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Journal of Membrane Science 474 (2015) 39–56

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Journal of Membrane Science
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Recent advances in membrane distillation processes: Membrane
development, configuration design and application exploring
Peng Wang a,b, Tai-Shung Chung b,n
GE Global Research, China Technology Center, 1800 Cailun road, Zhangjiang High-tech Park, Pudong, Shanghai 201203, P.R. China
Department of Chemical & Biomolecular Engineering, National University of Singapore, 4 Engineering Drive 4, Singapore 117576, Singapore

art ic l e i nf o a b s t r a c t

Article history: Membrane distillation (MD) is a separation process based on the vapor transport across the hydrophobic
Received 1 July 2014 microporous membrane driven by the vapor pressure gradient across the membrane. This process can be
Received in revised form used for various applications such as seawater desalination, wastewater treatment, separation of volatile
9 September 2014
compounds, concentration of non-volatile compounds and processing of dairy fluids. Comparing with
Accepted 10 September 2014
other separation processes, the MD process possesses unique characteristics such as 100% (theoretical)
Available online 19 September 2014
rejection, mild operation conditions, insensitive to feed concentration and stable performance at high
Keywords: contaminant concentrations. Due to high oil prices in recent years, extensive research has been devoted
Membrane distillation to MD in the areas of membrane materials, module configurations, process applications and hybrid
MD configuration
systems. This review aims to summarize the recent advances in MD and provide perspectives for its
MD application
future R&D.
Membrane development
Hybrid processes & 2014 Elsevier B.V. All rights reserved.


1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40
2. Membrane development . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40
2.1. Membrane materials and fabrication . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40
2.2. Polymer blend and additives & modification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43
2.3. Membrane geometry and micro-structure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44
3. MD configurations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45
3.1. Basic MD configurations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45
3.2. New MD configurations. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46
3.2.1. Multi-stage and multi-effect membrane distillation (MEMD) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46
3.2.2. Vacuum multi-effect membrane distillation (VMEMD) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
3.2.3. Hollow fiber multi-effect membrane distillation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
3.2.4. Material gap membrane distillation (MGMD) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
4. Applications and Hybrid systems of MD processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
4.1. Applications of MD processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
4.1.1. Seawater/brackish water desalination. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
4.1.2. Removal of small molecule contaminants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48
4.1.3. Recovery of valuable components. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
4.2. MD based Hybrid separation processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
4.2.1. Integration with the existing desalination process. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
4.2.2. Forward osmosis-membrane distillation (FO-MD) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
4.2.3. Membrane distillation-crystallizer (MD-C) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50
4.2.4. Membrane distillation-bioreactor (MDBR) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50

Corresponding author. Tel.: þ (65) 6516 6645; fax: þ65 6779 1936.
E-mail address: (T.-S. Chung).
0376-7388/& 2014 Elsevier B.V. All rights reserved.

. MD membranes should have good thermal pores of the hydrophobic membranes [1–8]. . . The vapors are then collected or condensed by of water vaporization and condensation. The first MD patent was issued in 1963 [17]. MD processes centration of non-volatile compounds and separation of volatile have demonstrated promising results in seawater desalination. . . . . . . . . . . . . . . . Introduction Membrane wetting happens during continuous MD operations. . 50 Acknowledgements . electro-spinning [34] and other technologies have membrane development. . . . .40 P. and (5) less requirements on membrane mechanical treatment of wastewater containing specific contaminants. . . . . . . . . . Hence. . . air gap. . . sweep (PP) and polyvinylidene fluoride (PVDF) [10. modification. . . . . . The applications of MD process for desalination and cially available MD membranes with high performance. . materials for some MD studies [35–38]. . . . . . . Better wetting resistance requires a membrane with higher hydro- Membrane distillation (MD) is an emerging membrane tech- phobicity and uniformly distributed smaller pores [1].1 shows the characteristic properties of Membrane commercially available low surface energy polymers commonly used for MD membranes.g. . . . . (3) lower operating tions with reduced energy consumption. . . . . . . thermally- applications and hybrid systems must also be explored. . .1. . . . . new MD nonsolvent induced phase separation (NIPS) [28–30]. . . . vacuum. namely. . a high flux MD hydrophobic membrane. the feed liquid from entering membrane pores due to the surface The second portion of this review focuses on the improvement of tension. . . . conducted an in-depth review on MD and its historical develop. . . . . . .16]. . Membrane materials and fabrication high temperature. . . . . . . [10] and other research teams [21. . . 1) the lack of commercially available high their characteristics of easy fabrication. polypropylene Permeate stream (direct contact. . . . . a minimum energy consumption of around 628 kWh is Comparing with other membrane separation processes. . . hydrophobic polymers are preferred due to by two factors. With- et al. In this work. . . extensive efforts are needed to design MD configura- (2) relatively low operating temperatures. . . . . 50 5. pressures than conventional pressure-driven membrane separation The last portion of this review emphasizes on the exploration processes. . As a vaporize at the liquid/vapor interface and diffuse across the dry distillation-based process.-S. . . . the feed liquid directly contact- thermal conductivity to prevent heat loss across the membrane ing the membrane must not be allowed to penetrate into the dry [10–26]. . . . . we aim to review the recent advances in MD technology in terms of sintering [33]. . .2. In recent years. . .41]. Wang. . . wastewater treatment and many other applications [11–16]. . . . 1. . .22]. . . Conclusions and future directions . . properties and applications. . Comprehensive reviews were then made by Alklaibi and Lior [18]. 1. . . (4) insensitive to feed concentration for seawater of new MD applications. . . induced phase separation (TIPS) [31]. . . . . macromolecules and other non-volatile compounds. . stability and chemical resistance. . . .40. the desired MD membrane must have excellent anti-wetting properties. . . With a nology based on the vapor pressure gradient across the porous coupled heat and mass transport mechanism. Khayet has reviewed out a suitable membrane. . . . . So far. .23. . . . [23. . .18. . . . . . . . while the state- offers a number of advantages: (1) 100% (theoretical) rejection of of-art reverse osmosis (RO) technology only needs 2–3 kWh/m3 inorganic ions. . . . MD needed for MD to produce one ton of clean water. . . . . . . . . . . . . . . . . Feed stream Materials such as silicone coated glass fibers and nylon were investi- gated in the early stage of MD development but showed unsatisfactory wetting resistance [39]. . Different fabrication processes such as expand and fully harvest the advantages of MD process. . it is hard to materialize MD as a viable the theoretical modeling of MD process [23]. . . . . the MD process involves in the latent heat membrane pores. . 52 References . . . . .1. . . With these unique advantages. and scale-up performance membranes and 2) high energy consumption [24. . . T. . energy-saving configuration design. 2. . . . . . . . . . . . the most popular polymers used in MD membranes are still polytetrafluoroethylene (PTFE).1. . . . . Meanwhile. . .16. Chung / Journal of Membrane Science 474 (2015) 39–56 4. As illustrated in stability and chemical stability (e. . . . ceramic. . . Illustration of the MD process. . . . . design. . the volatile components in the hot feed energy efficiency in the design of various configurations. . . . . . .5. . . . melt extrusion stretching [32]. . . design of suitable MD membranes will be reviewed from tubes (CNTs) and metals have also been explored as membrane the aspects of membrane materials and fabrication. . . . . . . . . . .c. carbon nano- Firstly. separation technology. . . system been employed to fabricate MD membranes depending on polymer hybridization and exploration of new applications. Since hydrophobicity is the essential requirement for MD mem- branes in most applications. . gas. . . . . . . . . . . . . Renewable/waste energy driven membrane distillation . . . . . . . .) PTFE has the lowest surface energy of around 920  10  3 N/m [45]. .23]. As a micro. . . . . . . sufficient water purification have been reviewed by Gryta [14]. . . . . . con- properties [1–10]. . . . . . . Lawson et al. . . . . It is a highly crystalline polymer with excellent thermal Fig. Since only volatile vapor molecules can membrane should have low vapor transfer resistance and low transport across the membranes. .27]. . .25]. . . . . . . In addition. and e. porous physical barrier. . potential fouling and scaling [15. . . Among the materials investigated or utilized The commercialization of MD process has been constrained mainly for MD membranes. . . . Since PTFE is a non-polar polymer. the membranes must be made from intrinsic or modified hydrophobic polymers with low surface energy. . . . desalination. To as well as low costs [15. . . . . . . . . . the hydrophobic nature of the MD membrane prevents the elevated operating temperatures and chemical cleaning [19]. . . . . . . Examples include seawater desalination. El-Bourawi One of major difficulties in MD processes is the lack of commer- et al. . . . . . . compounds from its aqueous solutions. . Table 2. . . . . . . acid and base) in order to handle Fig. . . . . . . Without a heat recovery different methods. . . . high flux and resistance towards 2. . . Tomaszewska [19]. . . . . . . Curcio and Drioli [15. . . Membrane development ment [1].t. . .16]. 52 1. . . [20]. . . Camacho wetting resistance and minimized fouling/scaling tendency. . . . .

