The ignition,combustion and flame structure of carbon monoxide/hydrogen mixtures. Note 1: Detailed kinetic modeling of syngas combustion also in presence of nitrogen compounds

The kinetic characterization of the _H2/CO${\mathrm{H}}_2/\mathrm{CO}$ system is of interest right now due mainly to its role in sustainable combustion processes. The aim of this paper is to revise and validate a detailed kinetic model of hydrogen and carbon monoxide mixture combustion with particular focus not only on _NOx${\mathrm{NO}}_x$ formation but also on interactions with nitrogen species. Model predictions and experimental measurements are discussed and compared across a wide range of operating conditions. This study moves from the detailed analysis of species profiles in syngas oxidation in flow reactor and laminar premixed flames to global combustion properties (ignition delay times and laminar flame speeds) by referring to a large set of literature data. According to recent literature, the validation of the kinetic scheme confirmed there was a need to slightly modify the kinetic parameters of two relevant _CO2${\mathrm{CO}}_2$ formation reactions (CO+OH=_CO2+H$\mathrm{CO}+\mathrm{OH}={\mathrm{CO}}_2+\mathrm{H}$ and CO+O+M=_CO2+M$\mathrm{CO}+\mathrm{O}+\mathrm{M}={\mathrm{CO}}_2+\mathrm{M}$) and of reaction HONO+OH=_NO2+_H2O$\mathrm{HONO}+\mathrm{OH}={\mathrm{NO}}_2+{\mathrm{H}}_2\mathrm{O}$.     

Evaluation of conversion efficiency of light to hydrogen energy by Anabaena variabilis

Cyanobacteria provide an efficient system for producing _H2${\mathrm{H}}_2$ from water using solar energy. The energy conversion efficiency can be defined by the ratio of _H2${\mathrm{H}}_2$ produced to the light energy absorbed. An IR and opalescent plate method was used to measure the light energy absorbed. Since cyanobacteria absorb light in the visible range but not in the infrared range, the net amount of light energy absorbed by the cells can be estimated by measuring the IR and visible light intensities transmitted through the biochamber. A rectangular biochamber was used for measuring the conversion efficiency from light energy to _H2${\mathrm{H}}_2$ energy. A quantum meter and radiometer were used to measure the light intensity transmitted through the chamber. Anabaena variabilis was cultured in a BG11 medium with 3.6 mM NaNO₃${}_3$ and the light intensity was 40–50 μmol/m²/s$\mathrm{\mu }\mathrm{mol}/{\mathrm{m}}^2/\mathrm{s}$ in the growth phase and 120–140 μmol/m²/s$\mathrm{\mu }\mathrm{mol}/{\mathrm{m}}^2/\mathrm{s}$ in the _H2${\mathrm{H}}_2$ production phase. The maximum _H2${\mathrm{H}}_2$ production was 50 ml for 40 h and cell density was 1.2 g/l. The _H2${\mathrm{H}}_2$ production rate was 4.1 ml _H2/g${\mathrm{H}}_2/\mathrm{g}$ dry cell weight/h. Based on the light absorbed in the _H2${\mathrm{H}}_2$ production phase, the energy conversion efficiency from light to _H2${\mathrm{H}}_2$ was 1.5% on average and 3.9% at the maximum. Based on the light energy absorbed in the cell growth and _H2${\mathrm{H}}_2$ production phases, the energy conversion efficiency was 1.1% on average.     

Hydrogen storage capability of Se@C120 system

A single-walled, capped and selenium doped, carbon nanotube, Se@C₁₂₀, was doped endohedrally with hydrogen molecules to obtain a series of (n_H2+Se)@_C120$(n{\mathrm{H}}_2+\mathrm{Se})@{\mathrm{C}}_{120}$, (n  : 0–11) systems. Then, they were subjected to quantum chemical treatment using PM3 method at the level of RHF approach. Calculations indicated that these systems were stable but endothermic in nature. In (10_H2+Se@_C120)$(10{\mathrm{H}}_2+\mathrm{Se}@{\mathrm{C}}_{120})$ and (11_H2+Se@_C120)$(11{\mathrm{H}}_2+\mathrm{Se}@{\mathrm{C}}_{120})$ systems, the hydrogen molecule nearest to the Se atom tends to dissociate to form a quasi-_H2Se${\mathrm{H}}_2\mathrm{Se}$ structure.     

