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.     

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.     

Absorption enhanced reforming of light alcohols (methanol and ethanol) for the production of hydrogen: Thermodynamic modeling

Thermodynamic modeling of the steam reforming of light alcohols using CaO, CaO*MgO, Na₂ZrO₃, Li₂ZrO₃ and Li₄SiO₄ as CO₂ absorbents was carried out to determine promising operating conditions to produce a high hydrogen yield (YH₂)$\left(Y_{{\text{H}}_2}\right)$ and concentration (% H₂). Ethanol and methanol were studied at 300–800 °C and 1 atm. Steam to alcohol (S/COH) feed molar ratio varied from 1:1 (stoichiometric) to 6:1 for methanol and from 3:1 (stoichiometric) to 6:1 for ethanol. Thermodynamic simulations employed the Gibbs free energy minimization technique. Results indicate no carbon formation at S/COH ≤ stoichiometric. For both alcohols reforming at 600 °C and S/COH = 6, using CaO, CaO*MgO, and Na₂ZrO₃ produced optimal YH₂$Y_{{\text{H}}_2}$ and hydrogen purity (% H₂). In both reforming systems most favorable thermodynamics were obtained with CaO, CaO*MgO and Na₂ZrO₃ as absorbents. A Thermal efficiency analysis performed in all system confirmed the superiority of the CO₂ absorption systems against conventional reforming processes.     

Kinetic study on nonisothermal dehydrogenation of TiH2 powders

The nonisothermal dehydrogenation of TiH₂ powders was studied using thermogravimetry and differential scanning calorimetry. The reaction model was established by estimating the activation energy. The results show the nonisothermal dehydrogenation occurred in a four-step process. The hydrogen released from the TiH_1.5∼2$\text{Ti}{\mathrm{H}}_{1.5\sim 2}$ phase in the first step, which led to the decrease of activation energy. The second step was derived from the formation of βH${\beta }_H$ in δ$\delta$ phase and the reaction model was Phase boundary reaction. In the third step, the hydrogen started to release from the βH${\beta }_H$ phase, and then the βH→αH${\beta }_{\mathrm{H}}\to {\alpha }_{\mathrm{H}}$ phase transformation happened. So the activation energy Eα$E_{\alpha }$ underwent a decrease followed by a quick increase. The fourth step corresponded to the formation of αH${\alpha }_H$ in βH${\beta }_H$ phase, and the slight oxidation resulted in the small fluctuation of activation energy.     

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.     

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$\mathrm{HONO}+\mathrm{OH}={\mathrm{NO}}_2+{\mathrm{H}}_2\mathrm{O}$.     

Combustion of micron-sized aluminum particle,liquid water,and hydrogen peroxide mixtures

The combustion of aluminum particle, liquid water, and hydrogen peroxide (H₂O₂) mixtures is studied theoretically for a pressure range of 1–20 MPa and particle sizes between 3 and 70 μm. The oxidizer-to-fuel (O/F) weight ratio is varied in the range of 1.00–1.67, and four different H₂O₂ concentrations of 0%, 30%, 60%, and 90% are considered. A multi-zone flame model is developed to determine the burning behaviors and combustion-wave structures by solving the energy equation in each zone and enforcing the temperature and heat-flux continuities at the interfacial boundaries. The entrainment of particles is taken into account. Key parameters that dictate the burning properties of mixtures are found to be the thermal diffusivity, flame temperature, particle burning time, ignition temperature, and entrainment index of particles. When the pressure increases from 1 to 20 MPa, the flame thickness decreases by a factor of two. The ensuing enhancement of conductive heat flux to the unburned mixture thus increases the burning rate, which exhibits a pressure dependence of the form r_b = ap^m. The exponent, m, depends on reaction kinetics and convective motion of particles. Transition from diffusion to kinetically-controlled conditions causes the pressure exponent to increase from 0.35 at 70 μm to 1.04 at 3 μm. The addition of hydrogen peroxide has a positive effect on the burning properties. The burning rate is nearly doubled when the concentration of hydrogen peroxide increases from 0 to 90%. For the conditions encountered in this study, the following correlation for the burning rate is developed: _rb[cm/s]=4.97(p[MPa])^0.37(_dp[μm])^-0.85(O/F)^-0.54exp(0.0066CH₂O₂).$r_b[\text{cm}/\text{s}]=4.97{(p[\text{MPa}])}^{0.37}{(d_p[\mathrm{\mu }\text{m}])}^{-0.85}{(\text{O}/\text{F})}^{-0.54}\exp (0.0066{\text{C}}_{{\text{H}}_2{\text{O}}_2})\text{.}$     

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.     

Shock-tube studies on the ignition of ethylene-oxygen-argon mixtures

Ignition induction times were measured for 9 different ethylene-oxygen-argon mixtures with stoichiometric ratios between 0.125 and 2, with ethylene mole fractions ranging from 0.0025 to 0.02 and total pressures of 3 and 12 atm. The overall correlation equation is

τ=10^−11.9[C₂H₄]^0.3[O₂]^−1.1[Ar]^0.4e34.200/RT$\tau ={10}^{-11.9}{[C_2{H}_4]}^{0.3}{[O_2]}^{-1.1}{[Ar]}^{0.4}{e}^{34.200/RT}$

