Carbon nanotube membranes for brackish groundwater desalination and removal of organic micropollutants from water

Abstract

This thesis reports on the synthesis and characterisation of various types of oxidised multiwalled carbon nanotubes (O-MWCNTs) modified polymeric membranes. These OMWCNT modified polymeric membranes were then assessed in terms of their remediation potential, in particular for the removal of estrogenic hormones, dissolved proteins and salts from brackish water sources. The fabricated O-MWCNT-based polyethersulfone (PES) membranes were applied as (i) adsorptive membranes, (ii) molecular-sieving membranes and (iii) as membrane substrates for thin-film composite nanofiltration (NF) membrane preparation. The research work commences with the preparation of MWCNTs via a facile catalytic chemical vapour deposition method and their chemical oxidation with strong acids in order to introduce hydrophilic carboxylic (–COOH) and hydroxyl (–OH) surface functional group moieties on the MWCNT outer walls. Intrinsically, MWCNTs are chemically inert and tend to form agglomerated nanoclusters (due to van der Waals interaction forces), which induce further difficulties in their homogenous dispersion in polar solvents (such as N-methyl-2- pyrrolidone and dimethylacetamide) employed to dissolve the polymers in the study. The introduction of these oxygen-containing moieties was therefore necessary to aid the dispersion of MWCNTs in organic solvents and for their enhanced interaction with PES and sulfonated polysulfone (SPSf). The PES/O-MWCNT ultrafiltration (UF) membranes were produced via a non-solvent induced phase separation (NIPS) method and employed in the adsorptive removal of natural hormone estrone (E1). The PES/O-MWCNT UF membranes thus prepared were characterised using SEM, AFM, zeta potential measurements and MWCO experiments. It was found that the adsorption of E1 initially increased with an increase in O-MWCNT content followed by a constant decline on further increments. Moreover, the inclusion of OMWCNTs (0.5 wt.%) in the PES membrane matrix resulted in an increase in the maximum adsorption capacity for E1 compared to pristine PES membrane, i.e., 31.25 mg/g adsorption capacity was achieved for PES/O-MWCNT compared to 23.81 mg/g for bare PES UF membrane. Based on the correlation coefficients, the Freundlich isotherm provided a better fit for the adsorption data and the adsorption kinetics followed the pseudo-second order kinetic model. Interestingly, after five regeneration cycles, the PES/O-MWCNT membranes were found to maintain similar adsorption efficiencies. The PES/O-MWCNT membranes thus prepared, present a viable approach for the removal of natural hormones and other endocrine disruptors present in water systems compared to the use of common adsorbents such as activated carbon, which end up generating large amounts of chemical sludge that require disposal in the environment. The third part of the study focused on the controlled formation of macrovoid-free polyethersulfone/sulfonated polysulfone (PES/SPSf) UF membranes with high water permeabilities, mechanical strength and antifouling properties, in the presence of O-MWCNTs. To date, the majority of polymeric nanocomposite membranes modified with O-MWCNTs as nanofillers, generally have finger-like structures and macrovoids in the membrane sublayer. While the presence of finger-like structures is favoured for the reduction in mass flow resistance, their presence induces mechanically weak points in the membrane and reduces the nanocomposite membranes’ mechanical strength properties and long-term performance stability. As such macrovoid-free PES/SPSf/O-MWCNT membranes were fabricated via the NIPS techniques, using H2O and polyethylene glycol (PEG 20 kDa) as non-solvent additives. The SEM cross-sectional images showed that a fully sponge-like morphology of the PES/SPSf membrane can be achieved in the presence of different loadings of O-MWCNTs. This was attributable to the formation of stronger hydrogen bonds between the SPSf polymer and non-solvent additives i.e., H2O, PEG 20kDa and OMWCNTs. The combination of the macrovoid-free morphology and homogenous distribution of high mechanical strength O-MWCNTs in the membrane matrix provided excellent mechanical strength enhancements for PES/SPSf/O-MWCNT membranes. Additionally, pure water flux initially increased from 598 L/m2 .h to 713 L/m2 .h followed by a decline to 578 L/m2 .h upon further increments in O-MWCNT contents, due to agglomeration of O-MWCNTs at higher loadings. The fabricated PES/SPSf/O-MWCNT membranes also displayed superior antifouling properties (FRR > 90%) and antibacterial