Fritz Soot, Rollenbild, Kniestück

Signatur des Originals: S 36/F06628

Numerical simulation of the upward propagation of a flame in a vertical tube filled with a very lean mixture.

Upwardpropagation of a premixed flame in averticaltubefilled with a very leanmixture is simulated numerically using a single irreversible Arrhenius reaction model with infinitely high activation energy. In the absence of heat losses and preferential diffusion effects, a curved flame with stationary shape and velocity close to those of an open bubble ascending in the same tube is found for values of the fuel mass fraction above a certain minimum that increases with the radius of the tube, while the numerical computations cease to converge to a stationary solution below this minimum mass fraction. The vortical flow of the gas behind the flame and in its transport region is described for tubes of different radii. It is argued that this flow may become unstable when the fuel mass fraction is decreased, and that this instability, together with the flame stretch due to the strong curvature of the flame tip in narrow tubes, may be responsible for the minimum fuel mass fraction. Radiation losses and a Lewis number of the fuel slightly above unity decrease the final combustion temperature at the flame tip and increase the minimum fuel mass fraction, while a Lewis number slightly below unity has the opposite effect.

Curvature and velocity of methane-air Bunsen flame tips.

PIV and photographic recording are used to measure the velocity of the fresh gas and the shape of the reaction layer in a region around the tip of a methane-air Bunsen flame attached to a cylindrical burner. The results compare well with numerical simulations carried out with an infinite activation energy reaction model. The experimental and numerical results confirm that the well-known linear relation between flame velocity and flame stretch derived from asymptotic theory for weakly curved and strained flames is valid for small and moderate values of the flame stretch if the modified definition of stretch introduced by Echekki and Mungal (Proc Combust Inst 23:455–461, 1990) and Poinsot et al. (Combust Sci Technol 81:45–73, 1992) is used. However, the relation between flame velocity and modified stretch ceases to be linear and approaches a square root law for large values of the stretch, when the curvature of the flame tip becomes large compared to the inverse of the thickness of a planar flame.

Local burning velocity in a Bunsen jet flame

A PIV-based system has been set-up for the simultaneous measurement of the local burning velocity of premixed flames and the flame stretch due to the flame front curvature and the incoming flow strain rate. For moderately short jet flames, these measurements allow an indirect determination of the Markstein length, according to Clavin and Joulin (C–J) theory. For tall flames, the flame curvature becomes relatively large in a region around the tip where the C–J theory breaks down. However, our experiments confirm the appearance of a new linear relation between burning velocity and curvature at the flame tip. This relation defines a new proportionality factor which is probably associated to the evolution from rounded tips to slender tips when the jet velocity is increased.

Curvature and velocity of methane-air Bunsen flame tips

PIV and photographic recording are used to measure the velocity of the fresh gas and the shape of the reaction layer in a region around the tip of a methane- air Bunsen flame attached to a cylindrical burner. The results compare well with numerical simulations carried out with an infinite activation energy reaction model. The experimental and numerical results confirm that the well-known linear relation between flame velocity and flame stretch derived from asymptotic theory for weakly curved and strained flames is valid for small and moderate values of the flame stretch if the modified definition of stretch introduced by Echekki and Mungal (Proc Combust Inst 23:455–461,1990) and Poinsot et al. (Combust Sci Technol 81:45–73,1992) is used. However, the relation between flame velocity and modified stretch ceases to be linear and approaches a square root law for large values of the stretch, when the curvature of the flame tip becomes large compared to the inverse of the thickness of a planar flame

