Online analysis of carbon dioxide from a direct ethanol fuel cell

Carbon dioxide yields from a direct ethanol fuel cell have been monitored by using a commercial infrared CO₂ monitor. The time dependence is reported as a function of temperature, current density, and anode catalyst (Pt vs. PtRu). Yields increased strongly with temperature, with a Faradaic yield of 76% being obtained at 100 °C with a Pt black anode. PtRu gave lower yields than Pt by a factor of ca. 3 at 80 and 100 °C, but higher yields than Pt at ambient temperature. The superior ability of PtRu to strip adsorbed CO is important at low temperatures, but not a key factor at 100 °C.     

Effect of gas flow rates and Boudouard reactions on the performance of Ni/YSZ anode supported solid oxide fuel cells with solid carbon fuels

The effects of carrier gas flow rates and Boudouard reaction on the performance of Ni/YSZ anode-supported solid oxide fuel cells (SOFCs) have been studied with coconut coke fuels at 800 °C. Decreasing flow rates of carrier gas from 1000 to 50 ml min⁻¹ increased open circuit voltages and current densities from 0.71 to 0.87 V and from 0.12 to 0.34 A cm⁻², respectively. The increased cell performance was attributed to the increasing extent of electrochemical oxidation of CO, a product of Boudouard reaction. The contribution of CO oxidation to current generation was estimated to 66% in flowing inert carrier gas at 50 ml min⁻¹. The pulse transient studies confirmed the effect of flow rates on cell performance and also revealed that CO and CO₂ can displace adsorbed hydrogen on carbon fuels. Flowing CO₂ over coconut coke fuel produced CO via Boudouard reaction. The presence of CO led to a highest power density of 95 mW cm⁻², followed by a concurrent decline of power density and CO concentration. The declined power density along with decreasing CO concentration further verified contribution of gaseous CO to the power generation of C-SOFC; the decreasing CO concentration showed a typical kinetics behavior of Boudouard reaction, suggesting the loss of active sites on carbon surface for the reaction.     

Partial oxidation of ethanol in a membrane reactor for high purity hydrogen production

Partial oxidation of ethanol was performed in a dense Pd–Ag membrane reactor over Rh/Al₂O₃ catalyst in order to produce a pure or, at least, CO_x-free hydrogen stream for supplying a PEM fuel cell. The membrane reactor performances have been evaluated in terms of ethanol conversion, hydrogen yield, CO_x-free hydrogen recovery and gas selectivity working at 450 °C, GHSV ∼ 1300 h⁻¹, O₂:C₂H₅OH feed molar ratio varying between 0.33:1 and 0.62:1 and in a reaction pressure range from 1.0 to 3.0 bar. As a result, complete ethanol conversion was achieved in all the experimental tests. A small amount of C₂H₄ and C₂H₄O formation was observed during reaction. At low pressure and feed molar ratio, H₂ and CO are mainly produced, while at stronger operating conditions CH₄, CO₂ and H₂O are prevalent compounds. However, in all the experimental tests no carbon formation was detected. As best results of this work, complete ethanol conversion and more than 40.0% CO_x-free hydrogen recovery were achieved.     

Carbon monoxide-fueled solid oxide fuel cell

This study explored CO as a primary fuel in anode-supported solid oxide fuel cells (SOFCs) of both tubular and planar geometries. Tubular single cells with active areas of 24 cm² generated power up to 16 W. Open circuit voltages for various CO/CO₂ mixture compositions agreed well with the expected values. In flowing dry CO, power densities up to 0.67 W cm⁻² were achieved at 1 A cm⁻² and 850 °C. This performance compared well with 0.74 W cm⁻² measured for pure H₂ in the same cell and under the same operating conditions. Performance stability of tubular cells was investigated by long-term testing in flowing CO during which no carbon deposition was observed. At a constant current of 9.96 A (or, 0.414 A cm⁻²) power output remained unchanged over 375 h of continuous operation at 850 °C. In addition, a 50-cell planar SOFC stack was operated at 800 °C on 95% CO (balance CO₂), which generated 1176 W of total power at a power density of 224 mW cm⁻². The results demonstrate that CO is a viable primary fuel for SOFCs.     

