Separation of CO2 from flue gas using electrochemical cells

Past research with high temperature molten carbonate electrochemical cells has shown that carbon dioxide can be separated from flue gas streams produced by pulverized coal combustion for power generation. However, the presence of trace contaminants, i.e., sulfur dioxide and nitric oxides, will impact the electrolyte within the cell. If a lower temperature cell could be devised that would utilize the benefits of commercially-available, upstream desulfurization and denitrification in the power plant, then this CO₂ separation technique can approach more viability in the carbon sequestration area. Recent work has led to the assembly and successful operation of a low temperature electrochemical cell. In the proof-of-concept testing with this cell, an anion exchange membrane was sandwiched between gas-diffusion electrodes consisting of nickel-based anode electrocatalysts on carbon paper. When a potential was applied across the cell and a mixture of oxygen and carbon dioxide was flowed over the wetted electrolyte on the cathode side, a stream of CO₂ to O₂ was produced on the anode side, suggesting that carbonate/bicarbonate ions are the CO₂ carrier in the membrane. Since a mixture of CO₂ and O₂ is produced, the possibility exists to use this stream in oxy-firing of additional fuel.From this research, a novel concept for efficiently producing a carbon dioxide rich effluent from combustion of a fossil fuel was proposed. Carbon dioxide and oxygen are captured from the flue gas of a fossil-fuel combustor by one or more electrochemical cells or cell stacks. The separated stream is then transferred to an oxy-fired combustor which uses the gas stream for ancillary combustion, ultimately resulting in an effluent rich in carbon dioxide. A portion of the resulting flow produced by the oxy-fired combustor may be continuously recycled back into the oxy-fired combustor for temperature control and an optimal carbon dioxide rich effluent.     

Effects of imidazolium salts as cocatalysts on the copolymerization of CO2 with epoxides catalyzed by (salen)CrCl complex

Imidazolium salts, most of which are room temperature ionic liquids (ILs), have been introduced as effective and tunable cocatalysts in the copolymerization of CO₂ with epoxides catalyzed by (salen)Cr^IIICl complex for the first time. Effects of imidazolium salts with different alkyl chains as well as with different anions on the copolymerization were investigated. The results showed that the copolymerization was influenced obviously by the property of anion. In addition, the cation of imidazolium salts with longer alkyl chain length such as n-dodecyl (TOF, 242.5 h⁻¹, carbonate linkages > 99%) displays better activities and selectivity in the copolymerization as compared with N-MeIm (TOF, 72.5 h⁻¹, carbonate linkages 94%). These results are instructive for further design of task-specific ILs as effective cocatalysts to improve the copolymerization of CO₂ with epoxides.     

Phase stability and electric conductivity of Er2O3-Nb2O5 co-doped Bi2O3 electrolyte

Two oxides, Er₂O₃ and Nb₂O₃, are used to stabilize delta-phase Bi₂O₃ used as electrolyte of solid oxide fuel cell. Optimization of dopant ratio and total doping concentration (TDC) is determined by X-ray diffraction, and successfully reduce the TDC (Er + Nb) to 10-15 mol.%. Conductivities of different compositions are measured by two-probe method. The results show that highest conductivity appears at the minimum doping concentrations. Phase stability of ENSB samples with Er/Nb ratio of 2/1 and TDC of 10-20 mol.% at 650 °C up to 300 h is analyzed showing two newly formed (alpha- and gamma-) phases in the samples. Degradation of conductivity at 650 °C is studied in detail by DTA and TEM. The abnormity of lattice contraction of delta-phase is discussed.     

Cation driven actuation for free standing PEDOT films prepared from propylene carbonate electrolytes containing TBACF3SO3

Free standing PEDOT [poly(3,4-ethylenedioxythiophene)] films (with surface conductivities of 200-400 S cm⁻¹) were generated in tetrabutylammonium trifluromethanesulfonate (TBACF₃SO₃) electrolytes by potentiostatic (E_P 1.05 V vs. Ag wire) electropolymerisation in propylene carbonate (at −27 °C) and methyl benzoate (at −4 °C). Films obtained in the TBACF₃SO₃ electrolytes showed a length increase of 2-3% during scans to negative potentials under isotonic (constant load 1.35 MPa) and stress of 0.3 MPa under isometric (constant length) conditions. Cation movement occurred due to immobilisation of CF₃SO₃⁻ anions during electropolymerisation. The system showed good stability and low creep during square wave electrochemical cycling in the potential range from 0.0 to 1.0 V. The surface morphology (SEM) of the PEDOT films showed that the polymer structure is dependent upon the solvent used during the polymerisation process.     

