Fuel-rich methane oxidation in a high-pressure flow reactor studied by optical-fiber laser-induced fluorescence,multi-species sampling profile measurements and detailed kinetic simulations

A versatile flow-reactor design is presented that permits multi-species profile measurements under industrially relevant temperatures and pressures. The reactor combines a capillary sampling technique with a novel fiber-optic Laser-Induced Fluorescence (LIF) method. The gas sampling provides quantitative analysis of stable species by means of gas chromatography (i.e. _CH4${\mathrm{CH}}_4$, _O2,CO,_CO2${\mathrm{O}}_2\text{,}\mathrm{CO}\text{,}{\mathrm{CO}}_2$, _H2O,_H2${\mathrm{H}}_2\mathrm{O}\text{,}{\mathrm{H}}_2$, _C2${\mathrm{C}}_2$_H6${\mathrm{H}}_6$, _C2${\mathrm{C}}_2$_H4${\mathrm{H}}_4$), and the fiber-optic probe enables in situ detection of transient LIF-active species, demonstrated here for C_H2${\mathrm{H}}_2$O. A thorough analysis of the LIF correction terms for the temperature-dependent Boltzmann fraction and collisional quenching are presented. The laminar flow reactor is modeled by solving the two-dimensional Navier–Stokes equations in conjunction with a detailed kinetic mechanism. Experimental and simulated profiles are compared. The experimental profiles provide much needed data for the continued validation of the kinetic mechanism with respect to _C1${\mathrm{C}}_1$ and _C2${\mathrm{C}}_2$ chemistry; additionally, the results provide mechanistic insight into the reaction network of fuel-rich gas-phase methane oxidation, thus allowing optimization of the industrial process.     

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.     

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.     

Kinetic characteristics of sodium borohydride formation when sodium meta-borate reacts with magnesium and hydrogen

Sodium borohydride is attracting considerable interests as a hydrogen storage medium. In this paper, we investigated the effects of hydrogen pressure, reaction temperature and transition metal addition on sodium borohydride synthesis by the reaction of sodium meta-borate with Mg and _H2${\mathrm{H}}_2$. It was found that higher _H2${\mathrm{H}}_2$ pressure was beneficial to _NaBH4${\mathrm{NaBH}}_4$ formation. The increase in reaction temperature first improved _NaBH4${\mathrm{NaBH}}_4$ formation kinetics but then impeded it when the temperature was raised to near the melting point of Mg. It was also found that some additions of transition metals such as Ni, Fe and Co in the _NaBO2+Mg+_H2${\mathrm{NaBO}}_2+\mathrm{Mg}+{\mathrm{H}}_2$ system promoted the _NaBH4${\mathrm{NaBH}}_4$ formation, but Cu addition showed little effect. The activation energy of the _NaBH4${\mathrm{NaBH}}_4$ formation from Mg, _NaBO2${\mathrm{NaBO}}_2$ and _H2${\mathrm{H}}_2$ was estimated to be 156.3 kJ/mol _NaBH4${\mathrm{NaBH}}_4$ according to Ozawa analysis method.     

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.     

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.     

Recent progress in the development of visible light-driven powdered photocatalysts for water splitting

Many photocatalyst materials for water splitting have been developed, particularly since the second half of the 1990s. Highly efficient water splitting on tantalate photocatalysts under UV irradiation has been achieved. Moreover, band engineering by doping, valence band formation, and synthesis of solid solutions, has led to the development of a large number of visible light-driven photocatalysts for _H2${\mathrm{H}}_2$ or _O2${\mathrm{O}}_2$ evolution from aqueous solutions containing electron donors or acceptors. Z-scheme photocatalyst systems for water splitting to _H2${\mathrm{H}}_2$ and _O2${\mathrm{O}}_2$ under visible light irradiation have been developed. This progress in the development of visible light-driven photocatalysts for water splitting is reviewed.     

