Rückgewinnung von Metallen aus niedrigkonzentrierten Lösungen

Recycling of metals from low concentrated solutions. A review is given of processes used for the separation of metals from aqueous solutions, especially low concentration waste waters. Purification processes for waste water used only to reach values set by law are compared with processes that allow recovery of metals. Precipitation with and without additives, adsorption, processes with ion exchange resins, solvent extraction and membrane processes, especially liquid membrane permeation, are described. As a result of these considerations, a qualitative comparison of all the described processes becomes possible. For the separation of zinc from a waste water stream, a special economic comparison is also shown between precipitation processes and the liquid membrane permeation process. Finally, the latest developments in the fields of solvent extraction and liquid membrane permeation are discussed.     

Separation Characteristics of Dimethylformamide/Water Mixtures through Alginate Membranes by Pervaporation,Vapor Permeation and Vapor Permeation with Temperature Difference Methods

Abstract

In this study permeation and separation characteristics of dimethylformamide (DMF)/water mixtures were investigated by pervaporation (PV), vapor permeation (VP), and vapor permeation with temperature difference (TDVP) methods using alginate membranes crosslinked with calcium chloride. The effects of membrane thickness (30–90 µm), feed composition (0–100 wt%), operating temperature (30–50°C) on the permeation rates and separation factors were investigated. The permeation rate was found to be inversely proportional to the membrane thickness whereas separation factor increased as the membrane thickness was increased. It was observed that the permeation rates in VP and TDVP were lower than in PV however the highest separation factors were obtained with TDVP method. Alginate membranes gave permeation rates of 0.97–1.2 kg/m² h and separation factors of 17–63 depending on the operation conditions and the method. In addition, sorption‐diffusion properties of the alginate membranes were investigated at the operating temperature and the feed composition. It was found that the sorption selectivity was dominant factor for the separating of DMF/water mixtures.     

高分子致密膜内渗透现象的同一性研究

在渗透汽化（PV）和蒸汽渗透（VP）膜分离过程,利用高分子膜材料对原料中不同组分的溶解度与扩散系数不同实现混合物分离.由于两种过程原料状态分别呈现液态和蒸汽形式,长期以来作为两种膜分离过程展开研究,其传质推动力都是组分在膜中的化学位梯度.为了从热力学和传质角度研究PV和VP膜分离过程,本文设计了特殊的渗透池,可以在同一渗透池中同时进行渗透汽化和蒸汽渗透膜分离过程,保持气液界面为热力学平衡状态.使用PVA/PAN复合膜进行水/乙醇混合物以及水/异丙醇混合物的PV和VP渗透实验,对两个过程中渗透通量随浓度变化情况进行了分析和比较.实验结果和理论分析表明：溶液的PV过程和与之呈相平衡的蒸汽相的VP过程在一定温度范围内,当原料中水含量较低的情况下具有相同的渗透通量,其传质遵从溶解扩散机理;当原料溶液中水含量较高时,PV过程中膜溶胀现象较为严重,渗透通量存在一定差别.     

Separation of Water/Ethanol Vapor Mixtures through Chitosan and Crosslinked Chitosan Membranes

Abstract

The separation of water/ethanol vapor mixtures through chitosan membranes and crosslinked chitosan membranes was studied by means of the vapor permeation technique. The permeation performance was discussed in terms of separation factor and permeation flux. Crosslinking the chitosan membrane by glutaraldehyde enhanced the selectivity. The highest separation factor obtained was 6000 for a crosslinked chitosan membrane with a degree of deacetylation of 100%.     

