Preferential diffusion effects on flame characteristics in H2/CO syngas diffusion flames diluted with CO2

Numerical study is conducted to clarify preferential diffusion effects of H₂ and H on flame characteristics in synthetic diffusion flames of the compositions of 80% H₂/20% CO and 20% H₂/80% CO as representatively H₂-enriched and CO-enriched H₂/CO flames. Impacts of CO₂ addition to the flames are also examined through the variation of added CO₂ mole fraction from 0 to 0.5. A comparison was made by employing a mixture-averaged diffusivity and the suppression of the diffusivities of H and H₂. It is found that preferential diffusion effects on maximum flame temperature cannot be explained by the well-known behavior between maximum flame temperature and scalar dissipation rate but by chemical processes. The concrete evidence is also presented through the examination of the behavior of maximum H mole fraction and the behavior of importantly-contributing reaction steps to overall heat release rate.     

Investigation of the oxygen reduction reaction on the carbon electrodes loaded with MnO2 catalyst

The oxygen reduction reaction has been studied on gas diffusion electrodes made with various activated carbon materials and on the edge/basal orientations of pyrolitic graphite. A MnO₂ catalyst was loaded on all carbon surfaces. The MnO₂ catalyst demonstrated significant catalytic activity for the oxygen reduction reaction. The specific catalytic activity was found to relate to the concentration of the edge orientation of carbon materials loaded with MnO₂ catalyst. The higher the percentage of edge orientations, the higher the specific catalytic activity would be. MnO₂ may not participate in the reduction of O₂, but catalyze the disproportionation of HO₂⁻.     

Elevated temperature pressure swing adsorption process for reactive separation of CO/CO2 in H2-rich gas

Purification of CO and CO₂ to the ppm level in H₂-rich gas without losing H₂ is one of the technical difficulties for fuel cell power systems. In this work, a two-column seven-step elevated temperature pressure swing system with high purification performance was proposed. The concept of reactive separation by adding water gas shift catalysts into the columns filled with elevated temperature CO₂ adsorbents was adopted. The H₂ recovery ratio and H₂ purity were greatly improved by the introduction of steam rinse and steam purge, which could be realized due to the increasing operating temperature (200–450 °C). An optimized operating region to both achieve high efficiency and low energy consumption was proposed. The optimized case with 0.09 purge-to-feed ratio and 0.15 rinse-to-feed ratio could achieve 99.6% H₂ recovery ratio and 99.9991% H₂ purity at a stable state for a feed gas containing 1% CO, 1% CO₂, 10% H₂O, and 88% H_2. No performance degradation was observed for at least 1000 cycles. The proposed (ET-PSA) system possessed self-purification ability while the columns were penetrated by CO₂. It is however suggested that periodical heat regeneration should be adopted to accelerate performance recovery during long-term operation.     

Electrolysis of coal slurries to produce hydrogen gas: Relationship between CO2 and H2 formation

The purpose of this study was to produce hydrogen gas by electrolysis of coal slurries and to investigate the relation between hydrogen (H₂) and carbon dioxide (CO₂) formation. Electrolysis of coal slurries was evaluated at 40 °C and 1.0 V cell potential to examine H₂ and CO₂relationship. When electrolysis was performed after the coal slurry was mixed with Fe(II)/Fe(III) ions and stirred overnight (>12 h), no CO₂ gas was observed at the anode compartment. The results of total organic carbon (TOC) indicated that after electrolysis, few organic compounds were transformed into the solution and these organic compounds did not convert into CO₂. GC analysis, on the other hand, revealed that the H₂ collected at the cathode was pure and did not require any further purification process. Hydrogen generation or electrolysis efficiency of coal slurries cannot be calculated or estimated by examining CO₂ generation as reported in the literature. Low temperature and low cell potential were not sufficient to oxidize coal quantitatively.     

