Influence of polypropylene membrane surface porosity on the performance of membrane distillation process

Two kinds of polypropylene capillary membranes were used in the membrane distillation (MD). These membranes exhibited a similar morphology, but one of them has an additional low porosity layer on the internal surface of capillaries. The changes of membrane performance during MD process of tap water were investigated. The presence of low porosity layer (thickness below 1 μm) caused that the air permeability was reduced from 1.365 to 0.863 dm³/m² s kPa, whereas the MD permeate flux was decreased only by 15%. A significantly larger decline of the flux was caused by CaCO₃ deposit formed during distillation of tap water. This deposit was removed every 30–70 h by rinsing the modules with a 2–5 wt.% HCl. Unfortunately, a repetition of this operation several times resulted in a gradual decline of the maximum permeate flux (distilled water as a feed). However, the module efficiency with the membranes covered by a surface layer of low porosity was found to decreases twice as slowly. The investigations revealed that a low surface porosity does not limit the possibility of surface wetting of polypropylene membranes, but hindered the scale formation inside the pores.     

Omniphobic membranes for distillation: Opportunities and challenges

As an emerging thermal-driven membrane technology, membrane distillation (MD) has attracted immense attention for desalination and water purification. The membranes for MD generally have hydrophobic or superhydrophobic properties to enable vapor permeation without liquid passage (e.g., wetting). However, conventional MD membranes cannot undergo long term stable operations due to gradual wetting in practical applications where the feed solution often contains multiple low-surface tension contaminants (e.g., oil). Recently, omniphobic membranes repelling all sorts of liquids and typically having ultralow surface energy and re-entrant structures have been developed for robust MD to mitigate wetting and fouling. In this paper, we aim to provide a comprehensive review of recent progress on omniphobic membranes. Fundamentals, desirable properties, advantages and applications of omniphobic membranes are discussed. We also summarize the research efforts and methods to engineer omniphobic membranes. Finally, the challenges and future research directions on omniphobic membranes are discussed.     

Membrane distillation: theory and experiments

A theoretical approach is presented that describes membrane distillation processes due to the simultaneous action (in a proactive or in a counteractive way) of temperature and concentration differences through porous hydrophobic membranes. The model developed emphasizes the importance of the boundary layers, shows the existence of a coupling term between the two thermodynamic forces acting on the system, and permits the definition and characterization of the so-called steady states. In order to check the model, two membranes have been studied in different experimental conditions. The influence of some relevant parameters, such as solution concentration, stirring rate, mean temperature and temperature difference has been considered and the theoretical predictions of the model have been applied to the obtained results. The accordance may be considered good.     

Concentrating the extract of traditional Chinese medicine by direct contact membrane distillation

This study applies direct contact membrane distillation (DCMD) to concentrating the extract of traditional Chinese medicine (TCM). The trans-membrane flux under various operation conditions was measured in real-time during concentration process. By decoupling the factors affecting the trans-membrane flux decline, it was found that the observed flux decline throughout the process could be attributed to the membrane fouling, the reduction of water vapor pressure and the increase of transport resistance at feed side. Analysis of the combined factors was given to show in detail the mechanism of flux decline. Factors that may affect the flux level, such as feed velocity, feed temperature and pretreatment were experimentally examined. Gas bubbling or sparging was introduced into DCMD system for reducing membrane fouling, and it was found that both gas–liquid two-phase flow at the feed side and gas back-washing within membrane module are effective ways to control membrane fouling.     

Removal of 2,4-dichlorophenol from wasterwater by vacuum membrane distillation using hydrophobic PPESK hollow hiber membrane

2,4-Dichlorophenol was removed from wasterwater using a new hydrophobic poly(phthalazinone ether sulfone ketone) (PPESK) hollow fiber membrane by vacuum membrane distillation(VMD).     

Hydrophobic modification of poly(phthalazinone ether sulfone ketone) hollow fiber membrane for vacuum membrane distillation

New hydrophobic poly(phthalazinone ether sulfone ketone) (PPESK) hollow fiber composite membranes were obtained by surface-coated modification method.     

Fouling in direct contact membrane distillation process

The formation of deposit on the membrane surface (fouling) is one of the major operating problems of membrane distillation process. The influence of fouling on the performance of this process was investigated during the concentration of wastewater with proteins, bilge water, brines, and the production of demineralized water. The experiments were performed with polypropylene capillary membranes. The morphology and composition of the fouling layer were studied using Fourier transform infrared with diffuse reflectance spectroscopy and scanning electron microscopy coupled with the energy dispersing spectrometry. Fouling with various intensity was observed in most of the studied cases. Permeate flux decline was mainly caused by an increase in the heat resistance of the fouling layer. However in the case of non-porous deposit, a magnitude of the permeate flux was also determined by a resistance of water transport through the deposit layer. It was found the deposits were formed not only on the membrane surface, but also inside the pores. Salt crystallization in the membrane pores besides their wetting, also caused the mechanical damage of the membrane structure. The intensity of the fouling can be limited by the pretreatment of feed and a selection of the operating conditions of membrane distillation.     

