In this PhD thesis, seawater desalination by Membrane Distillation (MD) has been explored from the perspective of process and membrane. Regarding the process, an innovative, energy efficient, and environmentally friendly Zero Thermal Input Membrane Distillation (ZTIMD) process was proposed. ZTIMD uses thermal energy stored in seawater, which makes the process sustainable by being independent of the external sources of thermal energy, which is one of the major contributors to the cost and energy consumption of conventional MD desalination processes. Economic feasibility study was carried out for the ZTIMD process, and it was demonstrated that drinking water could be produced with a cost of $0.28/m3, which is approximately half of the cost of conventional desalination processes. Regarding the membrane, novel MD membranes were developed through incorporation of nanomaterials in polyvinylidene fluoride (PVDF). Different nanomaterials including superhydrophobic SiO2, amine modified hydrophilic SiO2, CuO, and CaCO3 were used for this purpose. It was shown that membrane structure and consequently its performance could be affected by the nanoparticle properties, concentration, presence of backing material, PVDF blend ratio, and penetration time. In a best membrane developed in this work, almost 2500% increase was observed in the Vacuum Membrane Distillation (VMD) flux over that of the neat PVDF membrane at a feed temperature of 27.5 °C and vacuum pressure of 1.2 kPa, when 7.0 wt.% hydrophilic SiO2 nanoparticles were added into a PVDF membrane supported with Non-Woven Fabric (NWF) polyester. The membrane possessed near perfect selectivity.

Membrane distillation (MD) is an emerging thermal separation technology which proved its efficiency in desalination of highly saline waters, including seawater, brines and impaired process waters. In a long-term prospective, MD can reinforce sustainability of the clean water production and mitigate the water-energy stress caused by lacking suitable freshwater recourses. However, just like in any other membrane separation process, MD membrane is susceptible to biofouling which presents a significant challenge by substantially reducing its performance and deteriorating permeate quality. This study evaluated different cleaning methods aimed at controlling biofilm development on a surface of hydrophobic MD membrane in a direct contact MD (DCMD) process fed by the Red Sea water. This was achieved by applying physical (hydraulic) cleaning and chemical cleanings with a range of chemicals utilized in membrane separation processes including citric acid (mineral acid), ethylenediaminetetraacetic acid (EDTA, metal-chelating agent) and sodium hypochlorite (NaOCl, oxidant). Flux recovery and changes in biofilm morphology, including its thickness and structure as well as microbial and extracellular polymeric substances (EPS) contents before and after cleanings have been analyzed to elucidate cleaning mechanisms and suggest effective strategies of biofilm removal. The results showed that 0.3% EDTA exhibited the best cleaning performance resulting in the highest permeate flux recovery (93%), followed by 0.3% NaOCl (89%), 3% citric acid (76%), and hydraulic (66%) cleanings. Application of EDTA and NaOCl has also resulted in the lowest number of bacterial cells and substantial reduction of the peak intensities caused by protein-like compounds and tyrosine-containing proteins present on the membrane surface after its treamtent. The observed trends are in a good correlation with the optical coherence tomography (OCT) observations which revealed substation changes in biofilm morphology leading to a significant reduction of biofilm thickness which followed the order of hydraulic cleaning < citric acid cleaning < NaOCl cleaning < EDTA cleaning. This study suggests that selection of an appropriate cleaning type and formulation is critical for achieving sustainable MD plant operations, both technically and economically.

