Separation of organic binary mixtures by pervaporation

Pervaporation is a membrane separation process which has the inherent advantage of excellent selectivity for a number of mixtures that are otherwise difficult to separate (e.g. azeotropic mixtures or mixtures of liquids with only small differences in vapor pressures). Important parameters for pervaporation are the operating pressure on the permeate side and the temperature drop at the membrane interface caused by the phase change from liquid to vapor. This paper presents a mathematical model for the mass transport of binary mixtures within the membrane. The calculations are based on the transport equations of Shelden and co-workers [1]. These equations were solved without any simplifying assumptions and tested experimentally with benzene—cyclohexane mixtures. The limitations of the mathematical model and possible methods of improving it are discussed. The temperature drop at the membrane interface and its influence on the rate of permeation are also examined.     

Pervaporation-based hybrid process: a review of process design,applications and economics

Pervaporation is one of the developing membrane technologies that can be used for various industrial applications but for a predefined task, the optimal process design is unlikely to consist solely of pervaporation. Often the optimised solution becomes a hybrid process combining pervaporation with one or more other separation technologies. A distinction will be made between hybrid and integrated processes. Hybrid processes are important and consequently need to be considered in process design. This paper focuses on pervaporation–based hybrid processes that have been realised on an industrial scale. Both present and future prospects of applying these process combinations will be reviewed. The emphasis of this paper is, therefore, on pervaporation combined with distillation and with chemical reactors. The economic potential of these hybrid processes is evaluated, for various applications, by cost comparisons between the pervaporation-based hybrid processes and alternative separation processes. Pervaporation-based processes for waste water treatment and biotechnology applications involve other types of pervaporation based hybrid processes and have been excluded from this review.     

On the integration of jet ejectors into hybrid dehydration processes

Hybrid processes of distillation and membrane separation are considered as promising alternatives to azeotropic and extractive distillation. However, the membrane process, which is basically pervaporation or vapor permeation, is still a niche operation with a limited number of applications. The relatively high cost of the membrane units, and the lack of long time industrial experience are the main obstacles. Great efforts are being undertaken to improve the membrane properties and to optimize the membrane process. Additional savings in the effective cost of the membrane unit could be achieved by its proper integration into the overall process. In this work, the use of steam jet ejectors as a process integration alternative for hybrid dehydration processes is investigated. Favorable implementation regions are defined. Advantages and limitations of this modification are discussed.     

Pervaporation in chemical analysis

Unlike thermal processes such as distillation, pervaporation relies on the relative rates of solute permeation through a membrane and is a combination of evaporation and gas diffusion. The analytical pervaporation systems consist of a membrane module suitable for liquid sample introduction and a vacuum (or a sweeping gas) on the permeate side. It has been used in a wide range of applications including the analysis of various organic and inorganic compounds, and sample concentration. It has been directly interfaced with gas chromatography, spectrophotometry, capillary electrophoresis, electrochemical detectors, liquid chromatography, and mass spectrometry. A wide range of liquids, slurries, and solids samples has been analyzed using these techniques. This review highlights the basic principles of the pervaporation and the state of its current development as applied to analytical chemistry.     

Design of extractive distillation process with mixed entrainer

The separation of two systems containing minimum boiling azeotropes (acetone—methanol and tetrahydrofuran (THF)—water) was performed using extractive distillation with a heavy boiling mixed entrainer consisting of two compounds. The entrainer constituents did not form new azeotropes with each other and with the components of the original mixture. An analysis of the mixed entrainer influence on the vapor-liquid equilibrium (VLE) and relative volatility provides an understanding of the cases in which the separation by extractive distillation (ED) in the presence of the mixed entrainer revealed energy benefits over their individual constituents. New results for application of the mixed entrainer monoethanolamine (MEA)—ethylene glycol (EG) and dimethyl-sulphoxide (DMSO)—glycerol for the separation of THF—water and acetone—methanol, respectively, are presented for the first time. The individual selective agents were chosen from the efficient entrainers discussed in the literature. The calculations were performed using the platform Aspen Plus 7.3. Different extractive distillation flowsheets are provided for the zeotropic mixed agents, viz. with two or three columns. For the ED of the binary mixtures investigated, the structures of the different separation schemes, the operating parameters of the columns, and the energy consumptions are presented and compared. The application of the mixed entrainer MEA—EG fed into the ED column with pre-mixing can be recommended, providing up to 1.7 % of energy saving for acetone—methanol separation. In the case of THF—water, the mixed entrainer DMSO—glycerol provides 0.8 % of energy saving. The separate inputs of the individual constituents of the mixed entrainer led to a significant increase in the energy consumptions of the flowsheet because of the third regeneration column, hence this flowsheet cannot be recommended for use in the separation of both mixtures.     