The effect of CO2 dissolved in a diesel fuel on the jet flame characteristics

This paper is concerned with an experimental study of the jet diffusion flame characteristics of fuel containing CO₂. Using diesel fuel containing dissolved CO₂ gas, experiments were performed under atmospheric conditions with a diesel hole-type nozzle of 0.19 mm orifice diameter at constant injection pressure. In this study, four different CO₂ mass fraction in diesel fuel such as 3.13%, 7.18%, 12.33% and 17.82% were used to study the effect of CO₂ concentration on the jet flame characteristics. Jet flame characteristics were measured by direct photography, meanwhile the image colorimetry is used to assess the qualitative features of jet flame temperature. Experimental results show that the CO₂ gas dilution effect and the atomization effect have a great influence on the flame structure and average temperature. When the injection pressure of diesel fuel increased from 4 MPa to 6 MPa, the low temperature flame length increased from 18.4 cm to 21.7 cm and the full temperature flame length decreased from 147.6 cm to 134.7 cm. With the increase of CO₂ gas dissolved in the diesel fuel, the jet flame full length decreased for the jet atomization being improved greatly meanwhile the low temperature flame length increased for the CO₂ gas dilution effect; with the increase of CO₂ gas dissolved in the diesel fuel, the average temperature of flame increases firstly and then falls. Experimental results validate that higher injection pressure will improve jet atomization and then increased the flame average temperature.     

Heteropolyacid in glass electrolytes for the development of H2/O2 fuel cells

The scope of the present work was to investigate and evaluate the electrochemical activity of H₂/O₂ fuel cells based on the influence of a heteropolyacid glass membrane with a Pt/C electrode at low temperature. A new trend of sol-gel derived PMA (H₃PMo₁₂O₄₀) heteropolyacid-containing glass membranes inherent of a high proton conductivity and mechanical stability, was heat treated at 600 °C and implemented to H₂/O₂ fuel cell activities through electrochemical characterization. Significant research has been focused on the development of H₂/O₂ fuel cells using optimization of heteropolyacid glasses as electrolytes with Pt/C electrodes at 30 °C. A maximum power density of 23.9 mW/cm² was attained for operation with hydrogen and oxygen, respectively, at 30 °C and 30% humidity with the PMA glass membranes (4-92-4 mol%). Impedance spectroscopy measurements were performed on a total ohmic cell resistance of a membrane-electrode-assembly (MEA) at the end of the experiment.     

Electrocatalyst materials for fuel cells based on the polyoxometalates—K7 or H7[(P2W17O61)Fe(H2O)] and Na12 or H12[(P2W15O56)2Fe4(H2O)2]

Free acids of the iron substituted heteropoly acids (HPA), H₇[(P₂W₁₇O₆₁)Fe^III(H₂O)] (HFe1) and H₁₈[(P₂W₁₅O₅₆)₂Fe^III₂(H₂O)₂] (HFe2) were prepared from the salts K₇[(P₂W₁₇O₆₁)Fe^III(H₂O)] (KFe1) and Na₁₂[(P₂W₁₅O₅₆)₂Fe^III₄(H₂O)₂] (NaFe4), respectively. The iron-substituted HPA were adsorbed on to XC-72 carbon based GDLs to form HPA doped GDEs after water washing with HPA loadings of ca. 1 μmol. The HPA was detected throughout the GDL by EDX. Solution electrochemistry of the free acids are reported for the first time in sulfate buffer, pH 1-3. The hydrogen oxidation reaction was catalyzed by KFe1 at 0.33 V, with an exchange current density of 38 mA/cm². Moderate activity for the oxygen reduction reaction was observed for the iron substituted HPA, which was dramatically improved by selectively removing oxygen atoms from the HPA by cycling the fuel cell cathode under N₂ followed by reoxidation to give a restructured oxide catalyst. The nanostructured oxide achieved an OCV of 0.7 V with a Tafel slope of 115 mV/decade. Cycling the same catalysts in oxygen resulted in an improved catalyst/ionomer/carbon configuration with a slightly higher Tafel slope, 128 mV/decade but a respectable current density of 100 mA/cm² at 0.2 V.     

