Role of ion exchange membranes and capacitive electrodes in membrane capacitive deionization (MCDI) for CO2 capture.

Recently we showed that membrane capacitive deionization (MCDI) can be used to capture CO2, but we found that the performance decreases with decreasing current density. In the present study, we investigate the effect of electrodes and ion exchange membranes by performing experiments with two membranes (CO2-MCDI), with one membrane (cation or anion exchange membrane), and without membranes (CO2-CDI). We find that the anion exchange membrane is essential to keep high CO2 absorption efficiencies ( [Formula: see text] /ncharge), while the absorption efficiency of the CO2-CDI cell was lower than expected (Λa≈0.5 for CO2-MCDI against Λa≈0.18 for CO2-CDI). Moreover, we theoretically investigate ion adsorption mechanisms in the electrodes by comparing experimental data of a CO2-CDI cell with theoretical results of the classic amphoteric-Donnan model developed for conventional CDI. By comparing the experimental results with the amph-D model, we find that the model overestimates the absorption efficiency in CO2-CDI experiments. To understand this discrepancy, we investigate the effects of other phenomena, i.e., (i) low ion concentration, (ii) passive CO2 absorption, and (iii) the effect of acid-base reactions on the chemical surface charge.

Solvent-Free CO2 Capture Using Membrane Capacitive Deionization.

Capture of CO2, originating from both fossil fuels, such as coal combustion, and from renewables, such as biogas, appears to be one of the greatest technological challenges of this century. In this study, we show that membrane capacitive deionization (MCDI) can be used to capture CO2 as bicarbonate and carbonate ions produced from the reaction of CO2 with water. This novel approach allows capturing CO2 at room temperature and atmospheric pressure without the use of chemicals. In this process, the adsorption and desorption of bicarbonate ions from the deionized water solution drive the CO2(g) absorption-desorption from the gas phase. In this work, the effects of the current density and the CO2 partial pressure were studied. We found that between 55 and 75% of the electrical charge of the capacitive electrodes can be directly used to absorb CO2 gas. The energy requirement of such a system was found to be ≈40 kJ mol-1 at 15% CO2 and could be further improved by reducing the ohmic and non-ohmic energy losses of the MCDI cell.

Revisiting Morrison and Osterle 1965: the efficiency of membrane-based electrokinetic energy conversion.

We revisit Morrison and Osterle (1965) who derived a phenomenological expression for the 'figure-of-merit' [Formula: see text] of the electrokinetic energy conversion (EKEC) of a pressure difference into electric energy (and vice versa) using charged nanotubes, nanopores or ion-exchange membranes. We show the equivalence with Morrison and Osterle of a novel expression of [Formula: see text] derived by Bentien et al (2013). We analyze two physical models for ionic and solvent flow which directly relate [Formula: see text] to nanopore characteristics such as pore size and wall charge density. For the uniform potential model, we derive an analytical expression as a function of pore size, viscosity, ion diffusion coefficients and membrane charge density, and compare results with the full space-charge model by Osterle and co-workers as a function of pore size and ion diffusion coefficient. We present a novel expression for [Formula: see text] for salt solutions with ions with unequal diffusion coefficients (mobilities) and show that to increase [Formula: see text] the counterion mobility must be low and the coion mobility high.

Energy from CO2 using capacitive electrodes - a model for energy extraction cycles.

A model is presented for the process of harvesting electrical energy from CO2 emissions using capacitive cells. The principle consists of controlling the mixing process of a concentrated CO2 gas stream with a dilute CO2 gas stream (as, for example, exhaust gas and air), thereby converting part of the released mixing energy into electrical energy. The model describes the transient reactive transport of CO2 gas absorbed in water or in monoethanolamine (MEA) solutions, under the assumption of local chemical equilibrium. The model combines the selective transport of ions through ion-exchange membranes, the accumulation of charge in the porous carbon electrodes and the coupling between the ionic current and the produced electrical current and power. We demonstrate that the model can be used to calculate the energy that can be extracted by mixing concentrated and dilute CO2 containing gas streams. Our calculation results for the process using MEA solutions have various counterintuitive features, including: 1. When dynamic equilibrium is reached in the cyclical process, the electrical charge in the anode is negative both during charging and discharging; 2. Placing an anion-exchange membrane (AEM) in the system is not required, the energy per cycle is just as large with or without an AEM.