Hydrogen production by autothermal reforming of LPG for PEM fuel cell applications

Indirect partial oxidation, or oxidative steam reforming, tests of a bimetallic Pt–Ni catalyst supported on δ$\delta$-alumina were conducted in propane–n  -butane mixtures (LPG) used as feed. _H2${\mathrm{H}}_2$ production activity and _H2/CO${\mathrm{H}}_2/\mathrm{CO}$ selectivity were investigated in response to different S/C, C/_O2$\mathrm{C}/{\mathrm{O}}_2$ and W/F ratios. It was confirmed that higher steam content in the reactant stream increases both the activity and the _H2/CO${\mathrm{H}}_2/\mathrm{CO}$ selectivity of the process. Low residence times created a positive impact on catalyst activity not only for hydrogen but also for carbon monoxide production due to the increased amount of fresh hydrocarbon in the feed stream. Hence, the highest selectivity level was obtained at intermediate residence times. The response of the system to C/_O2$\mathrm{C}/{\mathrm{O}}_2$ ratio was found to depend on the available steam content due to the complex nature of IPOX. The Pt–Ni catalyst was very prone to catalyst deactivation at low S/C ratios accompanied by high C/_O2$\mathrm{C}/{\mathrm{O}}_2$ ratios, but this problem was not encountered at high S/C ratios. A comparison of catalyst performance for different propane-to-n-butane ratios in the LPG feed indicated that the Pt–Ni catalyst has slightly better activity and selectivity at higher n-butane contents at the expense of becoming more sensitive to coke deposition.     

A comparison of hydrogen storage technologies for solar-powered stand-alone power supplies: A photovoltaic system sizing approach

This paper compares the performance of three different solar based technologies for a stand-alone power supply (SAPS) using different methods to address the seasonal variability of solar insolation—(i) photovoltaic (PV) panels with battery storage; (ii) PV panels with electrolyser and hydrogen (_H2)$({\mathrm{H}}_2)$ storage; and (iii) photoelectrolytic (PE) dissociation of water for _H2${\mathrm{H}}_2$ generation and storage. The system size is determined at three different Australian locations with greatly varying latitudes—Darwin (12^°S${12}^{°}\mathrm{S}$), Melbourne (38^°S${38}^{°}\mathrm{S}$) and Macquarie Island (55^°S${55}^{°}\mathrm{S}$). While the PV/electrolyser system requires fewer PV panels compared to the PV/battery scenario due to the seasonal storage ability of _H2${\mathrm{H}}_2$, the final number of PV modules is only marginally less at the highest latitude due to the lower energy recovery efficiency of _H2${\mathrm{H}}_2$ compared to batteries. For the PE technology, an upper limit on the cost of such a system is obtained if it is to be competitive with the existing PV/battery technology.     

CO2 reforming of CH4 by combination of thermal plasma and catalyst

Experiments on synthesis gas preparation from dry reforming of methane by carbon dioxide with thermal plasma only and cooperation of thermal plasma with commercial catalysts have been performed. In all experiments, nitrogen gas was used as the plasma gas to form a high-temperature jet injected into a tube reactor. A mixture of _CH4${\mathrm{CH}}_4$ and _CO2${\mathrm{CO}}_2$ was fed vertically into the jet. Both kinds of experiments were conducted in the same conditions, such as total flux of feed gases, the molar ratio of _CH4/_CO2${\mathrm{CH}}_4/{\mathrm{CO}}_2$, and the plasma power except with or without catalysts in the tube reactor. Higher conversion of _CH4${\mathrm{CH}}_4$ and _CO2${\mathrm{CO}}_2$, higher selectivity of _H2${\mathrm{H}}_2$ and CO, and higher specific energy of the process were achieved by thermal plasma with catalysts. For example, the conversions of _CH4${\mathrm{CH}}_4$ and _CO2${\mathrm{CO}}_2$ were high to 96.33% and 84.63%, and the selectivies of CO and _H2${\mathrm{H}}_2$ were also high to 91.99% and 74.23%, respectively. Both were 10–20%$10–20\%$ higher than those by thermal plasma only.     

