的加合性得到总传质系数;应用理论传质系数计算传质效率,与实验值进行了比较.研究结果表明,在微尺度混合条件下,直接影响传质系数的因素是停留时间和液滴直径,传质系数随着停留时间的减小而增大.膜分散萃取的传质系数可以达到1.2×10^-4m&#8226;s^-1,比传统的萃取方式大10～100倍;不能像塔式萃取设备一样,用简单地忽略某一相的传质阻力或用总体平均的简化计算公式来计算微尺度混合的传质性能;考虑滴内滴外传质系数,并考虑时间的影响,利用现有公式分别计算滴内滴外传质系数,并采用阻力加合,可以较为准确地计算微混合条件下的总传质系数,计算值与实验值符合很好.     

溶胀对膜萃取传质性能的影响

溶剂对膜的溶胀,使膜的物理结构发生变化,进而对膜萃取传质性能产生一定的影响。本文以３０％ＴＢＰ（煤油）－醋酸－水,正丁醇－醋酸－水和２０％７３０１（煤油）－醋酸－水为实验体系在聚砜和聚四氟乙烯微孔平板膜器中系统地了溶胀地膜萃取总传质系数的影响。结果表明,微孔膜发生溶胀后孔隙率发生明显的变化,其总传质系数有较大的下降。     

Permeation study on the hollow-fiber supported liquid membrane for the extraction of Cobalt(II)

The transport of Co(II) through hollow-fiber-supported liquid membrane containing di-(2-ethylhexyl) phosphoric acid (D2EHPA) diluted in kerosene was examined. The mass transfer rate, expressed as permeability, P, focused on diffusion through the aqueous layer in the feed solution, the organic layer and the aqueous layer in the stripping solution. Experiments were performed as a function of aqueous feed solution velocity (100-500 ml/min), carrier concentration (0.1-20% v/v), aqueous stripping solution velocity (100-1,000 ml/min) and feed concentration (100-1,000 ppm) with 0.1 M HCl in the product phase. pH of the feed solution was 5.0. The measured permeabilities were compared to generally accepted mass transfer correlations. The validity of the prediction was evaluated with the experimental data, and the data were found to tie in well with the theoretical values. The model is the reported describing that the rate limiting step in the transport of the ion was the diffusion through both aqueous films, feed and stripping, whereas the organic resistance of the membrane was negligible. From this study, the model has good potential for the prediction of permeability of Co(II).     

螺旋状中空纤维膜萃取传质特性

在对中空纤维膜萃取以及螺旋管技术进行充分调研的基础上 ,选择水 -苯酚 - 30 %TBP煤油为实验体系 ,溶质由水相萃取到有机相 ,在不同结构的单束螺旋状中空纤维膜器中研究了螺旋管纤维膜管内外流速以及螺旋管结构等因素对传质系数的影响 .实验结果表明 ,螺旋管中空纤维膜可以有效地提高中空纤维膜的传质特性 .随着管内流速的增加 ,传质系数将有很大提高 ,而管外流速对于传质系数的影响则较小 .至于螺旋结构的影响为 :随着螺旋内径的减小或者是螺旋螺距的减小 ,总传质系数相应地有很大提高 .最后得到了在本实验条件下计算总传质系数K的关联式     

Recycle effect on membrane extraction through cross-flow rectangular modules

The effects of recycle on membrane extraction through a cross-flow rectangular module have been studied both theoretically and experimentally. Theoretical analysis of mass transfer in cross-flow device with and without recycle is analogous to heat transfer in cross-flow heat exchangers. Experiments were carried out with the use of a membrane sheet made of microporous polypropylene as a permeable barrier to extract acetic acid from aqueous solution by methyl isobutyl ketone. Theoretical predictions are in agreement with the experimental results. In contrast to a device without recycle, improvement in mass transfer is achievable if cross-flow membrane extraction is operated in a device of same size with recycle which provides the increase of fluid velocity, resulting in reduction of mass-transfer resistance. It is shown that recycle can enhance mass transfer, especially for large feed-concentration solution with high distribution coefficient operated under high reflux ratio.     

Interfacial mass transfer in stripping of phenylalanine in a liquid-liquid extraction process

Stripping of L-phenylalanine from organic phase containing ALIQUAT 336 (tri-octyl-methyl-ammonium chloride) as complexing agent was studied using a stirred transfer cell. The study investigated the effects of concentration of the stripping agent, potassium chloride, in strip solution and temperature on mass transfer rates. A two-film model based on organic and aqueous phases mass transfer resistances was proposed to estimate mass transfer coefficients and it predicted adequately the experimental time-concentration data at different conditions studied. A comparison of mass transfer coefficients for stripping and previously published results on extraction for the same system was made.     

Separation of mercury and arsenic from produced water via hollow fiber contactor: Kinetic and mass transfer analysis

The separation of Hg(II) and As(V) from produced water by hollow fiber contactors was investigated. Two identical hollow fiber modules were employed. The first module was used for extraction, while the second module was used for stripping. The optimum conditions achieved were 14% (v/v) of Aliquat336, 0.07 M thiourea, volumetric flow rate of 100 mL/min for aqueous solution and 0.02 M HCl of stripping solution. At such conditions, the maximum extraction of Hg(II) and As(V) attained 100% and 78.78%, respectively. Concurrently, the maximum stripping of Hg(II) and As(V) reached 47.88% and 6.66%, respectively. The overall mass transfer coefficients of Hg(II) and As(V) extraction were 2.31×10^?6 and 1.15×10^?6m/s, while the Hg(II) and As(V) stripping exhibited the overall mass transfer coefficients of 8.37×10^?7 m/s and 9.05×10^?7 m/s, respectively. Mass transfer coefficients of the organic layer diffusion (k₀) had the most effect on the overall mass transfer coefficients.     

