Temperature and Pressure Effects of Desalination Using a MFI-Type Zeolite Membrane.

Zeolites are potentially a robust desalination alternative, as they are chemically stable and possess the essential properties needed to reject ions. Zeolite membranes could desalinate "challenging" waters, such as saline secondary effluent, without any substantial pre-treatment, due to the robust mechanical properties of ceramic membranes. A novel MFI-type zeolite membrane was developed on a tubular α-Al2O3 substrate by a combined rubbing and secondary hydrothermal growth method. The prepared membrane was characterised by scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and single gas (He or N2) permeation and underwent desalination tests with NaCl solutions under different pressures (0.7 MPa and 7 MPa). The results showed that higher pressure resulted in higher Na+ rejection and permeate flux. The zeolite membrane achieved a good rejection of Na+ (~82%) for a NaCl feed solution with a TDS (total dissolved solids) of 3000 mg·L-1 at an applied pressure of 7 MPa and 21 °C. To explore the opportunity for high salinity and high temperature desalination, this membrane was also tested with high concentration NaCl solutions (up to TDS 90,000 mg·L-1) and at 90 °C. This is the first known work at such high salinities of NaCl. It was found that increasing the salinity of the feed solution decreased both Na+ rejection and flux. An increase in testing temperature resulted in an increase in permeate flux, but a decrease in ion rejection.

Effect of surface structure of kaolinite on aggregation, settling rate, and bed density.

The flocculation and solid/liquid separation of four well-characterized kaolinites (2 well, 2 poorly crystallized) have been studied for comparison of surface structure (SEM), aggregate structure during flocculation (cryo-SEM), settling rate, and bed density (with raking). It is shown that major differences in these properties are largely due to crystallinity and consequent surface structure of the extensive (larger dimension "basal") face. Well-crystallized kaolinites, with higher Hinckley indices and lower aspect ratios, have relatively smooth, flat basal surfaces and thicker edge planes promoting both effective initial bridging flocculation (largely edge-edge) and structural rearrangement to face-face during the raking process. This results in faster settling rates and more compact bed structures. Poorly crystallized kaolinites, with low Hinckley indices and high aspect ratios, exhibit ragged, stepped structures of the extensive face with a high proportion of nanosized islands forming cascade-like steps (i.e., multiple edges) contributing up to 30% of the specific surface area and providing flocculant adsorption sites (hydroxyl groups) across this extensive face. This leads to bridging flocculation taking place on both edge and extensive ("basal") planes, producing low-density edge-face structures during flocculation which leads to slow settling rates and poor bed densities. In particular, the complex surface morphology of the poorly crystallized kaolinites resists the transformation of edge-face structures to dense face-face structures under shear force introduced by raking. This results in low sediment density for poorly crystallized kaolinites. The studies suggest that the main influence on settling rates and bed densities of kaolinites in mineral tailings is likely to be related to the crystallinity and surface morphology of the kaolinite. They also suggest that interpretation of kaolinite behavior based on models of a flat (001) basal plane and edge sites only at the particle boundaries is not likely to be adequate for many real, less-crystallized kaolinites.

Kaolinite flocculation structure.

Effective flocculation and dewatering of mineral processing streams containing colloidal clays has become increasingly urgent. Release of water from slurries in tailings streams and dam beds for recycle water consumption, is usually slow and incomplete. To achieve fast settling and minimization of retained water, individual particles need to be bound, in the initial stages of thickening, into large, high-density aggregates, which may sediment more rapidly with lower intra-aggregate water content. Quantitative cryo-SEM image analysis shows that the structure of aggregates formed before flocculant addition has a determinative effect on these outcomes. Without flocculant addition, 3 stages occur in the mechanism of primary dewatering of kaolinite at pH 8: initially, the dispersed structures already show edge-edge (EE) and edge-face (EF) inter-particle associations but these are open, loose and easily disrupted; in the hindered settling region, aggregates are in adherent, chain-like structures of EE and stairstep face-face (FF) associations; this network structure slowly partially rearranges from EE chains to more compact face-face (FF) contacts densifying the aggregates with increased settling rates. During settling, the sponge-like network structure with EE and FF string-like aggregates, limits dewatering because the steric effects in the resulting partially-gelled aggregate structures are dominant. With flocculant addition, the internal structure and networking of the pre-aggregates is largely preserved but they are rapidly and effectively bound together by the aggregate-bridging action of the flocculant. The effects of initial pH and Ca ion addition on these structures are also analyzed. Statistical analysis from cryo-SEM imaging shows that there is an inverse correlation of intra-aggregate porosity with Darcian inter-aggregate permeability whereas there is a strong positive correlation of Darcian permeability with settling and primary dewatering rate as a function of pH in suspension. Graphs of partial void contributions also suggest that it is not total porosity that dominates permeability in these systems but the abundance of larger intra-aggregate voids.

Using mesoporous carbon electrodes for brackish water desalination.