Synthesis of diethyl carbonate from dimethyl carbonate and ethanol using KF/Al2O3 as an efficient solid base catalyst

Diethyl carbonate, an efficient oxygen-containing fuel additive was synthesized from dimethyl carbonate and ethanol using KF/Al₂O₃. The catalysts prepared with different KF loading were characterized using X-ray diffraction, BET surface area and basicity measurement analyses. The effects of different reaction parameters such as temperature, reactant ratio and amount of catalyst were optimized. Among the different alkali halides, 20 wt.% KF supported on alumina exhibited 61.6% diethyl carbonate selectivity with 96% dimethyl carbonate conversion under optimum reaction conditions. The plausible reaction mechanism is proposed based on the results obtained. The possibility of recycling the catalyst was ensured without appreciable loss in activity for four cycles.     

Study on impedance spectra of La0.7Sr0.3MnO3 and Sm0.2Ce0.8O1.9-impregnated La0.7Sr0.3MnO3 cathode in single chamber fuel cell condition

Impedance spectroscopy was used to study the electrochemical performance of pure and ion-impregnated La_0.7Sr_0.3MnO₃ (LSM) cathodes on YSZ (Y₂O₃-stabilized ZrO₂) electrolytes in single chamber fuel cell conditions, i.e. a mixture gas with oxygen as oxidant, methane as fuel and nitrogen as dilute gas. Measurements were taken at the furnace temperature range of 550-750 °C and the CH₄/O₂ ratios from 1 to 2. Polarization resistances (R_p) for pure and impregnated LSM cathodes increased obviously as the CH₄/O₂ ratio increased at 650-750 °C. Polarization resistances of Sm_0.2Ce_0.8O_1.9 (SDC) impregnated LSM cathode were much smaller than the ones of pure LSM cathode under the same conditions. Overtemperatures were occurred at both cathodes due to the partial oxidation of methane.     

Separation and capture of carbon dioxide from CO2/H2 syngas mixture using semi-clathrate hydrates

The relation between anthropogenic emissions of CO₂ and its increased levels in the atmosphere with global warming and climate change has been well established and accepted. Major portion of carbon dioxide released to the atmosphere, originates from combustion of fossil fuels. Integrated gasification combined cycle (IGCC) offers a promising fossil fuel technology considered as a clean coal-based process for power generation particularly if accompanied by precombustion capture. The latter includes separation of carbon dioxide from a synthesis gas mixture containing 40 mol% CO₂ and 60 mol% H₂.A novel approach for capturing CO₂ from the above gas mixture is to use gas hydrate formation. This process is based on selective partition of CO₂ between hydrate phase and gas phase and has already been studied with promising results. However high-pressure requirement for hydrate formation is a major problem.We have used semiclathrate formation from tetrabutylammonium bromide (TBAB) to experimentally investigate CO₂ capture from a mixture containing 40.2 mol% of CO₂ and 59.8 mol% of H₂. The results shows that in one stage of gas hydrate formation and dissociation, CO₂ can be enriched from 40 mol% to 86 mol% while the concentration of CO₂ in equilibrium gas phase is reduced to 18%. While separation efficiency of processes based on hydrates and semi-clathrates are comparable, the presence of TBAB improves the operating conditions significantly. Furthermore, CO₂ concentration could be increased to 96 mol% by separating CO₂ in two stages.     

