Dynamic modes of infiltration-mediated combustion in a tubular reactor

In this work, we analyzed some regularities of frontal steady-state filtration combustion in moving porous media in tubular reactors. We analyzed the profiles temperature, concentration, pressure, rate of heat release, and velocity of combustion front propagation. Analysis was carried out in terms of 1D model from the moment of reaction ignition until onset of steady-state frontal regime. Special emphasis was made on the processes of front stabilization, non-uniqueness of steady-state regimes, and stable periodical regimes. Analyzed is the stability on combustion waves arising in the reactor. The results can be expected to extend the applicability range for the theory of filtration combustion.      

Initiation of combustion of a CH<Subscript>4</Subscript>-O<Subscript>2</Subscript> mixture in a supersonic flow with excitation of O<Subscript>2</Subscript> molecules by an electric discharge

The possibility of intensification of ignition of a methane-oxygen mixture in a supersonic flow behind the front of an oblique shock wave by means of excitation of O₂ molecules to the states a ¹Δ_g and b ¹Σ_g⁺ in an electric discharge is discussed. Through numerical simulations, activation of O₂ molecules by an electric discharge is demonstrated to speed up chain reactions in the CH₄-O₂ mixture and to reduce the induction-zone length. Even a small amount of energy input to O₂ molecules in the discharge (≈3·0⁻² J/cm³) can reduce the ignition-delay length by a factor of hundreds and initiate combustion at distances of ≈1 m from the discharge zone at comparatively low temperatures of the gas behind the front (≈1000 K) and moderate pressures (≈10⁵ Pa). Excitation of O₂ molecules by an electric discharge is much more efficient than simple heating of the mixture. __________ Translated from Fizika Goreniya i Vzryva, Vol. 44, No. 3, pp. 3–16, May–June, 2008.     

Effect of heat release conditions on the phase composition of the combustion products of a Fe<Subscript>2</Subscript>O<Subscript>3</Subscript>/TiO<Subscript>2</Subscript>/Al/C thermite mixture

An X-ray method was used to study the phase composition of the combustion products of a Fe₂O₃/TiO₂/Al/C thermite composite mixture, in particular, during combustion of samples under cooling by water. The data of the experiments are compared with the results of thermodynamic calculations. A probable explanation of the reasons of the angular displacement of the line of iron in the X-ray spectrum of the combustion products and a mechanism for the crystallization of an eutectic TiC + α-Fe mixture from the melt of the Ti/Fe/C ternary system. The composition of the combustion products was found to be different from the equilibrium one, which is manifested in the presence of defects in the carbon sublattice of titanium carbide. A probable explanation of the deficiency of carbon is proposed. __________ Translated from Fizika Goreniya i Vzryva, Vol. 44, No. 4, pp. 39–43, July–August, 2008.     

Field-activated pressure-assisted combustion synthesis of MoSi<Subscript>2</Subscript>

The simultaneous synthesis and densification of MoSi₂ starting from elemental Mo and Si was carried out through a process of field-activated pressure-assisted combustion synthesis (FAPACS). After heating up to 922°C, the synthesis reaction occurs in the mode of thermal explosion but is ceased subsequently due to a sudden shock. The product consists of MoSi₂, residual Mo and amorphous Si with precipitation of very small MoSi₂ primary crystals containing. There is no transition phase layer between Mo and MoSi₂ as well as Si and MoSi₂. This indicates that metallic Mo reacts with molten Si directly forming MoSi₂ in the FAPACS process, without any intermediate reaction steps involved. The formation of MoSi₂ occurs via dissolution of Mo into Si melt followed by MoSi₂ precipitation from the melt.      

