The effect of diluent on flame structure and laminar burning speeds of JP-8/oxidizer/diluent premixed flames

Experimental studies have been performed to investigate the flame structure and laminar burning speed of JP-8/oxidizer/diluent premixed flames at high temperatures and pressures. Three different diluents including argon, helium, and a mixture of 14% CO₂ and 86% N₂ (extra diluent gases), were used. The experiments were carried out in two constant volume spherical and cylindrical vessels. Laminar burning speeds were measured using a thermodynamics model based on the pressure rise method. Temperatures from 493 to 700 K and pressures from 1 to 11.5 atm were investigated. Extra diluent gases (EDG) decrease the laminar burning speeds but do not greatly impact the stability of the flame compared to JP-8/air. Replacing nitrogen in the air with argon and helium increases the range of temperature and pressure in the experiments. Helium as a diluent also increases the temperature and pressure range of stable flame as well as the laminar burning speed. Power law correlations have been developed for laminar burning speeds of JP-8/air/EDG and JP-8/oxygen/helium mixtures at a temperature range of 493-700 K and a pressure range of 1-10 atm for lean mixtures.     

Comparative study of CO and CO2 hydrogenation over supported Rh–Fe catalysts

The hydrogenation of CO, CO + CO₂, and CO₂ over titania-supported Rh, Rh–Fe, and Fe catalysts was carried out in a fixed-bed micro-reactor system nominally operating at 543 K, 20 atm, 20 cm³ min^− 1 gas flow (corresponding to a weight hourly space velocity (WHSV) of 8000 cm³ g_cat^− 1 h^− 1), with a H₂:(CO + CO₂) ratio of 1:1. A comparative study of CO and CO₂ hydrogenation shows that while Rh and Rh–Fe/TiO₂ catalysts exhibited appreciable selectivity to ethanol during CO hydrogenation, they functioned primarily as methanation catalysts during CO₂ hydrogenation. The Fe/TiO₂ sample was primarily a reverse water gas shift catalyst. Higher reaction temperatures favored methane formation over alcohol synthesis and reverse water gas shift. The effect of pressure was not significant over the range of 10 to 20 atm.     

Influence of vent air valve opening on combustion characteristics of a down-fired pulverized-coal 300 MWe utility boiler

Industrial experiments have been performed on a down-fired pulverized-coal 300 MWe utility boiler with vent air valve opening of 100% and 40%. The gas temperature distribution along the primary air and coal mixture flow, gas temperature distribution in the furnace, and gas components such as O₂, CO, CO₂ and NO_x in the near-wall region were measured for the first time. The influence of vent air valve opening on coal combustion in the furnace was determined. The results indicate that ignition of the primary air and pulverized-coal mixture is delayed. The position of the gas temperature peak is above the arches. Emission of NO_x is up to 2101 mg/m³ (at 6% O₂ dry) with vent valve opening of 40%.     

Liquid fuel production from syngas using bifunctional CuO-CoO-Cr2O3 catalyst mixed with MFI zeolite

CuO-CoO-Cr₂O₃ mixed with MFI Zeolite (Si/Al = 35) prepared by co-precipitation was used for synthesis gas conversion to long chain hydrocarbon fuel. CuO-CoO-Cr₂O₃ catalyst was prepared by co-precipitation method using citric acid as complexant with physicochemical characterization by BET, TPR, TGA, XRD, H₂-chemisorptions, SEM and TEM techniques. The conversion experiments were carried out in a fixed bed reactor, with different temperatures (225-325 °C), gas hourly space velocity (457 to 850 h⁻¹) and pressure (28-38 atm). The key products of the reaction were analyzed by gas chromatography mass spectroscopy (GC-MS). Significantly high yields of liquid aromatic hydrocarbon products were obtained over this catalyst. Higher temperature and pressure favored the CO conversion and formation of these liquid (C₅-C₁₅) hydrocarbons. Higher selectivity of C₅ + hydrocarbons observed at lower H₂/CO ratio and GHSV of the feed gas. On the other hand high yields of methane resulted, with a decrease in C₅+ to C₁₁+ fractions at lower GHSV. Addition of MFI Zeolite (Si/Al = 35) to catalyst CuO-CoO-Cr₂O₃ resulted a high conversion of CO-hydrogenation, which may be due to its large surface area and small particle size creating more active sites. The homogeneity of various components was also helpful to enhance the synergistic effect of Co promoters.     