circular pores were also [46.40 Poor Good Melt-extrusion TIPS PVDF 30. such as Celgards have been fabricated by the melt-extrusion. Meanwhile. lacetamide (DMAC) and dimethylformamide (DMF). a micro-porous PVDF membranes fabricated by the two methods. The final amorphous locking process was common solvents such as n-Methyl-2-Pyrrolidone (NMP). Fig. a porous membrane is formed. flat sheet PTFE process [60. TIPS or a combination obtained by extruding PTFE melt coupling with a rapid draw down of TIPS and NIPS process [65–71].25 Good Good Sintering Melt-extrusion PP 30 0. Utilizing the aforementioned polymers. PVDF also used for PTFE membrane fabrication [47. membranes with flat sheet stretching method by taking the unique hard elastic properties of and hollow fiber configurations have been fabricated by both mem- PP [55–59]. membranes fabricated via NIPS possess an asymmetric structure PP also has a highly crystalline structure but higher surface consisting of a dense surface and many macrovoids in the cross- energy (30.2 Good Good NIPS .2–20 μm [54]. by companies such as PALL. Unlike PTFE and PP. T. it The polymer melt extrusion method followed by stretching is has a relatively low melting temperature of 170 1C.1 Characteristic properties of commercial polymer materials commonly used for MD membranes [10. Polymer materials Chemical structure Surface energy Thermal conductivity Thermal stability Chemical stability Fabrication methods (  10  3 N m  1) (W m  1 K  1) PTFE 9–20 0. In this method.19 Moderate Good NIPS TIPS Electro-spinning PVDF-HFP – – Good Good NIPS Electro-spinning Hyflons – 0. solid- TIPS processes. Eventually.1 (A) and (B) show PP membranes various operation conditions [49–51]. dimethy- carried by annealing the membrane at 370 1C for 5 mins.3  10  3 N/m. However. P.2 shows the SEM images of during the stretching. Recently.72–74]. Hollow fiber PTFE membranes have been produced by Toyobo and Table 2. For example.17 Moderate Good Melt-extrusion TIPS PE 28-33 0.23. a homogeneous solution is firstly membranes with polyester (PET) or PP supports have been produced formed by dissolving PP in diluents at a temperature above Tm.40–44]. respectively [56]. the resultant membranes are further stretched from used in the commercial and pilot MD systems because of their good single/dual directions to re-align the crystal structure and balance wetting resistance. PTFE membranes are most often some cases. The formed paste is then extruded into a sheet or obtained by a bi-axially stretching after the melt-extrusion process hollow fiber forms which is then heated and expanded in order to [62]. it can be easily dissolved in highly-porous structure. Besides. the membrane performance is generally lower due to As an example of the sintering process.69.0  10  3 N/m) than PTFE [10]. applications [32]. The membrane needs to be relatively advantageous in material and manufacturing costs. Chung / Journal of Membrane Science 474 (2015) 39–56 41 it is difficult to fabricate PTFE membranes by common NIPS and Once the membranes are fabricated by casting or spinning. 2.48. mechanical stress is applied to the direction of drawing so that a PVDF membranes fabricated via TIPS tend to have a relatively relatively uniform porous structure is formed with a pore size uniform porous structure without macrovoids. After the annealing and cooling processes. Gore. Therefore. with elliptical pores fabricated from the melt-extrusion-stret- The sintering process begins with a mixture of very fine PTFE ching method and circular pores fabricated from mono-axially powders and volatile lubricating agents (e. the paste PVDF is a semi-crystalline polymer with a surface energy of was bi-axially stretched for five times at 225 1C to generate the 30. PP membranes are also fabricated by the TIPS brane manufacturers and researchers.3 0. cal) [53]. Inert gas such as nitrogen is often introduced to avoid oxidation. stabilized in an amorphous locking step by thermal annealing. Wang. 2. The hydrophobic PTFE membranes used for MD liquid separation and liquid-liquid separation as well as diluent applications are normally produced using sintering method or extraction take place. PTFE films are membranes can be fabricated either by NIPS. while most of PVDF distribution in the range of 0. In melt-extrusion method [46–48]. Membrane Solutions and GE [10]. satisfactory water flux and excellent stability in the mechanical properties.61].52].g. PP membranes are produce a microporous membrane. Gore fabricated a highly. As compared with other MD membranes. After removing the volatile lubricant by drying. Porous PP membranes section [41. the symmetric structure and the moderate thermal stability at porous PTFE membrane using a paste with PTFE powder and elevated temperatures.-S. Fig.48]. hydrocarbon) stretching. These may limit PP potential for MD volatile lubricant Isopar™ isoparaffinic fluids (ExxonMobil Chemi.