Hydrogen purification using compact pressure swing adsorption system for fuel cell

Adsorption of CO and CO₂ in mixtures of H₂/CO/CO₂ was achieved using compact pressure swing adsorption (CPSA) system to produce purified hydrogen for use in fuel cell. A CPSA system was designed by combining four adsorption beds that simultaneously operate at different processes in the pressure swing adsorption (PSA) process cycle. The overall diameter of the cylindrical shell of the CPSA is 35 cm and its height is 40 cm. Several suitable adsorbent materials for CO and CO₂ adsorption in a hydrogen stream were identified and their adsorption properties were tested. Activated carbon from Sigma–Aldrich was the adsorbent chosen. It has a surface area of 695.07 m²/g. CO adsorption capacity (STP) of 0.55 mmol/g and CO₂ at 2.05 mmol/g were obtained. The CPSA system has a rapid process cycle that can supply hydrogen continuously without disruption by the regeneration process of the adsorbent. The process cycle in each column of the CPSA consists of pressurization, adsorption, blowdown and purging processes. CPSA is capable of reducing the CO concentration in a H₂/CO/CO₂ mixture from 4000 ppm to 1.4 ppm and the CO₂ concentration from 5% to 7.0 ppm CO₂ in 60 cycles and 3600 s. Based on the mixture used in the experimental work, the H₂ purity obtained was 99.999%, product throughput of 0.04 kg H₂/kg adsorbent with purge/feed ratio was 0.001 and vent loss/feed ratio was 0.02. It is therefore concluded that the CPSA system met the required specifications of hydrogen purity for fuel cell applications.     

Ethanol electrooxidation on a carbon-supported Pt catalyst at elevated temperature and pressure: A high-temperature/high-pressure DEMS study

The electrooxidation of ethanol on a Pt/Vulcan catalyst was investigated in model studies by on-line differential electrochemical mass spectrometry (DEMS) over a wide range of reaction temperatures (23–100 °C). Potentiodynamic and potentiostatic measurements of the Faradaic current and the CO₂ formation rate, performed at 3 bar overpressure under well-defined transport and diffusion conditions reveal significant effects of temperature, potential and ethanol concentration on the total reaction activity and on the selectivity for the pathway toward complete oxidation to CO₂. The latter pathway increasingly prevails at higher temperature, lower concentration and lower potentials (∼90% current efficiency for CO₂ formation at 100 °C, 0.01 M, 0.48 V), while at higher ethanol concentrations (0.1 M), higher potentials or lower temperatures the current efficiency for CO₂ formation drops, reaching values of a few percent at room temperature. These trends result in a significantly higher apparent activation barrier for complete oxidation to CO₂ (68 ± 2 kJ mol⁻¹ at 0.48 V, 0.1 M) compared to that of the overall ethanol oxidation reaction determined from the Faradaic current (42 ± 2 kJ mol⁻¹ at 0.48 V, 0.1 M). The mechanistic implications of these results and the importance of relevant reaction and mass transport conditions in model studies for reaction predictions in fuel cell applications are discussed.     

Hydrogen production and end-product synthesis patterns by Clostridium termitidis strain CT1112 in batch fermentation cultures with cellobiose or α-cellulose

Hydrogen (H₂) production and end-product synthesis were characterized in a novel, mesophilic, cellulolytic, anaerobic bacterium, Clostridium termitidis strain CT1112, isolated from the gut of the termite, Nasutitermes lujae. Growth curves, pH patterns, protein content, organic acid synthesis, and H₂ production were determined. When grown on 2 g l⁻¹ cellobiose and 2 g l⁻¹ α-cellulose, C. termitidis displayed a cell generation time of 6.5 h and 18.9 h, respectively. The major end-products synthesized on cellobiose included acetate, hydrogen, CO₂, lactate, formate and ethanol, where as on cellulose, the major end-products included hydrogen, acetate, CO₂ and ethanol. The concentrations of acetate were greater than ethanol, formate and lactate on both cellobiose and α-cellulose throughout the entire growth phase. Maximum yields of acetate, ethanol, hydrogen and formate on cellobiose were 5.9, 3.7, 4.6 and 4.2 mmol l⁻¹ culture, respectively, where as on cellulose, the yields were 7.2, 3.1, 7.7 and 2.9 mmol l⁻¹ culture, respectively. Hydrogen and ethanol production rates were slightly higher in C. termitidis cultured on cellobiose when compared to α-cellulose. Although, the generation time on α-cellulose was longer than on cellobiose, H₂ production was favored corresponding to acetate synthesis, thereby restricting the carbon flowing to ethanol. During log phase, H₂, CO₂ and ethanol were produced at specific rates of 4.28, 5.32, and 2.99 mmol h⁻¹ g dry weight⁻¹ of cells on cellobiose and 2.79, 2.59, and 1.1 mmol h⁻¹ g dry weight⁻¹ of cells on α-cellulose, respectively.     