Second law analysis of forced convection in a circular duct for non-Newtonian fluids

The second law characteristics of fluid flow and heat transfer inside a circular duct under fully developed forced convection for non-Newtonian fluids are presented. Heat flux is kept constant at the duct wall. Analytical expressions for dimensionless entropy generation number (_NS$N_{\mathrm{S}}$), irreversibility distribution ratio (Φ  ), and Bejan number (Be$\mathit{Be}$) are obtained as functions of dimensionless radius (R$R$), Peclet number (Pe$\mathit{Pe}$), modified Eckert number (Ec$\mathit{Ec}$), Prandtl number (Pr), dimensionless temperature difference (Ω  ), and fluid index (m$m$ or n$n$). Spatial distributions of local and average entropy generation number, irreversibility ratio, and Bejan number are presented graphically. For a particular value of fluid index, n=1$n=1$ (or m=2$m=2$), the general entropy generation number expression for a non-Newtonian power-law fluid reduces to the expression for Newtonian fluid as expected. Furthermore, entropy generation minimization is applied to calculate an optimum fluid index (_nEGM$n_{\mathrm{EGM}}$). A correlation is proposed that calculates _nEGM$n_{\mathrm{EGM}}$as a function of group parameter (Ec×Pr/Ω$\mathit{Ec}\times \mathit{Pr}/\Omega$) and Peclet number (Pe$\mathit{Pe}$) within ±5% accuracy. Finally, for some selected fluid indices, the governing equations are solved numerically in order to obtain Nusselt number. It is observed that the numerically obtained asymptotic Nusselt number shows excellent agreement with the analytically obtained Nusselt number.     

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.     

Experimental investigation on the effect of natural gas composition on performance of autothermal reforming

This paper presents experimental study on catalytic autothermal reforming (ATR) of natural gas (NG) for hydrogen (_H2${\mathrm{H}}_2$) production over sulfide nickel catalyst supported on gamma alumina. The experiments are conducted on a cylindrical reactor of 30 mm in diameter and 200 mm in length with “simulated” NG of different composition under thermal-neutral conditions and fed with different molar air to fuel ratio (A/F$A/F$) and molar water to fuel ratio (W/F)$(W/F)$. The results showed that reforming performance is significantly dependent on A/F$A/F$, W/F$W/F$ and concentration of _C2+${\mathrm{C}}_{2+}$ hydrocarbons in inlet fuel. Fuels containing higher _C2+${\mathrm{C}}_{2+}$ hydrocarbons concentration have optimum performance in terms of more _H2${\mathrm{H}}_2$ at higher A/F$A/F$ and W/F$W/F$ but lower conversion efficiency. Good performance for ATR of fuel containing 15%–20% _C2H6${\mathrm{C}}_2{\mathrm{H}}_6$ can be achieved at A/F=5–7$A/F=5–7$ and W/F=4–6$W/F=4–6$, much higher than that for optimum performance of ATR of methane (A/F=3,W/F=2–2.5$A/F=3,W/F=2–2.5$). _CO2${\mathrm{CO}}_2$ in the inlet fuel does not have significant effect on the reversed water–gas shift reaction. Its effect on reforming performance is mainly due to the dilution of inlet fuel and products.     

Catalytic hydrogen storage in cerium nickel and zirconium (or aluminium) mixed oxides

Interaction of hydrogen with a series of cerium nickel and zirconium (or aluminium) mixed oxides _CeM0.5NixOy${\mathrm{CeM}}_{0.5}{\mathrm{Ni}}_x{\mathrm{O}}_y$ (M=Zr$\mathrm{M}=\mathrm{Zr}$ or Al, 0?x?3$0?x?3$) has been studied in the 50–800 °C temperature range. Hydrogenation of 2-methyl-1,3-diene (isoprene) under helium flow in the absence of gaseous hydrogen is used to reveal and titrate reactive hydrogen species present in the solid previously treated under _H2${\mathrm{H}}_2$ at various temperatures. The _CeM0.5NixOy${\mathrm{CeM}}_{0.5}{\mathrm{Ni}}_x{\mathrm{O}}_y$ mixed oxides are large catalytic hydrogen reservoirs and among the solids studied, the highest amount of hydrogen (about 10 wt%, 540 g/L) is stored in _CeZr0.5Ni1Oy${\mathrm{CeZr}}_{0.5}{\mathrm{Ni}}_1{\mathrm{O}}_y$ pretreated in _H2${\mathrm{H}}_2$ at about 200 °C. Compared to the binary mixed oxides _CeNixOy${\mathrm{CeNi}}_x{\mathrm{O}}_y$, the presence of M allows to increase the hydrogen storage and give a better stability to the system, in particular, with temperature. Different physico-chemical techniques (TPR, TGA …) have been used to characterize the solids studied.     