Energy from CO2 using capacitive electrodes--theoretical outline and calculation of open circuit voltage.

Recently, a new technology has been proposed for the utilization of energy from CO2 emissions (Hamelers et al., 2014). The principle consists of controlling the dilution process of CO2-concentrated gas (e.g., exhaust gas) into CO2-dilute gas (e.g., air) thereby extracting a fraction of the released mixing energy. In this paper, we describe the theoretical fundamentals of this technology when using a pair of charge-selective capacitive electrodes. We focus on the behavior of the chemical system consisting of CO2 gas dissolved in water or monoethanolamine solution. The maximum voltage given for the capacitive cell is theoretically calculated, based on the membrane potential. The different aspects that affect this theoretical maximum value are discussed.

High rate heptanoate production from propionate and ethanol using chain elongation.

Heptanoate (or enanthate), a saturated mono-carboxylate with seven carbon atoms, is a commercially produced biochemical building block with versatile applications. Currently, heptanoate is mainly derived from the oxidation of heptaldehyde, which can be obtained after pyrolysis of castor oil. The objective of this investigation was to achieve efficient high rate heptanoate production using a mixed culture chain elongation process based on propionate and ethanol. An efficient high rate heptanoate production using chain elongation could offer an alternative for heptanoate production from castor oil. The investigation was performed in an upflow anaerobic filter with a hydraulic retention time of 17 h. A heptanoate production rate of 4.5 g l(-1) d(-1) was achieved with a heptanoate concentration of 3.2 g l(-1). These results show sufficient potential to consider this approach as an alternative for heptanoate production from castor oil. Future research should make heptanoate production from propionate and ethanol more cost-effective.

Improving medium chain fatty acid productivity using chain elongation by reducing the hydraulic retention time in an upflow anaerobic filter.

The objective of this investigation was to further increase the medium chain fatty acid (MCFA) production rate by reducing the hydraulic retention time (HRT) in an upflow anaerobic filter. The results showed that the volumetric MCFA production rate was increased to 57.4 g MCFA l(-1) d(-1), more than 3 times higher than previous work. Despite the lower MCFA concentrations at 4h HRT, the MCFA selectivity remained above 80%. Extra carbon dioxide additions and higher yeast extract concentrations were required to increase the MCFA production rate. More research related to substrates and (micro)nutrients in mixed culture continuous reactors needs to be performed to reduce yeast extract use in chain elongation.

Selective carboxylate production by controlling hydrogen, carbon dioxide and substrate concentrations in mixed culture fermentation.

This research demonstrated the selective production of n-butyrate from mixed culture by applying 2 bar carbon dioxide into the headspace of batch fermenters or by increasing the initial substrate concentration. The effect of increasing initial substrate concentration was investigated at 8, 13.5 and 23 g COD/L with potato processing waste stream. Within 1 week of incubation, n-butyrate fraction selectively increased up to 83% by applying 2 bar hydrogen or 78% by applying carbon dioxide into the headspace whereas it was only 59% in the control reactor. Although the fraction of n-butyrate was elevated, the concentration remained lower than in the control. Both the highest concentration and fraction of n-butyrate were observed under the highest initial substrate concentration without headspace addition. The concentration was 10 g COD/L with 73% fraction. The operational conditions obtained from batch experiments for selective n-butyrate production were validated in a continuous process.

Chain elongation of acetate and ethanol in an upflow anaerobic filter for high rate MCFA production.

