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Fluorographite-co-polydimethylsiloxane coated polyvinylidene-fluoride membrane for desalination of highly saline water with humic acid in direct contact membrane distillation
Highlights: • Surface modifications by FGi particles with PDMS binder of PVDF microporous membranes shown improvement in DCMD. • LEP with DI water & performance of M2-M4 modified membranes in DCMD was enhanced with 1M NaCl & 10 ppm HA feed solution. • Amphiphobicity was evidenced by CA with low surface tension liquids upto 38 dyne/cm as well as with canola oil. • EDX analysis proved enhancement in FC ratio and membrane surface analysis lead to understand enhanced performance in DCMD. Membranes with amphiphobic properties are crucial for desalination of concentrated saline water with organic foulant by membrane distillation. In this research, we coated Fluorographite (FGi) particles on polyvinylidene-fluoride (PVDF) flat sheet membranes with 0.8% v/v polydimethylsiloxane (PDMS) as binder by filtration coating method. We evaluated its amphiphobicity via contact angles which were observed by DI water, canola oil and organic solutions as mimicking for oleophobicity. Surface modifications by FGi particles on the surface of membranes was introduced with PDMS binder which brought bifunctionality of amphiphobicity to enhance hydrophobicity and oleophobicity. We also investigated performance of coated membranes in direct contact membrane distillation (DCMD) with 1 molar concentrated NaCl solution along with humic acid being organic foulant and compared with virgin membrane (M1 membrane) and Liquid entry pressure (LEP) was also evaluated. LEP was measured by dynamic method which shown considerable improvement in coated membranes. M3 membrane showed overall better performance in terms of salt rejection higher than 99.87% and flux as compared to M1 membrane. Furthermore, the evaluation of surface characterizations was done by FESEM with EDX, AFM and FTIR. Surface morphology confirmed the coating of FGi on membrane surface while EDX evidenced increase in atomic percent of fluorine in turn F:C ratio.
Impact of Organic and Volatile Compounds in Produced Water from Unconventional Reservoirs on Direct Contact Membrane Distillation Permeate Quality
The expansion of oil and gas extraction from unconventional reservoirs has led to an increase in the amount of produced water that has to be managed by this industry. Direct contact membrane distillation (DCMD) is a promising technology for treatment of produced water to enable water recovery and reduce the environmental footprint of this industry. The feasibility of DCMD for the treatment of highly saline produced water from the Permian Basin in TX with commercially available polyethylene and polytetrafluoroethylene membranes was evaluated in this study. An increase in water recovery by a DCMD system operated in the batch (concentrating) mode led to an increase in permeate conductivity. Partial removal of organic compounds from the produced water by biodegradation, chemical oxidation, and/or activated carbon adsorption could not resolve deterioration in permeate quality, and none of the organics observed in the permeate contributed to its conductivity. The observed increase in permeate conductivity was attributed to the passage of ammonia vapor from the feed side followed by protonation on the permeate side. Furthermore, this study revealed that permeate conductivity may not always be a reliable indicator of membrane wetting and underscores the importance of understanding the interactions between specific solutes and membrane materials.
Comparative Energetics of Various Membrane Distillation Configurations and Guidelines for Design and Operation
This paper presents a comparative performance study of single-stage desalination processes with major configurations of membrane distillation (MD) modules. MD modules covered in this study are (a) direct contact MD (DCMD), (b) vacuum MD (VMD), (c) sweeping gas MD (SGMD), and (d) air gap MD (AGMD). MD-based desalination processes are simulated with rigorous theoretical MD models supported by molecular thermodynamic property models for the accurate calculation of performance metrics. The performance metrics considered in MD systems are permeate flux and energy efficiency, i.e., gained output ratio (GOR). A general criterion is established to determine the critical length of these four MDs (at fixed width) for the feasible operation of desalination in a wide range of feed salinities. The length of DCMD and VMD is restricted by the feed salinity and permeate flux, respectively, while relatively large AGMD and SGMD are allowed. The sensitivity of GOR flux with respect to permeate conditions is investigated for different MD configurations. AGMD outperforms other configurations in terms of energy efficiency, while VMD reveals the highest permeate production. With larger MD modules, utilization of thermal energy supplied by the hot feed for evaporation is in the order of VMD > AGMD > SGMD > DCMD. Simulation results highlight that energy efficiency of the overall desalination process relies on the efficient recovery of spent for evaporation, suggesting potential improvement in energy efficiency for VMD-based desalination.