Nature of flow on sweeping gas membrane distillation

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.     

Concentration and temperature polarization effects during osmotic membrane distillation

Pineapple juice is one of the popular fruit juice due to its pleasant aroma and flavor. Concentration of clarified pineapple juice was carried out by osmotic membrane distillation in a plate and frame membrane module. Concentration and temperature polarization effects are found to have significant role on flux reduction during osmotic membrane distillation process. The contribution of these polarization effects on reduction of the driving force (in turn the flux) at various process conditions such as osmotic agent concentration (2–10 mol/kg (1 molality = 1 mol/kg)), flow rate (25–100 ml/min) of feed and osmotic agent are studied. Concentration polarization has more significant effect on flux reduction when compared to temperature polarization. The experimental fluxes were in good agreement with theoretical fluxes when calculated by considering both concentration and temperature polarization effects. The pineapple juice was concentrated up to a total soluble solids content of 62°Brix at ambient temperature.     

Effect of operating conditions on water transport during the concentration of sucrose solutions by osmotic distillation

A recent membrane technique, osmotic distillation (OD), is used to concentrate binary water–sucrose solutions at ambient temperature under atmospheric pressure. The principle is based on the extraction of water vapour from a dilute aqueous solution, which is put in contact with a hypertonic salt solution by means of a macroporous hydrophobic membrane. The concentration difference between both solutions translates into a transmembrane vapour pressure drop, that constitutes the driving force for mass transfer. An experimental device is designed at laboratory scale for this study, allowing achievement of vapour fluxes of 10 kg m⁻² h⁻¹ under standard conditions. The effect of various operating parameters on vapour flux is studied. The solute content results in the most influencing variable via water activity in brine and via viscosity in sugar solutions. The effect of concentration polarisation on the brine side is not negligible and would have to be taken into account for process optimisation. This phenomenon could not be quantified on the sugar solution side due to pressure drop limits of the pilot rig. Eventually, the vapour flux can be significantly increased by adding a temperature difference to the transmembrane concentration difference, when pure water is evaporated.     

Chemical pretreatment of feed water for membrane distillation

Membrane distillation was used to produce demineralized water from ground water. The influence of feed water pretreatment carried out in a contact clarifier (softening with Ca(OH)₂ and coagulation with FeSO₄ · 7H₂O) followed by filtration, on the process effectiveness was evaluated. It was found that the chemical pretreatment decreased the membrane fouling; however, the degree of water purification was insufficient because precipitation of small amounts of deposit on the membrane surface during the process operation was still observed. The permeate flux was gradually decreasing as a result of scaling. The morphology and composition of the fouling layer were studied using scanning electron microscopy coupled with energy dispersion spectrometry. The presence of significant amounts of silica, apart from calcium and magnesium, was determined in the formed deposit. The removal of foulants by heterogeneous crystallization performed inside the filter (70 mesh), assembled directly at the module inlet, was found to be a solution preventing the membrane scaling. Presented at the 34th International Conference of the Slovak Society of Chemical Engineering, Tatranské Matliare, 21–25 May 2007.     

Thermo- and pH-responsive polypropylene microporous membrane prepared by the photoinduced RAFT-mediated graft copolymerization

Thermo- and pH-responsive polypropylene microporous membrane prepared by photoinduced reversible addition–fragmentation chain transfer (RAFT) graft copolymerization of acrylic acid and N-isopropyl acrylamide by using dibenzyltrithiocarbonate as a RAFT agent. Attenuated total reflection-Fourier transform infrared spectroscopy (ATR/FT-IR), X-ray photoelectron spectroscopy (XPS) and field emission scanning electron microscopy (FE-SEM) were used to characterize the structural and morphological changes on the membrane surface. Results of ATR/FT-IR and XPS clearly indicated that poly(acrylic acid) (PAAc) and poly(N-isopropyl acrylamide) (PNIPAAm) were successfully grafted onto the membrane surface. The grafting chain length of PAAc on the membrane surface increased with the increase of UV irradiation time, and decreased with the increase of the concentration of chain transfer agent. The PAAc grafted membranes containing macro-chain transfer agents, or the living membrane surfaces were further functionalized via surface-initiated block copolymerization with N-isopropyl acrylamide in the presence of free radical initiator, 2,2′-azobisisobutyronitrile. It was found that PNIPAAm can be grafted onto the PAAc grafted membrane surface. The results demonstrated that polymerization of AAc and NIPAAm by the RAFT method could be accomplished under UV irradiation and the process possessing the living character. The PPMMs with PAAc and PNIPAAm grafting chains exhibited both pH- and temperature-dependent permeability to aqueous media.     