Laminar burning velocities of n-heptane, iso-octane, ethanol and their binary and tertiary mixtures

Measurements of the adiabatic laminar burning velocities of n-heptane, iso-octane, ethanol and their binary and tertiary mixtures are reported. Non-stretched flames were stabilized on a perforated plate burner at 1 atm. The Heat Flux method was used to determine burning velocities under conditions when the net heat loss from the flame to the burner is zero. Initial temperatures of the gas mixtures with air were 298 and 338 K. Uncertainties of the measurements were analyzed and assessed experimentally. The overall accuracy of the burning velocities was estimated to be better than ±1 cm/s. These new measurements were compared with the literature data when available. Experimental results in lean ethanol + air mixtures are systematically higher than previous measurements under similar conditions. Good agreement for n-heptane + air flames and for iso-octane + air flames was found with the experiments performed in counter-flow twin flames with linear extrapolation to zero stretch.     

Modeling of non-catalytic partial oxidation of natural gas under conditions found in industrial reformers

Non-catalytic partial oxidation of natural gas/O₂/H₂O mixture at elevated pressures was simulated kinetically using Chemkin package incorporating detailed reaction mechanisms of methane oxidation. The dependence of reaction time was investigated as a function of inlet temperature, system pressure, and O₂/CH₄ ratio. The conversion to products was predicted to complete within a residence time of less than 0.1 ms at pressures greater than 30 atm and temperatures higher than 1450 K. A minimum O₂/CH₄ ratio of 0.64 was found necessary for a complete methane conversion at the conditions typical for the industrial reformer. The effect of O₂/H₂O in the feed gas was examined computationally, and the results suggested that adding H₂O in the feed gas could be a viable tool for adjusting the H₂/CO ratio in the products and for controlling the flame temperature. Formations of higher order hydrocarbons and soot, which may play important roles in the actual fuel-rich conversion environment, are not considered in the present study.     

Preparation, characterization and electrical conductivity studies of NdYb1−xGdxZr2O7 (0 ≤ x ≤ 1.0) ceramics

Several compositions of NdYb_1−xGd_xZr₂O₇ (0 ≤ x ≤ 1.0) ceramics were prepared by pressureless-sintering method at 1973 K for 10 h in air. The relative density, microstructure and electrical conductivity of NdYb_1−xGd_xZr₂O₇ ceramics were analyzed by the Archimedes method, X-ray diffraction, scanning electron microscopy and impedance plots measurements. NdYb_1−xGd_xZr₂O₇ (0 ≤ x ≤ 0.3) ceramics have a single phase of defect fluorite-type structure, and NdYb_1−xGd_xZr₂O₇ (0.7 ≤ x ≤ 1.0) ceramics exhibit a single phase of pyrochlore-type structure; however, the NdYb_0.5Gd_0.5Zr₂O₇ composition shows mixed phases of both defect fluorite-type and pyrochlore-type structures. The measured values of the grain conductivity obey the Arrhenius relation. The grain conductivity of each composition in NdYb_1−xGd_xZr₂O₇ ceramics gradually increases with increasing temperature from 673 to 1173 K. NdYb_1−xGd_xZr₂O₇ ceramics are oxide-ion conductor in the oxygen partial pressure range of 1.0 × 10⁻⁴ to 1.0 atm at all test temperature levels. The highest grain conductivity value obtained in this work is 1.79 × 10⁻² S cm⁻¹ at 1173 K for NdYb_0.3Gd_0.7Zr₂O₇ composition.     