Characterizations of polybenzimidazole based electrochemical hydrogen pumps with various Pt loadings for H2/CO2 gas separation

Carbon capture and storage (CCS) technologies have been intensively researched and developed to cope with climate change, by reducing atmospheric CO₂ concentration. The electrochemical hydrogen pumps with phosphoric acid doped polybenzimidazole (PBI) membrane are evaluated as a process to concentrate CO₂ and produce pure H₂ from anode outlet gases (H₂/CO₂ mixture) of molten carbonate fuel cells (MCFC). The PBI-based hydrogen pump without humidification (160 °C) can provide higher hydrogen separation performances than the cells with perfluorosulfonic-acid membranes at a relative humidity of 43% (80 °C), suggesting that the pre-treatment steps can be decreased for PBI-based systems. With the H₂/CO₂ mixture feed, the current efficiency for the hydrogen separation is very high, but the cell voltage increase, compared to the pure hydrogen operation, mainly due to the larger polarization resistance at electrodes, as confirmed by electrochemical impedance spectroscopy (EIS). The performance evaluation with various Pt loadings indicates that the hydrogen oxidation reaction at anodes is rate determining, and therefore the Pt loading at cathodes can be decreased from 1.1 mg/cm² to 0.2 mg/cm² without significant performance decay. The EIS analysis also confirms that the polarization resistances are largely dependent on the Pt loading in anodes.     

Ultrasonic spray pyrolysis synthesis of Ag/TiO2 nanocomposite photocatalysts for simultaneous H2 production and CO2 reduction

Simultaneous photocatalytic hydrogen production and CO₂ reduction (to form CO and CH₄) from water using methanol as a hole scavenger were investigated using silver-modified TiO₂ (Ag/TiO₂) nanocomposite catalysts. A simple ultrasonic spray pyrolysis (SP) method was used to prepare mesoporous Ag/TiO₂ composite particles using TiO₂ (P25) and AgNO₃ as the precursors. The material properties and photocatalytic activities were compared with those prepared by a conventional wet-impregnation (WI) method. It was found that the samples prepared by the SP method had a larger specific surface area and a better dispersion of Ag nanoparticles on TiO₂ than those prepared by the WI method, and as a result, the SP samples showed much higher photocatalytic activities toward H₂ production and CO₂ reduction. The optimal Ag concentration on TiO₂ was found to be 2 wt%. The H₂ production rate of the 2% Ag/TiO₂–SP sample exhibited a six-fold enhancement compared with the 2% Ag/TiO₂–WI sample and a sixty-fold enhancement compared with bare TiO₂. The molar ratio of H₂ and CO in the final products can be tuned in the range from 2 to 10 by varying the reaction gas composition, suggesting a viable way of producing syngas (a mixture of H₂ and CO) from CO₂ and water using the prepared Ag/TiO₂ catalysts with energy input from the sun.     

CO2 and H2O gas conversion into CO and H2 using highly exothermic reactions induced by mixed industrial slags

This communication reports conversion phenomena in which CO₂ and H₂O gases are transformed into CO and H₂, respectively, when exposed to a mixture of molten CaO-rich metallurgical slag and V₂O₃-rich gasifier slag. On reaction, CO₂ and H₂O are thermodynamically driven to become CO and H₂, respectively, by giving up oxygen over the formation of calcium orthovanadate in the slag. The concept was experimentally investigated with a synthetic slag heated to 1500 °C (an assumed slag tap-out temperature in the metallurgical industry) in a CO₂ saturated atmosphere. On heating, a rapid drop in oxygen partial pressure occurred between 1405 °C and 1460 °C, where 97% of CO₂ transformed to CO. Potential industrial applications with the H₂O-to-H₂ conversion are then explored using detailed process computations. If the process is made economically viable, CO₂ and H₂O could be converted into products that are environmentally and industrially attractive and that have the potential for energy savings and greenhouse gas reduction in a process.     

High performance composite hollow fiber membranes for CO2/H2 and CO2/N2 separation

The search for a clean energy source as well as the reduction of CO₂ emissions to the atmosphere are important strategies to resolve the current energy shortage and global warming issues. We have demonstrated, for the first time, a Pebax/poly(dimethylsiloxane)/polyacrylonitrile (Pebax/PDMS/PAN) composite hollow fiber membrane not only can be used for flue gas treatment but also for hydrogen purification. The composite membranes display attractive gas separation performance with a CO₂ permeance of 481.5 GPU, CO₂/H₂ and CO₂/N₂ selectivity of 8.1 and 42.0, respectively. Minimizing the solution intrusion using the PDMS gutter layer is the key to achieving the high gas permeance while the interaction between poly(ethylene oxide) (PEO) and CO₂ accounts for the high selectivity. Effects of coating solution concentration and coating time on gas separation performance have been investigated and the results have been optimized. To the best of our knowledge, this is the first polymeric composite hollow fiber membrane for hydrogen purification. The attractive gas separation performance of the newly developed membranes may indicate good potential for industrial applications.     