the modified PES membrane exhibited ACCURELs (Membrana) [76. polyoxadiazoles and polytriazoles by both phase inversion and Aside from polymeric materials.81]. The resultant membranes exhib.3-dioxole (TTD). diameter of 50 nm exhibited a high rejection and a reliable air gap vides a powerful technology to modify the membrane surface. alumina and tita- Besides using intrinsic hydrophobic polymers. modifications by silicone rubber and sol-gel polytrifluoropropylsilox- fluoromethoxy-1. flat sheet and hollow fiber PP modified membranes displayed a contact angle of around 1201. where the CNTs were held together solely and converted to hydrophobic membranes for MD [86].7 l m  2 h  1 (LMH) and a salt rejection as thoroughly evaluated the application of PP hollow fiber membranes high as 99. The plasma by Van der Waals forces [92].8 1C. Nunes and her solutions and the membrane with the optimal formulation exhibited co-workers fabricated MD membranes from aromatic fluorinated a high salt rejection of 99%. can also be made from hydrophilic polymer materials that have For example.2. the vacuum membrane distillation (VMD) [88]. processes. metal. Kong et al.7 LMH and close to Fluorine-containing monomers can be activated with plasma sources 100% salt rejection (converted from the original unit) at a feed to form a branched polymer and adhere to membrane surface [85]. PVDF and PTFE. fabricated pressure (LEP) of 0. MD membranes nium) need to be modified for improved hydrophobicity [35–38]..4-trifluoro-5-tri. SEM Image of a PVDF micro-porous membrane fabricated from (A) NIPS and (B) TIPS methods [65. Fig. nitrate (CN) membrane via plasma polymerization of octafluorocy- In addition to homo-polymers of PP. Gryta and his co-workers have a stable water flux of 66. 2.hexafluoropropylene) (PVDF-HFP) [29. .12 Mpa. zirconia. ceramic membranes (i. Chung / Journal of Membrane Science 474 (2015) 39–56 several research groups [75]. glass. Recent works also investigated the assembly For example.e. In another work.79].77].1.82]. modified a cellulose for MD applications [78. CNTs and inor- electro-spinning methods [83].-S. membrane distillation (AGMD) flux of around 4. (B) TIPS methods [63.72]. temperature of 95 1C. SEM images of micro-porous PP membranes fabricated from (A) a melt-extrusion-mono-axially-stretching. Wang. composite membranes was affected by the formulation of coating ide-co. surface modified poly(phthalazi- membranes can be made from their copolymers with enhanced none ether sulfone ketone) (PPESK) membranes were used for hydrophobicity and durability. Garcio-Payo et al. has been used by Gugliuzza and ane.64].42 P. to prepare asymmetric membranes with a phobic surface with a contact angle of 1101 and a higher liquid entry contact angle large than 1201 [80. ganic based materials were also evaluated for MD applications ited high porosity and super-hydrophobicity with an apparent [38. MD clobutane [87]. 2. Similar with the hydrophilic polymers used in MD contact angle up to 1621 [84]. The ultra-thin BP membranes with a Fig.89–91]. After surface-coating copolymer of tetrafluoroethylene (TFE) and 2. Hyflons AD (Solvay Plastics). the PPESK hollow fiber membrane exhibited a more hydro- Drioli and Arcella et al. hydrophilic polyethersufone (PES) ultrafiltration (UF) of CNTs into paper-like structures called Bucky-Papers (BP) as self- hollow fiber membranes can be plasma modified by CF4 monomer supporting membranes. Plasma polymerization pro. membranes are commercially available as Celgards (Pollypore) and During the 54 h DCMD test. Similarly. Similarly.97% at 73. T. surface modified zirconia membrane with a pore undergone hydrophobic modifications. The permeation flux of silicone rubber a series of hollow fiber membranes using poly (vinyldiene fluor.2.

neered the works of utilizing LiCl to prepare PVDF MD membranes aging and delamination were observed. dispersed in 99. the membranes in their work showed stable long-term performance up 2. permeation performance. Chung / Journal of Membrane Science 474 (2015) 39–56 43 narrow pore size were processed by vacuum filtration of CNTs electron donating groups of solvents could increase dope viscosity. macromolecules are acrylonitrile (PAN) membranes for the recovery of petroleum ether also utilized as pore forming additives. P. fouling properties. either hydrophilic or super-hydrophobic materials are membrane increases from  10 nm to 50 nm and no obvious preferred to produce an oleophobic surface [97].or nano. there are still concerns about the usage of diffuses across the membrane pores. Besides small molecules and inorganic salts. it helps form a sponge-like structure between the organic solution and the hydrophobic membrane with high porosity when its concentration is high. However. In most membrane manufacturing processes such as NIPS. matrix hollow fiber membranes by using hydrophobic modified Water. the VMD performance of hydrophobic PVDF and hydrophilic poly. the mixed matrix membranes could gain specific benefits small molecule nonsolvents. The fabricated membranes showed highly hydrophobic section and surfaces. Interestingly. the incorporation of additives in dope formulation is ical properties of various membranes [104–110].51 and performed well membrane preparation [30. inorganic salts or macromolecules as well from particles with various hydrophilicity. The complex formed between Li þ and in 5-day continuous DCMD experiments. improvements such as [28]. alcohols.98]. one can change solution rheology. fabricated nano-porous mixed brane formation and separation performance. Wang.2. the pore size of the like liquids.99]. (2) form hydrophilic rejection (498%). Similarly. Mean- anti-fouling properties. Inorganic salts like LiCl are also employed during characteristics with a contact angle of 147. Polyvinylpyrrolidone (PVP) from the solanesol extracting solution [97]. easily wetted and lost its selectivity. As non-solvents in the Chung and their coworkers incorporated PTFE micro-particles into PVDF-solvent binary system. Fig. In literatures. Similarly. the resultant et al. The addition of LiCI into the casting solution drastically altered surface grafting and coating have to be carried out to improve the membrane structure to an asymmetric porous structure with large membrane durability [93].7 kPa. The resultant membranes polymer solubility may increase dope viscosity as well as bring the showed a high contact angle of about 1301. in the case of oil. The fabricated membranes had finger- (PEG) are the examples of small-molecule pore forming agents that like macrovoids and exhibited a high flux of 72 LMH and close to have been widely used in membrane fabrication. However. hydrophobicity or anti- as their combinations plays an important role in determining mem. to 100% salt rejection at a feed temperature of 80 1C. Fig. desirable morphology. especially for NIPS. Schematic presentation of MD process with (a) hydrophilic membrane and (b) hydrophobic membrane [97]. The obtained material. In contrast.102].8% pure 2-propanol. Qu et al. As a result.3. With an addition of 3 wt% LiClO4. ethylene glycerol (EG) and poly-ethylene-glycerol nano-clay particles [107]. Edwie solution closer to the gelation point. . blended fluorinated silica particles (FSi) with a PVDF solution membranes may have a more porous structure at membrane cross. Yet in a hydrophilic membrane.3 illustrates the transport fabricated microporous hydrophobic PVDF hollow fibers by utilizing mechanisms of a feed mixture of solanesol and organic solvents water and PVP as the pore forming additives [103]. across hydrophilic and hydrophobic membranes in MD processes. ranes [100]. The membrane hydrophobicity was also increased after Hydrophobic materials have been used in the MD process for drying.size particles. Simone et al. hydrophobicity or alter phase inversion and control membrane morphology. However. 2. 2. The hydrophilic PAN with different molecular weights are used to (1) prepare mem- membrane showed a good VMD flux (415 LMH) and solute branes with desirable pore sizes and porosity. Teoh. the volatile solvent fibers exhibited a high porosity (up to 80%) and optimized pore evaporates from the liquid-vapor interface on the feed side and then size.-S. The self-supporting CNT BP affect dope precipitation rate. By incorporating an effective and widely used method to design a MD membrane with micro. Polymer blend and additives & modification to 2 months for VMD tests even though the contact angle was not reported. while the hydrophobic PVDF membrane was membranes and (3) reduce bio-fouling [101. Wang et al. enhance flux and control the pore sizes [30. TIPS or Mixed matrix membranes are known to improve physicochem- melt-extrusion. macrovoids. PVP in MD membranes due to its hydrophilicity. T. The choice of pore forming agents such as while. [114]. lithium perchlorate (LiClO4) was used as a pore seawater desalination and alcohol/water separation due to its large forming agent in the fabrication of PVDF hollow fiber memb- surface energy gaps with water [94–96]. compared change of pore size distribution was observed. and enhance the permeation properties membrane showed a DCMD flux of 12 LMH with 99% salt rejection by producing larger pores and higher porosity. In another work. A PVP promotes the formation of macorvoids when the PVP concen- hydrophobic membrane will be easily wetted due to the high affinity tration is low. Tomaszewska pio- at a water vapor partial pressure difference of 22. the addition of liquids with lower the PVDF polymer solution [111–113].