MEMBRANE SEPARATION TECHNOLOGIES: CURRENT DEVELOPMENTS

This article provides a brief overview of major developments in membrane separation technologies over the last six years until 1995. Progress in membrane separation processes, membrane separation techniques and membranes for given separation problems are of primary interest. The order of importance for membrane separation technologies is: already commercialized, being commercialized and having great potential based on laboratory performance. Separations involving liquid solutions, gaseous mixtures and particle removals have been covered. Notable recent developments in eight commercialized technologies namely, reverse osmosis, ultrafiltration, microfiltration, electrodialysis, dialysis, pervaporation, gas permeation, emulsion liquid membrane are illustrated first. New membrane-based equilibrium separation processes involving gas-liquid and liquid-liquid contacting, distillation and adsorption are then considered. The progress in new membrane-based rate-governed separation processes of vapor permeation and continuous deionization are treated next followed by a number of developing techniques, e.g., perstraction, facilitated transport, osmotic distillation, contained liquid membrane, supported liquid membrane and supported polymeric liquid membrane. Developments in hybrid separation processes where one of the techniques employs membranes are identified. The potential and current reality of membrane reactors is provided at the end.     

Natural Rubber/Acrylonitrile Butadiene Rubber Blend Membranes: Vapor Permeation Properties

Natural rubber (NR)/Acrylonitrile butadiene rubber (NBR) blend membranes, prepared by using dicumyl peroxide as the crosslinking agent, were tested for their vapor permeation characteristics. The permeation studies were conducted using three chlorinated hydrocarbons, viz. dichloro methane, chloroform, and carbon tetrachloride. The effects of the blend ratio, compatibilizer, penetrant size, and temperature on the vapor permeability of the membranes were investigated. The permeability of the blends was found to decrease with an increase in the NBR content, which has been attributed to the inherent solvent resistant nature of NBR. The permeation behavior of compatibilized blends was compared with those of the uncompatibilized blends. The separation efficiencies of the membranes were also tested using chloroform/acetone mixtures to complement the observations from the vapor permeation experiments.     

Effects of Membrane Parameters on Performance of Vapor Permeation through a Composite Supported Liquid Membrane

Abstract

Support liquid membranes have been used in air dehumidification due to their inherent high mass transfer rates. In this study, the effects of membrane structural parameters on vapor permeation through a LiCl solution based supported liquid membrane are investigated. To aid in the analysis, a mass transfer model has been proposed for moisture transfer through the membrane, which is composed of a supported liquid layer sandwiched by two hydrophobic protective layers. The model takes into account of the resistance in boundary layers, in the protective hydrophobic layers, and in the supported liquid layer. It is a transient model. It also reflects the distributed nature of moisture permeation through the membrane. The results found that the emission rate exhibits a non‐uniform distribution nature on the membrane surface. The structural parameters of the support and the protective layers, such as thickness, pore diameters, and porosity, have great effects on vapor permeation.     

Vapor permeation of ethyl acetate,propyl acetate,and butyl acetate with hydrophobic inorganic membrane

This study is focused on the permeation characteristics of ester compounds from aqueous solutions through hydrophobic membrane; ethyl acetate (EA), propyl acetate (PA) and butyl acetate (BA). A surface-modified tube-type alumina membrane (Al₂O₃) was used for ester compounds recovery by vapor permeation. Experiments were performed to evaluate the effects of the feed concentration (0.15–0.60 wt.%) and feed temperature (30–50 °C) on the separation of EA, PA, and BA from dilute aqueous solutions. It was found that the permeation flux increased with increasing feed ester concentration and operating temperature. The fluxes of EA, PA, and BA at 0.60 wt.% feed concentration and 40 °C were 282, 526, 661 g/m² h, which were much higher than those of polymer membranes. The separation factors for the 0.15–0.60 wt.% feed solution of EA, PA, and BA at 40 °C were in the range of 28.1–93.9, 83.6–129.4, and 190.7–209.9, respectively. The membrane tested showed high flux and high selectivity.     

Off-Gas Purification by Means of Membrane Vapor Separation Systems

Abstract

The separation and recovery of volatile hydrocarbon vapors from gasoline tank farm off-gases can in Europe be considered to be a state-of-the-art technology (1). A new application in the treatment of gasoline vapors is the installation of a membrane module in vapor return lines from petrol dispensers to storage tanks at gasoline stations to enhance the vapor recovery efficiency of this system. For solvent vapor recovery, some membrane systems have been installed in the chemical and pharmaceutical industry (2). This paper deals with design features and operating experience.     