Development of Membrane Distillation Technology Utilizing Waste Heat for Treatment of High Salinity Wastewaters
Membrane distillation (MD) can serve as a cost effective method to treat high salinity wastewaters, especially if waste heat is utilized for its operation. The goal of this work is to study the feasibility of employing MD technology for the treatment of high salinity wastewaters which are generated as a result of natural gas production and active reservoir management for CO 2 sequestration. This study also aimed at quantifying the availability of waste heat which could be used as the primary source of thermal energy to drive the MD process. Bench scale studies were carried out with several commercially available membranes using both synthetic and actual high salinity wastewaters. The membranes tested with real wastewater samples exhibited excellent rejection of dissolved ions, including naturally occurring radioactive material (NORM). Long term bench scale experiments with real produced water from the Marcellus shale play revealed that iron oxide could precipitate on the feed side of direct contact MD (DCMD) module but had a negligible effect on the performance of the system. Based on the bench scale experiments, an ASPEN Plus simulation, which incorporated a mathematical model with fundamental heat and mass transfer equations, was developed and used to evaluate the process energy requirements. Despite low operating temperature and pressure for MD, it had a large thermal energy requirement for operation, which could make this technology expensive compared to reverse osmosis (RO) and forward osmosis (FO). However, it is important to note that RO and FO have limited applicability for high salinity shale gas wastewater. Moreover, MD could be integrated with renewable energy sources such as wind or solar energy or industrial waste heat sources to offset the thermal energy requirements and enhance the economics of wastewater treatment. Natural gas compressor stations (NG CS) have been proposed in this study as the source of waste heat based on the estimate of quantity and quality of available waste heat in the exhaust streams of gas turbine and internal combustion compressor engines. Using the actual installed capacity and location of compressor stations in the U.S., this analysis revealed that an average of 610 TJ/day of thermal energy is available at existing NG CS and that this source of waste heat is of high quality with temperatures above 645 K. A systems-level integration of MD with waste heat from NG CS revealed that approximately 56% of available waste heat at NG CS in Pennsylvania is sufficient to concentrate (from 10% to 30% salinity) all wastewater associated with shale gas extraction. Techno-economic assessment (TEA) accounting for capital as well as operating and maintenance costs with and without waste heat integration was conducted for a hypothetical 0.5 million gallons per day (MGD) DCMD plant using experimental and modeling results from this study. TEA revealed that the total cost of shale gas wastewater treatment using MD is $5.7/m 3 feed for the base case scenario in which the thermal energy requirements are met by external steam, however, the total cost can be reduced to $0.74/m 3 feed when integrated with free waste heat from NG CS. Sensitivity analysis revealed that thermal energy cost and feed TDS are the most important factors in total cost of high salinity wastewater treatment using DCMD.