A bi-layered composite cathode of La0.8Sr0.2MnO3-YSZ and La0.8Sr0.2MnO3-La0.4Ce0.6O1.8 for IT-SOFCs

A bi-layered composite cathode of La_0.8Sr_0.2MnO₃ (LSM)-YSZ and LSM-La_0.4Ce_0.6O_1.8 (LDC) was fabricated for anode-supported solid oxide fuel cells with a thin YSZ electrolyte film. The cell with the bi-layered composite cathode displayed better performance than the cell with the corresponding single-layered composite cathode of LSM-LDC or LSM-YSZ. At 650 °C, the cell with the bi-layered composite cathode gave a higher maximum power density than the cells with the single-layered LSM-LDC and LSM-YSZ composite cathodes, by 52% and 175%, respectively. The impedance spectra results show that the thin LSM-YSZ interlayer not only improves the cathode/electrolyte interface but also reduces the polarization resistance of the cathode. The activation energy for oxygen reduction on the bi-layered composite cathode is much smaller than that on LSM-YSZ composite cathode, and it is suggested that the special redox property of Ce⁴⁺/Ce³⁺ in LDC facilitates the oxygen reduction process on the bi-layered composite cathode. The cell with the bi-layered composite cathode operated quite stably during a 100 h run.     

Nano-sized Sm0.5Sr0.5CoO3−δ as the cathode for solid oxide fuel cells with proton-conducting electrolytes of BaCe0.8Sm0.2O2.9

Nano-sized Sm_0.5Sr_0.5CoO_3−δ (SSC) was fabricated onto the inner face of porous BaCe_0.8Sm_0.2O_2.9 (BCS) backbone by ion impregnation technique to form a composite cathode for solid oxide fuel cells (SOFCs) with BCS, a proton conductor, as electrolyte. The electro-performance of the composite cathodes was investigated as function of fabricating conditions, and the lowest polarization resistance, about 0.21 Ω cm² at 600 °C, was achieved with BCS backbone sintered at 1100 °C, SSC layer fired at 800 °C, and SSC loading of 55 wt.%. Impedance spectra of the composite cathodes consisted of two depressed arcs with peak frequency of 1 kHz and 30 Hz, respectively, which might correspond to the migration of proton and the dissociative adsorption and diffusion of oxygen, respectively. There was an additional arc peaking at 1 Hz in the Nyquist plots of a single cell, which should correspond to the anode reactions. With electrolyte about 70 μm in thickness, the simulated anode, cathode and bulk resistances of cells were 0.021, 0.055 and 0.68 Ω cm² at 700 °C, relatively, and the maximum power density was 307 mW cm⁻² at 700 °C.     

Determination of open-circuit potentials at gas/electrode/YSZ boundary versus molten carbonate reference electrode at medium temperatures: I. Potentials of Au and Pt in O2 and H2 + H2O atmospheres

A double gas concentration cell as combination of the cell with the yttria stabilized zirconia (YSZ) electrolyte and the cell with molten Li₂CO₃ + Na₂CO₃ eutectics is proposed as an alternative cell system with a standard reference electrode for measurements of the open-circuit potential (OCP) values of electrodes in oxygen concentration cell with the yttria stabilized zirconia (YSZ) electrolyte. In this double-cell one electrode is common for the two cells and the reference electrode is the standard molten carbonate half-cell with 0.33O₂ + 0.67CO₂ atmosphere. This reference electrode should enable the monitoring of OCP and overpotential values in polarization studies in the three-electrodes configuration. If the possible reaction between the solid YSZ and liquid molten carbonates electrolyte is very slow, the measured values of the open-circuit-voltage (OCV) of this cell may be considered equal to the respective reversible electromotive forces (EMF). Very good resistance of the smooth YSZ products to the corrosion in highly dehydrated Li/Na molten carbonates has been shown in experiments lasting few 1000 h. Hence, the consistency of OCV values with the respective EMF values have been tested at various partial pressures of CO₂ and O₂ in the gas mixtures above the molten carbonate electrolyte and at various partial pressures of O₂ + Ar or H₂ + H₂O gas mixtures at the Au or Pt electrodes/YSZ interface. The results have shown the reliability of the double-cell in determination of the open-circuit potentials (OCP) of gas electrodes at the YSZ surface as measured versus the reference electrode with molten carbonate electrolyte. The consistency of OCP and EMF values has been shown satisfying and enhances to use the proposed double-cell in further investigations of OCP and overpotential values at TPB of electrode/YSZ/mixture of reacting gases. At high differences of O₂ partial pressures on both sides of the YSZ membrane some permeation of this gas through the YSZ membrane has been observed. Probably, this effect has an electrochemical character.     

