Kitty Nijmeijer

Fouling in reverse electrodialysis under natural conditions

Renewable energy can be generated from mixing salt water and fresh water in reverse electrodialysis. The potential for energy generation from mixing seawater and river water is enormous. To investigate the effect of fouling when such natural feed waters are used, the performance of three different setups for reverse electrodialysis was evaluated for 25 days using seawater and river water as feed water, with no other (pre-)treatment than a 20 μm filter. Due to the absence of other anti-fouling treatments, a mixture of fouling is observed on the membranes, composed of remnants of diatoms, clay minerals, organic fouling and scaling. The fouling type was dependent on the different membrane types. The anion exchange membranes attract mainly diatoms and clay minerals, whereas scaling was only found on the cation exchange membranes. As a reference, plastic sheets without charge were used, which results in significant cleaner surfaces. Additionally, the setups without spacers in between the membranes (i.e. profiled membranes) appear significant less sensitive to fouling. This was quantified by the pressure drop over the feed waters and the power density obtained from the membrane piles. The pressure drop increases four times slower and the power density remains higher when profiled membranes are use instead of flat membranes with spacers. Although the obtained power density reduced with approximately 40% in the first day under these conditions, caused by organic fouling, several strategies are available to maintain a high power output using reverse electrodialysis.

Tailor‐Made Anion‐Exchange Membranes for Salinity Gradient Power Generation Using Reverse Electrodialysis

Reverse electrodialysis (RED) or blue energy is a non-polluting, sustainable technology for generating power from the mixing of solutions with different salinity, that is, seawater and river water. A concentrated salt solution (e.g., seawater) and a diluted salt solution (e.g., river water) are brought into contact through an alternating series of polymeric anion-exchange membranes (AEMs) and cation-exchange membranes (CEMs), which are either selective for anions or cations. Currently available ion-exchange membranes are not optimized for RED, whereas successful RED operation notably depends on the used ion-exchange membranes. We designed such ion-exchange membranes and for the first time we show the performance of tailor-made membranes in RED. More specifically, we focus on the development of AEMs because these are much more complex to prepare. Herein we propose a safe and more environmentally friendly method and use halogenated polyethers, such as polyepichlorohydrin (PECH) as the starting material. A tertiary diamine (1,4-diazabicyclo[2.2.2]octane, DABCO) was used to introduce the ion-exchange groups by amination and for simultaneous cross-linking of the polymer membrane. Area resistances of the series of membranes ranged from 0.82 to 2.05 Ω cm² and permselectivities from 87 to 90 %. For the first time we showed that tailor-made ion-exchange membranes can be applied in RED. Depending on the properties and especially membrane thickness, application of these membranes in RED resulted in a high power density of 1.27 W m⁻², which exceeds the power output obtained with the commercially available AMX membranes. This shows the potential of the design of ion-exchange membranes for a viable blue energy process.

Clean energy generation using capacitive electrodes in reverse electrodialysis

Capacitive reverse electrodialysis (CRED) is a newly proposed technology to generate electricity from mixing of salt water and fresh water (salinity gradient energy) by using a membrane pile as in reverse electrodialysis (RED) and capacitive electrodes. The salinity difference between salt water and fresh water generates a potential difference over ion selective membranes, which can be used as a renewable power source. The strength and unique characteristic of CRED in comparison to the other technologies is that it allows multiple membrane cells between a single set of electrodes and at the same time avoids redox reactions using capacitive electrodes. The capacitive electrodes use activated carbon on a support of Ti/Pt mesh to store ions and their charge. A periodic switching of the feed waters, combined with a switching of the direction of the electric current, ensures that the capacitive electrodes do not get saturated. The large membrane pile enables the electrodes to be charged more than in previous approaches for capacitive mixing. As a consequence, the energy cycle of CRED has a larger range in both voltage and accumulated charge compared to previous capacitive mixing technologies. The power density obtainable with CRED stacks with capacitive electrodes is an order of magnitude higher than in previous attempts for capacitive energy extraction and close to or even better than similar RED stacks with conventional redox based electrode systems. CRED is considered to be a stable, safe, clean and high performing technology to obtain energy from mixing of salt water and fresh water.

Subambient temperature CO(2) and light gas permeation through segmented block copolymers with tailored soft phase.

