Water scarcity, population growth, and climate change are causing a shortage of water resources globally. Industries are turning to the reclamation and reuse of wastewater, including oily wastewater, which is a major byproduct of oil and gas extraction. The small droplet size of oil-in-water emulsions, however, makes them difficult to remove using traditional methods like coagulation and flocculation, gravitational settling, dissolved air flotation, hydrocyclone, and adsorption.
Membrane separation has emerged as one of the most promising techniques to deal with oil-in-water emulsions due to its high removal efficiency and small footprint. The main challenge for the wider adoption of membrane technology for oily wastewater treatment is membrane fouling. Membrane fouling is a pervasive problem in water purification membranes. It could cause serious negative effects, such as a decline in water production, higher operational pressure and associated higher energy consumption.
Ceramic membranes, particularly SiC membranes, are a promising method for removing small oil droplets from water. They are physically and chemically stable and have high fouling resistance to oil droplets. SiC membranes have better permeability and lower fouling tendency compared to other ceramic membranes. However, their high cost limits their widespread application in the market.
In this research, extensive literature reviews were first performed (Chapters 2 and 3) and then we proposed a new method, low-pressure chemical vapor deposition (LPCVD), to prepare SiC-deposited ceramic membranes for oily wastewater treatment. With LPCVD, a layer of SiC was deposited on alumina supports at a lower temperature (750 ˚C), compared to 2000 ˚C for commercial SiC preparations. Due to the low water contact angle (< 5˚) and negatively charged surface, these SiC-deposited alumina ceramic membranes are expected to be more fouling resistant to oil emulsions than the pristine alumina membranes. The performance of deposited membranes is influenced not only by the coated SiC layer but also by the filtration modes used for evaluation. As a result, we respectively used constant pressure and constant flux filtration to assess the fouling of ceramic membranes with and without SiC deposition. Additionally, the emulsion chemistry, such as surfactant concentration, pH, salinity, and Ca2+, plays a crucial role in the interactions between oil droplets and the membrane surface, which can cause membrane fouling. Understanding these mechanisms can be a crucial step towards the feasibility of using LPCVD to prepare SiC membranes for treating oily wastewater with lower fouling.
First, novel SiC-deposited ceramic membranes were developed by LPCVD at a relatively low temperature (750 ˚C) (Chapter 4). Different deposition times varying from 0 to 150 min were used to tune membrane pore size. The pure water permeance of the membranes only decreased from 350 L m-2 h-1 bar-1 to 157 L m-2 h-1 bar-1 when the deposition time was increased from 0 to 120 min. Correspondingly, the membrane pore size was narrowed down from 71 to 47 nm. Increasing the deposition time from 120 to 150 min mainly resulted in the formation of a thin, dense layer on top of the support instead of in the pores. Notably, the SiC layer rendered the pristine membrane surface more hydrophilic and negatively charged, effectively reducing membrane fouling during oil emulsion filtration.
Next, the fouling of SiC-deposited ceramic membranes and the pristine alumina membrane was respectively compared at constant pressure and constant flux filtration conditions (Chapter 5). The threshold flux of the membranes was first determined by flux-stepping experiments. Afterwards, membrane filtration was respectively conducted at below and above the threshold flux. In single cycle constant flux filtration experiment, the fouling tendency of the membranes was consistent with the results of threshold flux experiments. However, the inclusion of backwash in constant flux experiments led to a change in the fouling tendency, which was also dependent on the permeate flux. The improved surface hydrophilicity and charge made backwash more efficient for the modified membranes while extensive modification has a negative effect on membrane fouling resistance due to the huge loss in membrane permeance. In contrast, constant transmembrane pressure experiments showed that the order of membrane fouling was only related to membrane permeance, and no effect of surface properties was observed. Therefore, constant flux filtration experiments with backwash are recommended to be applied to evaluate the performance of the membranes with and without modification.
Finally, the impact of emulsion chemistry and operational parameters on the fouling of alumina membranes with and without a SiC deposition was systematically studied under constant flux filtration mode with backwash (Chapter 6). The results showed that the SiC-deposited membrane had a lower reversible and irreversible fouling when permeate flux was below 110 Lm-2h-1. In addition, a higher permeance recovery after physical and chemical cleaning was observed, as compared to the alumina membranes. The fouling of both membranes was decreased with the increase of sodium dodecyl sulphate (SDS) concentration in the feed, but to a higher extent in the alumina membranes. Increasing the pH of the emulsion could reduce the fouling of both membranes due to the enhanced electrostatic repulsion between oil droplets and membrane surface. Under high salinity conditions (100 mM NaCl), the screening of surface charge resulted in only a small difference in irreversible fouling between the alumina and SiC-deposited membranes. The presence of Ca2+ in the emulsion led to high irreversible fouling of both membranes, because of the compression of diffusion double layer and the interactions between Ca2+ and SDS. The low fouling tendency and/or high cleaning efficiency of the SiC-deposited membranes indicated their potential for oily wastewater treatment.
Overall, this dissertation shows that the fouling of SiC-deposited ceramic membranes is lower than that of the pristine alumina membranes towards oil-in-water emulsion treatment. Although there are still limitations, these SiC-deposited membranes show the potential for further development.