High capacity potassium-promoted hydrotalcite for CO2 capture in H2 production

This paper presents an experimental study for a newly modified K₂CO₃-promoted hydrotalcite material as a novel high capacity sorbent for in-situ CO₂ capture. The sorbent is employed in the sorption enhanced steam reforming process for an efficient H₂ production at low temperature (400–500 ^°C). A new set of adsorption data is reported for CO₂ adsorption over K-hydrotalcite at 400 °C. The equilibrium sorption data obtained from a column apparatus can be adequately described by a Freundlich isotherm. The sorbent shows fast adsorption rates and attains a relatively high sorption capacity of 0.95 mol/kg on the fresh sorbent. CO₂ desorption experiments are conducted to examine the effect of humidity content in the gas purge and the regeneration time on CO₂ desorption rates. A large portion of CO₂ is easily recovered in the first few minutes of a desorption cycle due to a fast desorption step, which is associated with a physi/chemisorption step on the monolayer surface of the fresh sorbent. The complete recovery of CO₂ was then achieved in a slower desorption step associated with a reversible chemisorption in a multi-layer surface of the sorbent. The sorbent shows a loss of 8% of its fresh capacity due to an irreversible chemisorption, however, it preserves a stable working capacity of about 0.89 mol/kg, suggesting a reversible chemisorption process. The sorbent also presents a good cyclic thermal stability in the temperature range of 400–500 °C.     

Chemical effects of added CO2 on the extinction characteristics of H2/CO/CO2 syngas diffusion flames

Chemical effects of added CO₂ on flame extinction characteristics are numerically studied in H₂/CO syngas diffusion flames diluted with CO₂. The two representative syngas flames of 80% H₂ + 20% CO and 20% H₂ + 80% CO are inspected according to the composition of fuel mixture diluted with CO₂ and global strain rate. Particular concerns are focused on impact of chemical effects of added CO₂ on flame extinction characteristics through the comparison of the flame characteristics between well-burning flames far from extinction limit and flames at extinction. It is seen that chemical effects of added CO₂ reduce critical CO₂ mole fraction at flame extinction and thus extinguish the flame at higher flame temperature irrespective of global strain rate. This is attributed by the suppression of the reaction rate of the principal chain branching reaction through the augmented consumption of H-atom from the reaction CO₂ + H→CO + OH. As a result the overall reaction rate decreases. These chemical effects of added CO₂ are similar in both well-burning flames far from extinction limit and flames at extinction. There is a mismatching in the behaviors between critical CO₂ mole fraction and maximum flame temperature at extinction. This anomalous phenomenon is also discussed in detail.     

Flame characteristics in H2/CO synthetic gas diffusion flames diluted with CO2: Effects of radiative heat loss and mixture composition

Numerical study is conducted to understand the impact of fuel composition and flame radiation in flame structure and their oxidation process in H₂/CO synthetic gas diffusion flame with and without CO₂ dilution. The models of Sun et al. and David et al., which have been well known to be best-fitted for H₂/CO synthetic mixture flames, are evaluated for H₂/CO synthetic mixture flames diluted with CO₂. Effects of radiative heat loss to flame characteristics are also examined in terms of syngas mixture composition. Importantly contributing reaction steps to heat release rate are compared for the synthetic gas mixture flames of high contents of H₂ and CO, individually, with and without CO₂ dilution. The modification of the oxidation pathways is also addressed.     

Direct formation of Pt catalyst on gas diffusion layer using sonochemical deposition method for the application in polymer electrolyte membrane fuel cell

In this study, the facile and direct formation of platinum catalyst on a carbon paper (gas diffusion layer) via the sonochemical deposition method is demonstrated. An ultrasound irradiation with a carbon paper substrate in a platinum precursor solution formed interconnected platinum grains on the carbon paper surface. The surface morphology and deposition amount of platinum were strong functions of both ultrasound parameters (power and time) and solution composition. The platinum-deposited carbon paper was then directly used as a gas diffusion electrode in PEMFC without adding the ionomer. This exhibited high stability in the accelerated stress test in a single cell operation. The interconnected grains of platinum on carbon paper had high resistance to dissolution in an oxidizing environment and the absence of carbon support also enhanced resistance to carbon oxidation. Although the overall performance did not exceed that of the commercial Pt/C, this approach may be an option to form a stable platinum catalyst for PEMFCs.     