Rigorous modelling and optimization of hybrid separation processes based on pervaporation

Hybrid separation processes are becoming more and more important in the practice if membrane technologies are also involved. In this work, a systematic investigation is completed for three sequence alternatives of distillation and pervaporation. These are the following: pervaporation followed with distillation (PV+D), distillation followed with pervaporation (D+PV), two distillation columns and a pervaporation unit between them (D+PV+D). The hybrid separation process alternatives are evaluated with rigorous modelling tools, but first, a rigorous simulation algorithm is determined for the pervaporation. The three hybrid separation processes are rigorously modelled with CHEMCAD, and optimized with the dynamic programming optimization method for the case of the separation of ethanol-water mixture. The objective function is the total annual cost (TAC). The energy consumption is also investigated. The selection of the ethanol-water mixture has two motivations: (i) it is quite often studied and well known, and (ii) to make biofuel (ethanol) production more economical, membrane technologies might also be applied. The results are compared with each other and with the classical separation completed with heteroazeotropic distillation. The optimized TAC shows that the distillation column followed with pervaporation is the most economical hybrid separation process alternative. Its TAC is about 66% of that of the classical separation.      

Sorption and pervaporation of dilute aqueous solutions of organic compounds through polymer membranes

Pervaporation of dilute aqueous binary mixtures of four organic compounds (benzene, chloroform, acetone and ethanol) through nitrile—butadiene and styrene—butadiene copolymers was investigated. A pervaporation device has been built, which allows measurement of the pervaporation flux and selectivity of a membrane as a function of the upstream composition of the feed and the downstream total pressure of the pervaporate. In order to relate pervaporation results to equilibrium properties of the membranes, the sorption of water and dilute aqueous solutions was mainly investigated. The pervaporation of dilute aqueous solutions of benzene and chloroform has been extensively studied, including the separation of traces of chloroform, and is modelled through a “sixcoefficients exponential model” [1]. This model is derived from a solution—diffusion analysis of the selective transfer, assuming an exponential dependence of both diffusivities on concentrations of both permeants. Semi-quantitative information about the potential interactions existing in the system solute i—solvent j—membrane and about the concentration profiles at steady-state may be derived from these coefficients.     

On the behaviour of asymmetric membranes in pervaporation

Symmetric and asymmetric membranes of the Loeb type are compared with respect to their performance in pervaporation. The experiments are carried out with water—isopropanol mixtures, employing cellulose acetate membranes of different structure, but of the same total thickness. These results are compared with calculations based on a 2-layer model for asymmetric membranes. Design criteria for optimal asymmetric membranes for pervaporation, as well as the performance characteristics for the two possible modes of installation — active layer facing the feed or facing the permeate — are discussed. Contrary to reverse osmosis, the installation of the membrane with the active layer facing the permeate proves to be superior — at least for low permeabilities of the membrane material. The interdependencies between thickness and permeability of the active layer, and porosity and thickness of the support layer are much stronger than in reverse osmosis.     

渗透气化法分离液体混合物

渗透气化法是一种用来分离液体混合物的膜分离方法。本综述简要地讨论了渗透气化法的机理。本法用于乙醇-水混合物的分离,对于从生物源生产乙醇具有重要意义。乙醇-水混合物的分离膜可以分成二类:亲水性膜和亲乙醇膜。使用若干物理方法可改进渗透气化过程。最后,作者认为渗透气化膜的发展趋势是从均质膜,不对称膜向复合膜过渡。     

Production of process water using integrated membrane processes

Application of ultrafiltration, nanofiltration, reverse osmosis, membrane distillation, and integrated membrane processes for the preparation of process water from natural water or industrial effluents was investigated. A two-stage reverse osmosis plant enabled almost complete removal of solutes from the feed water. High-purity water was prepared using the membrane distillation. However, during this process a rapid membrane fouling and permeate flux decline was observed when the tap water was used as a feed. The precipitation of deposit in the modules was limited by the separation of sparingly soluble salts from the feed water in the nanofiltration. The combined reverse osmosis—membrane distillation process prevented the formation of salt deposits on the membranes employed for the membrane distillation. Ultrafiltration was found to be very effective removing trace amounts of oil from the feed water. Then the ultrafiltration permeate was used for feeding of the remaining membrane modules resulting in the total removal of oil residue contamination. The ultrafiltration allowed producing process water directly from the industrial effluents containing petroleum derivatives. Presented at the 33rd International Conference of the Slovak Society of Chemical Engineering, Tatranské Matliare, 22–26 May 2006.     