Enhanced oxygen permeation through perovskite hollow fibre membranes by methane activation

Hollow fibre membranes of mixed conducting perovskite La_0.6Sr_0.4Co_0.2Fe_0.8O₃ (LSCF) were prepared via the combined phase inversion and sintering technique. The fibres were tested for air separation with a home-made reactor under the oxygen partial pressure gradient generated by the air/He streams. Some fibres were in situ activated by introducing methane in the He sweeping gas at high temperatures. The activated membranes with new morphology were created by transforming the inner densified surface layer to a porous structure. Compared to the original membranes, the activated gave appreciable higher oxygen fluxes. At 800 °C, the oxygen fluxes were increased by a factor of 10 after activation was carried out at 1000 °C for 1 h.     

Performance of a slurry bubble column reactor for Fischer-Tropsch synthesis: Determination of optimum condition

The CO conversion and selectivity to C₁+ and C₁₁+ wax products over Co/Al₂O₃ as well as Ru/Co/Al₂O₃ Fischer-Tropsch (F-T)catalysts were investigated by varying reaction temperature (210-250 °C), system pressure (1.0-3.0 MPa), GHSV (1000-6000 L/kg/h), superficial gas velocity (1.7-13.6 cm/s) and slurry concentration (9.09-26.67 wt.%) in a slurry bubble column reactor (0.05 m diameter × 1.5 m height) to determine the optimum operating conditions. Squalane or paraffin wax was used as initial liquid media. The overall CO conversion increased with increasing reaction temperature, system pressure and catalyst concentration. However, the local maximum CO conversion was exhibited at GHSV of 1500-2000 L/kg/h and superficial gas velocity of 3.4-5.0 cm/s. The CO conversion in the case of Ru/Co/Al₂O₃ was much higher and stable than that in the case of Co/Al₂O₃. The selectivity to C₁₁+ wax products increased slightly with increasing GHSV; on the other hand, it decreased with increasing reaction temperature, system pressure, and solid concentration in a slurry bubble column reactor. It could be concluded that the optimum operating conditions based on the yield of hydrocarbons and wax products were; U_G = 6.8-10 cm/s, Cs = 15 wt.%, T = 220-230 °C, P = 2.0 MPa in a slurry bubble column reactor for F-T synthesis.     

Effects of the operating variables on hydrotreating of heavy gas oil: Experimental, modeling, and kinetic studies

The effects of H₂ purity, pressure, gas/oil ratio, temperature, and LHSV on hydrotreating activities were investigated in a micro-trickle bed reactor using a commercial NiMo/γ-Al₂O₃ catalyst. Heavy gas oil (HGO) from Athabasca bitumen was used as feed. Due to their significant effects on H₂ partial pressure, H₂ purity, pressure, and gas/oil ratio were chosen and used in a central composite design (CCD) method. Experimental conditions used were H₂ purity, pressure, and gas/oil ratio were: 75-100 vol.% (with the rest methane), 7-11 MPa, and 400-1200 mL/mL, respectively. The effect of LHSV (0.65-2 h⁻¹) and temperature (360-400 °C) were studied in a separate set of experiments. Vapor/liquid equilibrium (VLE) calculations were performed to determine the inlet and outlet H₂ partial pressures. It was observed that the enhancing effects of H₂ purity on hydrodenitrogenation (HDN) and hydrodearomatization (HDA) activities were greater than that of gas/oil ratio; however, it was comparable to pressure. Hydrodesulphurization (HDS) activity was not considerably affected by H₂ purity, pressure, or gas/oil ratio. Increasing LHSV led to a decrease in HDS, HDN, and HDA activities while increasing temperature resulted in an increase in HDS and HDN; HDA had maximum activity at about 385 °C. Kinetic fitting of the data to a pseudo-first-order power law model suggested that conclusions on hydrotreating activities’ responses to a changing H₂ pressure could be equally drawn from either inlet or outlet H₂ partial pressure. However, from the catalyst deactivation standpoint, it is recommended that such conclusions are drawn from the outlet H₂ partial pressure.     