SHS of composite ceramics from mechanochemically treated and thermally carbonized SiO<Subscript>2</Subscript> powders

New ceramic composites have been synthesized upon combined use of mechanochemical treatment (MCT) of SiO₂, its thermal carbonization (followed by baking), and SHS in a mixture of thus activated (carbonized) SiO₂ with Al powder. MCT and thermal carbonization were found to result in formation of fiber-like carbon structures on the surface of silica particles. The rigid carbon frameworks formed on the surface of silicon dioxide were found to improve the physicochemical properties of resultant carbon-containing refractory materials.      

Investigation of a new lead-free Bi<Subscript>0.5</Subscript>(Na<Subscript>0.40</Subscript>K<Subscript>0.10</Subscript>)TiO<Subscript>3</Subscript>-(Ba<Subscript>0.7</Subscript>Sr<Subscript>0.3</Subscript>)TiO<Subscript>3</Subscript> piezoelectric ceramic

Lead-free piezoelectric compositions of the (1-x)Bi_0.5(Na_0.40K_0.10)TiO₃-x(Ba_0.7Sr_0.3)TiO₃ system (when x = 0, 0.05, 0.10, 0.15, and 0.20) were fabricated using a solid-state mixed oxide method and sintered between 1,050°C and 1,175°C for 2 h. The effect of (Ba_0.7Sr_0.3)TiO₃ [BST] content on phase, microstructure, and electrical properties was investigated. The optimum sintering temperature was 1,125°C at which all compositions had densities of at least 98% of their theoretical values. X-ray diffraction patterns that showed tetragonality were increased with the increasing BST. Scanning electron micrographs showed a slight reduction of grain size when BST was added. The addition of BST was also found to improve the dielectric and piezoelectric properties of the BNKT ceramic. A large room-temperature dielectric constant, ε _r (1,609), and piezoelectric coefficient, d ₃₃ (214 pC/N), were obtained at an optimal composition of x = 0.10.     

Electrochemical treatment of ammonia in wastewater by RuO<Subscript>2</Subscript>–IrO<Subscript>2</Subscript>–TiO<Subscript>2</Subscript>/Ti electrodes

This study investigated the removal of ammonia in wastewater by an electrochemical method using titanium electrodes coated with ruthenium and iridium (RuO₂–IrO₂–TiO₂/Ti) with low chlorine evolution over-voltage. The effects of operating parameters, including chloride ion concentration, current density and initial pH, were also investigated. The results were evaluated primarily by considering the efficiency of the elimination of NH₄⁺-N. The removal of ammonia by electrochemical oxidation mainly resulted from the indirect oxidation effect of chlorine/hypochlorite produced during electrolysis. The direct anodic oxidation efficiency of ammonia was less than 5%, and the current efficiency was less than 10%. The ammonia removal followed pseudo-first-order kinetics. The electrochemical process can be applied successfully as a final polishing step, or as an alternative method to biological nitrification. The process seems to be most beneficial for small coastal cities     

Adsorption characteristics analysis of CO<Subscript>2</Subscript> and N<Subscript>2</Subscript> in 13X zeolites by molecular simulation and N<Subscript>2</Subscript> adsorption experiment

The adsorption characteristics of CO₂ and N₂ in 13X zeolites have been studied by the molecular simulation and N₂ adsorption experiment. It is found that the simulation results by Dreiding force fields are in an agreement with the published data. The influence of the σ and ε parameters of O_Z and Na⁺ on the adsorption performance is discussed. Then the optimized force field parameters are obtained. Specific surface area (S _B ) is calculated by simulation and experiment. Its relative error is just only 4.3 %. Therefore, it is feasible that S _B of 13X zeolites is obtained by the simulation methods. Finally, the impacts of pressure and temperature on adsorption characteristics are investigated. At low pressure, CO₂ adsorption in 13X zeolites belongs to the surface adsorption. As the pressure increase, the partial multilayer adsorption appears along with the surface adsorption. N₂ adsorption in 13X zeolites is different from that of CO₂. At low temperature of 77 K, two primary peaks are caused by the surface adsorption and multilayer adsorption respectively regardless of pressure variation. When the temperature is 273 K, the energy distribution curve appears undulate at low pressures. Then it becomes stable with the pressure increase. The surface adsorption plays an important role at the relative high pressures. The results will help to provide the theory guide for the optimization of force field parameters of adsorbents, and it is very important significance to understand the adsorption performance of zeolites.     