2.1–0. 83.. a single-layer MD In order to maximize vapor diffusion. The MBF membranes fabricated from the optimal maintain its super-hydrophobic property after fouling tests using spinning conditions not only demonstrated high permeation model seawater and humic acid solutions. The right choices of dope and flux. the membranes phologically designed membranes and (2) hydrophilic/hydrophobic must be designed with the maximal vapor transportation but dual-layer hollow fiber membranes [7. open-cell pore structure. the MF membranes. the flux decline due to Fig. Unlike sponge-like structure could maintain the wetting resistance. As compared with other UF and Due to the unique heat and mass transfer mechanisms. where the hydrophobic and increasing membrane porosity [107].85 times [126]. entirely wetted pores would result in the loss hydrophobic dual-layer hollow fiber membranes [108. the MBF membranes increase in flux). the membrane showed high salt rejec.125– ization to modify a hydrophilic membrane have been reviewed.6 LMH was obtained during the DCMD desalination [7]. while that of a rates of these two layers during phase inversion. In this approach.e. At the [138–140]. a membrane of high hydrophobicity. while wetting by inner-layer and a sponge-like outer-layer [7]. permeation flux and fiber with high surface porosity was fabricated by applying the thermal efficiency. the desired MD membrane is preferably to have triple-orifice spinneret with a two-phase flow consisting of a a high porosity and a relative large pore size in the range of solvent and a dope solution in the air-gap region during spinning 0. spinneret Similarly.-S. The resultant fibers have two to . rectangular membranes for various MD applications [30. permeation flux for a MD finger-like macrovoids could minimize the tortuosity and mass membrane can be affected two possible mechanisms. Membrane geometry and micro-structure ent compositions are co-extruded from the two channels of the tri- orifice spinneret [136]. During the 300 h DCMD operation. fiber membrane they have made exhibited a water flux of geometries: (1) Hollow fiber membranes and (2) Flat sheet mem. while the other membrane separation processes. hollow fiber membranes have larger be also used to tailor the micro-structure of single-layer hollow specific surface areas [120]. between these two layers.3 mm to reduce the mass transfer resistance and minimize [117]. 1. Wang. a vapor transfer resistance and temperature polarization effect superior flux of 98. 127]. Chen and her co-workers utilized sol-gel prepared TiO2 design and effects of spinning parameters were explored. For example. CNTs were also employed fluxes (67 LMH at 90 1C feed temperature). ductivity of air inside membrane pores is much lower than that Khayet. path and the enhanced pore hydrophobicity were responsible for the The development of dual-layer hollow fiber membranes is another improvements. respectively. but also exhibited to modify the membrane surface inside pores [116]. the mass transfer resistance can be experiments with a feed inlet temperature of 80 1C. both layers was to improve molecular inter-diffusion and to avoid small pore size and high tortuosity is highly desired [108. permeated side water. Illustrated in tortuosity. while a blend of PVDF. Chung / Journal of Membrane Science 474 (2015) 39–56 In previous sections.119. During spinning. one can lower thermal conductivity by modified macromolecules (SMM). The best hollow Traditionally. Chung and his co-workers fabricated the hydrophilic- worst situation. the main drawbacks of current MD hollow fibers are low fiber membranes for MD [137]. To overcome it.4 nanoparticles to modify the MD membranes [115].997% salt rejection.4 LMH at an 80 1C feed temperature. This greatly reduces the functional layer mal conductivity across the membrane. thin functional layer and small was initially introduced in the early 90's [138].137]. Emerging appli- tion (99%) at lower feed salinity (10 mg/L) but low rejection (15%) at cations of dual-layer hollow fiber membranes include gas separation. morphological characteristics for these two parameters and proposed It has been pointed out that membranes with large pores and a dual-layer hollow fiber consisting of a fully finger-like macrovoid high porosity are preferred for vapor transport.108. transfer resistance.114. Interestingly. forward osmosis (FO). of membrane selectivity when the feed and permeate solutions They used a mixture of PVDF/hydrophobic particles for the at both streams are in direct contact [19]. great innovation in membrane fabrication [128–130]. Fig. methods as plasma or chemical polymer. 2. single-layer macrovoid-free and highly permeable PVDF hollow However.119]. analyzed the key performance. the macro-geometry and micro-structure of MD permeation flux and long-term stability of a MD membrane are highly membranes play more important roles in determining membrane dependent on its micro-structure. thickness and transport distance of water vapors in MD processes. delamination between the dual-layer [108. Since the thermal con. pioneered multi-bore hollow fiber (MBF) and section of the PVDF hollow fibers. T. In the field of MD membrane fabrication. The membrane was able to membranes. To improve the clay as well as CNT for the hydrophilic layer. The outer layer with a contacting liquids or contaminants should not occur [118]. A typical plate & frame or spiral wound fiber membranes. weak mechanical properties and higher risk of scaling and coagulant chemistry were the keys to induce de-lamination clogging [117–129].3. However. biofuel pervaporation and many other applica- tions [131–135]. Comparing to flat sheet membranes with plate & frame and The triple-orifice spinneret used in the dual-layer spinning can spiral-wound configurations.124]. Basically.44 P. namely. there is a risk of pore of the flat sheet membranes during the phase inversion processes wetting by vapor condensation and liquid penetration. wetting of hydrophobic layer. In their works. minimized by fabricating membranes with large pore sizes and The concept of hydrophilic-hydrophobic dual-layer membranes porosity. by manipulating the shrinkage module has a packing density of 200–800 m2/m3. one can obtain hollow fiber module could range from 500–9000 m2/m3 [121]. branes. Wang et al. two polymer solutions with differ- 2. the The structure and chemistry of MD membranes are critical in dual-layer hollow fiber technology has been used to produce (1) mor- achieving high and stable performance. hydrophilic segments of the SMM moved to top and bottom parts During the continuous MD operation. minimal wetting or fouling [117]. Through the second mechanism. In another example. The water contact shows the microscopic images of the round and rectangular MBF angle increased from 1251 to 1661. the hydrophilic layer can be easily wetted by the temperature polarization can be mitigated by reducing the ther. Wang et al.123.137]. Via the first mechanism. It was observed that the outer solvent cause membranes suffering from weak mechanical properties in induced delay demixing that greatly enhanced the outer surface both axial and radial directions. the dope solution and the solvent were co- the temperature polarization [108. higher salinity (34000 mg/L). Matsuura and their co-workers have worked on surface of the polymer matrix. The authors believed that the additional diffusion maintained its permeation flux and 99. The use of PVDF in wetting resistance and LEP. The incorporation superior stability and robustness in long term operation tests of CNTs led to a significant increase in MD performance (i. Therefore. and porosity and eliminated the macrovoid formation in the cross- Teoh et al. PAN and hydrophilic membrane pores should always be avoided.114].109. the detailed formation mechanisms.5. In addition to high energy efficiency of 94%. the discharged from the middle and outer channels of a triple orifice large pore size and high porosity in both bulk and surfaces also spinneret. there are two common types of membrane macro.