Recently, interest has regained for medium chain fatty acids (MCFAs) as a low cost feedstock for bio-based chemical and fuel production processes. To become cost-effective, the volumetric MCFA production rate by chain elongation should increase to comparable rates of other fermentation processes. We investigate the MCFA production process at a hydraulic retention time of 17 h in an upflow anaerobic filter to improve the volumetric MCFA production rate. This approach resulted in a MCFA production with a volumetric production rate of 16.6 g l(-1) d(-1), which is more than seven times higher than the current production rate. Moreover the rate is now in the range of other fermentation processes like methane, butanol and ethanol production. Increasing the ethanol load lead to higher volumetric production rates and a high MCFA selectivity of 91%. During operation, methane percentages lower than 0.1% were detected in the headspace of reactor.

Effect of hydrogen and carbon dioxide on carboxylic acids patterns in mixed culture fermentation.

This study investigated the carboxylate spectrum from mixed culture fermentation of three organic waste streams after supplying 2 bar hydrogen and carbon dioxide or a mixture of these two gases to the headspace. Under any modified headspace, propionate production was ceased and butyrate, caproate and the total carboxylate concentrations were higher than in the reactors with N(2) headspace (control). Production of one major compound was achieved under hydrogen and carbon dioxide mixed headspace after 4 weeks of incubation. Both the highest acetate concentration (17.4 g COD/l) and the highest fraction (87%) were observed in reactors with mixed hydrogen and carbon dioxide headspace independent of the substrate used. In the control reactor, acetate made up maximum 67% of the total products. For other products, the highest concentration and fraction were seldom observed together. Selective butyrate production reaching a 75% fraction was found under the carbon dioxide headspace on the carbohydrate rich waste.

Ammonium recovery and energy production from urine by a microbial fuel cell.

Nitrogen recovery through NH(3) stripping is energy intensive and requires large amounts of chemicals. Therefore, a microbial fuel cell was developed to simultaneously produce energy and recover ammonium. The applied microbial fuel cell used a gas diffusion cathode. The ammonium transport to the cathode occurred due to migration of ammonium and diffusion of ammonia. In the cathode chamber ionic ammonium was converted to volatile ammonia due to the high pH. Ammonia was recovered from the liquid-gas boundary via volatilization and subsequent absorption into an acid solution. An ammonium recovery rate of 3.29 g(N) d(-1) m(-2) (vs. membrane surface area) was achieved at a current density of 0.50 A m(-2) (vs. membrane surface area). The energy balance showed a surplus of energy 3.46 kJ g(N)(-1), which means more energy was produced than needed for the ammonium recovery. Hence, ammonium recovery and simultaneous energy production from urine was proven possible by this novel approach.

New plant-growth medium for increased power output of the Plant-Microbial Fuel Cell.

In a Plant-Microbial Fuel Cell anode-conditions must be created that are favorable for plant growth and electricity production. One of the major aspects in this is the composition of the plant-growth medium. Hoagland medium has been used until now, with added phosphate buffer to reduce potential losses over the membrane because of differences in pH between anode and cathode. We developed a new, improved plant-growth medium that improves current production, while the plant keeps growing. This medium is a nitrate-less, ammonium-rich medium that contains all macro- and micro-nutrients necessary for plant growth, with a balanced amount of bicarbonate buffer. Sulphate presence in the plant-growth medium helps to keep a low anode-potential. With the new plant-growth medium the maximum current production of the Plant-Microbial Fuel Cell increased from 186 mA/m(2) to 469 mA/m(2).

Water Desalination with Wires.

We show the significant potential of water desalination using a novel capacitive wire-based technology in which anode/cathode wire pairs are constructed from coating a thin porous carbon electrode layer on top of electrically conducting rods (or wires). By alternately dipping an array of electrode pairs in freshwater with and in brine without an applied cell voltage, we create an ion adsorption/desorption cycle. We show experimentally how in six subsequent cycles we can reduce the salinity of 20 mM feed (brackish) water by a factor of 3, while application of a cation exchange membrane on the cathode wires makes the desalination factor increase to 4. Theoretical modeling rationalizes the experimental findings, and predicts that system performance can be significantly enhanced by material modifications. To treat large volumes of water, multiple stacks of wire pairs can be used simultaneously in a "merry-go-round" operational mode.