Structural, thermal and mechanical properties of transparent Yb:(Y0.97Zr0.03)2O3 ceramic

Yb doped (Y_0.97Zr_0.03)₂O₃ transparent ceramics were fabricated by solid state reaction and vacuum sintering. The microstructure, thermal and mechanical properties of Y₂O₃ ceramic, as well as the effect of Yb doping concentration on these properties were investigated in detail. The lattice parameter and unit cell volume decrease with the increasing of Yb content, whereas thermal expansive coefficient increases. With Yb content increasing from 0 to 8 at.%, the mean grain size increases from 15.82 μm to 26.54 μm, and the thermal conductivity at room temperature (RT) decreases from 11.97 to 6.39 W/m/K. The microhardness decreases with Yb content, and the microhardness and fracture toughness of (Y_0.97Zr_0.03)₂O₃ transparent ceramic is 11.11 GPa and 1.29 MPa m^1/2, respectively.     

Coal devolatilization and char conversion under suspension fired conditions in O2/N2 and O2/CO2 atmospheres

The aim of the present investigation is to examine differences between O₂/N₂ and O₂/CO₂ atmospheres during devolatilization and char conversion of a bituminous coal at conditions covering temperatures between 1173 K and 1673 K and inlet oxygen concentrations between 5 and 28 vol.%. The experiments have been carried out in an electrically heated entrained flow reactor that is designed to simulate the conditions in a suspension fired boiler. Coal devolatilized in N₂ and CO₂ atmospheres provided similar results regarding char morphology, char N₂-BET surface area and volatile yield. This strongly indicates that a shift from air to oxy-fuel combustion does not influence the devolatilization process significantly. Char combustion experiments yielded similar char conversion profiles when N₂ was replaced with CO₂ under conditions where combustion was primarily controlled by chemical kinetics. When char was burned at 1573 K and 1673 K a faster conversion was found in N₂ suggesting that the lower molecular diffusion coefficient of O₂ in CO₂ lowers the char conversion rate when external mass transfer influences combustion. The reaction of char with CO₂ was not observed to have an influence on char conversion rates at the applied experimental conditions.     

Influence of temperature and relative humidity on performance and CO tolerance of PEM fuel cells with Nafion-Teflon-Zr(HPO4)2 higher temperature composite membranes

The carbon monoxide (CO) poisoning effect on carbon supported catalysts (Pt-Ru/C and Pt/C) in polymer electrolyte membrane (PEM) fuel cells has been investigated at higher temperatures (T > 100 °C) under different relative humidity (RH) conditions. To reduce the IR losses in higher temperature/lower relative humidity, Nafion^®-Teflon^®-Zr(HPO₄)₂ composite membranes were applied as the cell electrolytes. Fuel cell polarization investigation as well as CO stripping voltammetry measurements was carried out at three cell temperatures (80, 105 and 120 °C), with various inlet anode relative humidity (35%, 58% and 100%). CO concentrations in hydrogen varied from 10 ppm to 2%. The fuel cell performance loss due to CO poisoning was significantly alleviated at higher temperature/lower RH due to the lower CO adsorption coverage on the catalytic sites, in spite that the anode catalyst utilization was lower at such conditions due to higher ionic resistance in the electrode. Increasing the anode inlet relative humidity at the higher temperature also alleviated the fuel cell performance losses, which could be attributed to the combination effects of suppressing CO adsorption, increasing anode catalyst utilization and favoring OH_ads group generation for easier CO oxidation.     