T.1 illustrates the mechanisms of these four basic config- be directly collected at the lower pressure side. Electro-spinning utilizes an electrical charge to draw extra fine fibers with a sub-micron diameter from a liquid form. fabricated PVDF-hydrophobic clay nano-composite membranes using the electro-spinning process.145]. The addition of clay nano-particles in the electro-spun fibers increased the contact angle of MD membrane to 154. This structure provides very high porosity and inner-connected pores [34.143]. Wang. 2.6 C) shows the micro-structure of modified fiber fabricated for DCMD [108]. the permeated vapor urations [1]. The MD materials. 2. 2. Besides hydrophobic PVDF or PVDF-HFP processes can be classified into four basic configurations. Basic MD configurations Unlike pressure-driven membrane processes where permeate can Fig.6 A) shows the mechanism and typical set-up of the electro- spinning process where nano.4. print have been proposed by many research teams [96. conducted a comprehensive review on recent develop.147. Liao et al. Both polymer solution and polymer melt with a liquid form can be used for the electro-spinning process. the membranes assembled from the electro-spun nanofibers have a non-woven like structure.141. In ment of electro-spun membranes for MD applications [146]. 3.83. 2. Owing to the characteristics of the electro- spinning process. proposed heat-press post- treatment and super-hydrophobic modifications to improve the mechanical integrity and wetting resistance of electro-spun mem.6 B).142].83.148]. In other works. we will review both basic and newly developed MD configurations.1. Shown in Fig.144. Some new configurations with surfaces were also evaluated for MD applications [44. Prince et al. configuration plays an important role in determining the separation zoles and polytriazoles. P. better permeation flux or smaller foot Tijing et al. needs to be condensed via different methods. Chung / Journal of Membrane Science 474 (2015) 39–56 45 Fig.or micro-meter diameter polymer fibers can be evenly distributed on a support under high voltage. this chapter. three times higher fluxes than those obtained from the standard dry-jet wet-spun fibers. The schematic illustration of a hydrophilic/hydrophobic dual-layer hollow branes [141. MD configurations 3. polystyrene (PS) and polyimide with rough performance and operation cost. the morphology of PVDF electro-spun mem- branes is very suitable for a MD application. electro-spun membranes with super-hydrophobic properties and multi-level roughness. other polymers such as aromatic fluorinated polyoxadia. Fig. Depending on the methods to induce vapor pressure gradient across the membrane and (a) Direct contact membrane distillation (DCMD): An aqueous solu- to collect the transported vapors from the permeate side. improved energy efficiency. 3. SEM images of MBF PVDF membrane: (A) round-shape 7-bore (B) round-shape 6-bore and (C) rectangular 7-bore membranes [125–127]. 2. Fig.201 [34].-S.5. Fig. MD tion with a lower temperature is in direct contact with the .

saturation pressure of volatile molecules in the feed solution. volatile molecules evaporate at the hot liquid/vapor [15. Besides AGMD modules. Scarab Development AB. The module was designed extensive works have been carried on the multi-effect or multi. With Fig.2.145. recovery based on the concepts of multi-stage and multi-effect (b) Air gap membrane distillation (AGMD): A thin air gap is designed distillation for seawater desalination. SGMD and VMD are often used to remove A microporous PTFE membrane from Gore-tex has been used in VOCs from aqueous solutions [157. The Fraunhofer Institute for Solar Energy Systems (ISE) developed a full-scale multi-effect spiral-wound MD module with a membrane 3. As the air gap The AGMD Memstils MD module with heat recovery was devel- provides a significant vapor transport resistance. developed the Condensation may or may not occur outside of the membrane heat recovery AGMD module with a plate and frame design [172]. in literature and laboratories for desalination and concentration of aqueous solutions [1–4. the flux of a oped in the late 1990 s by Netherlands Organization for Applied typical AGMD is lower than DCMD or VMD configurations [154]. Fig. Aquastill also the permeate side of the membrane module. New MD configurations area of 5 or 14 m2 and named it as permeate gap membrane distillation (PGMD) [96].168. Scientific Research (TNO) and later licensed to Aquastil and Keppel Utilizing the integrated cooling plate in the AGMD configuration. The Memstills module was designed for seawater and (c) Sweep gas membrane distillation (SGMD): A cold inert or sweep brackish water desalination [147].168]. A micro-porous PTFE membrane was used in [155. The energy consumption of this module was reported as 810 kWh/m3 [154]. The system enables feed pre-heating and low thermal efficiency has limited the commercialization of MD permeate condensation within the membrane module. nanofiltration (NF) or MSF.3 shows process [166]. easily higher than 1256 kwh/m3 (estimated from gain output ratio) Consequently. After the pilot trials. 2.96. As membrane is the only barrier to separate the hot feed and cold 3. This could result in an additional equipment cost.169].2 illustrates the AGMD module consisting of internal heat among four basic configurations.148]. Seghers for commercialization [147. Memstills claimed to have are condensed outside the membrane module by an external a very low specific energy consumption of 56 to 100 kWh/m3 condenser [157].2. extensive works have been carried out to develop interface. Hence. The pre-heated feed molecules pass through both the membranes and the air gap solution is further heated before it enters the feed channel.46 P. The temperature difference traditional MD configurations without heat recovery design can be across the membrane induces the vapor pressure difference. As the most simplified configuration. Wang. 3. Pilot desalination plants have been gas sweeps through the permeate channel and collects vapor tested in Singapore. A typical PGMD module consists of a feed Comparing with RO. 3.6. condensation operated at ambient pressure and lower temperature. DCMD modules with heat recovery (d) Vacuum membrane distillation (VMD): Vacuum is applied at were also developed based on the same technology [10].161–165].149–151]. transport across the membrane pores in vapor phase new MD configurations and membrane modules with higher thermal and condense in the cold liquid/vapor interface at the permeate efficiency [49.147. MD can be channel. DCMD has the highest conductive heat loss Fig. module [158–160].-S. DCMD is widely studied introduced in this section.166. (A) The mechanism and typical set-up of an electro-spinning process. A heating source of 50–100 1C is stage membrane modules with improved thermal efficiency supplied to the system. Multi-stage and multi-effect membrane distillation (MEMD) permeate solutions. and then condense on the cold surface [152.143.11. The evaporated volatile the permeated vapors as well as to gain heat. T. (B) morphology of an electro-spun PVDF membrane. hydrophobic membrane. the specific energy consumption of the schematic and photos of spiral wound PGMD module [96]. . However.146]. with a spiral wound configuration. Some of these new configurations are side. To provide the announced the development of 24 m2 module with counter-current driving force. In most cases. permeate channel.156]. this module [173].126. Chung / Journal of Membrane Science 474 (2015) 39–56 permeate side of the membrane.153].167]. the applied vacuum must be lower than the flows [171]. Netherland and other countries to address the molecules from the membrane surface. The Sweden company.107–109.137. (C) surface modified electro-spun membranes with multi-level roughness [34. For example. the surface and condensate. [147. the module. the vapors technical issues [170].1. The cold feed solution was between the membrane and a condensation surface (typically a placed beneath the condensation surface as a coolant to condense thin dense polymer or metal film).