Calcium sulphate scaling in membrane distillation process

Formation of precipitates containing CaSO₄ during membrane distillation, applied to the concentration of aqueous salt solutions, is discussed in this paper. It was found that the concentration of SO₄²⁻ ions in such solutions should not exceed 600 mg L⁻¹ when they are subjected to concentration. However, concentration of sulphates at the level of 800 mg L⁻¹ in the feed is permissible provided that the excess of CaSO₄ is removed in a crystallizer. Crystallisation of salts, mainly CaSO₄ · 2H₂O, on the surface and inside the membrane was observed at higher feed concentrations, causing damage of the module. Precipitation of calcium sulphate was also observed during the production of demineralised water when high values of the water recovery coefficient (above 90 %) were used. In this case, the formed precipitate also contained CaCO₃, the co-precipitation of which significantly changed the properties of the scaling layer. The precipitate containing both CaSO₄ and CaCO₃ was formed mainly on the membrane surface and it could easily be removed by rinsing the module with a HCl solution. Presented at the 35th International Conference of the Slovak Society of Chemical Engineering, Tatransé Matliare, 26–30 May 2008.     

Direct contact membrane distillation of humic acid solutions

Direct contact membrane distillation process has been conducted for the treatment of humic acid solutions using microporous polytetrafluoroethylene and polyvinylidene fluoride membranes. The membranes were characterized in terms of their non-wettability, pore size and porosity. Water advancing and receding contact angles on the top membrane surfaces were measured. Experiments were also carried out employing pure water as feed at different mean temperatures and the water vapor permeance of each membrane was determined. Different humic acid concentrations in the feed solution, pH values and transmembrane temperature difference were tested. The direct contact membrane distillation technique is more adequate for the treatment of humic acid solutions than the applied pressure-driven separation processes, as lower membrane fouling was detected.     

Hydrophobic modification of poly（phthalazinone ether sulfone ketone） hollow fiber membrane for vacuum membrane distillation

New hydrophobic poly（phthalazinone ether sulfone ketone） （PPESK） hollow fiber composite membranes were obtained by surface-coated modification method.     

Performance evaluation of the different nano-enhanced polysulfone membranes via membrane distillation for produced water desalination in Sert Basin-Libya

A Polysulfone-Polyethylene glycol (PS/PEG) flat sheet membrane was prepared by phase inversion technique. Dimethyl Formamide (DMF) was utilized as a solvent and deionized water was utilized as the coagulant. Polyethylene glycol (PEG) of a various dose of PEG 2000 was utilized as the polymeric improvers and as a pore-forming agent in the casting mixture. The single-walled carbon nanotube (SWCNTs), multi-walled carbon nanotube (MWCNTs), aluminum oxide (Al₂O₃) and copper oxide (CuO) nanoparticles (NPs) were utilized to improve the PS/PEG membrane performances. The characterizations of the neat PS, PS/PEG, PS/PEG/Al2O3 (M1) PS-PEG/CuO (M2), PS-PEG/SWCNTs (M3) and PS/PEG/MWCNTs (M14) nanocomposite (NC) modified membranes were acquired via Fourier-transform infrared analysis (FTIR), water contact angle estimation (WCA), scanning electron microscope (SEM), dynamic mechanical analyzer (DMA) and thermogravimetric analysis (TGA). Enhanced Direct contact membrane distillation (EDCMD) unit was used for estimating the efficiency of the performance of the synthesized NC membranes via 60 °C feed synthetic water and/or saline oil field produced water samples containing salinities 123,14 mg/L. Adjusting the operational procedures and water characteristics confirmed a high salt rejection of 99.99% by the synthesized NC membranes. The maximum permeate flux achieved in the order of SWCNTs (20.91) > Al₂O₃ (19.92) > CuO (18.92) > MWCNT (18.20) (L/m².h) with adjusted concentration of 0.5, 0.75, 0.75, 0.1 wt% compared with PS weight, i.e. 16%. The optimum operational circumstances comprised feed and permeate temperatures 60 °C and 20 °C, respectively. The achieved flux was 5.97 L/m².h, using brine oil field produced water, via PS/PEG/SWCNTs membrane with 0.5 wt% of SWCNTs. Moreover, the membrane indicated sustaining performance stability in the 480 min continuous desalination testing, showing that the synthesized PS/PEG/SWCNTs NC modified membrane may be of magnificent potential to be activated in EDCMD procedure for water desalination.     