Membrane distillation (MD) is an emerging technology capable of treating high-saline feeds and operating with low-grade heat energy. However, commercial implementation of MD is limited by so-called temperature polarization, which is the deviation in the temperature at the feed-membrane interface with respect to the bulk fluid. This work presents solutions to alleviate temperature polarization in MD by employing a localized heating concept to deliver heat at the vicinity of the feed-membrane interface. This can be realized in multiple ways, including Joule heating, photothermal heating, electromagnetic induction heating, and nanofluid heating. In the first experiment, a Joule heating concept was implemented and tested, and the results showed a 45% increase in permeate flux and a 57% decrease in specific energy consumption. This concept was further improved by implementing a new dead-end MD configuration, which led to a 132% increase in the gained output ratio. In addition, the accumulation of foulants on the membrane surface could be successfully controlled by intermittent flushing of feedwater. Three-dimensional CFD calculations of conjugate heat transfer revealed a more uniform heat transfer and temperature gradient across the membrane due to the increased feedwater temperature over a larger membrane area. In another approach, a photothermal MD concept was used to heat the feed water locally. A 2-D photothermal material, MXene, recently known for its photothermal property, was used to coat commercial MD membranes. The coated membranes were evaluated under one-sun illumination to yield a permeate flux of 0.77 kg.m$^{−2}$h$^{−1}$ with a photothermal efficiency of 65.3% for a feed concentration of 0.36 g.L$^{−1}$. The system can produce around 6 liters of water per day per square meter of membrane. An energy analysis was also performed to compare the efficiency of various energy sources. Considering the sun as a primary energy source, the performance of different heating modes was compared in terms of performance and scale-up opportunities. Overall this work demonstrates that the application of localized heating will enable the scale-up and the use of renewable energy sources to make the MD process more efficient and sustainable. / The illustrative figure was produced by Ana Bigio, scientific illustrator, KAUST.

Hydrophobic microporous membranes have been widely used in water and wastewater treatment by microfiltration, ultrafiltration and membrane distillation. Poly(vinylidene fluoride) (PVDF) materials are one of the most popular polymeric membrane materials because of their high mechanical strength, excellent thermal and chemical stabilities, and ease of fabrication into asymmetric hollow fiber membranes. In this work, specialty PVDF materials (Kynar 741, 761, 461, 2851, RC-10186 and RC10214) newly developed by Arkema Inc. were used to develop hollow fiber membranes via the dry/wet phase inversion. These materials were evaluated from thermodynamic and kinetic perspectives. The thermodynamic analysis was performed by measuring the cloud points of the PVDF solution systems. The experimental results showed that the thermodynamic stability of the PVDF solution system was affected by the type of polymer and the addition of additive (LiCl); and the effects of the additive (LiCl) depended on the type of polymer. The kinetic experiments were carried out by determining the solvent evaporation rate in the “dry” step and the small molecules (solvent, additive) diffusion rate in the “wet step”. Solvent evaporation in the early stage could be expressed quantitatively. In the “wet” step, the concentrations of solvent and additive had a linear relationship with respect to the square root of time (t1/2) at the early stage of polymer precipitation, indicating that the mass-transfer for solvent-nonsolvent exchange and additive LiCl leaching was diffusion controlled. The kinetic analysis also showed that the slope of this linear relationship could be used as an index to evaluate the polymer precipitation rate (solvent-nonsolvent exchange rate and LiCl leaching rate). The extrusion of hollow fiber membranes was explored, and the effects of various fabrication parameters (such as dope extrusion rate, internal coagulant flow velocity and take-up speed) on the structure and morphology of the hollow fiber membranes were also investigated. The properties of the hollow fiber membranes were characterized by gas permeation method and gas-liquid displacement method. The morphology of the hollow fibers was examined by scanning electron microscope (SEM). It was found that Kynar 741 and 2851 were the best among the PVDF polymers studied here for the fabrication of hollow fiber membranes. In order to reduce the problems associated with the hydrophobicity of PVDF on hollow fiber module assembly, such as tubesheet leaking through problem and fouling problem, amine treatment was used to modify PVDF membranes. Contact angle measurements and filtration experiments were performed. Fourier-transform infrared (FT-IR) spectroscopy and energy dispersive x-ray analysis (EDAX) were used to analyze the modified polymer. It was revealed that the hydrophilicity of the modified membrane was improved by amine treatment and conjugated C=C and C=O double bonds appeared along the polymer backbone of modified PVDF. Hollow fiber membranes fabricated from Kynar 741 were tested for water desalination by vacuum membrane distillation (VMD). An increase in temperature would increase the water productivity remarkably. Concentration polarization occurred in desalination, and its effect on VMD could be reduced by increasing the feed flowrate. The permeate pressure build-up was also investigated by experiments and parametric analysis, and the results will be important to the design of hollow fiber modules for VMD in water desalination.