The permeation properties of a series of block copolymers based on poly(ethylene oxide)-ran-poly(propylene oxide) (PEO-ran-PPO) soft segments and monodisperse tetra-amide (T6T6T) hard segments have been studied. The polyether soft segment used in the current study differs from the commonly used pure poly(ethylene oxide) (PEO) soft segment by the fact that it contains 25 wt % randomly distributed poly(propylene oxide) (PPO). The presence of the methyl group of PPO suppresses crystallization of the soft segment and strongly improves the permeability of these materials, especially at subambient temperatures. In addition, the unique monodisperse character of the hard segment ensures a very well phase-separated morphology, resulting in a very pure soft phase. The soft segment length of these block copolymers was varied between 1000 and 10000 g/mol (62-89 wt %). High soft segment concentrations and flexibility were obtained resulting in high CO(2) permeabilities (up to 570 Barrer at 50 degrees C). Due to the random distribution of PPO in the predominantly PEO based soft segment crystallization of PEO was not observed at temperatures as low as -10 degrees C. CO(2) permeabilities exceeding 200 Barrer could be obtained at this low temperature. The CO(2)/light gas selectivity in these materials is governed by the solubility selectivity and consequently only slightly lowered because of the introduction of PPO in the soft segment. Comparison with literature revealed that this block copolymer system has exceptionally high CO(2) permeabilities combined with reasonable CO(2)/light gas selectivities. It is very interesting in CO(2) separation processes where subambient conditions are present (e.g., separation of CO(2) from natural gas), as at these low temperatures, one can take maximum advantage of the increased separation ability of the polymer materials while maintaining excellent transport characteristics.

Charged Micropollutant Removal With Hollow Fiber Nanofiltration Membranes Based On Polycation/Polyzwitterion/Polyanion Multilayers

Hollow fiber nanofiltration membranes can withstand much higher foulant concentrations than their spiral wound counterparts and can be used in water purification without pretreatment. Still, the preparation of hollow fiber nanofiltration membranes is much less established. In this work, we demonstrate the design of a hollow fiber nanofiltration membrane with excellent rejection properties by alternatively coating a porous ultrafiltration membrane with a polycation, a polyzwitterion, and a polyanion. On model surfaces, we show, for the first time, that the polyzwitterion poly N-(3-sulfopropyl)-N-(methacryloxyethyl)-N,N-dimethylammonium betaine (PSBMA) can be incorporated into traditional polyelectrolyte multilayers based on poly(styrenesulfonate) (PSS) and poly(diallyldimethylammonium chloride) (PDADMAC). Furthermore, work on model surfaces allows a good characterization of, and insight into, the layer build-up and helps to establish the optimal membrane coating conditions. Membranes coated with these multilayers have high salt rejection of up to 42% NaCl, 72% CaCl2, and 98% Na2SO4 with permeabilities of 3.7-4.5 l·m(-2)·h(-1)·bar(-1). In addition to the salt rejections, the rejection of six distinctively different micropollutants, with molecular weights between 215 and 362 g·mol(-1), was investigated. Depending on the terminating layer, the incorporation of the polyzwitterion in the multilayer results in nanofiltration membranes that show excellent retentions for both positively and negatively charged micropollutants, a behavior that is attributed to dielectric exclusion of the solutes. Our approach of combining model surfaces with membrane performance measurements provides unique insights into the properties of polyzwitterion-containing multilayers and their applications.

Building polyzwitterion-based multilayers for responsive membranes

We systematically investigate the assembly of multilayers based on a polyzwitterion (PSBMA) and a polycation (PDADMAC) for the development of ionic strength responsive membranes. Although the polyzwitterion is essentially charge neutral, we show that specific electrostatic interactions with the PDADMAC allow for the formation of stable multilayers. The growth of this LbL system is monitored on model surfaces (silica) via optical reflectometry for different pH values and ionic strengths. While no effect of pH on the layer growth is observed, we did observe a strong dependence on the ionic strength. Upon increasing the ionic strength during deposition from 0.005 to 0.5 M NaCl, the adsorbed amount is significantly decreased, a behavior that is opposite to classical LbL systems. Similar results to those obtained on silica are also observed on top of classical LbL systems and on polymeric membranes. This demonstrates that the growth of the polyzwitterion multilayers is independent of the substrate. Coating these polyzwitterion multilayers on hollow fiber membranes via dip-coating yields membranes that are stimuli responsive toward the ionic strength of the filtration solution, with an increase in permeability of up to 108% from 0 to 1.5 M NaCl. We show that the fabrication of the polyzwitterion multilayers is an easy and controlled way to provide surfaces, such as membranes, with the specific functionalities of polyzwitterions.