Hydrophobic modification of poly(phthalazinone ether sulfone ketone) hollow fiber membrane for vacuum membrane distillation

New hydrophobic poly(phthalazinone ether sulfone ketone) (PPESK) hollow fiber composite membranes coated with silicone rubber and with sol–gel polytrifluoropropylsiloxane were obtained by surface-coated modification method. The effects of coating time, coating temperature and the concentration of silicone rubber solution on the vacuum membrane distillation (VMD) properties of silicone rubber coated membranes were investigated. It was found that high water permeate flux could be gotten in low temperature and low concentration of silicone rubber solution. When the coating temperature is 60 °C, the coating time is 9 h and the concentration of silicone rubber solution is 5 g L⁻¹ the water permeate flux of the silicone rubber coated membrane is 3.5 L m⁻² h⁻¹. The prepolymerization time influence the performance of polytrifluoropropylsiloxane coated membranes, and higher prepolymerization time decrease the water permeate flux of the membrane. The water permeate flux and the salt rejection was 3.7 L m⁻² h⁻¹ and 94.6%, respectively in 30 min prepolymerization period. The VMD performances of two composite membranes during long-term operation were studied, and the results indicated that the VMD performances of two composite membranes are quite stable. The salt rejection of silicone rubber coated membrane decreased from 99 to 95% and the water permeate flux fluctuated between 2.0 and 2.5 L m⁻² h⁻¹. The salt rejection of polytrifluoropropylsiloxane coated membrane decreased from 98 to 94% and the water permeate flux fluctuated in 1 L m⁻² h⁻¹ range.     

聚偏氟乙烯膜蒸馏技术在水处理中的应用研究进展

膜蒸馏是一种以膜为介质,利用传统蒸发工艺开发的新型膜分离技术。随着高分子材料行业的进步和制膜工艺的成熟,膜蒸馏技术取得了巨大的进展,在水处理领域拥有十分广阔的市场前景。膜蒸馏技术的核心是膜的通量和使用寿命,而性能优良的膜材料是膜蒸馏技术发展的关键。聚偏氟乙烯(PVDF)因具有成膜性能好、表面张力大、化学稳定性强等优点,在膜蒸馏技术应用研究中备受青睐。同时PVDF与其他聚合物具有良好的相容性,为膜的改性研究奠定了基础,极大地扩展了应用范围。本文介绍了膜蒸馏技术的工作原理及工艺特点以及PVDF膜材料的特点及改性方法,重点对PVDF膜蒸馏技术在水处理领域的应用进行了梳理和总结,讨论了该技术亟待研究和解决的问题,以期为该工艺技术的进一步发展提供科学支撑和理论依据。     

Wettability of polypropylene capillary membranes during the membrane distillation process

Studies of membrane wettability in the membrane distillation process were performed with the application of hydrophobic capillary membranes made of polypropylene. Three kinds of Accurel PP membranes (Membrana GmbH, Germany) differing in the diameter of capillaries and pores as well as in the wall thickness were used. It was confirmed that membranes with lower wall thickness and larger pore size provide higher yields of the process. The studies demonstrated that the pores of used membranes located close to the external surface of capillaries are several times larger than those located inside the membrane wall. Based on air permeability measurements it was found that external surface of the membranes with such large pores was completely wetted by water after 50–80 h of membrane distillation. However, the pores located inside the wall with the diameter below 1 μm were not wetted and electrical conductivity of the obtained distillate was maintained at the level of 3–6 μS cm⁻¹.     

Potential of membrane distillation in seawater desalination: Thermal efficiency,sensitivity study and cost estimation

In this work, an extensive analysis on direct contact membrane distillation (DCMD) performance was developed to estimate the mass flux and the heat efficiency, considering transport phenomena, membrane structural properties and most sensitive process parameters, with the aim to provide optimization guidelines for materials and methods. The results showed that an increase of the temperature gradient resulted in the enhancement of both transmembrane flux and thermal efficiency. The investigation of the effects of membrane properties confirmed that better DCMD performance was achieved when using polymeric membranes characterized by low thermal conductivity (flux and thermal efficiency declined by 26% and 50%, respectively, when increasing thermal conductivity from 0.1 to 0.5 W/m K), and high porosity. An optimal thickness value (around 0.7 mm) was identified when operating at low temperature gradient (<5 °C). However, at higher temperature gradient (>10 °C), increasing the membrane thickness from 0.25 to 1.55 mm resulted in a flux decay of about 70% without a significant improvement in thermal efficiency.