膜蒸馏和膜吸收技术现状及发展

膜蒸馏和膜吸收是一种以蒸汽压差为推动力的新型高效的膜分离技术,作者介绍了膜蒸馏和膜吸收技术发展现状,机理及优缺点,并对其在有机废水处理中的应用及今后发展方向进行了论述。     

Analysis of a solar-powered membrane distillation system

Nowadays, in dry and rural areas, solar-powered membrane distillation (SPMD) technology is considered a feasiblemeans for the production of pure water from brackish water. Prior to the design and construction of a SPMD pilot plant, there is a need to predict its performance theoretically by means of a computational simulation program. Unlike previous approaches followed by other investigators to develop a mathematical model that can describe the components of a SPMD pilot plant, the developed mathematical model in this study is based on the fact that the SPMD process by nature is unsteady. The performance of a proposed SPMD pilot plant is then obtained by means of a numerical solution of the model with the aid of a simulation computer program. The results reveal that the proposed SPMD pilot plant has some unique features, which differ from a similar MD process operated at steady-state conditions in a laboratory. The analysis of the system has shown that heat recovery via an external heat exchanger is not only possible, but even effective, and an economical way to intensify the SPMD process. The plant productivity can be improved by increasing the heat-exchanger capacity (KA), decreasing the flow rates of both feed and permeate or otherwise by increasing the effective surface area of the membrane. The achieved enhancements in the SPMD pilot plant productivity are directly related to an improved heat recovery rate in the heat exchanger. However, further analysis reported in this paper shows that the increase in KA and membrane area should be optimized for any planned capacity in the design of a SPMD pilot plant.     

Characterization of membrane distillation membranes prepared by phase inversion

In this paper, flat membrane distillation membranes have been successfully manufactured from PVDF/DMAc and PVDF/DMF blends by using phase inversion induced by an immersion precipitation technique. The structure of the membranes is asymmetric with a porous top layer and macrovoids, as assessed by SEM. The existence of MD fluxes in these membranes is established by performing various pure water flux experiments. A maximum in the MD fluxes for a particular value of the polymer content in the casting solution from which the membrane is manufactured has been observed. The dependence of the magnitude of the fluxes on the membrane thickness is also discussed and the influence of temperature polarization evaluated.     

Desalination by membrane distillation adopting a hydrophilic membrane

Direct contact membrane distillation (MD) by means of composite membranes with a PVA/PEG hydrophilic layeron a hydrophobic PVDF substrate has been developed for desalination. The effects of brine temperature, salt concentration, running time and the addition of ethanol on the flux of composite membranes have been investigated. Results showed that the flux of the composite membrane did not deteriorate by adopting an additional hydrophilic membrane although durability was obviously improved. More than 99% of the separation coefficient in one run was achieved with the conductivity of the produced fresh water in the range of 6-10 μs/cm. The flux of the composite membrane retained 91% flux of substrate at 70°C, being 23.7 kg/h·m². When the brine temperature rose to 70°C, the composite membrane showed a declined concentration polarisation, with a smaller C_mb/C_b (3.89) than that of the substrate (5.79). Although the flux decreased with the increase of brine concentration, it retained 64% flux of pure water at brine solution containing 20% NaCl and was kept almost constant until 25% NaCl. In the continuous running experiments, there was no obvious drop of flux, even after adding 25% ethanol to the brine and running overnight. It is expected that adopting a hydrophilic layer can prohibit the wetting problem that faced traditional MD with hydrophobic membranes.     

A new enhancement technique on air gap membrane distillation

The most serious concern in the application of air gap membrane distillation (AGMD) configuration is the low permeate flux caused by an additional transport resistance owing to the air gap, by the temperature and concentration polarization and by the surface fouling. This paper presents an innovative design of a low-cost and high efficient membrane module with an advanced enhancement technique in an AGMD configuration, which not only yields a much improved permeate flux but also requires no additional facility for the enhancement. The new module design includes a tangent directional and rotational inlet turbulent flow of hot feed and a partial contact between the membrane and the cooling plate in a small air gap. The concrete structure of the module is introduced in detail in the paper. Using this new module the permeate flux can be obtained up to 119 kg/m²h for tap water when the temperature of the hot and cold water is 77 °C and 12 °C respectively, which is about a 2.5-fold improvement over the traditional AGMD technique at the almost the same conditions. Within the range of our experimental study, the optimum partial contact area ratio is about 75–80%. Mechanistically, the tangent and rotational inlet turbulent flow can accelerate the diffusive process of mass and heat, reduce the boundary layer thickness of temperature and concentration and wash the membrane surface so as to improve the temperature and concentration polarization near the membrane surface and to raise the efficiencies of mass and heat transfer. Because of the partial contact between the membrane and the cooling plate with a large area, the main heat transfer and permeate condensation in the gap both are carried out on the contact area, which is very different from either the common AGMD or DCMD (direct contact membrane distillation) so as to reduce the transport resistance in the gap and thus to raise the permeate flux significantly. The new enhancement technique is also applied for the desalination of 15 wt.% salt water, which shows the similar improvement in permeate flux.     