The structure of lean hydrogen-air flame balls

An analysis of the structure of flame balls encountered under microgravity conditions, which are stable due to radiant energy losses from H₂O, is carried out for fuel-lean hydrogen-air mixtures. It is seen that, because of radiation losses, in stable flame balls the maximum flame temperature remains close to the crossover temperature, at which the rate of the branching step H + O₂ -> OH + O equals that of the recombination step H + O₂ + M -> HO₂ + M. Under those conditions, all chemical intermediates have very small concentrations and follow the steady-state approximation, while the main species react according to the overall step 2H₂ + O₂-> 2H₂O; so that a one-step chemical-kinetic description, recently derived by asymptotic analysis for near-limit fuel-lean deflagrations, can be used with excellent accuracy to describe the whole branch of stable flame balls. Besides molecular diffusion in a binary-diffusion approximation, Soret diffusion is included, since this exerts a nonnegligible effect to extend the flammability range. When the large value of the activation energy of the overall reaction is taken into account, the leading-order analysis in the reaction-sheet approximation is seen to determine the flame ball radius as that required for radiant heat losses to remove enough of the heat released by chemical reaction at the flame to keep the flame temperature at a value close to crossover. The results are relevant to burning velocities at lean equivalent ratios and may influence fire-safety issues associated with hydrogen utilization.

Flammability conditions for ultra-lean hydrogen premixed combustion based on flame-ball analyses

It has been reasoned that the structures of strongly cellular flames in very lean mixtures approach an array of flame balls, each burning as if it were isolated, thereby indicating a connection between the critical conditions required for existence of steady flame balls and those necessary for occurrence of self-sustained premixed combustion. This is the starting assumption of the present study, in which structures of near-limit steady sphericosym-metrical flame balls are investigated with the objective of providing analytic expressions for critical combustion conditions in ultra-lean hydrogen-oxygen mixtures diluted with N2 and water vapor. If attention were restricted to planar premixed flames, then the lean-limit mole fraction of H2 would be found to be roughly ten percent, more than twice the observed flammability limits, thereby emphasizing the relevance of the flame-ball phenomena. Numerical integrations using detailed models for chemistry and radiation show that a onestep chemical-kinetic reduced mechanism based on steady-state assumptions for all chemical intermediates, together with a simple, optically thin approximation for water-vapor radiation, can be used to compute near-limit fuel-lean flame balls with excellent accuracy. The previously developed one-step reaction rate includes a crossover temperature that determines in the first approximation a chemical-kinetic lean limit below which combustión cannot occur, with critical conditions achieved when the diffusion-controlled radiation-free peak temperature, computed with account taken of hydrogen Soret diffusion, is equal to the crossover temperature. First-order corrections are found by activation-energy asymptotics in a solution that involves a near-field radiation-free zone surrounding a spherical flame sheet, together with a far-field radiation-conduction balance for the temperature profile. Different scalings are found depending on whether or not the surrounding atmosphere contains wáter vapor, leading to different analytic expressions for the critical conditions for flame-ball existence, which give results in very good agreement with those obtained by detailed numerical computations.

Preparation, characterisation and testing of CuO/Ce0.8Zr0.2O2 catalysts for NO oxidation to NO2 and mild temperature diesel soot combustion

CuO/ceria-zirconia catalysts have been prepared, deeply characterised (N2 adsorption–desorption isotherms at −196 °C, XRD, Raman spectroscopy, XPS, TEM and H2-TPR) and tested for NO oxidation to NO2 in TPR conditions, and for soot combustion at mild temperature (400 °C) in a NOx/O2 stream. The behaviour has been compared to that of a reference Pt/alumina commercial catalyst. The ceria-zirconia support was prepared by the co-precipitation method, and different amounts of copper (0.5, 1, 2, 4 and 6 wt%) were loaded by incipient wetness impregnation. The results revealed that copper is well-dispersed onto the ceria-zirconia support for the catalysts with low copper loading and CuO particles were only identified by XRD in samples with 4 and 6% of copper. A very low loading of copper increases significantly the activity for the NO oxidation to NO2 with regard to the ceria-zirconia support and an optimum was found for a 4% CuO/ceria-zirconia composition, showing a very high activity (54% at 348 °C). The soot combustion rate at 400 °C obtained with the 2% CuO/ceria-zirconia catalyst is slightly lower to that of 1% Pt/alumina in terms of mass of catalyst but higher in terms of price of catalyst.