Non-premixed fluidized bed combustion of C1-C4n-alkanes

The non-premixed combustion of C₁-C₄n-alkanes with air was investigated inside a bubbling fluidized bed of inert sand particles at intermediate temperatures: 923 K ? T_B ? 1123 K. For ethane, propane and n-butane, combustion occurred mainly in the freeboard region at bed temperatures below T₁ = 923 K. On the other hand, complete conversion occurred within 0.2 m of the injector at: T₂ = 1073 K. For methane, the measured values of T₁ and T₂ were significantly higher at 1023 K and above 1123 K, respectively. The fluidized bed combustion was accurately modeled with first-order global kinetics and one PFR model to represent the main fluidized bed body. The measured global reaction rates for C₂-C₄n-alkanes were characterized by a uniform Arrhenius expression, while the global reaction rate for methane was significantly slower. Reactions in the injector region either led to significant conversion in that zone or an autoignition delay inside the main fluidized bed body. The conversion in the injector region increased with rising fluidized bed temperature and decreased with increasing jet velocity. To account for the promoting and inhibiting effects, an analogy was made with the concept of induction time: the PFR length (b_i) of the injector region was correlated to the fluidized bed temperature and jet velocity using an Arrhenius expression. These results show that the conversion of C₂-C₄n-alkanes can be estimated with one set of critical bed temperatures and modeled with one Arrhenius kinetics expression.     

Effects of initial temperature on the structure of laminar CH4-air premixed flames

The growing popularity of natural gas as a eco-friendly fuel, is of paramount motivation of present investigation. In the present paper, the effect of initial temperature on the flame structure have been investigated in which laminar one-dimensional planar propagating flames of CH₄/air mixtures is simulated numerically using detailed chemical kinetic scheme and realistic transport models. The burning velocities are fundamentally important in developing models to predict progress of combustion. Hence, the burning velocities as a function of initial temperature of unburnt gas have been computed for stoichiometric mixture. The present predictions of burning velocities are compared with reported experimental data of Stone et al. [Combust. Flame. 114 (1998) 546], Hill and Huang [Combust. Sci. Technol. 60 (1980) 7] and Rallis and Garforth [Combust. Flame 31 (1978) 53]. The present prediction lies within the scatter of experimental data. A correlation in the form of S_u/S_u,0=(T_u/T_u,0)^1.575 has been developed to describe the dependence of initial temperature on the burning velocity for stoichiometric mixture. The structures of flame are investigated in details for initial temperature of 300 and 600 K which clearly indicate that detailed chemical kinetics are essential for prediction of the effects of initial temperature on the burning velocities. The present study will help in designing and developing the regenerative combustion systems.     

Upgrading biomass pyrolysis gas by conversion of methane at high temperature: Experiments and modelling

Biomass gasification at temperatures below 1273 K produces gas which contains methane and too much tar for Fischer-Tropsch synthesis. The aim of this study is to investigate methane conversion at high temperature. Experimental tests were performed between 1273 and 1773 K, with a mixture of gas representative of wood pyrolysis at 1100 K (main components only: CO, CO₂, CH₄, H₂, H₂O). Two different kinetic schemes were used to predict the gas composition, and PAH molecules formation. For a residence time of 2 s in the reactor, the gas must be heated to at least 1650 K to reach a methane conversion rate of 90%. A parametric study was performed at 1453 K, by varying the initial methane, steam and hydrogen contents, so as to find out which components are the most influent on methane conversion and soot production.     

Thermodynamic analysis of dry autothermal reforming of glycerol

Dry autothermal reforming of glycerol uses a combination of dry (CO₂) reforming and partial oxidation reactions to produce syngas rich product stream. Thermodynamic equilibrium data for dry autothermal reforming of glycerol was generated for temperature range 600-1000 K, 1 bar pressure, OCGR [feed O₂/C (C of glycerol only) ratio] 0.1 to 0.5 and CGR [feed CO₂/glycerol ratio] 1 to 5 and analyzed. The objective of the paper is to identify the thermodynamic domain of the process operation, study the variation of product distribution pattern and describe the optimum conditions to maximize yield of the desired product and minimize the undesired product formation. Higher OCGR and higher CGR yielded a syngas ratio (∼ 1), with lower carbon and methane formation, while lower CGR and lower OCGR yielded good hydrogen and total hydrogen, with low water and CO₂ production. The best thermoneutral condition for DATR of glycerol operation was seen at a temperature of 926.31 K at 1 bar pressure, OCGR = 0.3 and CGR = 1 that gave 2.67 mol of hydrogen, 4.8 mol of total hydrogen with negligible methane and carbon formations.     