Productive energy in the US economy

In this paper, methods of separation of primary work _EP$E_{\mathrm{P}}$, which is needed to provide the genuine work of production equipment, from the total amount of primary energy E$E$ are proposed. Direct estimates of primary work of production equipment _EP$E_{\mathrm{P}}$ on the base of available data for the US economy for the 20th century are compared with alternative evaluations of the same quantity calculated from time series for consumption of labour and primary energy. The relationship among primary energy E$E$, primary work of production equipment _EP$E_{\mathrm{P}}$, and genuine work of production equipment P$P$ (productive energy) is considered. The results allow one to estimate coefficient of efficiency of primary work of production equipment.     

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.     

Intake charge dilution effects on control of nitric oxide emission in a hydrogen fueled SI engine

Though hydrogen fueled spark ignition engine can operate at high thermal efficiency with almost zero emission of HC and CO, the high level of _NOx${\mathrm{NO}}_x$ poses problems. The high combustion temperature and lean mixtures used are the reasons. In this work, the effect of _N2${\mathrm{N}}_2$, _CO2${\mathrm{CO}}_2$ and hot EGR gas as diluents in the intake charge to suppress NO emission in a manifold injected hydrogen fueled SI engine was studied. Nitrogen as a diluent is not so effective at low loads while inducting smaller amounts, but very effective at higher loads where the mixture becomes richer and the dilution effect (oxygen depletion) is significant. On other hand, carbon dioxide is a good diluent with relatively better thermal effect and diluent effect and effectively controls NO emission at all output regions. However this is at the expense of thermal efficiency. Recirculating hot exhaust gas which contains both _N2${\mathrm{N}}_2$ and steam comes in between _N2${\mathrm{N}}_2$ and _CO2${\mathrm{CO}}_2$ in terms of its effectiveness. On the whole _N2${\mathrm{N}}_2$ is the most effective as it has minimum impact on thermal efficiency for a given level of permissible NO emission. Thus it is felt that cold EGR could be a good option. In all cases, a good control system is necessary to supply correct quantity of diluent.     

Effect of the equivalence ratio,Damköhler number,Lewis number and heat release on the stability of laminar premixed flames in microchannels

The effect of the equivalence ratio on the stability and dynamics of a premixed flame in a planar micro-channel with a step-wise wall temperature profile is numerically investigated using the thermo-diffusive approximation. To characterize the stability behavior of the flame, we construct the stability maps delineating the regions with different flame dynamics in the inlet mass flow rate m   vs. the equivalence ratio ?$?$ parametric space. The flame stability is analyzed for fuels with different diffusivity by changing the Lewis numbers in the range 0.3?_LeF?1.4$0.3?{\mathit{Le}}_F?1.4$. On the other hand, the Lewis number of the oxidizer is kept constant and equal to unity _LeO=1${\mathit{Le}}_O=1$. Our results show that, for very diffusive fuels, the stability of the flame varies significantly with the equivalence ratio, transitioning from stable flames for lean mixtures to highly unstable flames when ?>1$?>1$. As the fuel Lewis number approaches unity, the stability behavior of the flame for lean and rich mixtures becomes more similar to give, in the equidiffusional case _LeF=1${\mathit{Le}}_F=1$, a symmetric stability map around the stoichiometric mixture ?=1$?=1$. In all cases considered, the most stable flames are always found around the stoichiometric mixtures ?=1$?=1$, when the flame instabilities are completely suppressed for very diffusive fuels _LeF<1${\mathit{Le}}_F<1$, or are reduced to a narrow range of inflow velocities for fuel Lewis numbers equal or greater than unity.