Humic acid fouling in the membrane distillation process

This work investigates the extent of humic acid fouling during the membrane distillation process for water treatment. The effects of pH, ionic strength, and divalent ion on fouling were studied. The experiments were performed with a 0.22-μm PVDF flat-sheet membrane in a direct contact membrane distillation unit. Flux declines were negligible (less than 6%) for the ranges of humic acid concentration, ionic strength, and pH studied. The examination of the membrane surface by SEM revealed a thin deposit layer. The addition of divalent cations (Ca²⁺) into the solution considerably reduced flux when Ca²⁺ concentration exceeded the critical coagulation concentration. Ca²⁺ affected flux by forming complexes with humic acids and resulted in coagulation on the membrane surface. The normalized flux, J/J₀, was 0.57 after 18 h of operation when the CaCl₂ concentration was 3.775 mM. However, the deposit of humic acid coagulate on the membrane surface was loosely packed, and was rather easily removed. Rinsing of the fouled membrane with clean water and a 0.1 M NaOH solution gave 100% of flux recovery.     

Preparation and properties of PVDF-fabric composite membrane for membrane distillation

The flat sheet PVDF-fabric composite membrane used for membrane distillation was prepared by coating and wet phase inversion process. The composite membrane consisted of a PVDF porous membrane layer and a fabric layer. The thin polyester filament woven fabric with water-and-oil repellent finish was used as the support of composite membrane. The effects of fabric texture, PVDF concentration in casting solution and functional finishing of fabric on the preparation and properties of the composite membrane were investigated. The experimental results showed that fabric texture, PVDF concentration and functional finishing of fabric had great influence on the preparation and properties of the composite membrane. When the PVDF concentration in casting solution was 10-12% and the support fabric, with 435 warps/10 cm and 273 wefts/10 cm and the area weight of 79 g/m², was finished with 2 g/L water-and-oil repellent agent FK-501, the prepared composite membrane exhibited better performance in tensile strength, peeling strength and water vapor permeability, with mean pore size of 0.63 μm and overall porosity of 57.6%.     

A neural network-based optimizing control system for a seawater-desalination solar-powered membrane distillation unit

Several schemes have been proposed so far for coupling desalination processes with the use of renewable energy. One of their main drawbacks, however, is the nature of the energy source that requires a discontinuous and non-stationary operation, with some control and optimization problems. In the present work, a solar powered membrane distillation system has been used for developing an optimizing control strategy. A neural network (NN) model of the system has been trained and tested using experimental data purposely collected. Afterwards, the NN model has been used for the analysis of the process performance under various operating conditions, namely distillate production versus feed flow rate, solar radiation and cold feed temperature. On this basis, a control system that optimizes the distillate production under variable operating conditions has been developed, implemented and tested.     

Fouling evaluation on membrane distillation used for reducing solvent in polyphenol rich propolis extract

Membrane distillation (MD) has not been widely studied in the concentrate of phenolic rich solution in comparison to osmotic distillation.In this work,the potential of MD to reduce solvent in the polyphenol rich propolis extract was further investigated.Polyvinylidene fluoride (PVDF) membranes were engineered with the smaller pore size for the less hydrophobic surface in order to avoid wetting,allowing only the solvent vapor to be transferred from the warm feed into the cold permeate.All the membranes exhibited more than 95％ rejection of phenolic and flavonoid compounds.Although the hydrophilic membranes exhibited less fouling,they displayed a lower flux than the hydrophobic membrane due to the hindrance in the wetted pores.The hydrophobic membrane was seriously fouled by the phenolic acid as shown in the Fourier transform infrared spectroscopy spectrum.Pore plugging occurred on these hydrophobic membranes as confirmed in the scanning electron microscope images.     