Kinetic study on fermentation from CO2 and H2 using the acclimated-methanogen in batch culture

Methane was produced from H₂ and CO₂ using the acclimated-mixed methanogens in a 3.71 fermentor in batch culture at pH 7.2 and 37°C. The Fermentation kinetics parameter for the growth of methanogens, overall mass transfer coefficient of the reactor, and the conversion rate of H₂ and CO₂ to CH₄ by the acclimated-mixed culture were determined using the technique of Vega et al. The maximum specific growth rate (μ_max) and H₂ specific consumption rate (q_max) were found to be 0.064(h⁻¹) and 104.8 (mmol h⁻¹ g⁻¹) respectively. Monod saturation constants for growth (Kp) and for inhibition (K′p) were found to be 3.54 (kPa) and 0.57 (kPa), respectively. These findings indicate that without very low dissolved H₂ levels, the fermentations are carried out under μ_max, and the specific uptake rate (q) was almost not affected at any dissolved H₂ level in the range studied. The yield of CH₄ (Yp/s) was calculated to be 0.245 (mol CH₄ mol⁻¹ H₂), which is near the stoichiometric value of 0.25. DH₂ was also measured using the Teflon tubing method and was in good agreement with those estimated by kinetic calculations.     

IrFeOx/SiO2—A highly active catalyst for preferential CO oxidation in H2

A novel bifunctional catalyst IrFeO_x/SiO₂, which was very active and selective for preferential oxidation of CO under H₂-rich atmosphere, was developed in this study. XRD, H₂-TPR, and chemisorption were applied to characterize three kinds of IrFeO_x/SiO₂ catalysts prepared by different impregnation sequences. The results indicated that both FeO_x and Ir species were highly dispersed on the SiO₂ support; the reduction of Ir species in the Fe-promoted Ir/SiO₂ catalyst became easier than those in the Ir/SiO₂, together with the partial reduction of Fe₂O₃; the saturation uptake of O₂ adsorption was greatly enhanced. In-situ DRIFTS, XPS, and Mössbauer techniques were further applied to detect the structural information on the selected Ir-FeO_x/SiO₂ catalyst prepared by co-impregnation method. A non-competitive adsorption catalytic mechanism was proposed where CO adsorbed on Ir sites and O₂ adsorbed on FeO_x sites; the reaction probably took place at the interface of Ir and FeO_x or via a spill-over process.     

Plasma-assisted synthesis of Ag/ZnO nanocomposites: First example of photo-induced H2 production and sensing

Ag/ZnO nanocomposites were developed by a plasma-assisted approach. The adopted strategy exploits the advantages of Plasma Enhanced-Chemical Vapor Deposition (PE-CVD) for the growth of columnar ZnO arrays on Si(100) and Al₂O₃ substrates, in synergy with the infiltration power of the Radio Frequency (RF)-sputtering technique for the subsequent dispersion of different amounts of Ag nanoparticles (NPs). The resulting composites, both as-prepared and after annealing in air, were thoroughly characterized with particular attention on their morphological organization, structure and composition. For the first time, the above systems have been used as catalysts in the production of hydrogen by photo-reforming of alcoholic solutions, yielding a stable H₂ evolution even by the sole use of simulated solar radiation. In addition, Ag/ZnO nanocomposites presented an excellent response in the gas-phase detection of H₂, opening attractive perspectives for advanced technological applications.     

Promotional effect of alkaline earth over Ni-La2O3 catalyst for CO2 reforming of CH4: Role of surface oxygen species on H2 production and carbon suppression

Alkaline earth elements (Mg, Ca and Sr) on Ni-La₂O₃ catalyst have been investigated as promoters for syngas production from dry CO₂ reforming of methane (DRM). The catalysis results of DRM performance at 600 °C show that the Sr-doped Ni-La₂O₃ catalyst not only yields the highest CH₄ and CO₂ conversions (∼78% and ∼60%) and highest H₂ production (∼42% by vol.) but also has the lowest carbon deposition over the catalyst surface. The XPS, O₂-TPD, H₂-TPR and FTIR results show that the excellent performance over the Sr-doped Ni-La₂O₃ catalyst is attributed to the presence of a high amount of lattice oxygen surface species which promotes C-H activation in DRM reaction, resulting in high H₂ production. Moreover, these surface oxygen species on the Ni-SDL catalyst can adsorb CO₂ molecules to form bidentate carbonate species, which can then react with the surface carbon species formed during DRM, resulting in higher CO₂ conversion and lower carbon formation.     