Effects of ammonium concentration and charge exchange on ammonium recovery from high strength wastewater using a microbial fuel cell.

Ammonium recovery using a two chamber microbial fuel cell (MFC) was investigated at high ammonium concentration. Increasing the ammonium concentration (from 0.07 to 4 g ammonium-nitrogen/L) by addition of ammonium chloride did not affect the performance of the MFC. The obtained current densities by DC-voltammetry were higher than 6A/m(2) for both operated MFCs. Also continuous operation at lower external resistance (250 Ω) showed an increased current density (0.9A/m(2)). Effective ammonium recovery can be achieved by migrational ion flux through the cation exchange membrane to the cathode chamber, driven by the electron production from degradation of organic substrate. The charge transport was proportional to the concentration of ions. Nonetheless, a concentration gradient will influence the charge transport. Furthermore, a charge exchange process can influence the charge transport and therefore the recovery of specific ions.

Direct power production from a water salinity difference in a membrane-modified supercapacitor flow cell.

The entropy increase of mixing two solutions of different salt concentrations can be harnessed to generate electrical energy. Worldwide, the potential of this resource, the controlled mixing of river and seawater, is enormous, but existing conversion technologies are still complex and expensive. Here we present a small-scale device that directly generates electrical power from the sequential flow of fresh and saline water, without the need for auxiliary processes or converters. The device consists of a sandwich of porous "supercapacitor" electrodes, ion-exchange membranes, and a spacer and can be further miniaturized or scaled-out. Our results demonstrate that alternating the flow of saline and fresh water through a capacitive cell allows direct autogeneration of voltage and current and consequently leads to power generation. Theoretical calculations aid in providing directions for further optimization of the properties of membranes and electrodes.

Concurrent bio-electricity and biomass production in three Plant-Microbial Fuel Cells using Spartina anglica, Arundinella anomala and Arundo donax.

In a Plant Microbial Fuel Cell (P-MFC) three plants were tested for concurrent biomass and bio-electricity production and maximization of power output. Spartina anglica and Arundinella anomala concurrently produced biomass and bio-electricity for six months consecutively. Average power production of the P-MFC with S. anglica during 13weeks was 16% of the theoretical maximum power and 8% during 7weeks for A. anomala. The P-MFC with Arundo donax, did not produce electricity with a stable output, due to break down of the system. The highest obtained power density in a P-MFC was 222mW/m(2) membrane surface area with S. anglica, over twice as high as the highest reported power density in a P-MFC. High biomass yields were obtained in all P-MFC's, with a high root:shoot ratio, probably caused nutrient availability and anaerobia in the soil. Power output maximization via adjusting load on the system lead to unstable performance of the P-MFC.

Selective inhibition of methanogenesis to enhance ethanol and n-butyrate production through acetate reduction in mixed culture fermentation.

Acetate reduction is an alternative digestion process to convert organic waste into ethanol. Using acetate for fuel ethanol production offers the opportunity to use organic waste materials instead of sugar-containing feedstock. Methanogenesis, however, competes with acetate reduction for acetate and hydrogen and lowers the final efficiency. The aim of this research is to selectively inhibit methanogenesis and to enhance acetate reduction. Acetate reduction was stimulated in batch tests at pH between 4.5 and 8; and at pH 6 with and without thermal pre-treatment. It was found that methanogenesis was selectively inhibited while acetate reduction was enhanced after thermal pre-treatment incubated at pH 6. Initially the acetate reduction yielded 7.7+/-3.2mM ethanol with an efficiency of 60.2+/-8.7%, but later on it was consumed to form 7.02+/-0.85 mM n-butyrate with an efficiency of 76.2+/-14.0%. It was the first time demonstrated that n-butyrate can be produced by mixed cultures from only acetate and hydrogen.