Electrodialysis (ED) is a membrane-based process in which ions are transported under the influence of an externally applied electrical potential. Ion-exchange membranes (IEMs) are key components in ED processes. There are two types of IEMs: (1) cation-exchange membranes (CEMs), which contain fixed, negatively charged groups, and (2) anion-exchange membranes (AEMs), which contain fixed, positively charged groups. ED processes have been widely applied for water desalination. This thesis investigates the application of ED in the treatment of drainage water of greenhouses. A key objective in sustainable greenhouse horticulture is the recirculation of drainage water, thereby minimizing the water volume used, which would otherwise be disposed into the environment.[1] The drainage water of greenhouses contains both K+ and Na+. Whereas K+ is a valuable nutrient, Na+ is detrimental for plant growth. Because of its toxicity, the Na+ level should be controlled below the crop-specific threshold.[2-4] Because Na+ is not taken up by plants, it accumulates and the excess needs to be removed. The main challenge here is to selectively separate and remove Na+ without removing K+ and other key nutrients like Ca2+ and Mg2+. Na+ and K+ are two competitive cations ion separations as they have the same valence (+1), quite similar crystal and hydrated radii and a rather similar transport behavior (i.e. electrophoretic mobility), causing that separation by charge, size, and/or mobility is challenging. This thesis focusses on the development and characterization of a membrane-based process for the selective removal of Na+....@en

We investigated in detail the permeation selectivity in the electro-dialysis of Na⁺, K⁺, Mg²⁺ and Ca²⁺ in both binary and quaternary mixtures using a supported liquid membrane (SLM). The SLM consisted of the organic liquid 2-nitrophenyl octyl ether (NPOE) containing a lipophilic anion, i.e. tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, as the cation-exchanging site, which was used to fill the pores of the supporting membrane Accurel^R. We first determined the electro-phoretic mobilities of the migrating cations in single salt solutions, yielding: Na⁺ > K⁺ > Mg²⁺ > Ca²⁺. This order reflects the different size of the migrating cations. The monovalent cations Na⁺ and K⁺ migrate in the dehydrated state and the divalent cations Ca²⁺ and Mg²⁺ migrate in a (partly) hydrated state, a conclusion was supported by Karl Fisher titrations. Both binary and quaternary salt experiments showed a permeation selectivity in the following order: K⁺ > Na⁺ > Ca²⁺ > Mg²⁺. Since this order does not correlate with the order of electro-phoretic mobilities, we have determined the ion-exchange selectivity constant (K_ex) and found: K⁺ > Ca²⁺ > Mg²⁺ ≈ Na⁺. We conclude that the overall permeation selectivity is determined by the combination of ion-exchange selectivity and electro-phoretic mobility of the cations present in the membrane.

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High Na⁺ levels are detrimental for most crops. Selective membranes provide the possibility for the selective removal of Na⁺ while preserving beneficial ion species. The challenge is to separate two ion species of the same charge. This study evaluates the implementation of an electrodialysis (ED) system equipped with a supported liquid membrane (SLM) and a commercially available monovalent cation-selective membrane (CIMS) in the treatment of greenhouse drainage water. The SLM shows a (minimum) K⁺ over Na⁺, Ca²⁺ and Mg²⁺ permselectivity of 9, 15 and 30, respectively. Whereas the CIMS holds a high K⁺ over Ca²⁺ and Mg²⁺ permselectivity of 10 and 16, respectively, the K⁺ over Na⁺ permselectivity is just 1.3. With the experimentally obtained membrane characteristics at hand, the treatment of drainage water was simulated by a two-steps process with the two membrane types operating in series. Using real-life operational parameters, analysis revealed the optimal configuration and the ability to recover 96% of the K⁺ and approximately 80% of the water, Ca²⁺ and Mg²⁺. Summarized, this study not only shows the efficient separation of two ion species of the same valance but also the implementation of this technology in a real-life application.

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Selective ion removal has been a point of focus in capacitive deionization because of its industrial applications such as water purification, water softening, heavy metal separation and resource recovery. Conventionally, carbon is used as electrode material for selectivity. However, recent developments focus on intercalation materials such as Prussian Blue Analogues, due to their size-based preference towards cations. Selectivity of nickel hexacyanoferrate electrodes from a mixture of Na⁺, Mg²⁺, and Ca²⁺ ions was studied in this work. Here, a CDI cell with two identical NiHCF electrodes was operated in two desalination modes: (a) cyclic, in which ions are removed from and released into the same water reservoir and thus, the ion concentration remains the same after one cycle, and (b) continuous, in which ions are removed from one water reservoir and released back in a different reservoir. An average separation factor of ≈15 and 25, reflecting the selectivity of the electrodes, was obtained for Na⁺ over Ca²⁺ and Mg²⁺ from an equimolar solution of Na⁺, Ca²⁺ and Mg²⁺ in both, cyclic and continuous desalination. It was concluded that NiHCF, used in a symmetric CDI cell, is a promising material for highly selective removal of Na⁺ from a multivalent ion mixture.

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This study demonstrates the effective separation of alkali metal cations using a Supported Liquid Membrane (SLM) containing lipophilic, negatively charged borate moieties, operating under electro dialysis conditions. The selectivity of the membrane is essentially based on differences in dehydration energy and mobility between ion species. The system favors the ion species with the largest crystal radius, despite its lower mobility. In mixtures of K⁺ and Na⁺, the SLM separates K⁺ from Na⁺ with a separation efficiency ranging from ~20% to 90%, depending on the feed solution composition. With solutions containing either K⁺ or Na⁺ and Li⁺, the K⁺/Na⁺ over Li⁺ separation efficiency is nearly 100%. Addition of 15-crown-5 derivative does not improve SLM behavior, but slows down the K⁺ current by approximately 30% whereas the Na⁺ current remains unaffected. As supported by simulations, the free K⁺ and Na⁺ ratio in the membrane (and with that the current ratio) is entirely defined by partitioning and the feed concentration ratio, regardless the presence of 15-crown-5. As a result, the current ratio of two ion species can be described exclusively in terms of their feed concentrations and crystal radii because the latter parameter defines both partitioning and mobility.

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A model is presented for the Na⁺ and K⁺ levels in the irrigation water of greenhouses, specifically those for the cultivation of tomato. The model, essentially based on mass balances, not only describes the accumulation of Na⁺ but includes a membrane unit for the selective removal of Na⁺ as well. As determined by the membrane properties, some of the K⁺ is removed as well. Based on real-life process parameters, the model calculates the Na⁺ and K⁺ concentration at three reference points. These process parameters include the evapotranspiration rate, the K⁺ uptake by the plants, the Na⁺ and K⁺ content of the fertilizer, the Na⁺ leaching out from the hydroponic substrate material, and the Na⁺ and K⁺ removal efficiency of the membrane unit. Using these parameters and given a constant K⁺ concentration of the irrigation water entering the greenhouse of 6.6 mM (resulting in the optimal K⁺ concentration for tomato cultivation), the composition of the solution is completely defined at all three reference points per irrigation cycle. Prime aim of this investigation is to explore the requirements for the selective membrane that currently is developed in our lab. It is found that even for a limited Na⁺ over K⁺ selectivity of 6, after a number of cycles the Na⁺ level reaches steady state at a level below the upper (toxic) threshold for tomato cultivation (20 mM). Economic aspects and ways of implementation of such a system are briefly discussed.

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