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 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.

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.

A new concept to concentrate seawater up to 200 g/kg for producing vacuum salt using a reverse osmosis (RO) system hybridized with an electrodialysis (ED) system is presented. The RO system operates up to pressures of 120 bar and concentrates seawater up to 120 g/kg with the ED system concentrating RO brine to 200 g/kg. A parametric analysis to minimize the specific cost of brine concentration was conducted. Parameters varied were: the degree of RO-ED hybridization, ED current density, electricity prices and water prices. Optimal hybrid RO-ED designs reduced brine concentration costs by 33-70 % over standalone ED systems, with revenue generated from water co-production further subsidizing costs by 1-6 %. Optimizing ED current density reduced costs the most. Including a crystallizer, the total reduction in production cost over a standalone ED-crystallizer system was 19-55 %, with the production cost for a typical case being $111/tonne-salt. The proposed RO-ED-crystallizer (REC) systems were found to be techno-economically feasible in Cyprus, Japan, Kuwait, Saudi Arabia, and the USA. At a road transportation distance of 735 km, REC based seawater vacuum salt was competitive with conventional vacuum salt. REC systems may open up the potential of small-scale decentralized salt production.

We provide a thermoeconomic assessment of electrodialysis indicating that the technology is most productive and efficient for the partial desalination of feed streams at the higher end of the brackish range of salinities. After optimising the current density to minimise the sum of energy and equipment costs, we demonstrate that at low feed salinities the productivity, and hence equipment costs, of electrodialysis are hampered by the limiting current density. By contrast, at higher feed salinities both productivity and efficiency are hampered by the reduced chemical potential difference of salt in the diluate (low salinity) and concentrate (high salinity) streams. This analysis indicates the promise of further developing electrodialysis for the treatment of waters from oil, gas and coal-bed methane as well as flue-gas de-sulphurisation, where the partial desalination of streams at the high-end of the brackish range can be beneficial.

Humidification dehumidification (HDH) is a promising technology for small scale seawater desalination and has received widespread attention in recent years. The biggest roadblock to commercialization of this technology is its relatively high energy consumption. In this paper, we propose thermodynamic balancing of the humidifier or the dehumidifier through mass extraction and injection as a potential means of reducing the energy consumption of these systems. Balancing minimizes the entropy generation caused by imbalance in driving temperature and concentration differences. We outline a procedure to model the system, using on-design component variables, such that continuous or discrete extraction and/or injection of air from the humidifier to the dehumidifier or vice versa can be analyzed. We present an extraction profile (mass flow rate ratio versus non-dimensional position) in the dehumidifier and the humidifier for attaining close to complete thermodynamic reversibility in an HDH system with a 100% effective humidifier and dehumidifier. Further, we have examined in detail the effect of having finite-sized systems, of balancing the humidifier versus the dehumidifier, and that of the number of extractions.

Given simultaneous heat and mass transfer and a multiplicity of possible temperature and flow configurations, the optimisation of humidificationdehumidification desalination systems is complex. In literature, this optimisation has been tackled by considering moist air to follow the saturation curve in the humidifier and dehumidifier of a closed air water heated cycle. Under similar conditions and the same pinch point temperature differences, energy recovery was shown to improve with an increasing number of stages. In the present work, the limits upon the energy recovery and the water recovery (product water per unit of feed) of closed air water heated cycles are investigated. This is done by considering heat and mass exchangers to be sufficiently large to provide zero pinch point temperature and concentration differences with the humidifier and dehumidifier. For cycles operating with a feed temperature of 25• C and a top air temperature of 70 • C, GOR is limited to approximately 3.5 without extractions (i.e. single stage system) and 14 with a single extraction (i.e. dual stage system) while RR is limited to approximately 7% without extractions and 11% with a single extraction . GOR increases and RR decreases as the temperature range of the cycle decreases, i.e. as the feed temperature increases or the top air temperature decreases. A single extraction is shown to be useful only when heat and mass exchangers are large in size. In addition, the effects of salinity and the validity of ideal gas assumptions upon the modelling of HDH systems are discussed. * lienhard@mit.edu Keywords: desalination, water treatment, humidification-dehumidification, saturation curve, multiple stage, extraction, injection 2 MotivationHumidification-dehumidification (HDH) systems are commonly viewed as robust liquid purification systems, driven by low-grade heat and capable of operating on a small scale decentralized basis, [1,2]. In desalination applications, HDH systems purify saline feed water. From another perspective, the role of HDH systems could be to concentrate industrial waste water streams.The premise underlying HDH is that a volatile solvent containing a nonvolatile solute, may be separated by humidifying a suitable carrier gas with that solvent and subsequently condensing it in pure form. achieve this by transferring heat from the dehumidifier to the humidifier via a common heat transfer wall. HDH systems, by contrast thermally separate the humidification and dehumidification processes, as shown in Fig. 1.[ Figure 1 about here.]The system described in Fig. 1 is a closed air water heated HDH process. Air enters the humidifier and is heated and humidified by a counterflow of feed. The moist air then flows to the dehumidifier, in which the air is cooled and water vapor is condensed due to heat transfer to a counterflow of liquid feed. This feed is heated in the dehumidifier and then in the heater, before being cooled and partially evaporated in the humidifier. The feed remaining at the bottom of the humidifier, known a...