Hydrophobic microporous membranes have been widely used in water and wastewater treatment by microfiltration, ultrafiltration and membrane distillation. Poly(vinylidene fluoride) (PVDF) materials are one of the most popular polymeric membrane materials because of their high mechanical strength, excellent thermal and chemical stabilities, and ease of fabrication into asymmetric hollow fiber membranes. In this work, specialty PVDF materials (Kynar 741, 761, 461, 2851, RC-10186 and RC10214) newly developed by Arkema Inc. were used to develop hollow fiber membranes via the dry/wet phase inversion. These materials were evaluated from thermodynamic and kinetic perspectives. The thermodynamic analysis was performed by measuring the cloud points of the PVDF solution systems. The experimental results showed that the thermodynamic stability of the PVDF solution system was affected by the type of polymer and the addition of additive (LiCl); and the effects of the additive (LiCl) depended on the type of polymer. The kinetic experiments were carried out by determining the solvent evaporation rate in the “dry” step and the small molecules (solvent, additive) diffusion rate in the “wet step”. Solvent evaporation in the early stage could be expressed quantitatively. In the “wet” step, the concentrations of solvent and additive had a linear relationship with respect to the square root of time (t1/2) at the early stage of polymer precipitation, indicating that the mass-transfer for solvent-nonsolvent exchange and additive LiCl leaching was diffusion controlled. The kinetic analysis also showed that the slope of this linear relationship could be used as an index to evaluate the polymer precipitation rate (solvent-nonsolvent exchange rate and LiCl leaching rate). The extrusion of hollow fiber membranes was explored, and the effects of various fabrication parameters (such as dope extrusion rate, internal coagulant flow velocity and take-up speed) on the structure and morphology of the hollow fiber membranes were also investigated. The properties of the hollow fiber membranes were characterized by gas permeation method and gas-liquid displacement method. The morphology of the hollow fibers was examined by scanning electron microscope (SEM). It was found that Kynar 741 and 2851 were the best among the PVDF polymers studied here for the fabrication of hollow fiber membranes. In order to reduce the problems associated with the hydrophobicity of PVDF on hollow fiber module assembly, such as tubesheet leaking through problem and fouling problem, amine treatment was used to modify PVDF membranes. Contact angle measurements and filtration experiments were performed. Fourier-transform infrared (FT-IR) spectroscopy and energy dispersive x-ray analysis (EDAX) were used to analyze the modified polymer. It was revealed that the hydrophilicity of the modified membrane was improved by amine treatment and conjugated C=C and C=O double bonds appeared along the polymer backbone of modified PVDF. Hollow fiber membranes fabricated from Kynar 741 were tested for water desalination by vacuum membrane distillation (VMD). An increase in temperature would increase the water productivity remarkably. Concentration polarization occurred in desalination, and its effect on VMD could be reduced by increasing the feed flowrate. The permeate pressure build-up was also investigated by experiments and parametric analysis, and the results will be important to the design of hollow fiber modules for VMD in water desalination.

In this study, two different strategies were carried out to modify the polyvinylidene fluoride (PVDF) distillation membrane for desalination. The first strategy was the addition of TiO2 nanoparticles into the target membranes and a synergistic effect of hydrophilic and hydrophobic nanoparticles was found for the first time in this work. And the other strategy was the introduction of another polymer material, polytetrafluoroethylene (PTFE), to the PVDF membranes to fabricate a flat sheet PVDF-PTFE composite membrane and this is the first attempt that such a membrane to be made. Two types of membranes were characterized by scanning electron microscopy (SEM) detection, porosity measurement, energy dispersive X-ray spectroscopy (EDX), Attenuated total reflectance (ATR)-Fourier transformed infrared spectroscopy (FTIR), contact angle (CA) measurement, atomic force spectroscopy (AFM) detection and liquid entry pressure of water (LEPw) measurement. Their performance was evaluated by vacuum membrane distillation (VMD) experiments. And the best VMD pure water permeate flux of the membranes fabricated under these two modify strategies could achieve 4.26 kg/m2h (M-L5-B2) and 5.61 kg/m2h (M-40), respectively, when that of pure PVDF membrane is only 0.71 kg/m2h. The salt rejection of the prepared composite membranes are all stably higher than 99.5% which demonstrate their capacity for desalination.

