Demarcation of reaction effects on laminar burning velocities of diluted syngas–air mixtures at elevated temperatures

Laminar burning velocities of CO₂/N₂ (60%, 70%) diluted H₂/CO/air mixtures were measured at elevated temperatures using the externally heated diverging channel method. The computed burning velocities using the two reaction mechanisms (Davis et al., Proc. Combust. Inst. 2005;30(1):1283–1292; FFCM-1, http://nanoenergy.stanford.edu/ffcm1 ) are compared with the experimentally determined burning velocities. The accuracy of the chemical kinetic mechanisms at high dilution rates and elevated temperatures was investigated for various hydrogen fractions in the fuel composition. The burning velocity is observed to increase at high temperatures due to higher mixture enthalpy. The dilution effect on the variation of laminar burning velocity was stronger for the CO₂ dilution case compared to N₂ dilution. A comparison between the FFCM-1 mechanism and experimental measurements shows an accurate depiction of the reaction chemistry regarding the prediction of laminar burning velocities. The role of third-body reactions and direct inhibiting effect of N₂ and CO₂ molecules on burning velocity of diluted syngas–air mixtures is analyzed in detail. Detailed kinetic analysis revealed that the use of GRI 3.0 collision efficiency factors in the Davis mechanism helps in accurately predicting the burning velocities at elevated temperatures and high CO₂ dilution rates. The thermal effect dominates the reduction in laminar burning velocity for N₂ dilution case. The FFCM-1 mechanism agrees well with the experiments for syngas flames diluted with N₂ compared to the Davis mechanism. The addition of third-body efficiency of N₂ in the FFCM-1 mechanism improved the predictions of laminar burning velocities for the N₂ dilution case.     

Comparison of pulverized coal combustion in air and in O2/CO2 mixtures by thermo-gravimetric analysis

Thermo-gravimetric technique was used to study the combustion characteristics of pulverized coal in different O₂/CO₂ environments. The effects of combustion environment, oxygen concentration, particle size and heating rate were considered and the differences of pulverized coal pyrolysis, combustion and gaseous compounds release under two environments were analyzed. Results show that the coal pyrolysis in CO₂ environment can be divided into three stages: moisture release, devolatilization and char gasification by CO₂ in higher temperature zone. In the lower temperature zone, the mass loss rate of coal pyrolysis in CO₂ environment is lower than that in N₂ environment. The burning process of pulverized coal in O₂/CO₂ environment is delayed compared with that in O₂/N₂ environment for equivalent oxygen concentrations. With the oxygen concentration increase or the coal particle size decrease, the burning rate of coal increases and burnout time is shortened. As the heating rate increases, coal particles are faster heated in a short period of time and burnt in a higher temperature region, but the increase in heating rate has almost no obvious effect on the combustion mechanism of pulverized coal. During the programmed heating process, species in flue gas including H₂O, CO₂, CO, CH₄, SO₂ and NO were determined and analyzed using the Fourier-transform infrared (FTIR) spectrometer. Compared with pulverized coal combustion in O₂/N₂ environment, much more CO is produced in O₂/CO₂ coal combustion process, but the releases of SO₂ and NO are less than those released in O₂/N₂ environment. The present results might have important implications for understanding the intrinsic mechanics of pulverized coal combustion in O₂/CO₂ environment.     

The Effects of CO2 Additional on Flame Characteristics in the CH4/N2/O2 Counterflow Diffusion Flame

The effects (chemical, thermal, transport, and radiative) of CO₂ added to the fuel side and oxidizer side on the flame temperature and the position of the flame front in a one-dimensional laminar counterflow diffusion flame of methane/N₂/O₂ were studied. Overall CO₂ resulted in a decrease in flame temperature whether on the fuel side or on the oxidizer side, with the negative effect being more obvious on the latter side. The prominent effects of CO₂ on the flame temperature were derived from its thermal properties on the fuel side and its radiative properties on the oxidizer side. The results also highlighted the differences in the four effects of CO₂ on the position of the flame front on different sides. In addition, an analysis of OH and H radicals and the heat release rate of the main reactions illustrated how CO₂ affects the flame temperature.     