Electrosorptive deionisation is an alternative process to remove salt ions from the brackish water. The porous carbon materials are used as electrodes. When charged in low voltage electric fields, they possess a highly charged surface that induces adsorption of salt ions on the surface. This process is reversible, so the adsorbed salt ions can be desorbed and the electrode can be reused. In the study, an ordered mesoporous carbon (OMC) electrode was developed for electrosorptive desalination. The effects of pore arrangement pattern (ordered and random) and pore size distribution (mesopores and micropores) on the desalination performance was investigated by comparing OMC and activated carbon (AC). It were revealed from X-ray diffraction and N(2) sorption measurements that AC has both micropores and mesopores, whereas ordered mesopores are dominant in OMC. Their performance as potential electrodes to remove salt was evaluated by cyclic voltammetry (CV) and galvanostatic charge/discharge tests at a range of electrolyte concentrations and sweep rates. It is deduced that under the same electrochemical condition the specific capacitance values of OMC electrode (i.e. 133 F/g obtained from CV at a sweep rate of 1 mV/s in 0.1M NaCl solution) are larger than those of AC electrode (107 F/g), suggesting that the former has a higher desalting capacity than the latter. Furthermore, the OMC electrode shows a better rate capacity than the AC electrode. In addition, the desalination capacities were quantified by the batch-mode experiment at low voltage of 1.2V in 25 ppm NaCl solution (50 micros/cm conductivity). It was found that the adsorbed ion amounts of OMC and AC electrodes were 11.6 and 4.3 micromol/g, respectively. The excellent electrosorptive desalination performance of OMC electrode might be not only due to the suitable pore size (average of 3.3 nm) for the propagation of the salt ions, but also due to the ordered mesoporous structure that facilitates desorption of the salt. Based on the results, it was found that the development of an ordered mesoporous structure and the control of the number of micropores are two important strategies for optimising electrode material properties for electrosorptive deionisation.

Effects of chemical functional groups on the polymer adsorption behavior onto titania pigment particles.

The effects of functional groups on polymer adsorption onto titania pigment particles have been investigated as a function of pH and ionic strength using polyacrylic acid and modified polyacrylamides. The polyacrylamides include the homopolymer, an anionic copolymer with hydroxyl and carboxylate group substitution, and a nonionic copolymer with hydroxyl group substitution. Adsorption isotherms and infrared spectroscopy were used to examine the polymer-pigment interactions. The adsorption of the polyacrylic acid and anionic polyacrylamide on titania pigment is greatest when electrostatic repulsion is absent or reduced. At low pH values, below the pigment isoelectric point (IEP), or at high ionic strength, the adsorption density of the anionic polymers on titania pigment is high, while at higher pH values above the pigment IEP, the adsorption density decreases. But the adsorption of nonionic polymers on titania pigment is not influenced by either ionic strength or pH. Acrylamide groups were found to hydrogen bond with the titania pigment surface, independent of pH. With the inclusion of hydroxyl functional groups into the polyacrylamide chain, the polymer adsorption density increased without increased adsorption affinity. Carboxylate functional groups in the anionic polymers strongly interact with the pigment surface, producing the highest adsorption density at low pH values. All polymers exhibit Langmuir adsorption behavior with hydrogen bonding found as the dominant mechanism of adsorption in addition to electrostatic interaction occurring for the anionic polymers.

Sodium stearate adsorption onto titania pigment.

The interaction of sodium stearate with titania pigment particles from aqueous suspension has been investigated using thermal analysis and infrared spectroscopy combined with electrochemical studies. Thermogravimetric analysis (TGA) was used both to determine the adsorption isotherm and to investigate the interaction behavior. Monolayer coverage is determined to be 0.95 mg/m(2); however, unlike the case with organic solvents, multilayer adsorption occurs. Diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy, combined with TGA, revealed that the surface monolayer is chemically bound. DRIFT spectroscopic data also indicated that the stearate bridged across two aluminum atoms. Subsequent stearate layers were physisorbed to the stearate monolayer and were readily removed with acetone washing.

Influence of aluminum doping on titania pigment structural and dispersion properties.

The influence of aluminum concentration on the structural properties and rheological behavior of aqueous suspensions of aluminum-doped titania pigment from the chloride process was investigated. The variation in rheological properties correlates with the change in the pigment surface properties, determined from electrophoresis measurements and atomic surface concentrations. Pigment suspensions exhibited a maximum yield stress and viscosity at or near the isoelectric point (iep). The pH of the maximum yield value of the pigment suspension increases with increasing aluminum hydroxyl group density at the particle surface. For pigments with a high aluminum surface concentration, at pH values where the magnitude of the zeta potential was high, a low-viscosity, dispersed suspension was obtained. The pigment with the lowest aluminum concentration, however, retained high yield stresses over a large pH range even when the zeta potential was of considerable magnitude. Pigment particle interactions are chiefly dictated by van der Waals forces and electrostatic repulsive forces, likely to be influenced by heteroaggregation. The aggregate strength would therefore depend upon the proportion and distribution of aluminum and titanium surface groups of the heterogeneous pigment, which will influence both the Hamaker constant and the degree of heteroaggregation. Overall, very small additions to the total aluminum concentration translate to significant aluminum surface concentration disparities and subsequently to large particle interaction differences.

Kinetics of adsorption of high molecular weight anionic polyacrylamide onto kaolinite: the flocculation process.

The adsorption kinetics of anionic polyacrylamide flocculant onto kaolinite clay are examined as a function of flocculant dosage and pH. Special attention has been given to the flocculation effect during the adsorption process and the resulting inhibition of further adsorption. At pH 8.5 the adsorption capacity of anionic polyacrylamide on kaolinite is low while at pH 4.5, the adsorption capacity increases. Flocculant adsorption has been shown to be related to the amount of available surface area, pH, flocculant dosage, and the resulting floc strength, which controls the rate of new surface area exposure and hence the continuation of further adsorption. At both pH 4.5 and pH 8.5, complete adsorption is achieved at low flocculant dosages and adsorption equilibrium is achieved at high flocculant dosages after 1 day. In contrast, at intermediate flocculant dosages adsorption equilibrium is not reached over a 7-day period, due to a continuously increasing surface area.