RESUMEN
Graphene oxide (GO)-based membranes hold significant promise for applications ranging from energy storage to protective coatings, to saline water and produced water treatment, owing to their chemical stability and unique barrier properties achieving a high selectivity for water permeation. However, unmodified GO membranes are not stable when submerged in liquid water, creating challenges with their commercial utilization in aqueous filtration and pervaporation applications. To mitigate this, we develop an approach to modify GO membranes through a combination of low temperature thermal reduction and metal cation crosslinking. We demonstrate that Zn2+-rGO and Fe3+-rGO membranes had the highest permeation flux of 8.3 ± 1.5 l m-2h-1and 7.0 ± 0.4 l m-2h-1, for saline water separation, respectively, when thermally reduced after metal cross-linking; These membranes maintained a high flux of 7.5 ± 0.7 l m-2h-1, and 5.5 ± 0.3 l m-2h-1for produced water separation, respectively. All the membranes had a salt rejection higher than 99%. Fe3+crosslinked membranes presented the highest organic solute rejections for produced water of 69%. Moreover, long term pervaporation testing was done for the Zn2+-rGO membrane for 12 h, and only a minor drop of 6% in permeation flux was observed, while Zn2+-GO had a drop of 24%. Both modifiers significantly enhanced the stability with Fe3+-rGO membranes displaying the highest mechanical abrasion resistance of 95% compared to non-reduced and non-crosslinked GO. Improved stability for all samples also led to higher selectivity to water over organic contaminants and only slightly reduced water flux across the membrane.
RESUMEN
Oil and gas industries produce a huge amount of wastewater known as produced water which contains diverse contaminants including salts, dissolved organics, dispersed oils, and solids making separation and purification challenging. The chemical and thermal stability of graphene oxide (GO) membranes make them promising for use in membrane pervaporation, which may provide a more economical route to purifying this water for disposal or re-use compared to other membrane-based separation techniques. In this study, we investigate the performance and stability of GO membranes cast onto polyethersulfone (PES) supports in the separation of simulated produced water containing high salinity brackish water (30 g/L NaCl) contaminated with phenol, cresol, naphthenic acid, and an oil-in-water emulsion. The GO/PES membranes achieve water flux as high as 47.8 L m-2 h-1 for NaCl solutions for membranes operated at 60 °C, while being able to reject 99.9% of the salt and upwards of 56% of the soluble organic components. The flux for membranes tested in pure water, salt, and simulated produced water was found to decrease over 72 h of testing but only to 50-60% of the initial flux in the worst-case scenario. This drop was concurrent with an increase in contact angle and C/O ratio indicating that the GO may become partially reduced during the separation process. Additionally, a closer look at the membrane crosslinker (Zn2+) was investigated and found to hydrolyze over time to Zn(OH)2 with much of it being washed away during the long-term pervaporation.