174. Applications and Hybrid systems of MD processes 3. the Feed side specific energy consumption of this module for desalination can be as low as 130 kwh/m3. The water availability for human consumption is continuously heated to 90 1C before entering the MD module. The typical VMEMD consists of a heater. condensate vapor in the permeate side. Fig. As a result. multiple evaporation–condensa- (PR) of this module can reach 11. AGMD normally shows a MEVMD and built an automated manufacturing line for membrane lower permeation flux as compared with other MD configurations. Applications of MD processes Qin et al. (C) SGMD and (D) VMD. Memsys claimed a specific energy consumption value of 175–350 kWh/m3 [10]. Distillate is hence produced in both condensation stages and inside the condenser. This cooled feed studies of MD for brackish water desalination have gradually solution is fed back into the MD module and serves as the coolant to attracted interests from both academia and industry [6. The months [3].5. A vacuum condition is energy consumption around 55 kWh/m3 [177] employed at the air gap region to remove the excess air/vapor.2. from Chembrane Research & Engineering. patented a multi-effect AGMD hollow fiber module with internal heat 4. Due to the presence of a layer of stagnant air between the Memsys and its partners invented a series of plate-frame membrane and the condensation surface. (B) AGMD.1. developed a new 330 mm  700 mm  480 mm [50]. 3.1. or seawater.5.2 μm as the MD membrane and a 40 μm (MGMD) [178]. MD was originally designed for seawater desalination. which translates into a specific tion stages and an external condenser [49].2. but the ture is further cooled down by an external cooler. illustrates the multi-effect design of a MEVMD configuration. the concentrated feed solution at a reduced tempera.2. Wang. Francis et al.20. Chung / Journal of Membrane Science 474 (2015) 39–56 47 Feed stream Feed stream Membrane Permeate stream Membrane Cooling surface Permeate stream Cooling stream Feed stream Feed stream Membrane Membrane Sweep gap stream Vacuum Blower Condenser Vacuum pump Condenser Fig. As a multi-stage design. Seawater/brackish water desalination recovery [176]. The hot brine tested was either city water containing water flux of their modules for sweater desalination was around 3– salt at the level of 3.175].3. 6 or 10%. The plant was 10 LMH. an modules have been studied for groundwater purification. the performance ratio operated successfully with a very limited flux reduction at salt . solar-driven desalination and others the MGMD.179]. Inc. The Memsys MEVMD materials like sponge (polyurethane) and PP mesh. Illustration of an AGMD configuration with internal heat recovery. the A small pilot plant was set up by Song et al. the aid of heat recovery design and optimal operation conditions. Material gap membrane distillation (MGMD) and a multiple-effect characteristic. It uses a PTFE membrane with MD module design called material gap membrane distillation an average pore size of 0.-S.1.2. Hollow fiber multi-effect membrane distillation 4. 3.1. Illustration of a basic MD configurations: (A). for DCMD based effluent stream can serve as the feed solution for the next desalination and operated successfully on a daily basis for three membrane module to enhance heat recovery and efficiency. P. MD module. With optimal operation conditions.4. At the exit of the decreasing due to rapid industrialization and population growth.4 Fig. T. The feed in each stage recovers the condensation heat 3. modules. Membrane Permeate stream Heater Cooling surface 3. Vacuum multi-effect membrane distillation (VMEMD) VMEMD shares a similar concept with the multi-effect membrane Feed strean distillation (MEMD) except for the vacuum enhancement. Unlike the PGMD design. brine concentration. moisture increase of 200–800% in water vapor flux was observed during removal. DCMD. 4. 3.2. the feed solution is pre. The air gap in the module was filled with different dense PP film as the condensation layer. The dimension of a typical Memsys module is To abate this disadvantage. [51.