A new model for mass transfer in direct contact membrane distillation

The mass transfer process in direct contact membrane distillation (DCMD) for three kinds of membranes was measured. Water fluxes at different temperatures and the membrane distillation coefficients (MDC) for each membrane were obtained directly from experimental data. The fact that the MDC values of membranes with larger pore size increase with temperature indicates that Poiseuille flow plays an important role in the process of mass transfer through the membrane. Based on this conclusion, a three-parameter model, named the Knudsen diffusion-molecular diffusion-Poiseuille flow transition (KMPT) model, was developed to predict MDC and water flux for membrane distillation. The parameters of the KMPT model for each membrane employed in this study, by which MDC at various temperatures can be determined, were evaluated by a nonlinear regression. The values of MDC and water fluxes for each membrane predicted by KMPT model agree well with that obtained directly from the experiment results. A large contribution of Poiseuille flow to mass transfer was observed and can be attributed to the distribution of large pores in the membranes. The KMPT model also provides a method for estimation of the effect pore size using the ratio of the MDCs; the ratio of the Poiseuille flow to molecular diffusion MDC provides the best estimation.     

Exergy analysis of desalination by solar-powered membrane distillation units

There has been an increasing interest in using exergy as a potential tool for analysis and performance evaluation of desalination processes where the optimal use of energy is considered an important issue. Unlike energy, exergy is consumed or destroyed due to irreversibilies in any real process and thus provides deeper insight into process analysis. Exergy analysis method was employed to evaluate the exergy efficiency of the “compact” and “large” solardriven MD desalination units. The exergy efficiency of the compact and large units with reference to the exergy collected by the solar collector was about 0.3% and 0.5% but was 0.01% and 0.05%, respectively, when referenced to the exergy of solar irradiance. The exergy efficiency of the flat plate solar collectors in both units varied diurnally and the maxima was 6.5% ad 3% for the compact and large units, respectively. The highest exergy destruction was found to occur within the membrane distillation module.     

Concentration of apple juice using direct contact membrane distillation

The direct contact membrane distillation process (DCMD) has been used to investigate the concentration of apple juice. Results show that at a constant temperature of juice in the hot cell, an increase in the flux permeates of DCMD resulted in reducing the temperature of cooling water in the cold cell. Increasing the temperature of juice in the hot cell reduces influence of the cooling water temperature in the cold cell on the flux permeate of DCMD. The influence of temperature polarization on the effectiveness of DCMD in apple juice concentration has also been detected. The dependence of flux permeates on operating temperature. The concentration of soluble substances in concentrate and hydrodynamic conditions in the experimental equipment has also been studied. In the concentration of apple juice, 50% of solids content was obtained when the permeate flux reached about 9 l/m2·h. Further concentration of juice to 60–65% solids resulted in reduced productivity (3.8–3.0 l/m²·h) and therefore a decrease in the biological value of the concentrate.     

Design of an autonomous solar desalination plant using vacuum membrane distillation,the MEDINA project

The unit presented in this paper is designed to provide a high quality of potable water in remote coastal areas with bad infrastructure and without a network connection. The installation is designed completely autonomous; indeed the only source of energy is the sun.     

Seawater desalination by direct contact membrane distillation

Membrane fouling still posts as one of the major obstacles in membrane distillation (MD). This is why the MD approach still cannot successfully compete with other conventional seawater desalination methods. In this study, both the NaCl solution and real seawater are used as the feed of MD processes to investigate the differences in permeate flux, product water quality and membrane fouling. The results indicate the accumulation rate of membrane scale can be depressed by reducing the degree of polarization if NaCl solution is used as the feeding fluid, however, this kind of depression effect is not so obvious when real seawater is used as the feeding fluid. An ultrasonic cleaning technique is found to be an effective way to restore the flux rate for these MD processes and extend the life span of MD membrane.     

Economic evaluation of desalination by small-scale autonomous solar-powered membrane distillation units

Solar-powered desalination is an attractive and viable method for the production of fresh water in remote arid areas. One of the most important factors determining desalination decisions is economics. This paper presents an economic assessment performed to estimate the expected water cost, which is the ultimate measure of the feasibility of the stand-alone system. Based on the calculations, the estimated cost of potable water produced by the compact unit is $15/m³, and $18/m³ for water produced by the large unit. Membrane lifetime and plant lifetime are key factors in determining the water production cost. The cost decreases with increasing the membrane and/or the plant lifetime.     