Cycle analysis of low and high H2 utilization SOFC/gas turbine combined cycle for CO2 recovery

A major factor in global warming is CO₂ emission from thermal power plants, which burn fossil fuels. One technology proposed to prevent global warming is CO₂ recovery from combustion flue gas and the sequestration of CO₂ underground or near the ocean bed. Solid oxide fuel cell (SOFC) can produce highly concentrated CO₂, because the reformed fuel gas reacts with oxygen electrochemically without being mixed with air in the SOFC. We therefore propose to operate multi-staged SOFCs with high utilization of reformed fuel to obtain highly concentrated CO₂. In this study, we estimated the performance of multi-staged SOFCs considering H₂ diffusion and the combined cycle efficiency of a multi-staged SOFC/gas turbine/CO₂ recovery power plant. The power generation efficiency of our CO₂ recovery combined cycle is 68.5%, whereas the efficiency of a conventional SOFC/GT cycle with the CO₂ recovery amine process is 57.8%.     

Activity of Au/ZnO catalysts prepared by photo-deposition for the preferential CO oxidation in a H2-rich gas

In this work, Au supported over ZnO prepared by photodeposition was applied to prepare nano-size Au catalysts by utilizing UV light for the preferential oxidation (PROX) of CO. The results demonstrated that Au can be dispersed homogeneously over ZnO in the size range of 1–2 nm with a narrow size distribution. It was clearly seen that the preparation parameters (i.e. irradiation time, precipitant concentration, calcination, and storage condition) had a significant effect on the catalytic activity. Among the variables studied, low concentrations of precipitant and long irradiation time were by far the most influential on the catalytic activity.     

Effect of H2S on carbon-catalyzed methane decomposition and CO2 reforming reactions

The effect of H₂S on catalytic processing of methane is of a great practical importance. In this work, the effect of small quantities (0.5–1.0 vol.%) of H₂S present in the feedstock on the methane decomposition and CO₂ reforming reactions over carbon and metal based catalysts was investigated. Activated carbon (FY5), an in-house prepared alumina-supported Ni catalyst (NiA) and the mixture of both (FY5 + NiA) were used as catalysts in this study. It was found that CH₄ and CO₂ conversions were noticeably increased when H₂S was added to the reacting mixture, which points to (i) the tolerance of carbon catalyst to H₂S and (ii) the catalytic effect of H₂S on carbon-catalyzed decomposition and dry reforming of methane. In contrast, NiA catalyst and the mixture FY5 + NiA were deactivated in the presence of H₂S in both reactions. The effect of the heating system (i.e., conventional electric resistance vs microwave heating) on the products yield of the dry reforming reaction in the presence of H₂S is also discussed in this paper.     

Preferential oxidation of CO in H2 stream on Au/CeO2–TiO2 catalysts

A series of Au catalysts supported on CeO₂–TiO₂ with various CeO₂ contents were prepared. CeO₂–TiO₂ was prepared by incipient-wetness impregnation with aqueous solution of Ce(NO₃)₃ on TiO₂. Gold catalysts were prepared by deposition–precipitation method at pH 7 and 65 °C. The catalysts were characterized by XRD, TEM and XPS. The preferential oxidation of CO in hydrogen stream was carried out in a fixed bed reactor. The catalyst mainly had metallic gold species and small amount of oxidic Au species. The average gold particle size was 2.5 nm. Adding suitable amount of CeO₂ on Au/TiO₂ catalyst could enhance CO oxidation and suppress H₂ oxidation at high reaction temperature (>50 °C). Additives such as La₂O₃, Co₃O₄ and CuO were added to Au/CeO₂–TiO₂ catalyst and tested for the preferential oxidation of CO in hydrogen stream. The addition of CuO on Au/CeO₂–TiO₂ catalyst increased the CO conversion and CO selectivity effectively. Au/CuO–CeO₂–TiO₂ with molar ratio of Cu:Ce:Ti = 0.5:1:9 demonstrated very high CO conversion when the temperature was higher than 65 °C and the CO selectivity also improved substantially. Thus the additive CuO along with the promoter and amorphous oxide ceria and titania not only enhances the electronic interaction, but also stabilizes the nanosize gold particles and thereby enhancing the catalytic activity for PROX reaction to a greater extent.