H2 production with ultra-low CO selectivity via photocatalytic reforming of methanol on Au/TiO2 catalyst

_H2${\mathrm{H}}_2$ with ultra-low CO concentration was produced via photocatalytic reforming of methanol on Au/_TiO2$\mathrm{Au}/{\mathrm{TiO}}_2$ catalyst. The rate of _H2${\mathrm{H}}_2$ production is greatly increased when the gold particle size is reduced from 10 to smaller than 3 nm. The concentration of CO in _H2${\mathrm{H}}_2$ decreases with reducing the gold particle size of the catalyst. It is suggested that the by-product CO is mostly produced via decomposition of the intermediate formic acid species derived from methanol. The smaller gold particles possibly switch the HCOOH decomposition reaction mainly to _H2${\mathrm{H}}_2$ and _CO2${\mathrm{CO}}_2$ products while suppress the CO and _H2${\mathrm{H}}_2$O products. In addition, some CO may be oxidized to _CO2${\mathrm{CO}}_2$ by photogenerated oxidizing species at the perimeter interface between the small gold particles and _TiO2${\mathrm{TiO}}_2$ under photocatalytic condition.     

Biological hydrogen production in suspended and attached growth anaerobic reactor systems

Biological production of hydrogen gas has received increasing interest from the international community during the last decade. Most studies on biological fermentative hydrogen production from carbohydrates using mixed cultures have been conducted in conventional continuous stirred tank reactors (CSTR) under mesophilic conditions. Investigations on hydrogen production in reactor systems with attached microbial growth have recently come up as well as investigations on hydrogen production in the thermophilic temperature range. The present study examines and compares the biological fermentative production of hydrogen from glucose in a continuous stirred tank type bioreactor (CSTR) and an upflow anaerobic sludge blanket bioreactor (UASB) at various hydraulic retention times (2–12 h HRT) under mesophilic conditions (35 °C). Also the biohydrogen production from glucose in the CSTR at mesophilic and thermophilic (55 °C) temperature range was studied and compared. From the CSTR experiments it was found that thermophilic conditions combine high hydrogen production rate with low production of microbial mass, thus giving a specific hydrogen production rate as high as 104 mmole _H2/h/l/g${\mathrm{H}}_2/\mathrm{h}/\mathrm{l}/\mathrm{g}$ VSS at 6 h retention time compared to a specific hydrogen production rate of 12 mmole _H2/h/l/g${\mathrm{H}}_2/\mathrm{h}/\mathrm{l}/\mathrm{g}$ VSS under mesophilic conditions. On the other hand, the UASB reactor configuration is more stable than the CSTR regarding hydrogen production, pH, glucose consumption and microbial by-products (e.g. volatile fatty acids, alcohols etc.) at the HRTs tested. Moreover, the hydrogen production rate in the UASB reactor was significantly higher compared to that of the CSTR at low retention times (19.05 and 8.42 mmole _H2/h/l${\mathrm{H}}_2/\mathrm{h}/\mathrm{l}$, respectively at 2 h HRT) while hydrogen yield (mmole _H2/mmole${\mathrm{H}}_2/\mathrm{mmole}$ glucose consumed) was higher in the CSTR reactor at all HRT tested. This implies that there is a trade-off between technical efficiency (based on hydrogen yield) and economic efficiency (based on hydrogen production rate) when the attached (UASB) and suspended (CSTR) growth configurations are compared.     

Hydrogen storage and induced properties in non-metallic catalytic materials

Particular active sites, ^xM${}^x\mathrm{M}$–^yM^′${}^y{\mathrm{M}}^{\prime }$ (where x$x$ and y$y$ are the number of unsaturations, i.e. anionic vacancies, on each cation M and M^′${\mathrm{M}}^{\prime }$) involving reactive hydrogen are created during the activation of non-metallic catalytic materials. The anionic vacancies created in bulk and at the surface of the solid, by the loss of _H2O${\mathrm{H}}_2\mathrm{O}$ or _H2S${\mathrm{H}}_2\mathrm{S}$, are able to receive hydrogen in a hydridic form according to a heterolytic dissociation (X^2-Mⁿ⁺□+_H2→XH^-Mⁿ⁺H^-${\mathrm{X}}^{2-}{\mathrm{M}}^{n+}\square +{\mathrm{H}}_2\to {\mathrm{XH}}^{-}{\mathrm{M}}^{n+}{\mathrm{H}}^{-}$ with X=O$\mathrm{X}=\mathrm{O}$ or S). The non-metallic catalytic materials become catalytic hydrogen reservoirs. Besides a high reactivity, the hydrogen species, stored in the solid, present marked diffusion properties leading to a dynamic behavior of the solid and active sites.