Structure of an atmospheric-pressure H<Subscript>2</Subscript>/O<Subscript>2</Subscript>/N<Subscript>2</Subscript> flame doped with iron pentacarbonyl

This paper presents the measurement and simulation data on the thermal and chemical structure of an atmospheric-pressure premixed H₂/O₂/N₂ flame doped with iron pentacarbonyl Fe(CO)₅. Soft ionization molecular beam mass spectrometry was used to measure concentration profiles of the combustion products of iron pentacarbonyl: Fe, FeO₂, FeOH, and Fe(OH)₂. A comparison of experimental and simulated concentration profiles showed that they are in satisfactory agreement for FeO₂ and Fe(OH)₂ and differ significantly for Fe and FeOH. Thus, the previously proposed kinetic model for the oxidation of iron pentacarbonyl was tested and it was shown that the mechanism needs further elaboration.     

Separation characteristics of tetrapropylammoniumbromide templating silica/alumina composite membrane in CO<Subscript>2</Subscript>/N<Subscript>2</Subscript>, CO<Subscript>2</Subscript>/H<Subscript>2</Subscript> and CH<Subscript>4</Subscript>/H<Subscript>2</Subscript> systems

Nanoporous silica membrane without any pinholes and cracks was synthesized by organic templating method. The tetrapropylammoniumbromide (TPABr)-templating silica sols were coated on tubular alumina composite support ( γ-Al₂O₃/ α-Al₂O₃ composite) by dip coating and then heat-treated at 550 °C. By using the prepared TPABr templating silica/alumina composite membrane, adsorption and membrane transport experiments were performed on the CO₂/N₂, CO₂/H₂ and CH₄/H₂ systems. Adsorption and permeation by using single gas and binary mixtures were measured in order to examine the transport mechanism in the membrane. In the single gas systems, adsorption characteristics on the α-Al₂O₃ support and nanoporous unsupport (TPABr templating SiO₂/ γ-Al₂O₃ composite layer without α-Al₂O₃ support) were investigated at 20–40 °C conditions and 0.0–1.0 atm pressure range. The experimental adsorption equilibrium was well fitted with Langmuir or/and Langmuir-Freundlich isotherm models. The α-Al₂O₃ support had a little adsorption capacity compared to the unsupport which had relatively larger adsorption capacity for CO₂ and CH₄. While the adsorption rates in the unsupport showed in the order of H₂> CO₂> N₂> CH₄ at low pressure range, the permeate flux in the membrane was in the order of H₂≫N₂> CH₄> CO₂. Separation properties of the unsupport could be confirmed by the separation experiments of adsorbable/non-adsorbable mixed gases, such as CO₂/H₂ and CH₄/H₂ systems. Although light and non-adsorbable molecules, such as H₂, showed the highest permeation in the single gas permeate experiments, heavier and strongly adsorbable molecules, such as CO₂ and CH₄, showed a higher separation factor (CO₂/H₂=5-7, CH₄/H₂=4-9). These results might be caused by the surface diffusion or/and blocking effects of adsorbed molecules in the unsupport. And these results could be explained by surface diffusion. This paper is dedicated to Professor Hyun-Ku Rhee on the occasion of his retirement from Seoul National University.     