Effects of gas composition and flame sheathing on the spatial velocity profiles of laminar analytical acetylene flames

A recently developed technique has been employed to spatially map the rise velocity pronies (horizontal and vertical) of commonly used laminar analytical flames and to determine the influence on the profiles of fuel-to-oxidant ratio and the presence of a flame sheath. The rise velocities for fuel-rich, lean, and stoichiometric flames were found to differ substantially, the entire profile being greatest for the fuel-rich condition and lowest for the fuel-lean flame. In addition, the change in rise velocity with the addition of a solid (quartz tube) or gas (N₂) sheath was studied. The flowing sheath, at several different flow rates, affected each rise velocity profile principally by altering atmospheric entrainment and thereby changing secondary combustion in the flame. In contrast, a solid quartz tube used as a sheath produces an additional increase in the entire velocity profile of each flame, since it constrains gas expansion to the direction of flame propagation. The degree to which the velocity of each flame is affected by either a flowing N₂ and quartz sheath is strongly influenced by fuel-to-oxidant ratio.     

A study of oxy-coal combustion with steam addition and biomass blending by thermogravimetric analysis

The thermal characteristics of pulverized coal have been studied under oxy-fuel combustion conditions using non-isothermal thermogravimetric analysis (TG). The atmospheres used were 21%O₂/79%N₂, 21%O₂/79%CO₂, 30%O₂/70%O₂, and 35%O₂/65%CO₂. Coal blends of coal with 10 and 20% of biomass were also studied under these atmospheres. The addition of 10 and 20% of steam was evaluated for the oxy-fuel combustion atmospheres with 21 and 30% of O₂ in order to study the effect of the wet recirculation of flue gas. The results obtained were similar for all the different rank coals and indicated that replacing N₂ by CO₂ in the combustion atmosphere with 21% of O₂ caused a slight decrease in the rate of mass loss and delayed the burning process of the coal, biomass and coal/biomass blend samples. When the O₂ concentration was increased to 30 and 35% in the oxy-fuel combustion atmosphere, the rate of mass loss increased, the burning process occurred at lower temperatures and it was shorter in duration. An increase in the rate of mass loss and a reduction in burning time and temperature were observed after the addition of steam to the oxy-fuel combustion atmosphere. No relevant differences between the 10 and 20% steam concentrations were observed.     

Effects of inert gas CO2/N2 injection on coal low-temperature oxidation characteristic: Experiments and simulations

To deeply understand the mechanism of inert gases in inhibiting coal spontaneous combustion, the effects of dry air, CO₂, and N₂ on coal spontaneous combustion were analyzed experimentally. To this end, bituminous coal prepared from Dongrong No. 2 Coal Mine was considered the research object. Based on the adsorption configuration of the oxygen-containing coal, the displacement behavior of O₂ by CO₂ /N₂ was studied using the grand canonical Monte-Carlo (GCMC) and molecular dynamics (MD) methods. The obtained results show that the injection of CO₂ and N₂ reduces the ability of spontaneous combustion of coal. It is found that among the studied gases, CO₂ has a stronger inhibition effect on coal spontaneous combustion, which increases the temperature of CO occurrence by 5℃, decreases the concentration of CO by 29.91%, and inhibits low-temperature oxidation of coal. From the microscopic point of view, CO₂ /N₂ gases can effectively displace O₂ by diffusion and occupying adsorption sites. It is found that after the injection of CO₂, the concentration of O₂ molecules increases significantly in the vacuum layer. Compared with N₂, injection of CO₂ increases the diffusion activation of O₂ by 5.89%. This indicates that the injection of an inert gas significantly reduces the oxygen absorption capacity of coal, thereby decreasing the coal-oxygen combination reaction and preventing the spontaneous combustion of coal. The performed analyses demonstrate that CO₂ outperforms N₂ in restraining the spontaneous combustion of coal.     