Potentials of pervaporation to assist VOCs’ recovery by liquid absorption

Gas treatment by liquid absorption is a well-known process to remove volatile organic compounds (VOCs) from industrial waste gases. Usually the liquid is an organic solvent of high boiling point; however, after VOCs’ absorption it must be regenerated for the possible reuse and this step is classically achieved by heating the liquid. The paper presents the work directed to investigate an alternative regeneration step based on a liquid-vapour membrane separation, i.e. pervaporation. Because most of the energy required in pervaporation processes is consumed to remove the minor component from the initial mixture by selective permeation through the membrane, one can expect a significant energy cut in the operational costs linked to the regeneration of the liquid if the pervaporation step can substitute the heating one. The results reported here show that the technological possibility to use pervaporation is first governed by the stability of the membrane in the absorption liquid. The viability of the overall process is actually controlled by the mutual affinity between the VOCs, the solvent phase and the polymeric material. As a matter of fact, whereas VOCs have to exhibit strong affinities to both the solvent and the membrane material, the polymer has to be well resistant and even repellent to the solvent to avoid the possible sorption in the membrane that would drastically depress the pervaporation efficiency. In other words the membrane transport properties must be specific for the VOCs. This goal was reached following several experimental approaches, going from membrane modifications to the selection of suitable heavy protic solvents. Hence it has been shown for the case of dichloromethane (DCM) that low molecular weights polyalcohols (e.g. glycols) appeared to be suitable media to allow in particular the specific transport of DCM. On the other hand, polydimethylsiloxane (PDMS) based membranes were selected for their stability in these polyglycols and for their marked affinity for DCM. The simulation of the hybrid gas treatment process at pilot-scale was also achieved by a simple model relying on experimental data for both vapour liquid equilibria and permeation flux. A simple comparison of the energy needed to regenerate the heavy solvent by each possible step has also been made.     

Maxwell-Stefan理论模拟NaA沸石膜分离一氯甲烷中微量水的渗透特性

通过热浸渍晶种法制备了高质量的NaA沸石膜,并将其应用于蒸汽渗透脱除一氯甲烷中的微量水. 实验结果表明,NaA膜对该体系显示了优异的分离性能,水对一氯甲烷的分离系数高达74831,产品中的水含量从0.2582%(w)降低到0.005%(w). 将基于Maxwell-Stenfan理论和Langmuir理想吸附理论推导的吸附-扩散模型用于模拟水渗透流速与渗透侧真空度和进料温度的关系,预测趋势与实验值吻合很好,且拟合得到的参数与文献报道较接近,表明水蒸汽在NaA沸石膜中的传递为表面扩散机制,水蒸汽的吸附对渗透速率的贡献很大. 水蒸汽的吸附热为-34.15 kJ/mol.     

Application of Pervaporation and Vapor Permeation Processes to Separate Aqueous Ethanoi Solution through Chemically Modified Nylon 4 Membranes

ABSTRACT

The pervaporation performance of a nylon 4 membrane, chemically grafted by N,N-dimethylaminoethyl methacrylate (DMAEM), DMAEM-g-N4, was studied by measurement of the permeation ratio and the pervaporation separation index. It was found that the water permselectivity and permeationrate for the chemically modified Nylon 4 membrane were higher than those of the unmodified Nylon 4 membrane. Optimum pervaporation results, a separation factor of 28·3, and a permeation rate of 439 g/m²-h, were obtained when the degTee of grafting was 12·7%. It was also found that all the permeation ratios at low temperature were less than unity. In addition, compared with pervaporation, vapor permeation effectively increases the permselectivity of water.     