Optimization-based modeling and economic comparison of membrane distillation configurations for application in shale gas produced water treatment
Membrane distillation (MD) is an emerging membrane technology with great potential for treatment of hypersaline wastewater generated by unconventional (shale) oil and gas reservoirs. However, the low energy efficiency of this technology makes the operating cost of MD systems relatively high, especially in the absence of waste heat. There are several MD configurations with inherent advantages and disadvantages and varying performance. As such, there is a need for thermo-economic optimization of MD systems in a systematic manner to assess their economic performance. Here we present an optimization framework to model and compare the performance of six MD configurations (DCMD, AGMD, PGMD, CGMD, SGMD, and VMD) in continuous recirculation mode for treatment of hypersaline wastewater. The optimization results show that AGMD with small gap size operated at low stream Reynolds number outperforms all other configurations with treatment cost of 4.57 US $/m 3 of feed. However, restricting the system design to more practically relevant operating conditions, such as higher Reynolds number and larger gap size, diminishes the cost superiority of AGMD over other configurations. We also observed that treatment cost using PGMD configuration approaches those of CGMD and DCMD, particularly when modules with small gaps are used.
Optimization-based technoeconomic comparison of multi-stage membrane distillation configurations for hypersaline produced water desalination
Unconventional oil and gas production raises concerns regarding sustainable management of high salinity wastewaters generated in this process. Membrane distillation (MD) is a thermal desalination process capable of treating hypersaline brines such as produced water. The low single pass recovery in MD systems operated in a single stage requires a large recycle stream to achieve the desired recovery, resulting in high energy consumption and operating cost. Multistage configurations in continuous recirculation operation mode offer the potential to reduce the energy intensity of MD systems. However, rigorous analysis is needed to assess the performance of MD configurations when operating in multi-stage mode. Here, we present an optimization-based comparison of economic and energetic performance for five configurations of MD (including DCMD, AGMD, PGMD, CGMD, and VMD) operating in multi-stage continuous recirculation mode. Our findings demonstrate that multistage operation reduces the treatment cost and energy intensity of all MD configurations compared to single stage MD, with the greatest benefit for VMD and PGMD. AGMD with five stages outperforms other configurations with 3.58 $/m 3 feed treatment cost, followed by VMD, CGMD, DCMD, and PGMD with 3.8, 4.2, 5.4, and 9.06$/m 3 feed treatment costs corresponding to twelve, eight, eight, and sixteen stages, respectively.
A techno-economic assessment of membrane distillation for treatment of Marcellus shale produced water
Membrane distillation (MD) is a promising desalination technology for treatment of high salinity shale gas produced water. Techno-economic assessment (TEA) is necessary for evaluating the economic feasibility of MD for produced water treatment as compared to other shale gas produced water management strategies. A detailed TEA for a hypothetical 0.5 million gallons per day (MGD) direct contact MD (DCMD) that concentrates produced water from 10% (100,000 mg/L) Total Dissolved Solids (TDS) to 30% salinity is presented in this study. The model is developed based on a combination of experimental results, ASPEN Plus process model, best available engineering knowledge, and cost estimates. Analysis reveals that thermal energy cost for MD operation contributes the most to total cost of treating produced water in an MD plant. Additionally, the results of sensitivity analysis reveal that feed TDS level and thermal energy price have a significant impact on total cost of treating produced water. We also explore the implications of utilizing waste heat on the economics of the MD technology for produced water treatment. Here the results reveal that the total cost of treating produced water using MD is $\$$5.70/m 3 feed which decreases significantly to $\$$0.74/m 3 feed when MD is integrated with a source of waste heat.
Flexible operation of nuclear hybrid energy systems for load following and water desalination
Nuclear hybrid energy systems (NHES) have the potential to provide dependable and emission-free electricity to the grid while also increasing the flexibility and reliability of the electrical grid. Molten salt reactor (MSR) technology can provide consistent, carbon-free electricity while also increasing efficiency, security, and sustainability and reducing nuclear waste. This study investigates the integration of Molten Salt Reactors (MSR) and conventional Pressurized Water Reactors (PWR) with desalination technologies: Direct Contact Membrane Distillation (DCMD), Multi-Stage Flash Distillation (MSFD), and Reverse Osmosis (RO). Dynamic first-principles models were developed and tested using real grid data from the New York Independent System Operator. The results demonstrate that nuclear power is capable of flexibly responding to changing grid demand while simultaneously producing clean water, particularly during periods of low electricity demand. The MSR-RO system was found to be the most efficient in electricity generation and water production, and all hybrid systems reduced CO2 emissions by 356,000 to 682,000 tons annually. Economic analysis reveals that nuclear desalination technologies are cost-competitive with conventional systems, especially when paired with RO. Finally, these findings confirm the technical feasibility and environmental benefits of nuclear hybrid systems for sustainable electricity and water production.