Investigation of the correlation of sensitivity vectors of hydrogen combustion models

A well‐established method for the analysis of large reaction mechanisms is the calculation and interpretation of the sensitivity of the kinetic model output Y_i to parameter changes. Comparison of the sensitivity vectors s _i = {? Y_i/? p } belonging to different model outputs is a new tool for kinetic analysis. The relationship of the sensitivity vectors was investigated in homogeneous explosions, freely propagating and burner‐stabilized laminar flames of hydrogen–air mixtures, using either calculated adiabatic or constrained temperature profiles, for fuel‐to‐air ratios φ = 0.5–4.0. Sensitivity vectors are called locally similar, if the relationship s _i = λ_ij s _j is valid, where λ_ij is a scalar. In many systems, only approximate local similarity of the sensitivity vectors exists and the extent of it can be quantified by using an appropriate correlation function. In the cases of adiabatic explosions and burner‐stabilized flames, accurate local similarity was present in wide ranges of the independent variable (time or distance), and the correlation function indicated that the local similarity was not valid near the concentration extremes of the corresponding species. The regions of poor similarity were studied further by cobweb plots. The correlation relationships found could be interpreted by the various kinetic processes in the hydrogen combustion systems. The sensitivity vector of the laminar flame velocity is usually considered to be characteristic for the whole combustion process. Our investigations showed that the flame velocity sensitivity vector has good correlation with the H and H₂O concentration sensitivities at the front of the adiabatic flames, but there is poor correlation with the sensitivity vectors of all concentrations in homogeneous explosions. © 2004 Wiley Periodicals, Inc. Int J Chem Kinet 36: 238–252 2004     

Combustion of aluminum particles in a high-temperature furnace under various O2/CO2/H2O atmospheres

The study focusing on the combustion of flowing aluminum particles and the properties of condensed phase products has important guiding significance for the practical application of aluminum-based propellants. Based upon an in-house built dynamic combustion experimental system, the dynamic combustion process of aluminum particles and the properties of condensed phase products under different atmospheres were studied in detail. The microstructure, size distribution and active aluminum content of samples were analyzed by field emission scanning electron microscopy, laser particle analyzer and inductively coupled plasma atomic emission spectroscopy. By monitoring the temperature distribution at different points in the furnace, the heat release of the samples at different positions is approximated, and the combustion efficiency is calculated. In the atmosphere containing CO₂, the maximum combustion efficiency can reach the value of 94.41%, followed by that in H₂O atmosphere, which had the value of 81.19%. Finally, under the N₂ containing atmosphere, the combustion is the weakest, and has the value of only 53.91%, confirming that the combustion followed the following descending order: CO₂?>?H₂O?>?N₂. The condensed phase products were mainly composed of agglomerates formed by the aggregation of particles and alumina smoke. It is well known that the reaction of the sample in the furnace not only follows the melt-dispersion mechanism, but also the diffusion mechanism. The high-speed camera captured four typical combustion forms of aluminum particles during flow, which are stable combustion, release of alumina smoke, crushing and extinction. The average burning time of four stages were studied. The two reaction mechanisms occurring under the same reaction conditions are determined by the nature of aluminum particles themselves.

     

Uranium(VI) extraction with benzyloctadecyldimethylammonium chloride (BODMAC) from chloride and sulfate solutions

Summary The solvent extraction of uranium(VI) from concentrated chloride solutions by quaternary salt benzyloctadimethylammonium chloride (BODMAC, R₄NCl) in three diluents was studied. The composition of the extracted species was R₄N^. UO₂Cl₃and (R₄N)₂^. UO₂Cl₄in the three diluents investigated. The dependence of the distribution ratios on the concentration of hydrochloric acid, extractant, salting-out agents and temperature was investigated. The extraction efficiency of BODMAC strongly depends on the nature of the diluent. The presence of Mg(SO₄)₂basically alters the sequence of diluent extraction efficiency.     