PTFE多孔膜气体渗透数学模型和膜孔结构的影响

Membrane-based separation processes are new technology combined membrane separation with conventional separation. Hydrophobic porous membranes are often used in these processes. The structure of hydrophobic porous membrane has significant effect on mass transfer process. The permeabilities of five kinds of gas, He, N2,O2, CO2 and water vapor, across six polytetrafluoroethylene(PTFE) fiat membranes were tested experimentally.Results indicated that the greater the membrane mean pore size and the wider the pore size distribution are, the higher the gas permeability. A gas permeation model, including the effects of membrane structure parameter and gas properties, was established. A comprehensive characteristic parameter (including porosity, thickness and tortuosity) was found more effective to express the influence of membrane structure in gas permeation process. The predicted permeation coefficients were in good agreement with experimental data.     

新型纳滤膜分离电镀镍漂洗水的试验研究

本文介绍了TFC?-S型纳滤膜分离电镀镍漂洗水的试验研究,讨论了温度、操作压力、浓差极化、共存离子对膜分离性能的影响。结果表明,这种纳滤膜对电镀镍漂洗水中Ni2 的去除率高于99.5%,透过液中Ni2 质量浓度小于1mg/L;对CODCr的去除率大于96%,透过液中CODCr低于14mg/L,达到国家工业废水排放标准(GB8978-1996),可以直接排放或回用于镀件漂洗。     

蒸汽渗透技术在燃料乙醇生产中的应用研究进展

蒸汽渗透作为一种新型膜分离技术,可有效解决生物燃料乙醇生产中发酵产物浓度低、能源消耗量大、污染环境等诸多瓶颈问题。与渗透蒸发相比,蒸汽渗透技术具有分离性能好、进料清洁、能量损耗低、操作弹性大等优点,在燃料乙醇生产领域具备更广阔的应用前景。本文在比较渗透蒸发和气体分离技术的基础上,简述了蒸汽渗透过程的机理和特点。介绍了优先透水膜和优先透醇膜两类应用于燃料乙醇生产不同阶段的蒸汽渗透膜和这两类膜材料当前的研究进展,重点阐述了有机/无机杂化膜在成膜方法、杂化材料选择等方面的最新成果。回顾了蒸汽渗透在乙醇脱水方面的工业应用成果,指出该技术在发酵原位分离乙醇和替代精馏工艺方面所具有的优势,探讨了与固态发酵技术相结合进行一次相变生产燃料乙醇工艺实现的可能性,并提出未来亟待研究和解决的问题,为蒸汽渗透技术在燃料乙醇生产领域大规模发展提供参考。     

Separation of Organic Vapors by Means of Membranes

In many production processes it is impossible to prevent the occurrence of flue gas streams containing solvents even if production-oriented environmental protection measures are implemented consistently. This means that there is still an urgent need to minimize emissions by cleaning solvent-loaded process and flue gas streams. The thermal, catalytic or biological oxidation procedures that destroy organic solvents should only be used in cases where recovery is not reasonably possible. The procedures of choice are those that enable the solvent to be recovered and recycled. In the last ten years, major progress in the field of membrane separation technology has made gas permeation an interesting alternative to the conventional methods. The combination of a membrane separation step with direct or indirect condensation results in a hybrid process permitting gentle and contamination-free recovery of the organic components. The following article is a brief summary of the fundamental principles of the permeation of gas/vapor mixtures through polymer membranes.     

Application of water vapor and hydrogen-permselective membranes in an industrial fixed-bed reactor for large scale methanol production

Coupling reaction and separation in a membrane reactor improves the reactor efficiency and reduces purification cost in the next stages. In this work a novel reactor consisting two membrane layers has been proposed for simultaneous hydrogen permeation to reaction zone and water vapor removal from reaction zone in the methanol synthesis reactor. In this configuration conventional methanol reactor is supported by a Pd/Ag membrane layer for hydrogen permeation and alumina-silica composite membrane layer for water vapor removal from reaction zone. In this reactor syngas is fed to the reaction zone that is surrounded with hydrogen-permselective membrane tube. The water vapor-permselective membrane tube is placed in the reaction zone. A steady state heterogeneous one-dimensional mathematical model is developed for simulation of the proposed reactor. To verify the accuracy of the model, simulation results of the conventional reactor is compared with the available plant data. The membrane fixed bed reactor benefits are higher methanol production rate, higher quality of outlet product and consequently lower cost in product purification stage. This configuration has enhanced the methanol yield by 10.02% compared with industrial reactor. Experimental proof-of-concept is needed to establish the safe operation of the proposed configuration.     