Temperature drop of feed liquid during pervaporation

Heat transfer during pervaporation through a membrane module of silicone-rubber microtubes was studied for ammonia/water and ethanol/water feeds. The temperature drops of the feed mixture were measured as a function of flow rate, concentration and permeate side pressure. A model calculation with a vapor-phase driving force was compared with the data. The vapor permeability of the permeate components needed in the model were independently measured using an original measurement method with a differential transformer. The present simple model for heat and mass transfer during pervaporation proved to be applicable to the theoretical calculation for a membrane module of pervaporation to be used as a heat-transfer unit.     

Exergy analysis of a pervaporation system and its combination with a distillation column based on an energy utilization diagram

Based on an energy utilization diagram, energy and exergy analysis of a pervaporation system is performed by taking three subsystems into account, supply of heat, pervaporation, and suction. By this single diagram, the energy balance, the exergy loss in each subsystem, and the strength of forces driving processes can be disclosed. Energy transformation in the pervaporation system and the effects of manipulating variables are clarified by comparison with a distillation system. The energy utilization diagram is also applied to examine a system in which a pervaporator and a distillation column are combined. It is shown that separation by pervaporation is quite effective from the viewpoint of exergy, especially when the pervaporation system can proceed by the difference between the temperature of the feed liquid and that of the cooling water only. This is because in this case low-grade energy is utilized completely.     

Pervaporation separation of aqueous chlorophenols by a novel polyurethane urea–poly (methyl methacrylate) interpenetrating network membrane

A novel polymer membrane system consisting of interpenetrating network (IPN) of hydroxy terminated polybutadiene (HTPB) based polyurethane urea (PUU)–poly (methyl methacrylate) (PMMA) has been designed and developed as highly permselective membrane for pervaporation separation of toxic p-chlorophenol and 2,4-dichlorophenol from their dilute aqueous solutions. It was observed that 3 ppm 2,4-dichlorophenol in water could be reduced to 0.3 ppm 2,4-dichlorophenol using a PUU–PMMA IPN membrane of 28 cm² area and 150 μm thickness. This membrane has shown high selectivity towards p-chlorophenol and 2,4-dichlorophenol at very low concentration in feed. Feed concentration of p-chlorophenol was varied from 1000 to 7000 ppm and that of 2,4-dichlorophenol was varied from 3 to 4000 ppm. Fifty seven percent 2,4-dichlorophenol in permeate was obtained from 3 ppm concentration in feed compared to 87% 2,4-dichlorophenol in permeate from 1000 ppm in feed. Pervaporation studies were carried out by varying the temperature of feed, membrane thickness and PMMA content in the membrane. The results of this investigation have revealed that these membranes would be suitable for separation of chlorophenols from industrial effluents.     

Ultrasound-Enhanced Recovery of Butanol/ABE by Pervaporation

The search for renewable sources of energy has led to renewed interests on the biochemical route for the production of butanol. Butanol production suffers from several drawbacks, mainly caused by butanol inhibition to the butanol-producing microorganism which makes it economically uncompetitive against the chemical process. One possible solution proposed is the in situ recovery of acetone–butanol–ethanol (ABE). Among the in situ recovery options, membrane processes like pervaporation have a great potential. Thus, the effects of temperature, feed concentration, and ultrasound irradiation on permeate concentration and permeation flux for the recovery of butanol/ABE by pervaporation from aqueous solutions were investigated in this study. In the butanol–water system, permeate butanol concentration as well as flux increased with an increase in temperature and butanol feed concentration. When pervaporation studies with ABE–water mixture were carried out at 60 °C for 2, 4, 8, 16, and 24 h, pervaporation profile revealed an optimal permeate concentration as well as permeation flux. Applications of ultrasound irradiation on pervaporation improved permeate concentration by about 23 g/L for both butanol and ABE. Ultrasound irradiation also improved butanol and ABE mass permeation flux by about 13 and 11 %, respectively.     