Evaluation of pressure-temperature swing adsorption for sulfur hexafluoride (SF<Subscript>6</Subscript>) recovery from SF<Subscript>6</Subscript> and N<Subscript>2</Subscript> gas mixture

The separation/concentration of SF₆, a strong greenhouse gas, of 1.3% in N₂ was investigated using pressure-temperature swing adsorption (PTSA) with activated carbon. To screen an effective adsorbent to be used for PTSA, adsorption isotherms on the selected adsorbents were obtained. Among the studied adsorbents, AC-1, a coconut-shell based commercial activated carbon, showed the largest adsorption amount of 3.5 mmol-SF₆/g-carbon at 303.65 K and 3 atm and the highest selectivity among the adsorbents tested. Its adsorption isotherm was well fit into Langmuir-Freundlich model. Before feasibility test of PTSA, a series of experiments were performed to investigate the effect of operating parameters including adsorption pressure, feed flow rate, desorption temperature and evacuation time on the PTSA performance using the 3-step PTSA cycle (pressurization, adsorption and regeneration-recovery). As the adsorption pressure, desorption temperature and evacuation time were increased, respectively, purity and recovery increased. Increasing the feed flow rate resulted in low purity and recovery. The maximum purity of 19.5% and recovery of 50.1% were obtained with adsorption pressure of 2.5 atm, desorption temperature of 200 °C and evacuation of 1 hour.     

Impacts of Water Table Management on N<Subscript>2</Subscript>O and N<Subscript>2</Subscript> from a Sandy Loam Soil in Southwestern Quebec,Canada

Nitrous oxide (N₂O) is primarily produced as intermediate in denitrification and, to a lesser extent, through nitrification processes. Nitrous oxide emission and, consequently, its atmospheric impacts depend on the extent to which N₂O is reduced to dinitrogen gas (N₂) by denitrifiers. Field experiments were conducted from 1998 through 2000 growing seasons at St. Emmanuel, Quebec, Canada, to investigate the combined impact of water table management (WTM) and N fertilization rate on the soil denitrification (N₂O + N₂) rate, rate of N₂O production, and the N₂O:N₂O + N₂ ratio. Water table treatments included subirrigation (SI) with a target water table depth of 0.6 m and free drainage (FD) with open drains. The tile drains (75 mm diameter) were laid at a 1.0 m depth from the soil surface. Nitrogen fertilizer was applied at two rates:120 and 200 kg N ha⁻¹ as ammonium nitrate (34-0-0). The N₂O + N₂ evolution rates were greater in SI (12.9 kg N ha⁻¹) than in FD (5.8 kg N ha⁻¹) plots. The percentages of N₂O relative to overall N₂O + N₂ evolution were 35 and 11% for 1998, 29 and 8% for 1999, and 37 and 20% for 2000, under FD and SI, respectively. The reduced N₂O production under SI was due to a greater reduction of N₂O to N₂. Results indicate that greater N₂O + N₂ evolution under shallow water tables are not necessarily accompanied by higher N₂O emissions.     

Gel-casted porous Al<Subscript>2</Subscript>O<Subscript>3</Subscript> ceramics by use of natural fibres as pore developers

An approach using ceramic shaping by gel-casting and addition of natural tropical fibres as burnable pore developers has been explored for development of porous alumina materials with predetermined pore structures. The fibres used have been characterized in terms of size, shape, water uptake and surface charge. The degree of fibres loading in slurry has been varied. It has been shown that the amount of added fibres correlates well with the measured porosity, the shape of the developed pores however deviating slightly with that of the introduced fibres. The ceramic bodies have been characterised in terms of porosity, shrinkage and flexural strength. It could be assumed that at fibres amount in slurry above 30% V, an open porosity appears which is accompanied by a sharp drop in strength. In order to explore the benefits of the gel-casting method for complex bodies development, two key issues need to be addressed: air evacuation prior to casting and lowering slurry viscosity at fibre loadings higher than the tested ones. For reaching the latter objective, surface modification of fibres has been undertaken.     