Fast pyrolysis of coals under N2 and CO2 atmospheres

Oxyfuel combustion represents one way for cleaner energy production using coal as combustible. The comparison between the oxycombustion and the conventional air combustion process starts with the investigation of the pyrolysis step. The aim of this contribution is to evaluate the impact of N₂ (for conventional air combustion) and CO₂ (for oxy-fuel combustion) atmospheres during pyrolysis of three different coals. The experiments are conducted in a drop tube furnace over a wide temperature range 800–1400 °C and for residence time ranging between 0.2 and 1.2 s. Coal devolatilized in N₂ and CO₂ atmospheres at low temperatures (?1200 °C) and longer residence times (>?0.5 s), the char-CO₂ reaction is clearly observed, whose intensity depends on the nature of the coal. Furthermore, the volatile yields are simulated using Kobayashi’s scheme and kinetic parameters are predicted for each coal. The char gasification under CO₂ is also accounted for by the model.

     

Sulfur evolution from coal combustion in O2/CO2 mixture

O₂/CO₂ coal combustion technology is considered as one of the most promising technologies for CO₂ sequestration due to its economical advantages and technical feasibility. It is significant to study the sulfur transfer behavior of coal in O₂/CO₂ atmosphere for organizing combustion properly and controlling SO₂ emission effectively. To clarify the effect of atmosphere on the sulfur transfer behavior, thermogravimetry coupled with Fourier Transform Infrared (TG-FTIR) system was employed to study the formation behavior of sulfur-containing gas species from Xuzhou bituminous coal pyrolysis in CO₂ atmosphere compared with that in N₂ atmosphere. Also the SO₂ formation behaviors during Xuzhou bituminous coal combustion in O₂/N₂ and O₂/CO₂ atmospheres were investigated. Results show that COS is preferentially formed during the coal pyrolysis process in CO₂ atmosphere rather than in N₂ atmosphere. When temperature is above 1000 K, sulfate in the CO₂ atmosphere begins to decompose due to the reduction effect of CO, which comes from the CO₂ gasification. During coal combustion process, replacing N₂ with CO₂ enhances the SO₂ releasing rate. SO₂ emission increases first and then decreases as O₂ fraction increases in the O₂/CO₂ mixture. XPS result of the ash after combustion indicates that higher O₂ concentration elevates the sulfur retention ability of the mineral matter in the coal.     

Adsorption of CO<Subscript>2</Subscript>-containing gas mixtures over amine-bearing pore-expanded MCM-41 silica: application for CO<Subscript>2</Subscript> separation

Adsorption of CO₂, N₂, CH₄ and H₂ on triamine-grafted pore-expanded MCM-41 mesoporous silica (TRI-PE-MCM-41) was investigated at room temperature in a wide range of pressure (up to 25 bar) using gravimetric measurements. The material was found to exhibit high affinity toward CO₂ in comparison to the other species over the whole range of pressure. Column-breakthrough dynamic measurements of CO₂-containing mixtures showed very high selectivity toward CO₂ over N₂, CH₄ and H₂ at CO₂ concentrations within the range of 5 to 50%. These conditions are suitable for effective removal of CO₂ at room temperature from syngas, flue gas and biogas using temperature swing (TS) or temperature-pressure swing (TPS) regeneration mode. Moreover, TRI-PE-MCM-41 was found to be highly stable over hundreds of adsorption-desorption cycles using TPS as regeneration mode.     

