More Electrodialysis/Reverse Osmosis Background
In an electrodialysis process, separation, removal, or concentration of ionic species is accomplished by the selective transport of the ions through ion exchange membranes under the influence of an electrical field. Flowing through the series of anion and cation exchange membranes arranged in an alternating pattern between the electrodes having an electrical potential difference, the water diluate (D) feed stream (e.g., seawater for desalination), concentrate (C) stream, and electrode (E) stream are allowed to circulate in the appropriate cell compartments. Under the influence of the electrical potential difference, the negatively charged chlorides, sulfates, and other anions in the diluate (D) stream migrate toward the anode. These ions pass through the positively charged anion exchange membrane, but are rejected by the negatively charged cation exchange membrane and therefore stay in the C stream, which becomes concentrated with the ionic contaminants. The positively charged species such as sodium and other metals in the D stream migrate toward the cathode and pass through the negatively charged cation exchange membrane. These ions also stay in the C stream, being rejected by the anion exchange membrane. The E stream is the electrode stream, which does not become contaminated with any ionic species from the diluate or concentrate streams, although small amounts of hydrogen are generated at the cathode and oxygen at the anode which are subsequently dissipated as the E streams are combined to maintain a neutral pH in the E stream holding tank. The overall result of the electrodialysis processing is an ion concentration increase in the concentrate stream with a depletion of ions in the diluted feed stream.
Electrodialysis has inherent limitations, working best at removing low molecular weight ionic components from a feed stream. Non-charged, higher molecular weight, and less mobile ionic species will not typically be significantly removed. This can be a disadvantage when potable water is produced from feed water sources having high suspended solids content or are contaminated by microorganisms, which would require additional pre-treatment processes for removal prior to electrodialysis processing. Furthermore, the concentration that can be achieved in the electrodialysis brine stream (concentrate or "C" stream) is limited by the membrane selectivity loss due to the Donnan exclusion mechanism and water transport from the diluate to the brine caused by osmosis; in particular, at very high concentration differences across the membrane between the concentration and diluate streams, diffusion of ions from the concentrate stream back into the diluate stream and transport of water across the membranes can offset separation resulting from the applied electric potential, resulting in a poor (i.e., higher ion concentration than desired) product. Despite this disadvantage, in general, significantly higher brine concentration can be achieved by a properly configured electrodialysis than by reverse osmosis and the problem of scaling (i.e., precipitation of insoluble di- or multi-valent salts such as calcium sulfate) is less severe in electrodialysis than in reverse osmosis since mono-valent ions are typically transported through the ion exchange membranes faster than multi-valent ions, resulting in a brine less concentrated in the multi-valent ions and so having less scaling potential. In contrast to reverse osmosis, electrodialysis becomes less economical when extremely low salt concentrations in the product are required, as the current density becomes limited and current utilization efficiency decreases as the feed salt concentration becomes lower: with fewer ions in the solution to carry current, both ion transport and energy efficiency greatly declines. Consequently, comparatively large membrane areas are required to satisfy capacity requirements for low concentration (and sparingly conductive) feed solutions.
Furthermore, at low feed concentrations, ionic concentration polarization becomes an important design issue for electrodialysis membranes. Ionic concentration polarization is the reduction of ion concentrations near the membrane surface compared to those in the bulk solution flowing through the membrane compartment. With substantial ionic concentration polarization, electrolytic water splitting occurs due to the deficiency of solute ions adjacent to the membranes that carry the requisite electric current needed for electrodialysis membrane operation. The electrolytic water splitting is detrimental to electrodialysis process stack efficiency because of the tendency of ionic concentration polarization to occur at the membrane surface due to the hydrodynamic characteristic of channel flow providing thin viscous boundary layers adjacent to confining surfaces (i.e. adjacent membranes). The thin viscous boundary layers impose a resistance to passage of ions much greater than that of a layer of like thickness in a turbulent area of channel flow, and hence increase the likelihood of ionic concentration polarization at the membrane surfaces. Ionic concentration polarization is objectionable due to an inefficient increase in energy consumption without increasing removal of ionic constituents, requiring increased membrane area, along with pH changes in the feed and concentrate streams due to water splitting causing scale deposition in electrodialysis stacks.
Nanofiltration and reverse osmosis processes have been widely utilized for a range of desalination and deionization applications. However, pressure-based membranes have several inherent technical and economical limitations, particularly where high feed recoveries are essential. The most severe impediment to high recovery is the osmotic pressure of the feed solution that has to be overcome by the applied hydrostatic (feed) pressure. The osmotic pressure of saline solutions such as brackish water and seawater can be significant. Moreover, since the osmotic pressure is determined by the salt concentration directly at the membrane surface, it can be affected by concentration polarization, which is the build-up of salt near the surface of the membrane due to incomplete mixing of the surface boundary layer fluid with the bulk solution, a phenomenon accentuated by high pressure fluid passing through the membrane material. Although concentration polarization can be minimized by design and operating parameters, it can never be completely excluded and must be overcome by increased applied hydrostatic (feed) pressure, particularly as feed recovery is increased. Overcoming high osmotic pressures and concentration polarization resulting from higher recoveries requires not only substantial energy to produce the necessary higher pressures and flow rates but also additional investment in capital cost for additional membrane area and pumping capacity. It can also result in shorter useful life of the membrane due to compaction effects and enhanced fouling that can occur at higher pressures and recoveries as a result of the concentration of scaling components near the surface of the membrane, particularly for membrane elements near the end of the process line where overall water recoveries are higher. Enhanced fouling increases the required frequency of membrane cleaning, increasing labor and chemical cost, and reducing throughput. For feeds with total dissolved solids (TDS) levels typical of seawater, recoveries approaching 50% and beyond are seldom feasible; for brackish water levels of TDS, recoveries beyond 80% are rarely economical, resulting in substantial waste of pretreated feed that must be returned to the source or alternatively disposed. Consequently, pressure based membrane systems inherently perform better at lower feed concentrations and lower recoveries in which the osmotic pressure of the feed and its fouling and scaling potential are minimized. Furthermore, membrane process equipment size is determined according to feed or concentrate flow requirements and decreases with increased recovery rate and lower feed concentration; conversely, pressure based membranes perform optimally, producing the best product quality and highest permeate flux rates, with low recoveries and low concentration feeds. Energy requirements are also directly related to feed pressures and feed water flow rates necessary to achieve a particular recovery. The design permeate flux rate predicted at a particular recovery likewise affects the number of pressure vessels, manifold connections, and size of membrane skid, as well as the size of the feed water supply systems and pretreatment equipment that are necessary.