Li<Subscript>2</Subscript>Cu<Subscript>2</Subscript>(MoO<Subscript>4</Subscript>)<Subscript>3</Subscript>/TiO<Subscript>2</Subscript> + SiO<Subscript>2</Subscript>/Ti compositions for the catalytic afterburning of diesel soot

Two methods were used to obtain a catalytically active oxide coating on the surface of titanium for the catalytic afterburning of diesel soot: plasma electrochemical formation of an oxide film on the surface of titanium and extraction pyrolytic deposition of the Li₂Cu₂(MoO₄)₃ compound. The Li₂Cu₂(MoO₄)₃/TiO₂ + SiO₂/Ti compositions synthesized by the single-step extraction pyrolytic treatment of the oxidized surface of titanium ensured a high burning rate of soot of ∼300°C. The subsequent deposition of Li₂Cu₂(MoO₄)₃ lowers the activity of the catalyst, due probably to the growth of molybdate phase crystallites and the filling of open oxide film pores. Double lithium-copper molybdate is able to reduce appreciably the concentration of CO in the oxidation products of soot. The advantages of these methods are the possibility of forming high-cohesion durable coatings on surfaces of any complexity, the simplicity of their implementation, and high productivity and low cost. The obtained results can be recommended for use in developing methods for creating composite coatings on catalytic soot filters.     

Fungal and bacterial contributions to codenitrification emissions of N<Subscript>2</Subscript>O and N<Subscript>2</Subscript> following urea deposition to soil

Grazed pastures contribute significantly to anthropogenic emissions of N₂O but the respective contributions of archaea, bacteria and fungi to codenitrification in such systems is unresolved. This study examined the relative contributions of bacteria and fungi to rates of denitrification and codenitrification under a simulated ruminant urine event. It was hypothesised that fungi would be primarily responsible for both codenitrification and total N₂O and N₂ emissions. The effects of bacterial (streptomycin), fungal (cycloheximide), and combined inhibitor treatments were measured in a laboratory mesocosm experiment, on soil that had received ¹⁵N labelled urea. Soil inorganic-N concentrations, N₂O and N₂ gas fluxes were measured over 51 days. On Days 42 and 51, when nitrification was actively proceeding in the positive control, the inhibitor treatments inhibited nitrification as evidenced by increased soil NH ₄ ⁺ -N concentrations and decreased soil NO ₂ ^? -N and NO ₃ ^? -N concentrations. Codenitrification was observed to contribute to total fluxes of both N₂O (≥ 33%) and N₂ (≥ 3%) in urine-amended grassland soils. Cycloheximide inhibition decreased NH ₄ ⁺ –¹⁵N enrichment and reduced N₂O fluxes while reducing the contribution of codenitrification to total N₂O fluxes by ≥ 66 and ≥ 42%, respectively. Thus, given archaea do not respond to significant urea deposition, it is proposed that fungi, not bacteria, dominated total N₂O fluxes, and the codenitrification N₂O fluxes, from a simulated urine amended pasture soil.     

Influences of phase transition and microstructure on dielectric properties of Bi<Subscript>0.5</Subscript>Na<Subscript>0.5</Subscript>Zr<Subscript>1-x</Subscript>Ti<Subscript>x</Subscript>O<Subscript>3</Subscript> ceramics

Bismuth sodium zirconate titanate ceramics with the formula Bi_0.5Na_0.5Zr_1-xTi_xO₃ [BNZT], where x = 0.3, 0.4, 0.5, and 0.6, were prepared by a conventional solid-state sintering method. Phase identification was investigated using an X-ray diffraction technique. All compositions exhibited complete solubility of Ti⁴⁺ at the Zr⁴⁺ site. Both a decrease of unit cell size and phase transition from an orthorhombic Zr-rich composition to a rhombohedral crystal structure in a Ti-rich composition were observed as a result of Ti⁴⁺ substitution. These changes caused dielectric properties of BNZT ceramics to enhance. Microstructural observation carried out employing SEM showed that average grain size decreased when addition of Ti increased. Grain size difference of BNZT above 0.4 mole fraction of Ti⁴⁺ displayed a significant increase of dielectric constant at room temperature.     

