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Abstract: Pressure retarded osmosis (PRO) is a promising membrane process to harvest the vast amount of free energy from the mixing of fresh and salty waters without adverse environmental impacts. A competent membrane for PRO should possess the features of high water permeability to allow water permeation, excellent salt rejection to maintain the osmotic driving force, low structure parameter to minimize the internal concentration polarization (ICP), and robust strength to withstand the required hydraulic pressure. In this work, we have developed a novel hollow fiber membrane by balancing these competing factors based on our prior experience in the thin-film composite (TFC) membranes. The newly developed TFC hollow fiber membrane can achieve a power density of 20.9W/m2 at a pressure of 15bar, using synthetic seawater brine (1.0M NaCl) as the draw solution and synthetic river water (1mM NaCl) as the feed water, respectively. The simultaneous specific reverse salt flux was found to be 0.03mol/L, which is much lower than reported flat-sheet membranes, as the self-supported hollow fiber membrane can eliminate the deformation-enhanced reverse salt diffusion that is typical for flat-sheet membranes. However it was observed that the water permeability and structure parameter of the TFC hollow fiber membrane varied noticeably corresponding to the change in the hydraulic pressure imposed in the fiber lumen. Over a certain range (ΔP<15bar), such variations of increasing A value and decreasing S value proved to have positive impacts, as they facilitate the water permeation and reduce the ICP in the PRO process. [Copyright &y& Elsevier]

Abstract: Hollow fiber membranes with a positively charged nanofiltration (NF)-like selective layer have been successfully fabricated by utilizing asymmetric microporous hollow fibers made of Torlon® polyamide–imide (PAI) material as the porous substrate followed by polyelectrolyte post-treatment using polyethyleneimine (PEI), which has not been reported previously. The reaction between PAI and PEI has been confirmed by experiments. The membrane structure and surface property are carefully tailored by adjusting polymer dope composition, spinning conditions and the post-treatment parameters. These membranes are, subsequently, characterized by a series of standard protocols in terms of membrane morphology, structure, permeability and salt rejection, and are applied in forward osmosis (FO) processes. The newly developed PAI hollow fiber membranes show a pure water permeability of 2.19–2.25L/m2 hbar and reasonable NaCl and MgCl2 rejections of 49% and 94% at 1bar, respectively. It is also found that in FO processes, when using 0.5M MgCl2 as a draw solution and DI water as the feed in the active layer facing feed water (AL-facing-FW) configuration at 23°C, the water fluxes of two PAI FO hollow fiber membranes are 8.36 and 9.74L/m2 h, respectively, and the J S /J V of the two membranes is smaller than 0.4g/L, which is lower than the data of 0.85g/L for commercial FO membrane from Hydration Technologies Inc. (HTI). Different from a neutral membrane, the positively charged FO membrane provides double electric repulsions to the salt transfer through the membrane in the AL-facing-FW configuration, leading to a reduction of salt penetration, while in the active layer facing draw solution (AL-facing-DS) configuration, the positive charges facilitate salt transportation. This study provides a simple and effective approach to make hollow fibers suitable for FO applications. [Copyright &y& Elsevier]

Abstract: Polyvinylidene fluoride-co-hexafluropropylene (PVDF-HFP) has received much attention recently as a promising membrane material for membrane contactor application. A systematic study has been carried out to investigate the effects of polyethylene glycol (PEG) with different molecular weights and different loadings as an additive on the fabrication of PVDF-HFP asymmetric microporous hollow fiber membranes. Moreover, the synergetic effects of coagulation temperature and the second additive (lithium chloride: LiCl) with PEG are also evaluated. Experiments revealed that the addition of PEG into the PVDF-HFP/NMP solution resulted in the system thermodynamically less stable in reaction with water, promoting rapid phase demixing in the phase inversion process. When the same 3wt% PEG was added into the dope solution, the dimension of finger-like macrovoids of the resultant membrane increased in parallel with the increase of PEG molecular weight from 200 to 600 and 6000kDa, and pure water permeability (PWP) also increased accordingly. An increase in PWP was also observed when PEG-200 loading in the dope solution was increased from 3 to 5 and 10wt%, corresponding to the morphology change of resultant membranes. As a synergetic effect of coagulation temperature with PEG, the finger-like pores occurred in the membrane at room temperature expanded to much larger macrovoids using 10°C water as the coagulant, and the big finger-like pores almost disappeared when the coagulation bath temperature was increased to 40°C because of delayed phase demixing. The big macrovoid size can also be suppressed by adding the second small molecule additive, LiCl, due to its strong interactions with NMP and PVDF-HFP to delay the dope precipitation. The irregular inner contour of the membrane can be eliminated by the increase of coagulation bath temperature to 40°C. The hollow fiber membrane made by a dope of PVDF-HFP/PEG-6000/LiCl/NMP (15/3/3/79 in weight) using 40°C water as the coagulant exhibited a high PWP of 117L/m2 hatm and reasonably good MWCO of 150kDa. An improvement has been made in the current work as compared to previous PVDF-HFP hollow fiber membranes reported in literatures. [Copyright &y& Elsevier]