properties (99% bacterial killing ratio) against E. coli bacteria. The fabricated support fabricfree PES/SPSf/O-MWCNT UF membranes with macrovoid-free sublayer morphologies displayed attractive features for use as UF membranes in the pre-treatment stages of water treatment and as support substrates for the preparation of TFC membranes. In general, sponge-like and macrovoid-free membrane structures are regarded as unfit for use as support membranes for TFC membrane preparation since they increase the membrane’s resistance to water flow, thereby reducing the overall TFC membrane permeability. This assumption has largely been based on sponge-like and macrovoid-free membranes structures achieved through the use of extremely high polymer concentrations, particularly using polysulfone (PSf) polymer. Hence, the sponge-like structures formed are very dense and less porous. Nevertheless, the macrovoid-free PES/SPSf/O-MWCNT membranes produced in this study, consisted of open cellular network microstructures within the membrane sublayer, which could be visualised at higher SEM magnifications. This part of the work therefore investigated the role of hydrophilic, macrovoid-free PES/SPSf and PES/SPSf/O-MWCNT as support membranes on the performance of TFC NF membranes. The TFC NF membranes were prepared via an efficient interfacial polymerization reaction between piperazine (PIP) and trimesoyl chloride (TMC). The deposition of the polyamide thin-film layer was confirmed by ATR-FTIR, SEM, AFM, contact angle and zeta potential measurements. Membrane performance results showed that TFC NF membranes fabricated on PES/SPSf/O-MWCNT support membranes displayed a 35% improvement in pure water flux with comparable salt rejections from those prepared on bare PES/SPSf support membranes. Salt rejection followed the order of Na2SO4 > MgSO4 > NaCl, which is typical for negatively charged NF membranes. It was established that the presence of hydrophilic O-MWCNTs in the support membrane allowed for the formation of a thin polyamide layer on the top surface of the support membrane, which gave rise to enhanced water permeability of the TFC NF membrane and the possibility of polyamide rejection layer within the support membrane pore channels. To further improve the performance of the TFC NF membranes, in particular, the monovalent/bivalent salt selectivity, a mixture of PIP and 2,4-diaminobenzene sulfonic acid (2,4-DABSA) at different weight ratios was prepared in the aqueous solution and reacted with TMC in the organic phase solution. It was found that the addition of low monomer weight ratio of 2,4-DABSA in the amine mixture, lead to the generation of a sulfonated TFC NF membrane with superior membrane performance in terms of pure water permeability (30.2 L/m2 .h), monovalent/bivalent salt selectivity (𝛼NaCl/Na2SO4 = 25.0) at low operating pressures (3 bar) and salt concentrations in the range of brackish waters. This was attributable to the combined presence of sulfonic acid groups on the membrane surface and the formation of the thin polyamide layer. Moreover, sulfonated TFC NF membranes exhibited good antifouling properties against bovine serum albumin (BSA), with FRR of 96.4% after three cycles of fouling and cleaning, with a fairly stable membrane performance over a 10-day period of pure water flux and Na2SO4 rejection testing. Indeed, the use of a macrovoid-free PES/SPSf/O-MWCNT support membrane did not only provide the mechanical strength for the deposition of TFC NF membrane, but also their open, cellular network microstructure, combined with high hydrophilicity and large surface pore sizes were beneficial in the reduction of polyamide layer thickness, and subsequently in the enhancement of TFC NF membrane performance. The study provided insightful information on lesser known aspects of O-MWCNT incorporated polymeric membranes, with regards to membrane structural configurations in relation to the membrane structure-performance relationships. It has been deduced that (i) the right combination of membrane surface characteristics and adsorbate solution chemistry is necessary for an open UF membrane to display reasonable removal efficiencies for low molecular-weight solutes, (ii) the combination of macrovoid-free membrane morphology with good dispersion of O-MWCNTs in the polymer matrix is necessary to realise significant enhancements in the mechanical properties of sulfonated membrane and (iii) formation of a thin sulfonated polyamide layer on top of the hydrophilic PES/SPSf/O-MWCNT support membrane is necessary to achieve high salt selectivity, and allow for the sulfonated TFC NF membrane to be operated at low pressures.