Effect of the addition of triphenylphosphine oxide,hexabromocyclododecane, and ethyl bromide on a CH<Subscript>4</Subscript>/O<Subscript>2</Subscript>/N<Subscript>2</Subscript> flame at atmospheric pressure

The chemical and thermal structure of a Mache-Hebra burner stabilized premixed rich CH₄/O₂/N₂ flame with additives of vapors of triphenylphosphine oxide [(C₆H₅)₃PO], hexabromocyclododecane (C₁₂H₁₈Br₆), and ethyl bromide (C₂H₅Br) was studied experimentally using molecular beam mass spectrometry (MBMS) and a microthermocouple method. The concentration profiles of stable and active species, including atoms and free radicals, and flame temperature pro.les were determined at a pressure of 1 atm. A comparison of the experimental and modeling results on the flame structure shows that MBMS is a suitable method for studying the structure of flames stabilized on a Mache-Hebra burner under near-adiabatic conditions. The relative flame inhibition effectiveness of the added compounds is estimated from changes in the peak concentrations of H and OH radicals in the flame and from changes in the flame propagation velocity. The results of the investigation suggest that place of action of the examined flame retardants is the gas phase. __________ Translated from Fizika Goreniya i Vzryva, Vol. 43, No. 5, pp. 12–20, September–October, 2007.     

Mechanism of reaction-front propagation in the Cr<Subscript>2</Subscript>O<Subscript>3</Subscript> + 2Al mixture

Results of a combustion study of a powder mixture of Cr₂O₃ and Al burnt in an argon flow are reported. The combustion process is affected by a pressure difference along the filler by evacuating one end of the reaction cell. Effects of the initial density, gasifiable additive (borax or sodium carbonate), and pressure difference on specific features of the combustion process are examined. The data obtained were interpreted within the convective-conductive combustion theory of heterogeneous condensed systems.     

Unexpected Support Effect in Hydrotreating: Evidence of a Metallic Character for ReS<Subscript>2</Subscript>/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> and ReS<Subscript>2</Subscript>/SiO<Subscript>2</Subscript> Catalysts

Abstract  

Rhenium sulfide based catalysts were prepared by the incipient wetness impregnation method over alumina and silica supports and evaluated for 4,6-dimethyldibenzothiophene hydrodesulfurization in a high-pressure stirred-tank reactor. The catalyst prepared over silica was about six times more active for hydrodesulfurization than the corresponding catalyst prepared over alumina and a NiMo/Al₂O₃ industrial reference catalyst. This surprising and positive SiO₂ support effect was explained by a metallic character of the supported sulfide, which was demonstrated using a kinetic approach of competitive hydrogenations and by XPS characterization.     

Embedding Noble-Metal-Free Ni<Subscript>2</Subscript>P Cocatalyst on g-C<Subscript>3</Subscript>N<Subscript>4</Subscript> for Enhanced Photocatalytic H<Subscript>2</Subscript> Evolution in Water Under Visible Light

Photocatalytic hydrogen evolution is considered as one of the promising pathways to settle the energy crises and environmental issues by utilizing solar energy. In this paper, noble-metal-free Ni₂P was used as cocatalyst to enhance g-C₃N₄ for photocatalytic hydrogen production under visible light irradiation (λ?>?420 nm). Characterization results indicated that Ni₂P nanoparticles were successfully loaded onto g-C₃N₄, which can significantly contribute to accelerate the separation and transfer of photogenerated electron. The hydrogen evolution rate reached ～?270 µmol h^?1 g^?1 and the apparent quantum yield (AQY) was ～?2.85% at 420 nm. Meanwhile, there is no obviously decrease of the hydrogen production rate even after 36 h under visible light illumination. In addition, the mechanism of photocatalytic hydrogen evolution was also elaborated in detail.

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