Active layers of two fully aromatic and two semi-aromatic nanofiltration membranes were studied along with surface charge at different electrolyte composition and effective pore size to elucidate their influence on separation mechanisms for inorganic ions by steric, charge, and dielectric exclusion. The membrane potential method used for pore size measurement is underlined as the most appropriate measurement technique for this application owing to its dependence on the diffusional potentials of inorganic ions. Crossflow rejection experiments with dilute feed composition indicate that both fully aromatic membranes achieved similar rejection despite the differences in surface charge, which suggests that rejection by these membranes is exclusively dependent on size exclusion and the contribution of charge exclusion is weak. Rejection experiments with higher ionic strength and different composition of the feed solution confirmed this hypothesis. On the other hand, increase in the ionic strength of feed solution when the charge exclusion effects are negligible due to charge screening strongly influenced ion rejection by semi-aromatic membranes. The experimental results confirmed that charge exclusion contributes significantly to the performance of semi-aromatic membranes in addition to size exclusion. The contribution of dielectric exclusion to overall ion rejection would be more significant for fully aromatic membranes.

A B S T R A C THydraulic fracturing used for natural gas extraction from unconventional onshore resources generates large quantities of produced water that needs to be managed efficiently and economically to ensure sustainable development of this industry. Membrane distillation can serve as a cost effective method to treat produced water due to its low energy requirements, especially if waste heat is utilized for its operation. This study evaluated the performance of commercially available hydrophobic microfiltration membranes in a direct contact membrane distillation system for treating very high salinity (i.e., up to 300,000 mg/L total dissolved solids) produced water. Polypropylene and polytetrafluoroethylene membranes yielded the highest permeate flux with membrane distillation coefficient of 5.6 l/m 2 /hr/kPa (LMH/kPa). All membranes showed excellent rejection of dissolved ions, including naturally occurring radioactive material (NORM), which is a significant environmental concern with this high salinity wastewater. Analysis of membranes after extended testing with actual produced waters revealed unevenly distributed inorganic deposits with significant iron content. A key finding of this study is that the iron oxide fouling layer had negligible effect on membrane performance over extended period of time despite its thickness of up to 12 µm. The results of this study highlight the potential for employing membrane distillation to treat high salinity wastewaters from unconventional gas extraction.

The impact of membrane cleaning with NaOH and HCl on the characteristics and associated changes in ion rejection was investigated in this study. NaOH affected the zeta potential of membranes with a greater concentration of carboxylic groups so that it was negative across the entire pH range investigated. Exposure to NaOH led to swelling of the active layer after each cleaning, especially for poly­(piperazineamide) membranes. A 23% increase in the effective pore radii for these membranes after NaOH cleaning for 18 h led to 25, 36, 53 and 62% decrease in the rejection of magnesium, calcium, sodium, and chloride ions, respectively. Sulfate rejection decreased only slightly even for poly­(piperazineamide) membranes (i.e., 7%) despite an appreciable increase in pore radii, which can be explained by the impact of charge exclusion on ion rejection that was enhanced by the 16% reduction in zeta potential. On the other hand, cleaning with HCl had a negligible impact on the zeta potential and performance of all membranes evaluated in this study. The increase in permeability after chemical cleaning was in agreement with the decrease in rejection of inorganic ions and correlated well with the effective pore radii measured using the membrane potential technique. The importance of charge exclusion in the rejection of inorganic ions was highlighted by the observed differences in rejection and permeability values when testing membranes after NaOH cleaning.

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