In situ spectroelectrochemical measurements during the electro-oxidation of ethanol on WC-supported Pt-black. Part II: Monitoring of catalyst aging by in situ Fourier transform infrared spectroscopy

As a continuation of a project on the spectroelectrochemical analysis of long-term behaviour of WC-supported Pt electrocatalysts (for SFG results, see part I: [1]), in this paper we report in situ FT-IR spectroscopy experiments, carried out during prolonged electro-oxidation of ethanol on Pt-black. From the analytical point of view, as expected, FT-IR spectra showed the presence of adsorbed acetic acid and ethanol, in addition to the well-known, dominant species: linearly adsorbed CO (2044-2063 cm⁻¹) and solution-phase CO₂ (2345 cm⁻¹). As far as quantitative spectroscopic results are concerned, a notable sensitivity of the interfacial chemistry to catalyst aging could be highlighted by this approach. The spectra recorded in three subsequent series of potential-cycling experiments showed a clear-cut dependence of spectral patterns and peak intensities, on the applied potential and on the oxidation duration. Qualitative spectral changes seem to suggest - coherently with in situ SFG results obtained with the same system [1] - that electrocatalyst aging correlates with a higher surface coverage with ethanol as compared with acetic acid. Quantitative analysis, based on fitting with Lorentzian lineshapes, yields information that can be used as a molecular-level diagnostic of the modification of the catalyst-adsorbate structure.     

Homolytic cleavage C-C bond in the electrooxidation of ethanol and bioethanol

Nowadays, the studies are focused on the search of better electrocatalysts that promote the complete oxidation of ethanol/bioethanol to CO₂. To that end, amorphous bi-catalytic catalysts of composition Ni₅₉Nb₄₀Pt_1−xY_x (Y = Cu, Ru, x = 0.4% at.) have been developed, obtained by mechanical alloying, resulting in higher current densities and an improvement in tolerance to adsorbed CO vs. Ni₅₉Nb₄₀Pt₁ catalyst. By using voltammetric techniques, the appearance of three oxidation peaks can be observed. The first peak could be associated with the electrooxidative process of ethanol/bioethanol to acetaldehyde, the second peak could be the oxidation of acetaldehyde to acetic acid, and the last peak might be the final oxidation to CO₂. Chrono-amperometric experiments show qualitative poisoning of catalytic surfaces. However, the in situ Fourier Transformed Infrared Spectroscopy, FTIR, is used for the quasi-quantitative determination with which can be observed the appearance and evolution of different vibrational bands of carbonyl and carboxylic groups of different species, as it moves towards anodic potential in the electrooxidative process.     

H2 production from stable ethanol steam reforming over catalyst of NiO based on flowerlike CeO2 microspheres

Catalyst of nickle oxide based on flowerlike cerium microspheres with high dispersion was made to achieve simultaneous dehydrogenation of ethanol and water molecules on multi-active sites. XRD, 77 K N₂ adsorption and FESEM were applied to analyse and observe the catalyst's structure, porosity and morphology. This special morphology catalyst represented novel stability more than 600 h for hydrogen production at low temperature ethanol steam reforming. Ethanol-water mixtures could be converted into H₂ with average selectivity value of 61.5 mol.% and average ethanol conversion 95.0 mol.% at 350 °C, with GHSV∼1.0 × 10⁵ h⁻¹, low CO selectivity about average value of 2.1 mol.%, during 550 h reforming stability test. Catalytic parameters with respect to yield of H₂, activity, selectivity towards hydrogen production and stability with time on stream were determined.     

