M. Khayet

Membranes and theoretical modeling of membrane distillation: a review.

Membrane distillation (MD) is one of the non-isothermal membrane separation processes used in various applications such desalination, environmental/waste cleanup, food, etc. It is known since 1963 and is still being developed at laboratory stage for different purposes and not fully implemented in industry. An abrupt increase in the number of papers on MD membrane engineering (i.e. design, fabrication and testing in MD) is seen since only 6 years ago. The present paper offers a comprehensive MD state-of-the-art review covering a wide range of commercial membranes, MD membrane engineering, their MD performance, transport mechanisms, experimental and theoretical modeling of different MD configurations as well as recent developments in MD. Improved MD membranes with specific morphology, micro- and nano-structures are highly demanded. Membranes with different pore sizes, porosities, thicknesses and materials as well as novel structures are required in order to carry out systematic MD studies for better understanding mass transport in different MD configurations, thereby improving the MD performance and looking for MD industrialization.

Preparation and characterization of polyvinylidene fluoride hollow fiber membranes for ultrafiltration

Polyvinylidene fluoride (PVDF) hollow fiber membranes were prepared using the solvent spinning method. N,N-dimethylacetamide was the solvent and ethylene glycol was employed as non-solvent additive. The effect of the concentration of ethylene glycol in the PVDF spinning solution as well as the effect of ethanol either in the internal or the external coagulant on the morphology of the hollow fibers was investigated. The prepared membranes were characterized in terms of the liquid entry pressure of water measurements, the gas permeation tests, the scanning electron microscopy, the atomic force microscopy, and the solute transport experiments. Ultrafiltration experiments were conducted using polyethylene glycol and polyethylene oxides of different molecular weights cut-off as solutes. A comparative analysis was made between the membrane characteristic parameters obtained from the different characterization techniques.

Application of surface modifying macromolecules for the preparation of membranes for membrane distillation

The top surface of polyetherimide (PEI) flat sheet membranes was modified using fluorinated surface modifying macromolecule (SMM). The SMM modified and unmodified membranes were prepared by the phase inversion method from casting solutions containing the solvent N, N-dimethylacetamide and the non-solvent y-butyrolactone (GBL). The effect of the base polymer concentration on the membrane properties has been investigated. It was found that SMM actively migrated to the air surface and changed the surface properties of the PEI membranes. Contact angle measurements indicate that the PEI membrane surface becomes more hydrophobic after adding the SMM to the PEI casting solutions, while X-ray photoelectron spectroscopy analysis shows enrichment of fluorine on the PEI membrane surfaces. The SMM modified and unmodified PEI membranes were also characterised by means of liquid entry pressure of water measurements (LEPw) and gas permeation test using nitrogen as standard gas. SMM modified PEI membranes have potential to be used in membrane distillation.

Theory and experiments on sweeping gas membrane distillation

Abstract A theoretical model is presented that describes sweeping gas membrane distillation processes through porous hydrophobic membranes. The approach considers the case in which the liquid feed and the sweeping gas counterflow in a plate and frame membrane module. The model developed emphasises the importance of the heat fluxes in the directions parallel and perpendicular to the membrane surface and permits to obtain the temperature profiles inside the fluid phases. In order to check the model, two membranes have been studied in different experimental conditions. The influence of some relevant parameters, such as the inlet and outlet temperatures or the circulation velocities of the fluids has been studied. The theoretical predictions of the model have been applied to the obtained results and the accordance may be considered good.

Study on the effect of a non-solvent additive on the morphology and performance of ultrafiltration hollow-fiber membranes

Hollow-fiber membranes were prepared by the dry/wet spinning technique from polyvinylidene fluoride (PVDF) dope solutions containing the solvent N, N-dimethylacetamide and the non-solvent additive 1,2-ethanediol. Ethanol aqueous solution, 50% by volume, was used as internal and external coagulants. The effect of the non-solvent additive concentration on the morphological properties of the hollow fibers was studied in terms of atomic force microscopy (AFM) and scanning electron microscopy (SEM). The pore size, the nodule size and the roughness parameters at the inner and outer surfaces of the hollow fibers were studied by AFM. The liquid entry pressure of water (LEPw) and the porosity of the hollow fibers were evaluated. The pore size was also determined by the gas permeation test and by the solute transport using ultrafiltration of polyethylene glycol (PEG) and polyethylene oxides (PEO). A comparative study was made between the membrane characteristics parameters obtained from the different characterization techniques.

Nature of flow on sweeping gas membrane distillation

Abstract The process of sweeping gas membrane distillation (SGMD), with the liquid feed and the sweeping gas counterflowing in a plate and frame membrane module, has been studied. A theoretical model, which was presented in a previous paper and permitted to obtain the temperature profiles inside the fluid phases, has been developed in order to analyse the physical nature of the transmembrane water flux. Two porous hydrophobic membranes have been studied in different experimental conditions. The influence of some relevant parameters, such as the inlet and outlet temperatures or the circulation velocities of the fluids, has been studied. The experimental results have been analysed according to the model and the conclusion is that the water transport takes place, apparently, via a combined Knudsen and molecular diffusive flow mechanism. From the temperature profiles, a local temperature polarisation coefficient may be defined. From this local value, an overall one for the whole system is then defined. The new theoretical predictions have been applied to the obtained results and the accordance may be considered good.