It goes without saying that water scarcity is a widespread and increasingly pressing global challenge. One of the methods which can mitigate water shortage is to increase freshwater production via desalination of saline waters. Seawater and saline aquifer sources represent 97.5% of all water on Earth. Hence, treating even a small portion of saline water could significantly reduce water shortage. Although reverse osmosis is one of the state-of-the-art pressure-driven membrane desalination technologies, it is incapable of desalinating high-salinity streams due to the very high osmotic pressure to overcome. Membrane distillation (MD) is one of the emerging methods, which has attracted much attention for desalinating highly saline brines. MD is a thermally driven process in which only vapor molecules pass through the pores of a microporous hydrophobic membrane. This process, however, has not been fully commercialized due to a number of challenges, including “pore wetting”. Pore wetting refers to the presence of liquid, instead of just water vapor, inside the membrane pores, which may cause a decrease in MD flux and/or deterioration of distillate quality. Herein, a comprehensive review on pore wetting is presented, and then this phenomenon is investigated from four aspects. In the first phase of this project, a theoretical model is presented according to which the pore size distribution of membrane, a parameter affecting pore wetting risk, is estimated by employing only a few experimental data points in accordance with the wet/dry method, reducing the number of data required to be recorded largely. In the next phase, an equation is presented for the estimation of liquid entry pressure (LEP), a membrane parameter closely related to pore wetting, using computational fluid dynamics (CFD) tools and genetic programming (GP) as an intelligent technique. This equation can estimate LEP in closer agreement to experimental values in comparison to the Young-Laplace equation. In the third phase, movement of liquid-gas interface inside the membrane pore is tracked using a well-founded model, and consequently, the pressure and velocity at the interface and the required time for replacement are studied. Finally, in the last phase, a model is developed for pore wetting in vacuum MD, considering heat and mass balances at the vapor-liquid interface. This model assumes that heat only enters the pore inlet and is removed due to liquid vaporization at the vapor-liquid interface, with heat transfer through the pore wall neglected. This model shows that partial pore wetting is possible since the vapor-liquid interface might remain within the pore at the steady-state condition. Further, this model can predict the decrease in temperature from the pore inlet to the vapor-liquid interface, a phenomenon that has been reported in the literature without any proof.

In this work polymeric materials were developed to be used as a solvent and heat resistance membrane for different applications. In ultrafiltration, poly (ether imide sulfone) membranes were manufactured by combining phase inversion and functionalization reaction between epoxy groups and amine modified polyether oligomers (Jeffamine®). Polysilsesquioxanes or oligo silsesquioxanes containing epoxy functionalities were in-situ grown in the casting solution and made available for further reaction with amines in the coagulation/annealing baths. Water permeances up to 1500 l m-2 h-1 bar-1 were obtained with sharp pore size distribution and a pore diameter peak at 66 nm, confirmed by porosimetry, allowing 99.2 % rejection of γ-globulin. The membranes were stable in 50:50 dimethylformamide/water, 50:50 N-methyl pyrrolidone/water and 100 % tetrahydrofuran. In pervaporation, Novel hydrophobic Hyflon®/Extem® and Hyflon®/PVDF were developed and investigated for ethylene glycol dehydration and n-butanol dehydration respectively. For ethylene glycol different Extem® concentrations were evaluated with regard to both flux and amount of water in the permeate side. Eighteen (18) wt% gave more than 90 wt% water in the permeate. Increasing feed temperature from 25 to 85°C increased the water flux from 31 to 91 g m-2 h-1 when using 5 wt% water in ethylene glycol as feed. The water flux of 40 wt% water:ethylene glycol at 45°C was found to be 350 g m-2 h-1. And for n-butanol dehydration the coating protocols for thin defect-free Hyflon® selective layer on the PVDF support was optimized. Water and n-butanol transport was measured, analyzing the effect of operating conditions. The water flux through the newly developed membranes was higher than 150 g m-2 h-1 with selectivity for water higher than 99 wt%. The membrane application can be extended to other solvents, supporting an effective and simple method for dehydration with hydrophobic membranes. In membrane distillation, PVDF and Extem® membranes before and after coating with Hyflon® were examined for ionic liquid dehydration on 23.6 mS cm-1 feed concentration. Different feed temperatures and flow rates were evaluated for flux as well as rejection. High flux was obtained at 70°C and increased at high flow rate from 2 Kg m2 h to 10 Kg m2 h.