Thermodynamic analysis of ethanol steam reforming using Gibbs energy minimization method: A detailed study of the conditions of carbon deposition

In this paper, a thermodynamic analysis of ethanol/water system, using the Gibbs energy minimization method, has been carried out. A mathematical relationship between Lagrange's multipliers and carbon activity in the gas phase was deduced. From this, it was possible to calculate carbon activities in both stable and metastable systems. For the system that corresponds to ethanol steam reforming at very low contact times, composed mainly of ethylene and acetaldehyde, carbon activities were always much greater than unity over the whole temperature range, changing from 1.2 × 10⁷ at 400 K to 1.1 × 10⁴ at 1200 K. Furthermore, there was practically no effect of the inlet steam/ethanol ratio on carbon activity values. These results indicate that such a system is highly favorable to carbon formation. On the other hand, by considering a more stable system, in order to represent high contact times, it was observed that carbon activities are much lower and depend greatly on the inlet steam/ethanol ratio employed. Besides, the complete conversion of ethylene and acetaldehyde into other species, such as CO, CO₂, CH₄ and H₂, lowers the total Gibbs energy of the system. By computing carbon activities in experimental systems, it was also possible to explain deviations between thermodynamic analysis and experimental results regarding carbon deposition.     

Ethanol oxidation on PtRuMo/C catalysts: In situ FTIR spectroscopy and DEMS studies

The electrooxidation of ethanol on carbon supported PtRuMo nanoparticles of different Mo compositions has been studied in the temperature range of 30–70 °C. Current–time curves have shown an increase of the current density with the Mo introduction during the ethanol oxidation at 0.5 V in a whole temperature range. The incorporation of different amount of MoO_x (∼Mo⁵⁺) like species over PtRu systems produces ternary catalyst with similar structural characteristics as particle size or crystal phases, but the catalytic behavior depended on both the surface amount of Mo and on the applied potential. In situ spectroelectrochemical studies have been used to identity adsorbed reaction intermediates and products (in situ Fourier transform infrared spectroscopy, FTIR) and volatile reaction products (differential electrochemical mass spectrometry, DEMS). For all catalysts, incomplete ethanol oxidation to C2 products (acetaldehyde and acetic acid) prevails under the conditions selected in this study. The higher CO tolerance of PtRuMo/C catalysts at very low potentials (<0.3 V) results to minimum or no CO poisoning of the Pt and Ru surfaces, in contrast to the PtRu/C catalyst, which are rapidly blocked by CO. Therefore, catalyst with higher amount of Mo allows a fast “replenishment” of the active sites leading to the formation of acetaldehyde and, especially, acetic acid at potentials above 0.3 V.     

A high performance composite ionic conducting electrolyte for intermediate temperature fuel cell and evidence for ternary ionic conduction

The performance of a composite electrolyte composed of a samarium doped ceria (SDC) and a ternary eutectic carbonate melt phase was examined. The formation temperature of a continuous carbonate melt phase is crucial to the high conductivity of this material. The electrolyte contains 30 and 50 wt% carbonate exhibited a sharp increase of conductivity at a temperature close to the melting point of the eutectic carbonate, ca 400 °C, which is more than 100 °C lower than those electrolytes using binary carbonate. At around 650 °C, and with CO₂/O₂ used as the cathode gas, the fuel cell gave a power output 720 mW cm⁻² at a current density 1300 mA cm⁻². Water was measured in both the anode and cathode outlet gases and CO₂ was detected in the anode outlet gas. When discharged at 800 mA cm⁻², a stable discharge plateau was obtained. The CO₂ in the cathode gas enhances the power output and the stability of the single cell. Based on these experimental facts, a ternary ionic conducting scheme is proposed and discussed.     

