Increasing global demand for fresh water is driving the development and implementation of a wide variety of seawater desalination technologies. Entropy generation analysis, and specifically, Second Law efficiency, is an important tool for illustrating the influence of irreversibilities within a system on the required energy input. When defining Second Law efficiency, the useful exergy output of the system must be properly defined. For desalination systems, this is the minimum least work of separation required to extract a unit of water from a feed stream of a given salinity. In order to evaluate the Second Law efficiency, entropy generation mechanisms present in a wide range of desalination processes are analyzed. In particular, entropy generated in the run down to equilibrium of discharge streams must be considered. Physical models are applied to estimate the magnitude of entropy generation by component and individual processes. These formulations are applied to calculate the total entropy generation in several desalination systems including multiple effect distillation, multistage flash, membrane distillation, mechanical vapor compression, reverse osmosis, and humidification-dehumidification. Within each technology, the relative importance of each source of entropy generation is discussed in order to determine which should be the target of entropy generation minimization. As given here, the correct application of Second Law efficiency shows which systems operate closest to the reversible limit and helps to indicate which systems have the greatest potential for improvement.

In the face of growing water scarcity, it is critical to understand the potential of saltwater desalination as a long-term water supply option. Recent studies have highlighted the promise of new membrane materials that could desalinate water while exhibiting far greater permeability than conventional reverse osmosis (RO) membranes, but the question remains whether higher permeability can translate into significant reductions in the cost of desalinating water. Here, we address a critical question by evaluating the potential of such ultra-permeable membranes (UPMs) to improve the performance and cost of RO. By modeling the mass transport inside RO pressure vessels, we quantify how much a tripling in the water permeability of a membrane would reduce the energy consumption or the number of required pressure vessels for a given RO plant. We find that a tripling in permeability would allow for 44% fewer pressure vessels or 15% less energy for a seawater RO plant with a given capacity and recovery ratio. Moreover, a tripling in permeability would result in 63% fewer pressure vessels or 46% less energy for brackish water RO. However, we also find that the energy savings of UPMs exhibit a law of diminishing returns due to thermodynamics and concentration polarization at the membrane surface. Broader contextThe development of affordable, reliable and energy-efficient technologies for converting saltwater into fresh water is one of the most important research goals of this century. Yet the best technology available today, reverse osmosis (RO), remains costly. Recent advances in materials research suggest that new membranes could reject salt while permeating water much faster than nonporous RO membranes. However, considerable confusion exists regarding the likelihood that future RO systems will continue to become smaller, more productive or more energy-efficient. Given the critical importance of water technology research for human development goals, it is essential to carefully evaluate what future RO systems can and cannot achieve on the basis of more permeable membranes. Beginning with fundamental transport equations and extending to applied engineering scenarios, we demonstrate that membranes with 3x higher permeability could reduce the energy consumption of RO by 15-46% for seawater and brackish water respectively, or alternatively reduce the number of pressure vessels by 44-63%. Given many recent advances in the design of RO membranes, this work highlights the likely development of a new generation of desalination plants with higher throughput and a smaller spatial footprint than what is achievable today. Motivation and research questionThe orders-of-magnitude increase in permeability that UPMs could potentially enable require an in-depth assessment of the physical mechanisms that occur at the membrane's surface.

We provide a comparison of the theoretical and actual energy requirements of forward osmosis and reverse osmosis seawater desalination. We argue that reverse osmosis is significantly more energy efficient and that forward osmosis research efforts would best be fully oriented towards alternate applications. The underlying reason for the inefficiency of forward osmosis is the draw-dilution step, which increases the theoretical and actual energy requirements for draw regeneration. As a consequence, for a forward osmosis technology to compete with reverse osmosis, the regeneration process must be significantly more efficient than reverse osmosis. However, even considering the optimisation of the draw solution and the benefits of reduced fouling during regeneration, the efficiency of an optimal draw regeneration process and of reverse osmosis are unlikely to differ significantly, meaning the energy efficiency of direct desalination with reverse osmosis is likely to be superior.

We propose the use of electrodialysis to desalinate produced waters from shale formations in order to facilitate water reuse in subsequent hydraulic fracturing processes. We focus on establishing the energy and equipment size required for the desalination of feed waters containing total dissolved solids of up to 192,000 ppm, and we do this by experimentally replicating the performance of a 10-stage electrodialysis system. We find that energy requirements are similar to current vapour compression desalination processes for feedwaters ranging between roughly 40,000-90,000 TDS, but we project water costs to potentially be lower. We also find that the cost per unit salt removed is significantly lower when removed from a high salinity stream as opposed to a low salinity stream, pointing towards the potential of ED to operate as a partial desalination process for high salinity waters. We then develop a numerical model for the system, validate it against experimental results and use this model to minimise salt removal costs by optimising the stack voltage. We find that the higher the salinity of the water from which salt is removed the smaller should be the ratio of the electrical current to its limiting value. We conclude, on the basis of energy and equipment costs, that electrodialysis processes are potentially feasible for the desalination of high salinity waters but require further investigation of robustness to fouling under field conditions.