also investigated the use of MD to treat wastewater containing radioactive substances [191]. reported a complete dye removal using VMD [187].181].170. MD has demonstrated its superior performance in with heat recovery design has been tested in different desalination the removal of boron contaminants with a rejection 499. North America and Australia [185]. a combined coagulation/flocculation.1. [51. Khayet et al.4. The AGMD Scarab AB system solutions [186]. Pilot desalination Boron-containing compounds are commonly found in waste- plants have been built with the commercialized MD systems water or saline water in Asia. A: Schematic of the spiral wound module concept: (1) condenser inlet. Removal of small molecule contaminants both laboratory and pilot systems. Almost complete rejections were also reported on other with heat recovery were tested in Singapore and Netherland heavy metals such as arsenic. However. been treated by gravity and skimming.187]. emulsification. contaminants and heavy metal ions are growing [183. T. Illustration of a MEVMD configuration [modified from [49]]. Chung / Journal of Membrane Science 474 (2015) 39–56 Fig. (5) distillate outlet.-S. B: Ready to use spiral wound desalination modules with a membrane area of 14 m2 [96].2. (3) evaporator inlet. dissolved air flotation. Wang. Hence. Free oily wastewater and dispersed oily wastewater have commonly MD has received attention because it may provide better rejec. adsorption and UF or pore and China [182]. RO and electro-dialysis alternative for liquid nuclear waste treatment. Bench and pilot Memstills modules [185.48 P. Guillén-Burrieza reported an optimal operation using However. plants with VMEMD Memsys systems were also tested in Singa. chromium or gold [188.184]. rejections of toxic boron-containing compounds by a RO a multi-stage AGMD module which showed a specific energy or ED process are only 30–50% depending on the pH value of feed consumption of 294 Kwh/m3 [180]. (8) condenser foil. . Demonstration desalination The treatment of colored wastewater is of big importance [190]. (2) condenser outlet. 3. (ED) have been widely used for wastewater treatment. Criscuoli et al. Brine Brine Brine Brine out 1 2 3 x Heater Condenser Vacuum Vacuum Vacuum Vacuum Membrane Membrane Membrane Condensation surface Condensation surface Membrane Condensation surface Brine in Permeate Fig. de- tions towards these contaminants. In recent Oil-water separation has received worldwide attention recently years.8% projects worldwide [173. NF are applied. (7) evaporator channel. MD was found to be an Membrane technologies such as NF. Usually. 3. concerns on poor removal efficiency of small molecule due to large amounts of discharged oily wastewater from industries.5% from sea water. (6) condenser channel. before being commercialized [147]. By using 4. (4) evaporator outlet.180]. coagulation and flocculation techniques.189].3. concentrations up to 19. (9) distillate channel and (10) hydrophobic membrane.

associated with the hydraulic fracturing process in the oil and gas De Andres et al. produced Qu et al.1. such as volatile diluted draw solution. chemicals as well as salty water. herbal extracts and small organic FO process draws clean water from the feed solution to the draw molecules by MD [209–212]. However.245. Yen et al.195]. draw solute leakage).242].5% was aromatic compounds.1 [223]. T. The ideal draw solution should have a high strongly affected by the feed temperature and ethanol/organic FO flux. Using a plasma-modified PVDF membrane. Draw solutes such as solutions were tested by AGMD and VMD configurations. On one Ge at al.1 wt% oil.196. trichloroethane and halogenated VOCs achieved. Forward osmosis-membrane distillation (FO-MD) 4. It is a promising desalination technology that MD process to recover water and acetic acid from produced water could utilize waste cold energy such as liquefied natural gas (LNG) [196]. high water flux and low salt leakage. Produced water contains dispersed oils. without pretreatments [11. brane processes for hybrid separation technologies [221]. The field test results showed no noticeable enhance the water recovery and the utilization efficiency of the decline in performance and stable performance with brine con- cold energy.228]. wastewater treatment. processes [153. Credit to the anti-fouling properties of FO processes. Chung / Journal of Membrane Science 474 (2015) 39–56 49 there is lack of an effective method to treat stable emulsified oily into the existing plant as it is not a pressure-driven process [222– wastewater [192. oil capability in volatile acid recycles [214–216].S. [197–201]. In order to ing process [156]. the low water recovery has system to concentrate produced water from the hydraulic fractur- severely limited the application of FD technology. The highest water vapor flux achieved was water is extracted by harvesting and melting the ice crystal from 195 LMH. the MD process with other membrane processes. Wang and Chung proposed the FD-MD process for centrations near saturation. As an example. it's difficult to The scaling of inorganic salt crystals is the main concern when MD treat the produced water with RO. MD 224]. dye removal and others [196. The permeate flux was found to be the suitable draw solution. Recovery of valuable components Besides the combination of membrane process and traditional Due to the unique transport mechanism. MD can be readily integrated had good solubility in water. Zhang et al.217–220].1. pioneered the real demonstration is the separation of volatile acid from its aqueous solutions [213]. the separation performance of the MD shows less fouling tendency and has potential for oily wastewater process is less affected by the high salt concentration. .164. The juices [206. 4.127. the Memsys Incorporation of MD into the desalination process can drama- system showed a stable 6-h operation with feed seawater containing tically reduce brine discharge and therefore enhance water recov- 0. A typical FO-MD process was shown in Fig. from both processes.e. several Based on the volatility and vapor pressure. Since no hydraulic pressure is applied. only dilute aqueous concentration polarization in the MD process. Specifically.227. Several works have reported positive results by Produced water is a byproduct wastewater stream normally integrating MD with NF or RO desalination [13.3. MD processes have separation technologies.-S. Integration with the existing desalination process membrane with fluoride to improve its oil resistance.236]. and synthesized based on different chemical structures [241. Inorganic salts in promising technology for desalting highly saline water with or the brine such as Ca2 þ will cause severe scaling in the MD process. MD was also widely removal. residue heat to process the produced water by DCMD comprising Freeze desalination (FD) refers to the process in which fresh PTFE membranes [195].2. these components can research groups have worked on the hybrid forward osmosis-MD (FO- be concentrated either in the feed stream or permeate stream.208] as well as sugar. pH [225. On the other hand.2.5% and 10%.230–233]. Wang.. integrated MD with an existing multi-effect industry. clean water was obtained were carried to remove organic contaminants such as ammonia. This section reviews various MD based hybrid processes and solution hydrodynamics were found as important parameters [221. The MD process has demonstrated its explored included heavy metal removal.225. designed an integrated forward osmosis and saline water [235].239. They must be treated and energy efficiency has increased by 7. seawater desalination [225]. novel draw solutes were proposed MD has been recognized as one of the most preferred mem. In 2013. The Memsys system was also evaluated for oil-water separation [194]. The brine from the FD process was Besides the contaminants mentioned above.242–244]. MD) process. As a result. P. concentration of sulfuric acid [237. It could preserve the proteins or pharmaceutical compounds (HCl) are commonly generated from rare earth mining and while maintaining high rejections. solution side. synthesized the draw solutes based on polyelectrolyte which hand. For instance. while the MD process is utilized to re-concentrate the Substances that are more volatile than water. integrated an accelerated precipitation softening process water from the steam assisted gravity drainage (SAGD) process is with DCMD with a high recovery for the desalination of RO brine typically at 80–130 1C and 2–3 atm.193]. Due to the high salinity. Studies were conducted to concentrate the fruit tions [239]. The overall production of fresh water particles. prior to being discharged. GE and Memsys have successfully tested its MD cold energy [225. However. Recently. suspended distillation (MED) unit [227]. respectively. researches have been carried out to integrate been widely explored for the recovery of valuable components. a stable MD can significantly enhance the total water recovery (TWR) performance was reported over 24 h with oily feed water [85]. were used in early stages [239.12. MD based Hybrid separation processes hybrid process is affected by the high reverse draw solute flux (i. FO refers to the spontaneous transport of water across a Examples include mineral acids. low reverse salt leakage and should not cause severe concentration in the feed [220]. are enriched in the permeate stream of MD The concept of combining FO and MD was firstly proposed in a U. MD operations further concentrated in the MD process. acids and alcohols.226].246]. the from 16% until 40% was reported with a separation coefficient of hybrid FO-MD process can be sustainable under robust feed condi- above 98% [207]. similar to the standalone FO process.2.238]. Singh and Sirkar utilized this [234]. it treatment. affecting oil fouling behavior.157.207]. inorganic salt and sugars. One of the major explored for the separation of alcohols and volatile organic challenges faced by the combined FO-MD process is the invention of compounds [152. ery [229]. MD has been proven as a is integrated into current desalination processes. Hence.2.202–206]. the current FO-MD 4. Wang et al. [241]. fruit juices. with a minimum capital cost. Later. sugar. alcohols and semi-permeable membrane driven by an osmotic pressure gradient others [158. One of most studied applications patent application [240]. A high total water recovery of 71. Other applications that have been metallurgical industry. explored the process for the concentration of Waste streams containing volatile acids such as hydrochloric acid proteins. By modifying the Memsys PTFE 4. 4.