Hydrogen production by steam reforming of ethanol over an Ir/CeO2 catalyst: Reaction mechanism and stability of the catalyst

Steam reforming of ethanol over an Ir/CeO₂ catalyst has been studied with regard to the reaction mechanism and the stability of the catalyst. It was found that ethanol dehydrogenation to acetaldehyde was the primary reaction, and acetaldehyde was then decomposed to methane and CO and/or converted to acetone at low temperatures. Methane was further reformed to H₂ and CO, and acetone was directly converted into H₂ and CO₂. Addition of CO, CO₂, and CH₄ to the water/ethanol mixture proved that steam reforming of methane and the water gas shift were the major reactions at high temperatures. The Ir/CeO₂ catalyst displayed rather stable performance in the steam reforming of ethanol at 650 °C even with a stoichiometric feed composition of water/ethanol, and the effluent gas composition remained constant for 300 h on-stream. The CeO₂ in the catalyst prevented the highly dispersed Ir particles from sintering and facilitated coke gasification through strong Ir–CeO₂ interaction.     

Hydrogen production by sorption enhanced steam reforming of oxygenated hydrocarbons (ethanol, glycerol, n-butanol and methanol): Thermodynamic modelling

Thermodynamic analysis of steam reforming of different oxygenated hydrocarbons (ethanol, glycerol, n-butanol and methanol) with and without CaO as CO₂ sorbent is carried out to determine favorable operating conditions to produce high-quality H₂ gas. The results indicate that the sorption enhanced steam reforming (SESR) is a fuel flexible and effective process to produce high-purity H₂ with low contents of CO, CO₂ and CH₄ in the temperature range of 723-873 K. In addition, the separation of CO₂ from the gas phase greatly inhibits carbon deposition at low and moderate temperatures. For all the oxygenated hydrocarbons investigated in this work, thermodynamic predictions indicate that high-purity hydrogen with CO content within 20 ppm required for proton exchange membrane fuel cell (PEMFC) applications can be directly produced by a single-step SESR process in the temperature range of 723-773 K at pressures of 3-5 atm. Thus, further processes involving water-gas shift (WGS) and preferential CO oxidation (COPROX) reactors are not necessary. In the case of ethanol and methanol, the theoretical findings of the present analysis are corroborated by experimental results from literature. In the other cases, the results could provide an indication of the starting point for experimental research. At P = 5 atm and T = 773 K, it is possible to obtain H₂ at concentrations over 97 mol% along with CO content around 10 ppm and a thermal efficiency greater than 76%. In order to achieve such a reformate composition, the optimized steam-to-fuel molar ratios are 6:1, 9:1, 12:1 and 4:1 for ethanol, glycerol, n-butanol and methanol, respectively, with CaO in the stoichiometric ratio to carbon atom.     

Effect of nickel loading on hydrogen production and chemical oxygen demand (COD) destruction from glucose oxidation and gasification in supercritical water

Gasification and partial oxidation of 0.25 molar glucose solution was conducted over different metallic nickel (Ni) loadings (7.5, 11, and 18 wt%) on different catalyst supports (θ-Al₂O₃ and γ-Al₂O₃) in supercritical water. Experiments were carried out at three different temperatures (T) of 400, 450, and 500 °C at constant pressure of 28 MPa and a 30 min reaction time (t). For comparison, some experiments were conducted using high loading commercial catalyst (65 wt% Ni on Silica–alumina). Hydrogen peroxide (H₂O₂) was used as a source of oxygen in the partial oxidation experiments. Oxygen to carbon molar ratios (MR) of 0.5–0.9 were examined to increase the hydrogen production via carbon monoxide (CO) production. Results showed that in the absence of the catalyst, the optimum molar ratio was 0.8 i.e. 80% of the amount of oxygen required for complete oxidation of glucose. At a molar ratio of 0.8, the hydrogen yield was 0.3 mol/mol, as compared to 0.2 mol/mol glucose at molar ratio of 0.5 and 0.9. This optimized oxygen dose was adopted as a base line for catalysts evaluation. The main gaseous products were carbon dioxide (CO₂), carbon monoxide (CO), hydrogen (H₂), and methane (CH₄). Results also showed that the presence of Ni increased the total gas yield increased in the 7.5–18 wt Ni/Al₂O₃ catalyst. An increase in MR from 0.55 to 0.8 increased the of carbon dioxide and hydrogen yields from 1.8 to 3.8 mol/mol glucose and from 0.9 to 1.1 mol/mol. The carbon monoxide and methane yields remain constant at 2 and 0.5 mol/mol glucose, respectively. The introduction of hydrogen peroxide (H₂O₂) prior to the feed injection inhibited the catalyst activity and did not increase the hydrogen yield whereas the introduction of H₂O₂ after 15 min of reaction time increased the hydrogen yield from 0.62 mol/mol to 1.5 mol/mol. This study showed that approximately the same hydrogen yield can be obtained from the synthesized low nickel alumina loading (18 wt%) catalyst as with the 65 wt% nickel on silica–alumina loading commercial catalyst. The highest H₂ yield of 1.5 mol/mol glucose was obtained with commercial Ni/silica–alumina with a BET surface area of 190 m²/g compared to 1.2 mol/mol with the synthesized Ni/θ alumina with a BET surface area of 46 m²/g.     