中空纤维膜组件分离酸性气体

研究了气体膜分离与溶剂吸收相结合的分离技术.以NaOH水溶液为吸收剂,在中空纤维膜组件中实现二氧化硫气体的选择性吸收.研究了在三种不同结构的疏水性聚丙烯中空纤维膜组件中,吸收剂浓度、液速、气速、气液两相在膜组件内的流程、膜结构等对分离过程的影响;根据膜结构的实际参数确定了多孔膜的曲率因子,总传质系数的计算值与实验值相符.     

Experimental and Numerical Investigations of Single Drop Mass Transfer in Solvent Extraction Systems with Resistance in Both Phases

Numerical simulation of transient mass transfer to a single drop controlled by the internal resistance or by the resistance in both phases was mathematically formulated and simulated in a boundary-fitted orthogonal coordinate system. The simulated results on the transient mass transfer dominated by the internal resistance are in good agreement with the Newman and Kronig-Brink models for drops with low Reynolds number. When the drop Reynolds number is up to 200, the mass transfer coefficient from numerical simulation is very low as compared with the Handlos-Baron model. The cases with mass transfer resistance residing in both the continuous and drop phases were simulated successfully and compared with the experimental data in three extraction systems recommended by European Confederation of Chemical Engineering (EFCE). For single drops with Re < 200, the numerically predicted values of the extraction fraction and overall mass transfer coefficient are in reasonable coincidence with the experimental data. I     

聚四氟乙烯中空纤维气态膜法浓海水提取溴素

以浓海水为含溴原料液,NaOH溶液为吸收剂,考察了用聚丙烯（PP）、聚偏氟乙烯（PVDF）和聚四氟乙烯（PTFE）3种材料制作的微孔疏水中空纤维气态膜组件从浓海水中提溴的性能和使用寿命。实验结果表明PTFE中空纤维膜具有更高的传质系数和更强的耐溴氧化能力,更适合用于浓海水提溴。进而考察了各种操作条件对PTFE气态膜组件传质系数K和提溴率η的影响以及该组件的长期操作稳定性。实验结果表明：K随温度增加而增大,随料液中NaCl含量的增大而略有减小,料液流速和含溴量、吸收液的流速和吸收剂浓度对传质系数影响不大。PTFE膜组件在连续运行的3个月内表现了良好的操作稳定性,为PTFE中空纤维气态膜法提溴工艺的工业化应用提供了技术基础。     

MASS TRANSFER OF SULFURIC ACID BY TRIOCTYLAMINE THROUGH A SUPPORTED LIQUID MEMBRANE

The extraction of sulfuric acid in a supported-liquid membrane (SLM) process, and the kinetics of extraction and stripping of sulfuric acid in a cell of constant interfacial area by trioctylamine (TOA)/kerosene solvent were investigated. The kinetics of extraction and stripping were determined by examining the effects of the operating variables. The extraction rate is a function of the activity of sulfuric acid and the concentration of TOA; the stripping rate is a function of the concentration of trioctylamine sulfate salts in the organic solution. A generalized transport model, which included the film diffusion of sulfuric acid in the aqueous phase, the membrane diffusion within the SLM, and the interfacial chemical reaction, was built. The permeability of sulfuric acid through the SLM using TOA as a mobile carrier was determined. The rate-determining step of the extraction of sulfuric acid through a SLM was analyzed using the data obtained from the experiments of extraction kinetics and the mass transfer in the aqueous phase. Diffusion within the membrane dominates the process of extraction process of sulfuric acid by TOA through a SLM.     

Extraction and pertraction of phenol through bulk liquid membranes

The extraction and pertraction of phenol through a bulk liquid membrane (BLM) with Cyanex^® 923, Amberlite^® LA‐2 and trioctylamine (TOA) as carriers were studied. Cyanex^® 923 was selected as the best carrier for pertraction. The distribution coefficient of phenol for solvents with carrier and pure n‐alkanes, the individual mass‐transfer coefficient at the extraction interface and the initial flux of phenol through the extraction interface (J_Fo) decreased in the order: Cyanex^® 923 > Amberlite^® LA‐2 > TOA ? pure n‐alkanes. The opposite order was observed for the value of the mass‐transfer coefficient in BLM and the maximum flux of phenol through the stripping interface (J_Rmax). At constant driving forces the maximum fluxes through the extraction and stripping interfaces were similar when amine carriers were used. However, J_Rmax was lower than J_Fo for Cyanex^® 923. Although the kinetics of stripping was the rate‐determining step, the flux of phenol was significantly higher than in pertraction with amine carriers. The adsorption of the carrier at aqueous phase/membrane interfaces was probably responsible for the rapid and slow transfer of phenol through the extraction and stripping interface, respectively. Copyright © 2004 Society of Chemical Industry     

Performance improving with temperature in liquid–liquid extraction using cumene–isobutyric acid–water chemical system

The performance of single drops was investigated in liquid–liquid extraction while temperature was changed within the range of 15–40 °C. The recommended system of cumene–isobutyric acid–water with mass transfer resistance mainly in aqueous phase was used. An average enhancement of 75.6% in the rate of transfer was revealed. The extraction efficiency is the most influencing term due to molecular diffusivity enhancement. For modeling, a simple correlation was proposed for the effective diffusivity in Newman's equation, while continuous phase mass transfer coefficient was directly included. Using this model, relative deviation of the overall mass transfer coefficient was within only ±5.6%.