The effects of air gap length on the internal and external morphology of hollow fiber membranes

Abstract A systematic study of the air gap effects on both the internal and the external morphology, permeability and separation performance of polyvinylidene fluoride (PVDF) hollow fiber membranes has been carried out. The hollow fibers were prepared using the dry-jet wet spinning process using a dope solution containing PVDF/ethylene glycol/ N , N -dimethylacetamide with a weight ratio of 23/4/73. Ethanol aqueous solution, 50% by volume, was used as internal and external coagulants. The inner and the outer surfaces of the prepared hollow fibers were analyzed by atomic force microscopy (AFM), while their cross-sectional structure was studied by scanning electron microscopy (SEM). Ultrafiltration experiments were conducted using non-ionic solutes of different molecular weights. The results show that both the pore sizes and nodule sizes have a log-normal distribution. The pore size, nodule size and roughness parameters of the inner and outer surfaces of the hollow fibers were affected by the air gap distance. Alignment of nodules to the spinning direction was observed. Experimental results indicate that an increase in air gap distance, from 1 to 80 cm , results in a hollow fiber with a lower permeation flux and a higher solute separation performance due to the decrease of the pore size. AFM analysis reveals that the air gap introduces an elongational stress because of gravity on the internal or external surfaces of the PVDF hollow fibers. At low air gap distance, the inner surface controls the ultrafiltration performance of the PVDF hollow fiber membranes because of its lower pore size, while at high air gap lengths the inner pore size becomes larger than the outer pore size. The turning point was observed at an air gap distance of 20.3 cm .

Morphological study of fluorinated asymmetric polyetherimide ultrafiltration membranes by surface modifying macromolecules

Phase inversion polyetherimide (PEI) flat sheet membranes were surface modified using fluorinated surface modifying macromolecules (SMMs) additives. Two SMM formulations were used. Each SMM was blended into polyetherimide casting solutions containing the solvent N,N-dimethyleacetamide and the non-solvent hydroxybutyric acid γ-lactone (GBL). The effects of the SMM and the PEI base polymer concentrations on the morphological properties of the prepared membranes have been investigated. Contact angle measurements indicate that PEI membrane surface becomes more hydrophobic after adding the SMMs to the PEI casting solutions, while X-ray photoelectron spectroscopy analysis shows enrichment of fluorine on the PEI membrane surfaces. The SMM modified and unmodified PEI membranes were also characterized by means of atomic force microscopy (AFM), gas permeation tests and ultrafiltration experiments using aqueous solutions of polyethylene glycol (PEG) and polyethylene oxide (PEO) of various molecular weights. Pore sizes and nodule sizes obtained from AFM images were remarkably fitted to the log-normal probability distribution curves. Mean pore sizes, pore size distributions, nodule sizes, nodule size distributions and roughness parameters of the membranes were determined. It was found that SMM actively migrated to the air surface and changed the surface properties of the PEI membranes. The mean pore size and the molecular weight cut-off (MWCO) of the SMM modified PEI membranes were lower than those corresponding to the unmodified membranes, while the nodule sizes were larger. The surface roughness parameters were reduced when SMMs were added.

Modelling mass transport through a porous partition: Effect of pore size distribution.

Abstract Direct contact membrane distillation process has been studied using microporous polytetrafluoroethylene and polyvinylidene fluoride membranes. The membranes were characterized in terms of their non-wettability, pore size distribution and porosity. The mean pore sizes and pore size distributions were obtained by means of wet/dry flow method. The mean pore size and the effective porosity of the membranes were also determined from the gas permeation test. A theoretical model that considers the pore size distribution together with the gas transport mechanisms through the membrane pores was developed for this process. The contribution of each mass transport mechanism was analyzed. It was found that both membranes have pore size distributions in the Knudsen region and in the transition between Knudsen and ordinary diffusion region. The transition region was the major contribution to mass transport. The predicted water vapor permeability of the membranes were compared with the experimental ones. The effect of considering pore size distribution instead of mean pore size to predict the water vapor permeability of the membranes was investigated.

Micellar enhanced ultrafiltration process for the treatment of olive mill wastewater

Olive mill wastewater (OMW) is an important environmental pollution problem, especially in the Mediterranean, which is the main olive oil production region worldwide. Environmental impact of OMW is related to its high organic load and particularly to the phytotoxic and antibacterial action of its phenolic content. In fact, polyphenols are known as powerful antioxidants with interesting nutritional and pharmaceutical properties. In the present work, the efficiency of OMW Micellar Enhanced Ultrafiltration (MEUF) treatment for removal and concentration of polyphenols was investigated, using an anionic surfactant (Sodium Dodecyl Sulfate salt, SDS) and a hydrophobic poly(vinyldene fluoride) (PVDF) membrane. The effects of the process experimental conditions on the permeate flux were investigated, and the secondary membrane resistance created by SDS molecules was evaluated. The initial fluxes of OMW processing by MEUF using SDS were 25.7 and 44.5 l/m2 h under transmembrane pressures of 3.5 and 4.5 bar, respectively. The rejection rate of polyphenols without using any surfactant ranged from 5 to 28%, whereas, it reached 74% when SDS was used under optimum pH (pH 2). The MEUF provides a slightly colored permeate (about 88% less dark), which requires clearly less chemical oxygen demand (COD) for its oxidation (4.33% of the initial COD). These results showed that MEUF process can efficiently be applied to the treatment of OMW and for the concentration and recovery of polyphenols.