Catalytic steam reforming of model biogas

Catalytic steam reforming of a model biogas (CH₄/CO₂ = 60/40) is investigated to produce H₂-rich synthesis gas. Gas engines benefit from synthesis gas fuel in terms of higher efficiency and lower NO_x production when compared to raw biogas or CH₄. The process is realized in a fixed bed reactor with a Ni-based catalyst on CaO/Al₂O₃ support. To optimize the performance, the reactor temperature and the amount of excess steam are varied. The experimental results are compared to the theoretical values from thermodynamic calculation and the main trends of CH₄ conversion and H₂ yield are analyzed and verified. Finally, optimal reactor temperature is pointed out and a range of potential steam to methane ratios is presented. The experimental results will be applied to design a steam reformer at an existing anaerobic biomass fermentation plant in Strem, Austria.     

La1−xSrxFeO3−δ perovskites as redox materials for application in a membrane reactor for simultaneous production of pure hydrogen and synthesis gas

This work reports on the preparation and characterization of perovskitic materials with the general formula La_1−xSr_xFeO₃ (x = 0, 0.3, 0.7, 1) for application in a dense mixed conducting membrane reactor process for simultaneous production of synthesis gas and pure hydrogen. Thermogravimetric experiments indicated that the materials are able to loose and uptake reversibly oxygen from their lattice up to 0.2 oxygen atoms per “mole” for SrFeO₃ with x = 1 at 1000 °C. The capability of the prepared powders to convert CH₄ during the reduction step, in order to produce synthesis gas, as well as their capability to dissociate water during the oxidation step, in order to produce hydrogen were evaluated by pulse reaction experiments in a fixed bed pulse reactor. The high sintering temperatures (1100-1300 °C) required for the densification of the membrane materials result in decreased methane conversion and H₂ yields during the reduction step compared to the corresponding values obtained with the perovskite powders calcined at 1000 °C. Addition of small quantities of NiO, by simple mechanical mixing, to the perovskites after their sintering at high temperatures, increases substantially both their methane decomposition reactivity, their selectivity towards CO and H₂ and their water splitting activity. Maximum H₂ yield during the reduction step is achieved with the La_0.7Sr_0.3FeO₃ sample mixed with 5% NiO and is 80% of the theoretically expected H₂, based on complete methane decomposition. In the oxidation - water splitting step, 912 μmol H₂ per gr solid are produced with the La_0.3Sr_0.7FeO₃ sample mixed with 5% NiO. The experimental results of this work can be equally well applied for the “chemical-looping reforming” process since they concern using the lattice oxygen of the perovskite oxides for methane partial oxidation to syngas, in the absence of molecular oxygen, and subsequent oxidation of the solid.     

Ultra-stability of gas hydrates at 1 atm and 268.2 K

This paper details creation of methane sI hydrates that are much more stable at 1 atm and 268.2 K than any previously reported. Extraordinarily stable natural gas sII hydrates at 1 atm and 268.2-270.2 K are reported for the first time. Test innovations that achieved ultra-stabilities give insight into hydrate self-preservation mechanisms. Water-surfactant liquid solutions were used to nucleate hydrate crystals that adsorbed as extremely small particles on surfaces of high thermal conductivity. The small hydrate particles packed and consolidated symmetrically upon Al or Cu cylindrical surfaces, minimizing internal void spaces and fractures in the accumulated 250-400 g hydrate mass. Resulting hydrate stability window is 268.2-270.2 K at 1 atm. Methane sI, as well as natural gas sII, hydrates exhibit only minimal decomposition upon reducing confining system pressure to 1 atm in the 268.2-270.2 K stability window. Total gas that evolved after 24 h at 1 atm in the stability window typically amounted to less than 0.5% of originally stored gas, and this ultra-stability was shown to persist when the test was allowed to run 256 h before terminating. The entire methane sI or natural gas sII hydrate mass remains stable during pressure reduction to 1 atm, whereas previous reports defined hydrate anomalous stability for only about 50% of fractional hydrate remnants.     