Selection of yeast strains for alcoholic fermentation of sugar beet thick juice and green syrup

Presented work aimed at determination of effect of various strains of yeast Saccharomyces cerevisiae and concentration of fermentation worts on dynamics and efficiency of alcoholic fermentation. Fermentation worts contained either thick juice or green syrup.It was found that yeast strains designated as M₁, M₂ and D-2 most efficiently fermented thick juice worts inoculated with yeast cream at a rate of 2 kg m⁻³ of wort. Fermentation processes lasted for approximately 2 days and ethanol yield approached 92-94% of the theoretical yield. Fermentations of green syrup worts were most efficient (ethanol yield reached 90-92% of the theoretical yield) when these processes were carried out by yeast strains M₁, M₂, D-2 and As4 (inoculum - 2 kg m⁻³ of wort).S. cerevisiae strains M₁ and M₂ dynamically and efficiently fermented thick juice worts with extract of 200 g kg⁻¹ and 250 g kg⁻¹ (89-94% of the theoretical yield) while strain D-2 preferred less dense worts (extract of 200 g kg⁻¹) and produced ethanol with the yield of over 92% of the theoretical yield. The optimum green syrup worts extract was 200 g kg⁻¹.     

Hydrogen production from steam reforming of ethanol using a ceria-supported iridium catalyst: Effect of different ceria supports

Catalytic activity of a ceria-supported Iridium (Ir/CeO₂) catalyst was investigated for steam reforming of ethanol within a temperature range of 300–500 °C. Three types of ceria were chosen to prepare the catalyst: commercial [assigned as CeO₂(C)] and prepared [using a simple reduction–oxidation method, CeO₂(R), and another combined with ultrasonic irradiation, CeO₂(U)] ceria. The Ir/CeO₂ catalyst with Ir loading of 2 wt.% was prepared by deposition–precipitation using iridium chloride (IrCl₃) as a precursor at 75 °C and pH = 9 (adjusted with 0.25 M Na₂CO₃). Catalytic activities toward the steam reforming of ethanol (SRE) were tested in a fixed-bed reactor. In order to better understand the effect of activation conditions of a catalyst on the reforming of ethanol, reduction pretreatment at 200 and 400 °C (assigned as H₂ and H₄) were conducted. The results indicated that only less sintering influences the catalytic activities for high temperature reduction. The ethanol conversion approached completion around 450 °C via reduction pretreatment for Ir/CeO₂(U) and Ir/CeO₂(C) samples under H₂O/EtOH molar ratio of 13 and 22,000 h⁻¹ GHSV. Not only was a high dispersion of both catalysts present but also no impurities (e.g., boron) interfered with the catalytic activities. The hydrogen yield (H₂ mole/EtOH mole) exceeds 5.0 with less content of CO and CH₄ (<2%).     

High activity Pt/C catalyst for methanol and adsorbed CO electro-oxidation

A high active Pt/C(b) catalyst was prepared by chemical reduction. The experimental results showed that the Pt/C(b) catalyst formed by reduction of hexachloroplatinic acid with formic acid has excellent catalytic properties for methanol and adsorbed CO(CO_ad) electro-oxidation. The electrocatalytic activity of the catalyst was characterized as having a specific surface activity of 33.38 mA cm⁻² at 0.6 V (versus Ag-AgCl). The Pt in the catalyst was well dispersed on carbon with an electrochemically-active specific surface area (ESA) of 84.16 m² g⁻¹ and a BET specific surface area of 192.34 m² g⁻¹ and an average particle size of about 2.6 nm. The catalyst showed a very good stability for 12 h.