NH3/Ir(100): Electronic structure and dehydrogenation

Density functional theory was employed to compute the geometric and electronic structures and the stepwise dehydrogenation of NH₃ on Ir(100). The NH₃, NH₂ and NH were found to bind predominately on top, bridge and four-fold hollow sites with adsorption energies to be 0.82 eV, 3.26 eV and 4.85 eV respectively. The mixings of 3a₁(₃NH)∼5dz²/6s(Ir)$3a_1\left({\text{NH}}_3\right)\sim 5{d_z}^2/6s\left(\text{Ir}\right)$, 3a₁/1b₁(NH₂) ∼ 5d_yz(Ir) and 3a₁ + 1a₂(NH) ∼ 5d_xz(Ir) and 2a₁(NH)∼5dz²(Ir)$2a_1\left(\text{NH}\right)\sim 5{d_z}^2\left(\text{Ir}\right)$ are responsible for the adsorption of NH₃, NH₂ and NH respectively. The reaction barriers are 0.88 eV, 0.97 eV, 0.94 eV and 0.63 eV for the first, second, third N–H bond breakings and N₂ formation respectively. The competition between decomposition and desorption for NH₃ was demonstrated, NH₂ was found to be the most stable surface species, its accumulation in practice would suppress the first N–H bond scission and thus make it to be the rate-determining step.     

Experimental and modeling study on auto-ignition characteristics of methane/hydrogen blends under engine relevant pressure

Auto-ignition characteristics of methane/hydrogen mixtures with hydrogen mole fraction varying from 0 to 100% were experimentally studied using a shock tube. Test pressure is kept 1.8 MPa and temperatures behind reflected shock waves are in the range of 900–1750 K and equivalence ratios from 0.5 to 2.0. Three ignition regimes are identified according to hydrogen fraction. They are, methane chemistry dominating ignition (XH₂≤40%)$\left(X_{{\text{H}}_2}\le 40\mathrm{\%}\right)$, combined chemistry of methane and hydrogen dominating ignition (XH₂=60%)$\left(X_{{\text{H}}_2}=60\mathrm{\%}\right)$, and hydrogen chemistry dominating ignition (XH₂≥80%)$\left(X_{{\text{H}}_2}\ge 80\mathrm{\%}\right)$. Simulated ignition delays using four models including USC Mech 2.0, GRI Mech 3.0, UBC Mech 2.1 and NUI Galway Mech were compared to the experimental data. Results show that USC Mech 2.0 gives the best prediction on ignition delays and it was selected to conduct sensitivity analysis for three typical methane/hydrogen mixtures at different temperatures. The results suggest that at high temperature, ignition delay mainly is governed by chain branching reaction H + O₂ ⇔ OH + O, and thus increasing equivalence ratio inhibits ignition of methane/hydrogen mixtures. At middle-low temperature, contribution of equivalence ratio on ignition delay of methane/hydrogen mixtures is mainly due to chemistries of HO₂ and H₂O₂ radicals.     

Hydrogen production from Chlamydomonas reinhardtii biomass using a two-step conversion process: Anaerobic conversion and photosynthetic fermentation

Chlamydomonas reinhardtii UTEX 90 accumulated 1.45 g dry cell weight and 0.77 g starch/L during photosynthetic growth using TAP media at 25 ^°C${}^{°}\mathrm{C}$ in presence of 2% _CO2${\mathrm{CO}}_2$ for 3 days. C. reinhardtii biomass was concentrated and then converted into hydrogen and organic acids by anaerobic fermentation with Clostridium butyricum. Organic acids in the fermentate of algal biomass were consecutively photo-dissimilated to hydrogen by Rhodobacter sphaeroides KD131. In the concentrated algal biomass 52% of the starch was hydrolyzed to 37.1 mmol _H2${\mathrm{H}}_2$/L-concentrated algal biomass and 13.6, 25.5, 7.4 and 493 mM of formate, acetate, propionate, and butyrate, respectively by C. butyricum. R. sphaeroides KD131 evolved 5.72 mmol _H2${\mathrm{H}}_2$ per ml-fermentate of algal biomass under illumination of 8 klux at 30 ^°C${}^{°}\mathrm{C}$. Only 80% of the organic acids, mainly butyrate, were hydrolyzed during photo-incubation. During anaerobic conversion, 2.58 mol _H2/mol${\mathrm{H}}_2/\mathrm{mol}$ starch–glucose was evolved using C. butyricum and then 5.72 mol _H2/L${\mathrm{H}}_2/\mathrm{L}$-anaerobic fermentate was produced by R. sphaeroides KD131. Thus, the two-step conversion process produced 8.30 mol _H2${\mathrm{H}}_2$ from 1 mol starch–glucose equivalent algal biomass via organic acids.     

Effect of medium composition on biohydrogen production by the extreme thermophilic bacterium Caldicellulosiruptor saccharolyticus

Up to now, the analysis of the effects of medium composition on biohydrogen production of Caldicellulosiruptor saccharolyticus was focused mainly on salt concentrations and complex compounds. Within this work we studied the effects of the presence of organic and/or inorganic nitrogen in the medium composition aiming to induce metabolic changes in C. saccharolyticus   to improve its hydrogen evolution rate (HER) and hydrogen specific productivity (qH₂)$\left(q_{{\text{H}}_2}\right)$. Biohydrogen productivities and hydrogen to substrate yield (Y₍H_2/s₎)$\left(Y_{\left({\text{H}}_2/\text{s}\right)}\right)$ of C. saccharolyticus   on xylose in batch mode were higher working in a complex medium than in a defined one; but no significant difference could be settled according to hydrogen to carbon dioxide yields (Y₍H_2/CO₂₎)$\left(Y_{\left({\text{H}}_2/{\text{CO}}_2\right)}\right)$. The specific growth rate of C. saccharolyticus on complex medium was settled at 0.1 h⁻¹ operating in chemostat mode to achieve the highest H₂-productivities under stable conditions. In chemostat mode on xylose, a reduction of the ammonium feed concentration in a defined medium until N-limiting conditions involved higher qH₂$q_{{\text{H}}_2}$ comparing with a straight C-limiting growth.