Modeling of H2O2 formation in PEMFCs

A model for H₂O₂ formation, transport, and reaction in PEMFCs is established for the first time. Profiles of oxygen and H₂O₂ concentration inside the fuel cell are simulated using the agglomerate model for the electrode. The predicted concentration of H₂O₂ shows the same trend as experimental data under different conditions, but the level was only of the same magnitude. Low humidity, high temperature, and high oxygen/hydrogen partial pressures were found to increase the concentration of H₂O₂. An increase in membrane thickness or metal ion contaminant level reduces the concentration of H₂O₂ in the membrane. Lowering the oxygen permeability in the ionomer is the most important and effective method to reduce the formation of H₂O₂. The simulation results also show little change in H₂O₂ concentration while operating the fuel cell above 0.6 V. Anodes designed with considerable thickness, high catalyst loadings and active areas can also help to suppress H₂O₂ formation. Finally, recommendations are made to mitigate the effects of H₂O₂ and prolong membrane lifetimes.     

Pyrolysis of cellulose, xylan and lignin with the K2CO3 and ZnCl2 addition for bio-oil production

The chemical structure of liquid products of the wood biopolymers, i.e. cellulose, xylan and lignin pyrolysis at 450 °C with and without the 10 wt.% addition of potassium carbonate or zinc chloride was investigated. The yield of liquid products of pyrolysis was in the range of 24-44 wt.% and their form was depending on the chemical structure of pyrolyzed material. The potassium carbonate and zinc chloride addition to biopolymers has also influenced the temperature range of samples decomposition as well as the structure of resulted bio-oils. All bio-oils from biopolymer were dark-brown water-oil emulsions. Contrarily, bio-oils obtained from biopolymer with K₂CO₃ or ZnCl₂ addition were orange liquids with well-separated water and oil phases. All analyses proved that the composition and the quality of bio-oil strongly depends on both the nature of the starting sample and the presence of the additive. The FT-IR analyses of oils showed that oxygen functionalities and hydrocarbons contents highly depend on the type of biopolymer. Results confirmed the significant removal and/or transformation of oxygen containing organic compounds due to the zinc chloride and potassium carbonate presence during pyrolysis process.     

Synthesis of CeAlO3/CeO2-Al2O3 for use as a solid oxide fuel cell functional anode material

A composite electrocatalyst was developed to be fitted for the purpose of satisfying the features required for use as a solid oxide fuel cell functional anode material. The main functionality searched for was the ability to make the direct oxidation of carbon containing fuels in an SOFC without being severely coked. The present paper deals with the synthesis and characterization of such material. Therefore, ceramic electrocatalysts composed of CeAlO₃, CeO₂ and Al₂O₃ were synthesized by the amorphous citrate method and calcined at temperatures ranging from 300 °C to 900 °C. The synthesis procedures were designed to produce nanometric sized powders for which the calcination conditions were selected in order to fulfill requirements such as ease to be sintered; formation of selected phases upon calcinations at different temperatures; particle size control; surface area and morphology well suited for the production of ceramic suspensions to be processed into an SOFC functional anode. The main results have shown that increasing the calcination temperature under an oxidizing atmosphere induces the CeAlO₃ phase with a tetragonal perovskite type structure to undergo a phase transformation to CeO₂ (and Al₂O₃) with cubic fluorite type structure. However, the structure is able to be reversed and reduced back to the CeAlO₃ phase if calcined under a hydrogen atmosphere. The increase in the calcination temperature increases the particle average size, reduces the surface area and increases the material density, considering the same phase and crystalline structure. It was shown that the synthesis and calcinations procedures hinder the crystallographic identification of the presence of alumina.     

Solubility of CO2 in aqueous solutions of NaCl, KCl, CaCl2 and their mixed salts at different temperatures and pressures

The solubility of CO₂ in water and aqueous solutions of NaCl, KCl, CaCl₂, NaCl + KCl (weight ratio = 1:1), NaCl + CaCl₂ (weight ratio = 1:1), KCl + CaCl₂ (weight ratio = 1:1), and NaCl + KCl + CaCl₂ (weight ratio = 1:1:1) was determined at 35.0, 45.0 and 55.0 °C up to 16 MPa, and the concentration of the salt was up to 14.3 wt%. It was demonstrated that solubility increased with increase in pressure, and decreased with increasing temperature. Addition of a salt or salt mixture resulted in reduction in the solubility due to the salting-out effect. At the same salt concentration (wt%), the salting-out effect of KCl was considerably smaller than those of NaCl and CaCl₂. The salting-out effect of a salt mixture is between those of its components.