A Vapor Permeation Processes for the Separation of Aromatic Compounds from Aliphatic Compounds

A number of rubbery and glassy membranes have been prepared and evaluated in vapor permeation experiments for separation of aromatic/aliphatic mixtures, using 5/95 (wt:wt) toluene/methylcyclohexane (MCH) as a model solution. Candidate membranes that met the required toluene/MCH selectivity of ≥ 10 were identified. The stability of the candidate membranes was tested by cycling the experiment between higher toluene concentrations and the original 5 wt% level. The best membrane produced has a toluene permeance of 280 gpu and a toluene/MCH selectivity of 13 when tested with a vapor feed of the model mixture at its boiling point and at atmospheric pressure. When a series of related membrane materials are compared, there is a sharp trade-off between membrane permeance and membrane selectivity. A process design study based on the experimental results was conducted. The best preliminary membrane design uses 45% of the energy of a conventional distillation process.     

Highly selective and efficient transport of toluene in bulk ionic liquid membranes containing Ag as carrier

Ionic liquids have very low vapour pressure and a very high boiling temperature and are therefore a potentially environmentally friendly solvent. In this paper, room-temperature ionic liquids are used as a bulk liquid membrane for separation of toluene from n-heptane. Aromatic hydrocarbon, toluene, is successfully transported through the ionic liquid membrane based on 1-methyl-3-octyl imidazolium chloride. Using silver ion as a carrier in 1-methyl-3-octyl imidazolium chloride membranes, batch wise extraction experiments are carried out. The separation performances, represented by the permeation rate and separation factor, are analyzed systematically by varying the operating parameters: the contact time, concentration of Ag⁺, stirring effect, initial feed phase concentration and temperature.     

Experimental validation of hybrid distillation‐vapor permeation process for energy efficient ethanol–water separation

BACKGROUND: The energy demand of distillation‐based systems for ethanol recovery and dehydration can be significant, particularly for dilute solutions. An alternative separation process integrating vapor stripping with a vapor compression step and a vapor permeation membrane separation step, termed membrane assisted vapor stripping (MAVS), has been proposed. The hydrophilic membrane separates the ethanol–water vapor into water‐rich permeate and ethanol‐enriched retentate vapor streams from which latent and sensible heat can be recovered. The objective of this work was to demonstrate experimentally the performance of a MAVS system and to compare the observed performance with chemical process simulation results using a 5 wt% ethanol aqueous feed stream as the benchmark. RESULTS: Performance of the steam stripping column alone was consistent with chemical process simulations of a stripping tower with six stages of vapor liquid equilibria (VLE). The overhead vapor from the stripper contained about 40 wt% ethanol and required 6.0 MJ of fuel‐equivalent energy per kg of ethanol recovered in the concentrate. Introduction of the vapor compressor and membrane separation unit and recovery of heat from both membrane permeate and retentate streams resulted in a retentate ethanol concentrate containing ca 80 wt% ethanol, but requiring only 2.2 MJ fuel kg^?1 ethanol, significantly less than steam stripping alone. CONCLUSION: Performance of the experimental unit with a 5 wt% ethanol feed liquid corroborated chemical process simulation predictions for the energy requirement of the MAVS system, demonstrating a 63% reduction in the fuel‐equivalent energy requirement for MAVS compared with conventional steam stripping or distillation. Published 2009 by John Wiley & Sons, Ltd.