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.
On-site treatment and reuse is an increasingly preferred option for produced water management in unconventional oil and gas extraction. This paper analyzes and compares the energetics of several desalination technologies at the high salinities and diverse compositions commonly encountered in produced water from shale formations to guide technology selection and to inform further system development. Produced water properties are modeled using Pitzer's equations, and emphasis is placed on how these properties drive differences in system thermodynamics at salinities significantly above the oceanic range. Models of mechanical vapor compression, multi-effect distillation, forward osmosis, humidification-dehumidification, membrane distillation, and a hypothetical high pressure reverse osmosis system show that for a fixed brine salinity, evaporative system energetics tend to be less sensitive to changes in feed salinity. Consequently, second law efficiencies of evaporative systems tend to be higher when treating typical produced waters to near-saturation than when treating seawater. In addition, if realized for high-salinity produced waters, reverse osmosis has the potential to achieve very high efficiencies. The results suggest a different energetic paradigm in comparing membrane and evaporative systems for high salinity wastewater treatment than has been commonly accepted for lower salinity water.
As global desalination capacity continues its rapid growth, the impetus for reducing the adverse environmental impacts of brine discharge grows concurrently. Although modern brine outfall designs have significantly limited such impacts, they are costly. Recovering valuable components and chemical derivatives from brine has potential to resolve both environmental and economic concerns. In this article, methods for producing sodium hydroxide ("caustic") from seawater reverse osmosis (SWRO) brine for internal re-use, which typically involve brine purification, brine concentration, and sodium chloride electrolysis, are reviewed. Because process energy consumption drives process cost and caustic purity determines product usability in drinking water systems, reviewed technologies are benchmarked against thermodynamic minimum energy consumption and maximum (stoichiometric) NaOH production rates. After individual reviews of brine purification, concentration, and electrolysis technologies, five existing facilities for caustic production from seawater and seawater concentrates are discussed. Bipolar membrane electrodialysis appears to have the best potential to meet the technoeconomic requirements of small-scale caustic production from SWRO brine. Finally, future research and demonstration needs, to bring the technology to commercial feasibility, are identified.
Water is an abundant resource across the world, and its purification and byproduct recovery methods are crucial for economical, environmentally safe, and sustainable utilization. Desalinating seawater generally produces brine as a byproduct that cannot be purified economically with current technologies and which is instead released to the environment. In this perspective, we discuss direct electrosynthesis of sodium hydroxide (NaOH) and hydrochloric acid (HCl) from seawater-desalination brine as an emerging alternative solution. In this direct electrosynthesis (DE) process, the water splitting reaction is used to produce H + and OH-, which combine with the brine stream to produce NaOH and HCl. After introducing the scope of the process, we describe developments in earth-abundant catalysts for water splitting and the competing chlorine evolution reaction (CER), as well as challenges in inefficiency and productivity. Finally, we discuss the economic impact and feasibility of direct electrosynthesis.
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