Effects of Hydrogen Enhancement in LPG/Air Premixed Flame

A numerical study of hydrogen-enhanced liquefied petroleum gas (LPG) + air flames was presented. The variations of the adiabatic burning velocity in different conditions of combustion (?=0.7-1.4) were studied extensively. The hydrogen content in the fuel was varied from 0% to 45% and the dilution factor was from 21% to 16%. Since the major components of LPG are butane and propane, an appropriate chemical kinetic model must be chosen to solve the chemical reaction of C3 and C4 species. Validation of the chemical kinetic model against the fundamental combustion data was performed to insure accuracy. In addition, independent simulations were conducted in the opposed-jet, symmetric, twin-flame configuration. The effects of fluid mechanics, as manifested by the induced strain rate, were also considered. The effects of extinction strain rate on flame temperature and the flammability limits were calculated and the results showed that hydrogen-enhanced LPG/air premixed flames were more stable at high flame strain. The lean flammability limits were extended by the H₂ addition.     

On the role of transport in the combustion kinetics of a steady-state premixed laminar CO + H2 + O2 flame

The role of mechanistic steps, diffusion, and their interrelation is explored in a steady-state premixed laminar CO + H₂ + O₂ flame using a numerical model. Sensitivity coefficients and Green's functions calculated for this system offer systematic characterization of the role of diffusion and exothermicity in carbon monoxide oxidation kinetics. The results reveal that the uncertainties in transport parameters are as important to the model predictions as those in the kinetic steps. The rate controlling steps of the CO + H₂ + O₂ reaction are found to be different for adiabatic and nonadiabatic premixed flames, and also for systems with and without transport. In particular, the reactions of the hydroperoxyl radical with hydrogen, oxygen, and hydroxyl radicals are found to be important at all temperatures in the fuel lean (40 torr) adiabatic flame studied here. The diffusive mixing of chemical species from the low and the high temperature portions of the flame and the larger heats of reaction associated with the hydroperoxyl radicals are found to be responsible for the increased importance of these reactions. © 1994 John Wiley & Sons, Inc.     

Development of a Joint Hydrogen and Syngas Combustion Mechanism Based on an Optimization Approach

A comprehensive and hierarchical optimization of a joint hydrogen and syngas combustion mechanism has been carried out. The Kéromnès et al. (Combust Flame, 2013, 160, 995–1011) mechanism for syngas combustion was updated with our recently optimized hydrogen combustion mechanism (Varga et al., Proc Combust Inst, 2015, 35, 589–596) and optimized using a comprehensive set of direct and indirect experimental data relevant to hydrogen and syngas combustion. The collection of experimental data consisted of ignition measurements in shock tubes and rapid compression machines, burning velocity measurements, and species profiles measured using shock tubes, flow reactors, and jet‐stirred reactors. The experimental conditions covered wide ranges of temperatures (800–2500 K), pressures (0.5–50 bar), equivalence ratios (? = 0.3–5.0), and C/H ratios (0–3). In total, 48 Arrhenius parameters and 5 third‐body collision efficiency parameters of 18 elementary reactions were optimized using these experimental data. A large number of directly measured rate coefficient values belonging to 15 of the reaction steps were also utilized. The optimization has resulted in a H₂/CO combustion mechanism, which is applicable to a wide range of conditions. Moreover, new recommended rate parameters with their covariance matrix and temperature‐dependent uncertainty ranges of the optimized rate coefficients are provided. The optimized mechanism was compared to 19 recent hydrogen and syngas combustion mechanisms and is shown to provide the best reproduction of the experimental data.     

Improving effect of boron carbide on the combustion and thermal oxidation characteristics of amorphous boron

Boron carbide (B₄C) is one of the main products from the primary combustion of boron (B)-based propellants and has a significant influence on the secondary combustion of B. To systematically evaluate its effects on the secondary combustion of B, mixtures of B₄C and B in different mass ratios were prepared. To study the ignition temperatures and combustion flames of the samples, a xenon lamp ignition experimental system and a flame shape test system were designed, respectively. A thermogravimetry–differential scanning calorimetry–Fourier transform infrared spectroscopy combined thermal analysis system was used to study the thermal oxidation characteristics and analyze the gaseous products of the samples. The results indicate that B₄C reduces the heat absorption at the beginning of the ignition, but subsequently prevents the rapid rise of sample temperature. During the stable combustion stage, the maximum flame length under optical density 10⁻⁴ (OD4) filter was 20.4 mm, and the maximum flame length under 580 nm + OD4 filters (represents the combustion of B element) was 16.7 mm. The samples contained a small amount of HBO₂ and H₃BO₃, which led to slight mass loss during the low temperature section of the thermal oxidation process. During the high temperature section, the oxidation of B and B₄C caused considerable mass gain. The gaseous products of the thermal oxidation process include CO₂, CO, and H₂O. In general, the B content of 60% was the most beneficial to decrease the oxidation temperature, increase the combustion intensity, and improve the heat-releasing ability of the samples.