membrane fabrication have been made for MD membranes. The incorporation of membranes into the bioreactors have greatly reduce the footprint and is widely used nowadays. As early as 1989. solar collectors are often employed as the main As MD is able to produce highly concentrated brine. a solar-MD system with two wastewater treatment [247]. breakthroughs in material development and Works have been carried out to integrate MD with a photo.195. 4.50 P. It is able to integrate with a polymeric heat exchanger for brine heating by solar energy. PTFE and aqueous solutions [252]. conditions. developed a laboratory scale MD wastewater.2 shows a unit with a planar geometry for solar seawater desalination [258]. [168. MD membranes made from low cost utilization efficiency of solar energy or waste heat is very high materials with excellent thermal stability and high hydrophobicity Fig. with the aid solar energy collection unit [255. Chung / Journal of Membrane Science 474 (2015) 39–56 When used in a standalone FO process. carbon nano-tubes. polyelectrolytes showed a [96. total dissolved Fabrication methods for MD membranes have also been advanced to solid and inorganic ions was achieved. The more expensive photo- of crystallizers (C). stage arrangement and internal heat recovery.-S. Due to the natural fluctuations of solar concentration so that salt crystals can be easily precipitated out by radiation. an almost materials. Phattaranawik et al. For example. Wang. Fig. 4.256]. Renewable/waste energy driven membrane distillation Currently. typical flow diagram for a continuous MD-C reported by Edwie Conceptually simple. Conclusions and future directions UF/MF process is not efficient enough in retaining biodegraded organic solutes. Materials catalysis process for the degradation of organic pollutants in from traditional hydrophobic materials such as PVDF. DCMD or Membrane bioreactors (MBR) employ UF or micro-filtration (MF) VMD processes with external heat exchangers were also investigated membranes to separate suspended solids from the treated effluent. for the utilization of solar energy [259–260]. namely. where wetting and the scaling are the most serious problems. comprise dual-layer hollow fiber spinning. Fig. In the FO-MD process. Other renewable heat sources such as lower flux due to its high viscosity [245].5. It is also mentioned that the membrane reported the study of MDC for concentrated salt solutions. . Membrane distillation-crystallizer (MD-C) driven MD processes.226. However. the original membrane module consists of multi- et al. Hence. In order to ensure high energy efficiency and lower cost in solar- 4. the microporous PTFE membrane dominates the appli- Comparing with RO processes. its high cost and difficulties in module sealing Since MD does not operate at extremely high temperature. 4. However. the organic content increases in the With the rapid changes in energy price and clean water shortage. no severe decline was polyolefins have been extended to new materials including inorganic observed in the MD permeation flux. MDBR has a better permeate quality but a lower flux ment and recovery of valuable compounds. 4. the are the major drawbacks. the 5.2.3 shows crystallization was observed outside the MD membrane module the flow diagram of two-loop solar-MD system [257]. 253–256].180. In addition.249].3. [249]. the energy consumption of MD cations in the commercial and pilot MD modules because of its high processes is high. protein solution and so on [13. As a result. from new applications. permeate stream [250]. Similar ideas have been applied to separate inorganic salts. the hybrid (MD-C) process could be a possible voltaic (PV) panel is only used when electricity needs to be supplied solution to achieve a higher recovery for seawater desalination and for the circulation pumps. complete rejection of the model dye contaminant. submerged a MD module the end use of MD has been expanded from initially seawater into a bioreactor for wastewater treatment [251].154. Unlike MF or UF.2.2. the flux obtained for each solar collector area varied the external crystallizer. The schematic design of a FO-MD process [223]. In another work. multi-bore fiber spinning. the geothermal energy. Cipollina et al. Comparing with the desalination to many other applications including wastewater treat- traditional MBR. there are many interests in utilizing hydrophobicity and excellent resistance towards harsh operation renewable energy and industrial waste heat to drive MD processes. [248]. solar collectors and PV panels were developed recovery and to concentrate the feed solution until a desired with four MD modules [257]. and modified hydrophophilic materials. Membrane distillation-bioreactor (MDBR) Besides AGMD based MD units with internal heat recovery. In any MD-C. residue heat from produced water and hot flux was significantly enhanced as the polyelectrolytes viscosity cooling tower water were also explored to drive MD processes decreased with increasing temperatures.254].4. T. 4. and electro-spinning. MD is used for water solar loops. To meet the demands in the range of 2–5 LMH at atmospheric pressure. Wu and Drioli have between 2–11 liter/day/m2.1.

attentions might be maximize the overall performance. drawn on the fabrication of membranes with better resistance towards As a non-pressure driven process. 4.-S.2. Process flow diagram of a membrane distillation crystallizer (MD-C) [249]. and others. . one should integrate MD with other separation membrane fabrication. T. high cialize the MD technology. hydrophobic ceramic salt concentrations. In addition to continuously use aforementioned the existing multi-effect distillation or others to lower the energy methods to fabricate MD membranes. Chung / Journal of Membrane Science 474 (2015) 39–56 51 are urgently needed. P. In addition. Wang. 4. focuses should also be given to consumption for MD systems. Flow diagram of a compact solar-MD system with solar collector and PV panel [257]. more research should revolutionary fabrication technologies such as nonwoven supported focus on the effective utilization of low-grade energy sources or PVDF hollow fiber spinning process. MD applications have fouling/scaling of organic matters and other contaminants. Considering the increasing MD technologies such as RO. More R & D and Fig. crystallization and bioreactor in order to application in contaminated water purification. Fig.3. combined thermal-nonsolvent renewable energy for MD operations. Since MD can operate at higher induced phase separation (TNIPS) process. traditional membrane processes have problems. for instance. One should consider using the design of salinity produced water from oil & gas fields. great potentials in those tough-to-treat wastewater streams where High energy consumption is the most challenge to fully commer. FO.

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