Robust super-hydrophobic inorganic nanoparticles modified layered structure Si2N2O membrane for membrane distillation

Robust super-hydrophobic ceramic membranes consisting of layered structure Si₂N₂O grains and organosilane-derived inorganic nanoparticles were successfully fabricated and employed for membrane distillation. First, phase inversion and sintering method were used to prepare porous Si₂N₂O membranes. The slurry composition and sintering temperature were optimized to obtain a pure phase Si₂N₂O membrane with high bending strength, tailored average pore size, and high permeability. Then, the Si₂N₂O membranes were modified with organosilane-derived inorganic nanoparticles through ammonolysis and pyrolysis reactions. Due to the micro and nano-hierarchical rough structures and the presence of -Si-CH₃ groups, the membranes showed super-hydrophobicity with a water contact angle of 152 ± 1°. Finally, the membranes were applied to desalinate seawater by sweeping gas membrane distillation. A stable water flux of 76 ± 0.9 L/(m² day) with a salt rejection of > 99% was recorded during 30 h distillation test at 75 °C, demonstrating the stability and durability of the membranes.     

Fabrication of low thermal conductivity yttrium silicate ceramic flat membrane for membrane distillation

This paper reports on the successful fabrication of γ-Y₂Si₂O₇ membranes with low thermal conductivity, which is an important membrane property for achieving high performance in membrane distillation process. Single-phase γ-Y₂Si₂O₇ powder was first synthesized by calcination of SiO₂ and Y₂O₃ powders, with 3 wt% LiYO₂ as a sintering aid. The membrane was produced by tape-casting of a suspension of this powder. After sintering at 1300 °C for 4 h, a flat membrane was obtained, which had a thickness of 0.5 mm, 49% porosity, 0.9 μm pore diameter, and low thermal conductivity of 0.497 W/m⋅K at 32 °C, and 0.528 W/m⋅K at 100 °C. The obtained membrane presented hydrophobic features (water contact angle was 132°) after surface modification, which resulted in formation of a strongly adhered robust hydrophobic SiNCO nanoparticle layer on its surface. The resultant hydrophobic membrane was tested in water desalination experiments using a sweeping gas membrane distillation (SGMD) device. High water flux of 10.07 L⋅ m⁻²⋅ h⁻¹ was achieved for a 20 wt% NaCl feeding solution and a temperature at the feed of 90 °C. Stable water flux and rejection rates were recorded in long-term experiments (>400 h).     

Towards practical implementations of membrane distillation

Membrane distillation, which combines thermal desalination and porous hydrophobic membrane as non-wetting contact media, is currently gaining increasing important in membrane processes. However, the vast researches and reported publications of membrane distillation (MD) are less followed by its practical/industrial applications. This paper review analyzes the reasons for MD has not widely being implemented in practical/industrial applications. In addition, the strategies towards practical application are presented. Thus, this review will complement previous review of MD papers.     

Simulation of membrane distillation modules for desalination by developing user's model on Aspen Plus platform

This paper presents a simulation study of direct contact membrane distillation (DCMD) and air gap membrane distillation (AGMD) for desalination. Simulation models are built on Aspen Plus^® platform as user defined unit operations for these two types of modules, respectively. Large scale modules for practical industrial applications are simulated and studied for the effects of design and operation variables, as well as the importance of heat and mass transfers of each phase. For each type of modules with heat recovery design, the response surface method (RSM) is applied to develop the performance-variables quadratic model, followed by the multivariable optimization. Optimal designs can realize separation efficiencies, defined as the ratio of water produced to the feed, of 8.2% and 5.8% for DCMD and AGMD, respectively.     

Fabrication and characterization of hydrophobic PVDF hollow fiber membranes for desalination through direct contact membrane distillation

The mixture of inorganic salt LiCl and soluble polymer polyethylene glycol (PEG) 1500 as non-solvent additive was introduced to fabricate hydrophobic hollow fiber membrane of polyvinylidene fluoride (PVDF) by phase inversion process, using N,N-dimethylacetamide (DMAc) as solvent and tap water as the coagulation medium. Compared with other three membranes from PVDF/DMAc, PVDF/DMAc/LiCl and PVDF/DMAc/PEG 1500 dope solution, it can be observed obviously by scanning electron microscope (SEM) that the membrane spun from PVDF/DMAc/LiCl/PEG 1500 dope had longer finger-like cavities, ultra-thin skins, narrow pore size distribution and porous network sponge-like structure owing to the synergistic effect of LiCl and PEG 1500. Besides, the membrane also exhibited high porosity and good hydrophobicity. During the desalination process of 3.5 wt% sodium chloride solution through direct contact membrane distillation (DCMD), the permeate flux achieved 40.5 kg/m² h and the rejection of NaCl maintained 99.99% with the feed solution at 81.8 °C and the cold distillate water at 20.0 °C, this performance is comparable or even higher than most of the previous reports. Furthermore, a 200 h continuously desalination experiment showed that the membrane had stable permeate flux and solute rejection, indicating that the as-spun PVDF hollow fiber membrane may be of great potential to be utilized in the DCMD process.