     

Frontispiece: Induced-Fit-Identification in a Rigid Metal-Organic Framework for ppm-Level CO2 Removal and Ultra-Pure CO Enrichment

Removing CO₂ from crude syngas via physical adsorption is an effective method to yield eligible syngas. However, the bottleneck in trapping ppm-level CO₂ and improving CO purity at higher working temperatures are major challenges. Here we report a thermoresponsive metal–organic framework ( 1 a-apz ), assembled by rigid Mg₂(dobdc) ( 1 a ) and aminopyrazine (apz), which not only affords an ultra-high CO₂ capacity (145.0/197.6 cm³ g⁻¹ (0.01/0.1 bar) at 298 K) but also produces ultra-pure CO (purity ≥99.99 %) at a practical ambient temperature (T_A). Several characterization results, including variable-temperature tests, in situ high-resolution synchrotron X-ray diffraction (HR-SXRD), and simulations, explicitly unravel that the excellent property is attributed to the induced-fit-identification in 1 a-apz that comprises self-adaption of apz, multiple binding sites, and complementary electrostatic potential (ESP). Breakthrough tests suggest that 1 a-apz can remove CO₂ from 1/99 CO₂/CO mixtures at practical 348 K, yielding 70.5 L kg⁻¹ of CO with ultra-high purity of ≥99.99 %. The excellent separation performance is also revealed by separating crude syngas that contains quinary mixtures of H₂/N₂/CH₄/CO/CO₂ (46/18.3/2.4/32.3/1, v/v/v/v/v).     

Numerical study of the laminar flame propagation in ethane-air mixtures

The structure of premixed free one-dimensional laminar ethane-air flames was investigated by means of numerical simulations performed with a detailed mechanism (GRI-Mech version 3.0) by means of COSILAB package. The work provides data on ethane-air mixtures with a wide range of concentrations ([C₂H₆] = 3.0–9.5 vol.%) at initial temperatures between 300 and 550 K and initial pressures between 1 and 10 bar. The simulations deliver the laminar burning velocities and the profiles of temperature, chemical species concentrations and heat release rate across the flame front. The predicted burning velocities match well the burning velocities measured in various conditions, reported in literature. The influence of initial concentration, pressure and temperature of ethane-air mixtures on maximum flame temperature, heat release rate, flame thickness and peak concentrations of main reaction intermediates is examined and discussed.      

The influence of Kr, CO2, and iso-C4H8 admixtures on the time of the formation of a stable flame front in mixtures of natural gas and isobutylene with oxygen and hydrogen with air under initiation with a spark discharge

High-speed color filming was used to study laminar spherical flame propagation at the initial stage in preliminarily mixed stoichiometric mixtures of natural gas and isobutylene with oxygen containing krypton and carbon dioxide and in hydrogen-air mixtures at atmospheric pressure in a bomb with a constant volume. Under experimental conditions (T ₀ = 298 K, p ₀ = 100 torr, spark discharge energy E ₀ = 0.91 J), the dilution of mixtures with Kr and CO₂ increased the time of formation of a stable flame front by more than 10 times. The introduction of a small chemically active admixture (1.2% isobutylene) into a stoichiometric mixture of hydrogen and air sharply increased the time of formation of a stable flame front, which was evidence of an important role played by the chemical mechanism of the reaction in the formation of the combustion field.