Behavior of different soot combustion catalysts under NOx/O2. Importance of the catalyst–soot contact

Four different catalysts (Pt/Al2O3, Ce0.8Zr0.2O2, PrO2−x and SrTiCuO3) have been investigated on a laboratory scale to evaluate their potential as diesel soot combustion catalysts under different experimental conditions, which simulate the situation found in a continuous regeneration technology trap (dual-bed configuration of catalyst and soot) or a catalyst-coated filter system (single-bed configuration, both catalyst and soot particles mixed under loose-contact mode). Under dual-bed configuration, the behavior of the catalysts towards soot combustion are very similar, despite the differences observed in the NO2 production profiles. However, under single-bed configuration, there are important differences in the soot combustion activities and in the NO2 slip profiles. The configurations chosen have an enormous impact on CO/(CO + CO2) ratios of combustion products as well. The most active catalyst under NOx + O2 is PrO2−x combining a high contribution of active oxygen-assisted soot combustion as well as high NO2 production activity along the catalytic bed.

Evaluation of hectorites, synthesized in different conditions, as soot combustion catalysts after impregnation with copper

Two microporous hectorites were prepared by conventional and microwave heating, and a delaminated mesoporous hectorite by an ultrasound-assisted synthesis. These three hectorites were impregnated with copper. The characterization techniques used were XRD, N2 adsorption, TEM and H2 reduction after selective surface copper oxidation by N2O (to determine copper dispersion). The catalytic activity for soot combustion of the copper-free and the copper-containing hectorites was tested under a gas mixture of 500 ppm NOx/5% O2/N2 (and 5% O2/N2 in some cases), evaluating their stability through three consecutive soot combustion experiments. The delaminated hectorite showed the highest surface area (353 m2/g) allowing the highest dispersion of copper. This copper-containing catalyst was the most active for soot combustion among those prepared and tested in this study. We have also concluded that the Cu/hectorite-catalyzed soot combustion mechanism is based on the activation of the O2 molecule and not on the NO2-assisted soot combustion.

Isotopic study of ceria-catalyzed soot oxidation in the presence of NOx

The ceria-catalyzed soot oxidation mechanism has been studied by a pulse technique with labeled O2 in the absence and presence of NO, using ceria–soot mixtures prepared in the loose contact mode. In the absence of soot, the ceria-catalyzed oxidation of NO to NO2 takes place with ceria oxygen and not with gas-phase O2. However, the oxygen exchange process between gas-phase O2 and ceria oxygen (to yield back O2, but with oxygen atoms coming from ceria) prevailed with regard to the ceria-catalyzed oxidation of NO to NO2. Gas-phase O2 did not react directly with soot when pulsed to a soot–ceria loose contact mixture. Instead, ceria oxygen is transferred to soot (this step does not require gas-phase molecular oxygen to be present), and gas-phase O2 fills up the vacancies created on the oxide in a further step. The transfer of oxygen between ceria and soot occurred directly in the absence of NO. However, in the presence of NO, NO2 is expected to be additionally generated by ceria oxygen oxidation, which also reacts with soot. The main reaction products of the ceria-catalyzed soot oxidation reaction with NO/O2 were CO2 and NO. Additionally, evidence of the reduction of NOx to N2 was found.

Structural and photoelectrochemical properties of porous TiO2 nanofibers decorated with Fe2O3 by sol-flame

The hybrid structure of Fe2O3 nanoparticles/TiO2 nanofibers (NFs), combines the merits of large surface areas of TiO2 NFs and absorption in ultraviolet light–visible light range. This structure can be used for many applications such as photoelectrochemical water splitting and photo-catalysis. Here, a sol-flame method is used for depositing Fe2O3 on TiO2 NFs that were prepared by hydrothermal on Ti sheets. The obtained materials were characterized by XRD, SEM, UV/Vis diffuse reflectance, Raman, and XPS. The results revealed the formation of rutile and anatase crystalline phases together with Fe2O3. This process moves the absorption threshold of TiO2 NFs support into visible spectrum range and enhances the photocurrent in comparison to bare TiO2 NFs, although no hole scavenger was used. The impedance measurement at low and high frequencies revealed an increase in series resistance and a decrease in resistance of charge transfer with sol-flame treatment time. A mechanism for explaining the charge transfer in these TiO2 NFs decorated with Fe2O3 nanoparticles was proposed.