In the kingdom of Saudi Arabia (KSA), the current seawater desalination technologies are completely relying on burning unsustainable crude oil as their main energy driver. Saudi authorities have realized that the KSA is not going to be protected from the future global energy crisis and have started to set up a plan to diversify its energy resources. Membrane Distillation (MD) has emerged as an attractive alternative desalination process. It combines advantages from both thermal and membrane-based technologies and holds the potential of being a cost-effective separation process that can utilize low-grade waste heat or renewable energy. MD has four different configurations; among them is Air Gap Membrane Distillation (AGMD) which is the second most commonly tested and the most commercially available pilot-plant design. AGMD has a stagnant thin layer of air between the membrane and the condensation surface. This layer introduces a mass transfer resistance that makes the process require a large membrane surface area if a large quantity of fresh water is desired. This dissertation reports on experimental and theoretical work conducted to enhance the AGMD flux by removing non-condensable gases from the module and replacing it with either vacuum, liquid water or porous materials. At first, a mathematical model for AGMD was developed and validated experimentally to create a baseline for improvements that could be achieved after the removal of non-condensable gases. The mathematical model was then modified to simulate the process under vacuum where it showed a flux enhancement that reached 286%. The Water Gap Membrane Distillation (WGMD) configuration improved the flux by almost the same percentage. Since enhancing the flux is expected to increase temperature polarization effects, a theoretical study was conducted on the effect of temperature polarization in a Vacuum Membrane Distillation (VMD) configuration. The study showed that the effect of temperature polarization at small temperature difference (3-7) degree Celsius between the bulk feed and coolant temperatures is significantly high. This may indicate the importance of mitigating the effect of temperature polarization in large scale modules operating at small temperature difference across the membrane. The dissertation concluded with some recommendations for future work.

An experimental characterisation of a pre-commercial spiral wound permeate gap membrane distillation module was carried out to test its performance at different operating conditions for the purpose of seawater desalination. The experimental setup consisted of a flat plate solar collector field indirectly coupled to the permeate gap membrane distillation module via an inertia tank. The operating parameters varied were the condenser inlet temperature (from 20 °C to 30 °C), evaporator inlet temperature (from 60 °C to 80 °C) and seawater feed flow rate (from 200 l/h to 400 l/h). Within this operational boundary, it was found that the maximum permeate/distillate flux was 4.135 l/(h∙m2) which equates to a distillate production/flow rate of close to 21.3 l/h. The maximum potential distillate production rate is expected to be significantly higher than this value though as the maximum manufacturer specified feed flow rate is 700 l/h and the maximum evaporator inlet temperature is rated at 90 °C. Both these parameters are positively related to the distillate production rate. The minimum specific thermal energy consumption was found to be 180 kWh/m3. A mathematical model of the overall system was developed, and experimentally validated, to mathematically describe the coupling of the membrane distillation module with a solar collector field. The effectiveness of internal heat recovery of the membrane distillation module was found to be an accurate and simple tool to evaluate the thermal energy demand of the distillation process at a given set of operation parameters. The mathematical model was used to further investigate the experimental findings and provide insights into the operational dynamics of the membrane distillation module. It was also used to determine some external conditions required for steady state operation, at a given distillation operating point, such as the minimum solar irradiation required for operation and the auxiliary cooling required in the solar collector loop for maintaining steady state conditions. Finally, general guidelines are provided toward better operational practices to improve the coupling of a solar thermal collector unit/field with a membrane distillation system using a storage tank or inertia tank.