Effects of temperature and composition on the laminar burning velocity of CH4 + H2 + O2 + N2 flames

This work summarises available measurements of laminar burning velocities in CH₄ + H₂ + O₂ + N₂ flames at atmospheric pressure performed using a heat flux method. Hydrogen content in the fuel was varied from 0% to 40%, amount of oxygen in the oxidiser was varied from 20.9% down to 16%, and initial temperature of the mixtures was varied from 298 to 418 K. These mixtures could be formed when enrichment by hydrogen is combined with flue gas recirculation. An empirical correlation for the laminar burning velocity covering a complete range of these measurements is derived and compared with experiments and other correlations from the literature.     

Hydrodynamic and mass transfer characterization of a flat-panel airlift photobioreactor with high light path

This work evaluates the volumetric mass transfer coefficient (k_La), the gas hold-up (?) and the mixing time (t_m) as a function of superficial gas velocity (U_G) in a flat-panel photobioreactor (PBR) with high light path. CO₂ utilization efficiency and volumetric power consumption (P/V) were also evaluated. A 50 L working volume photobioreactor was developed, 0.67 m in length, 0.57 m in height and 0.15 m in width (light path). The height-width ratio was 3.8, which is lower than reported in most PBRs. Initially, experiments were performed with air and tap water (biphasic system) and, subsequently, using a Spirulina sp. culture (triphasic system: air, culture medium, cells). Minimum and maximum superficial gas velocity values were 5 × 10⁻⁵ and 8.4 × 10⁻³ m s⁻¹, respectively. Maximum values for k_La and ? were 20.34 h⁻¹ (0.0057 s⁻¹) and 0.033 in the biphasic system, and 31.27 h⁻¹ (0.0087 s⁻¹) and 0.065 in the triphasic system. CO₂ utilization efficiency was 30.57%. Results indicate that the hydrodynamic and mass transfer characteristics of this photobioreactor are more efficient than those reported elsewhere for tubular and other flat-plate PBRs, which opens the possibility of using PBRs with higher light paths than yet proposed.     

Application of the thermal DeNOx process to diesel engine DeNOx: an experimental and kinetic modelling study

Diesel DeNO_x experiments have been conducted using the selective noncatalytic ‘thermal DeNO_x’ process in a diesel fuelled combustion-driven flow reactor which simulated a single cylinder (966 cm³) and head equipped with a water-cooling jacket and an exhaust pipe. NH₃ was directly injected into the cylinder to reduce NO_x emissions. A wide range of air/fuel ratios (A/F=20-40) was selected for NO_x reduction where an initial NO_x of 530 ppm was usually maintained with a molar ratio (β=NH₃/NO_x) of 1.5.The results indicate that a 34% NO_x reduction can be achieved from the cylinder injection in the temperature range, 1100-1350 K. Most of the NO_x reduction occurs within the cylinder and head section (residence time<40 ms), since temperatures in the exhaust are too low for additional NO_x reduction. Under large gas quenching rates, increasing β values (e.g. 4.0) substantially increase the NO_x reduction up to 60%, which is comparable with those achieved under isothermal conditions. Experimental findings are analysed by chemical kinetics using the Miller and Bowman mechanism including both N/H/O species and CO/hydrocarbon reactions to account for CO/UHC oxidation effects, based on practical nonisothermal conditions. Comparisons of the kinetic calculations with the experimental data are given as regards temperature characteristics, residence time and molar ratio. In addition, the effects of CO/UHC and branching ratio (α=k₁/(k₁+k₂)) for the reaction NH₂+NO=products are discussed in terms of NO reduction features, together with practical implications.