The Breathing Cell: Cyclic Intermembrane Distance Variation in Reverse Electrodialysis

The breathing cell is a new concept design that operates a reverse electrodialysis stack by varying in time the intermembrane distance. Reverse electrodialysis is used to harvest salinity gradient energy; a rather unknown renewable energy source from controlled mixing of river water and seawater. Traditionally, both river water and seawater compartments have a fixed intermembrane distance. Especially the river water compartment thickness contributes to a large extent to the resistance of the stack due to its low conductivity. In our cyclic approach, two stages define the principle of the breathing concept; the initial stage, where both compartments (seawater and river water) have the same thickness and the compressed stage, where river water compartments are compressed by expanding the seawater compartments. This movement at a tunable frequency allows reducing stack resistance by decreasing the thickness of the river water compartment without increasing permanently the pumping losses. The breathing stacks clearly benefit from the lower resistance values and low pumping power required, obtaining high net power densities over a much broader flow rate range. The high frequency breathing stack (15 cycles/min) shows a maximum net power density of 1.3 W/m2. Although the maximum gross and net power density ever registered (2.9 W/m2 and 1.5 W/m2, respectively) is achieved for a fixed 120 μm intermembrane distance stack (without movement of the membranes), it is only obtained at a very narrow flow rate range due to the high pressure drops at small intermembrane distance. The breathing cell concept offers a unique feature, namely physical movement of the membranes, and thus the ability to adapt to the operational conditions and water quality.

Anisotropic Dye Adsorption and Anhydrous Proton Conductivity in Smectic Liquid Crystal Networks: The Role of Cross-Link Density, Order, and Orientation

In this work, the decisive role of rigidity, orientation, and order in the smectic liquid crystalline network on the anisotropic proton and adsorbent properties is reported. The rigidity in the hydrogen-bonded polymer network has been altered by changing the cross-link density, the order by using different mesophases (smectic, nematic, and isotropic phases), whereas the orientation of the mesogens was controlled by alignment layers. Adding more cross-linkers improved the integrity of the polymer films. For the proton conduction, an optimum was found in the amount of cross-linker and the smectic organization results in the highest anhydrous proton conduction. The polymer films show anisotropic proton conductivity with a 54 times higher conductivity in the direction perpendicular to the molecular director. After a base treatment of the smectic liquid crystalline network, a nanoporous polymer film is obtained that also shows anisotropic adsorption of dye molecules and again straight smectic pores are favored over disordered pores in nematic and isotropic networks. The highly cross-linked films show size-selective adsorption of dyes. Low cross-linked materials do not show this difference due to swelling, which decreases the order and creates openings in the two-dimensional polymer layers. The latter is, however, beneficial for fast adsorption kinetics.

Effect of Divalent Cations on RED Performance and Cation Exchange Membrane Selection to Enhance Power Densities

Reverse electrodialysis (RED) is a membrane-based renewable energy technology that can harvest energy from salinity gradients. The anticipated feed streams are natural river and seawater, both of which contain not only monovalent ions but also divalent ions. However, RED using feed streams containing divalent ions experiences lower power densities because of both uphill transport and increased membrane resistance. In this study, we investigate the effects of divalent cations (Mg2+ and Ca2+) on RED and demonstrate the mitigation of those effects using both novel and existing commercial cation exchange membranes (CEMs). Monovalent-selective Neosepta CMS is known to block divalent cations transport and can therefore mitigate reductions in stack voltage. The new multivalent-permeable Fuji T1 is able to transport divalent cations without a major increase in resistance. Both strategies significantly improve power densities compared to standard-grade CEMs when performing RED using streams containing divalent cations.

Polymer Inclusion Membranes (PIM) for the Recovery of Potassium in the Presence of Competitive Cations

Potassium is an important nutrient used in fertilizers but is not always naturally available We investigated the properties of polymer inclusion membranes (PIM) regarding their selective recovery of K+ over competitive ions typically present in urine (Na+ and NH4+). The greatest flux was observed when the ratio of mass 2-nitrophenyl octyl ether (2-NPOE) used as plasticizer to cellulose triacetate (CTA) used as polymer was 0.25. The highest flux was achieved with a content of 24.8 wt % of dicyclohexan-18-crown-6 (DCH18C6) used as carrier, although the highest selectivity was observed with a content of 14.0 wt % of DCH18C6. We also studied whether the transport mechanism occurring in our system was based on co-transport of a counter-ion or ion exchange. Two different receiving phases (ultrapure water and 100 mM HCl) were tested. Results on transport mechanisms suggest that co-transport of cations and anions is taking place across our PIMs. The membrane deteriorated and lost its properties when the receiving phase was acidic; we suggested that this was due to hydrolysis of CTA. The greatest flux and selectivity were observed in ultrapure water as receiving phase.