Design and optimization of combined pervaporation/distillation processes for the production of MTBE

The purification of product streams in the production of MTBE requires complex processes due to the thermodynamic behaviour of the mixtures (i.e. formation of azeotropes). Combined processes consisting of distillation and pervaporation/vapour permeation might offer economically attractive alternatives as they can simplify the process structure, reduce the energy consumption and avoid entrainers. The paper presents possible process configurations and design strategies for an integration of pervaporation and vapour permeation into the Huels process. For all process calculations, the commercial simulation software ASPEN PLUS was used in combination with a compatible FORTRAN routine allowing the design and simulation of complete pervaporation units in ASPEN PLUS.     

渗透汽化膜分离研究的新进展

渗透汽化膜分离技术是当前分离膜研究领域的前沿课题之一.作为化学分离中的重要组成部分,近年来受到高度重视.本文按渗透汽化膜分离的三大类混合液体系有机液脱水、从水相中分离有机物和有机混合液的分离,综述了近几年渗透汽化膜分离技术研究的新进展.其中,又重点报道了有机混合液分离的最新研究成果,将其分为:极性/非极性化合物、芳香烃/脂肪烃体系、芳香烃/脂环烃体系、同分异构体、多元体系和汽油脱硫等六部分进行了详细叙述.文章最后还对渗透汽化膜分离研究进行了展望.     

Polymeric membrane pervaporation

Pervaporation is an efficient membrane process for liquid separation. The past decades had witnessed substantial progress and exciting breakthroughs in both the fundamental and application aspect of pervaporation. This review provided an analytical overview on the potential of pervaporation for separating liquid mixtures in terms of the solubility parameter and the kinetic parameter of solvents. Focus of the review was given to the fundamental understanding of the membrane. Research progress, challenges and opportunities, and the prospect of pervaporation were also discussed. The thermodynamic approach of pervaporation, featuring emphasizing membrane/species interactions, though gained great successes in the past decades, is now facing its toughest challenge in the org–org separation. A kinetic era of pervaporation, featuring emphasizing diffusion selectivity, as well as the synergy between the selective diffusion and sorption, is in the making, and this approach will eventually find solutions to the challenging org–org separation.     

Separation of benzo[a]pyrene and <Emphasis Type="Italic">n</Emphasis>-tetradecane mixtures using pervaporation technique and optimization

Benzo[a]pyrene is a carcinogen often present in diesel. For pervaporative removal of benzo[a]pyrene from n-tetradecane, representing a model diesel composition, both conventional as well as statistically designed experimental methods have been carried out. The effect of membrane composition, thickness, the effect of membrane pretreatment time and operating temperature on pervaporative separation have been investigated by response surface methodology, RSM for efficient permeation of target compound. The suitable membrane has been further used to study the effect of different physico-chemical parameters on permeation conventionally. RSM has also been applied to optimize the operational conditions of pervaporation process to maximize the response, i.e., the pervaporation separation index. With the design of experiments, the quadratic response surface models have been developed to link the response with input variables via mathematical relationships. The maximum value of Pervaporation Separation Index obtained is 1.9654 kg m^?2 h^?1. The optimized process condition’s run time is 10.79 h, the feed PAH concentration is 166.34 ppm with a permeate side pressure of 0.73 mmHg and an operating temperature of 451.25 K.     

Pervaporation of volatile organics from water: II. Influence of permeate pressure on partial fluxes

Hydrophobic pervaporation is being developed within the area of separation of volatile organic compounds from dilute aqueous solutions. Optimisation of the pervaporation process for these types of applications is often very complex due to the many different organic compounds which are to be separated simultaneously. The permeate pressure is one of the key process parameters that has a considerable impact on both selectivities and partial fluxes. In this study, a model for predicting the permeate pressure dependence of the partial fluxes of the organic compounds to be separated was developed. The model includes both the effect of external mass transfer and the effect of altered permeabilities due to membrane plasticisation for the various permeants. Both these effects were proved to effect the partial fluxes to a significant extent. The model was shown to be applicable to organic permeants within the groups of alcohols, esters and aldehydes. Adequate information about the membrane separation factor and the overall separation factor together with the total flux at one specific permeate pressure is all that is needed for the application of this model.