EXPERIMENTAL AND COMPUTATIONAL STUDY OF DIRECT CONTACT MEMBRANE DISTILLATION
Experimental and computational studies of direct contact membrane distillation (DCMD) are conducted. The permeate flux is measured in a module containing a flat sheet membrane. Polytetrafluoroethylene (PTFE) hydrophobic membrane (Membrane Solutions, FPB045A16) with a nominal pore size of 0.45 μm, the thickness of 179~239 μm, the porosity of 80% is used in the experiments. The feed solution is a binary mixture of water and NaCl. The inlet feed temperature is fixed at 70°C, and the feed Reynolds number is varied between 500 and 2000. Two inlet feed concentrations, 0 and 35g/L, are considered. The permeate flow rate was kept constant at Re of 1300 and temperature of 20°C. Three-dimensional steady-state computational fluid dynamics (CFD) simulations are performed using the laminar model. The Navier’s Stokes, energy, and mass transport equations in each channel coupled with flux boundary conditions imposed at the membrane surface are solved. The predicted module-averaged flux is compared to measured data for all operating conditions. Measured and predicted flux agrees well; validating both experiments and model, Temperature polarization in the feed and permeate channel and concentration polarization in the feed channel are characterized by validated CFD simulations.
PERFORMANCE CHARACTERIZATION OF THE DIRECT CONTACT MEMBRANE DISTILLATION MODULE OPERATED WITH HIGHLY CONCENTRATED SOLUTION
The experimental study was conducted to characterize the performance of the flat sheet Direct Contact Membrane Distillation. The length degradation was studied in a short and long module with and without spacers. The experimental study is validated using the predicted flux for a wide range of operating conditions using deionized water. Three different membranes are used in the parametric study for feed Reynolds number varied between 500 and 2000, and inlet feed temperature varied between 45°C and 80°C. PTFE membrane was shown to be more effective than the PVDF due to its higher permeability coefficient and higher hydrophobicity. Fouling study was conducted on the selected PTFE membrane with various feed Reynolds numbers between 500 and 2000 and feed inlet temperature between 50°C and 80°C. Membranes used in the fouling study were characterized using scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS) for the morphology and chemical composition of the fouling layer. 36 hours of operation with 10 wt% NaCl (100,000 ppm) at feed inlet temperatures 80°C and 60°C and fixed Reynolds 2000 demonstrated a drop in flux by 31% and 27%, respectively. Low flow rate and high temperature are favorable conditions for fouling formation and reduced permeate flux for highly concentrated solutions. The spacers improved the flux by 30.8% and 27.6% at the operating Reynolds numbers 2000 the short and long channel modules. This study helps to design and optimize DCMD modules for industrial-size desalination and water treatment applications.
Membrane Specifications for Multi-Configuration Membrane Distillation Model
The data includes the membrane properties and specifications used for multi-configuration membrane distillation desalination. In this study, membranes from CLARCOR, 3M, and Aquastill are tested in counter-current, co-current and air-gap configurations at Colorado School of Mines (CSM), Advanced Water technology Center ( Aqwatech) laboratories. In the data sheets: The "theoretical" worksheet, contains steady-state values of the experimental runs and also provides several calculated values. The "Specifications" worksheet contains the inputs to the experiment. The "Data" spreadsheet contains the entire set of data and the rest of the sheets "20-40", "20-45", ...etc., contain individual portions of the data with variation of feed temperatures.