Effect of gasification reactions on biomass char conversion under pulverized fuel combustion conditions

The effect of gasification reactions on biomass char conversion under pulverized fuel combustion conditions was studied by single particle experiments and modelling. Experiments of pine and beech wood char conversion were carried out in a single particle combustor under conditions of 1473-1723 K, 0.0-10.5% O₂, and 25-42% H₂O. A comprehensive progressive char conversion model, including heterogeneous reactions (char oxidation and char gasification with CO₂ and H₂O), homogeneous reactions (CO oxidation, water-gas shift reaction, and H₂ oxidation) in the particle boundary layer, particle shrinkage, and external and internal heat and mass transfer, was developed. The modelling results are in good agreement with both experimental char conversion time and particle size evolution in the presence of oxygen, while larger deviations are found for the gasification experiments. The modelling results show that the char oxidation is limited by mass transfer, while the char gasification is controlled by both mass transfer and gasification kinetics at the investigated conditions. A sensitivity analysis shows that the CO oxidation in the boundary layer and the gasification kinetics influence significantly the char conversion time, while the water-gas shift reaction and H₂ oxidation have only a small effect. Analysis of the sensitive parameters on the char conversion process under a typical pulverized biomass combustion condition (4% O₂, 13% CO₂, 13% H₂O), shows that the char gasification reactions contribute significantly to char conversion, especially for millimeter-sized biomass char particles at high temperatures.     

Effect of CO2 gasification reaction on oxy-combustion of pulverized coal char

For oxy-combustion with flue gas recirculation, as is commonly employed, it is recognized that elevated CO₂ levels affect radiant transport, the heat capacity of the gas, and other gas transport properties. A topic of widespread speculation has concerned the effect of the CO₂ gasification reaction with coal char on the char burning rate. To give clarity to the likely impact of this reaction on the oxy-fuel combustion of pulverized coal char, the Surface Kinetics in Porous Particles (SKIPPY) code was employed for a range of potential CO₂ reaction rates for a high-volatile bituminous coal char particle (130 μm diameter) reacting in several O₂ concentration environments. The effects of boundary layer chemistry are also examined in this analysis. Under oxygen-enriched conditions, boundary layer reactions (converting CO to CO₂, with concomitant heat release) are shown to increase the char particle temperature and burning rate, while decreasing the O₂ concentration at the particle surface. The CO₂ gasification reaction acts to reduce the char particle temperature (because of the reaction endothermicity) and thereby reduces the rate of char oxidation. Interestingly, the presence of the CO₂ gasification reaction increases the char conversion rate for combustion at low O₂ concentrations, but decreases char conversion for combustion at high O₂ concentrations. These calculations give new insight into the complexity of the effects from the CO₂ gasification reaction and should help improve the understanding of experimentally measured oxy-fuel char combustion and burnout trends in the literature.     

An analysis of the transient combustion and burnout time of carbon particles

The various coupled and transient processes controlling the gasification mechanism and burnout time of carbon particles were analyzed, with emphasis on the influence of the initial particle size for the size range that is relevant to the firing of pulverized solid fuels. The formulation recognizes the suppression of the envelop gas-phase CO flame because of the small particle size, and allows for the three surface reactions of C + O₂, C + CO₂, and C + H₂O, as well as radiation heat transfer because of the potential high temperature attainable by the carbon particle. Results show that while the particle temperature continuously increases during the combustion of sufficiently large particles, the gasification actually consists of three phases: namely an initial particle heating period, an activation period for the surface reactions, and a diffusion-controlled, d²-law gasification period characterized by perpetually maximized surface reaction rates in spite of the continuously decreasing particle size. Radiation heat transfer is shown to have the same magnitude as those of reaction heat release and conduction, and actively affects the particle gasification response. For smaller particles, activation of the surface reactions is either substantially delayed subsequent to the initial heating period, or is completely suppressed, which respectively leads to either long burnout times or incomplete particle gasification. Influences due to the ambient oxygen concentration and the presence of CO₂ and H₂O as the oxidizer were also studied. Comparisons with literature experimental data show adequate agreement.     

Second virial coefficient for a mixture of nonspherical molecules of arbitrary symmetry

The mixture and interaction second virial coefficients of a binary gas mixture of nonspherical molecules of arbitrary symmetry have been calculated for a set of unlike force parameters which is obtained from the force parameters for like interactions by using empirical combination rules. In the calculation molecular anisotropy of very general type has been accounted. The relative contribution of each branch of interactions has been evaluated as a function of temperature. The theoretical values of interaction second virial coefficient have been compared with the experimental data of N₂+A, N₂+He, N₂+H₂, N₂+O₂, N₂+C₂H₄, N₂+C₂H₆, CO₂+A, CO₂+H₂, CO₂+N₂, CO₂+O₂, CO₂+CO, CO₂+C₂H₄, CO₂+C₂H₆, O₂+A and H₂+CO. The agreement between theory and experiment is satisfactory for all the systems. Numerical estimations of the mixture second virial coefficients as a function of temperature and composition are given for the systems CO₂+A, CO₂+H₂, CO₂+N₂, CO₂+O₂ and CO₂+CO.     

Quantifying the effect of CO2 gasification on pulverized coal char oxy-fuel combustion

Previous research has provided strong evidence that CO₂ and H₂O gasification reactions can provide non-negligible contributions to the consumption rates of pulverized coal (pc) char during combustion, particularly in oxy-fuel environments. Fully quantifying the contribution of these gasification reactions has proven to be difficult, due to the dearth of knowledge of gasification rates at the elevated particle temperatures associated with typical pc char combustion processes, as well as the complex interaction of oxidation and gasification reactions. Gasification reactions tend to become more important at higher char particle temperatures (because of their high activation energy) and they tend to reduce pc oxidation due to their endothermicity (i.e. cooling effect). The work reported here attempts to quantify the influence of the gasification reaction of CO₂ in a rigorous manner by combining experimental measurements of the particle temperatures and consumption rates of size-classified pc char particles in tailored oxy-fuel environments with simulations from a detailed reacting porous particle model. The results demonstrate that a specific gasification reaction rate relative to the oxidation rate (within an accuracy of approximately +/- 20% of the pre-exponential value), is consistent with the experimentally measured char particle temperatures and burnout rates in oxy-fuel combustion environments. Conversely, the results also show, in agreement with past calculations, that it is extremely difficult to construct a set of kinetics that does not substantially overpredict particle temperature increase in strongly oxygen-enriched N₂ environments. This latter result is believed to result from deficiencies in standard oxidation mechanisms that fail to account for falloff in char oxidation rates at high temperatures.     

Elucidation of mechanisms of ion—molecule reactions by ICR

The mechanisms of some positive and negative ion—molecule reactions have been determined by a quantitative ion cyclotron double-resonance technique with isotopically labelled reactants. Four types of mechanism were elucidated: charge transfer, ion transfer, atom abstraction and complex formation. Thus, charge transfer is shown to be the only major reaction channel in the systems CO⁺ + CO₂, SO⁻ + SO₂, and O⁻ + NO₂, while in the system Cl₂⁻ + Cl₂ CO ion transfer is the main mechanism, and complex formation with oxygen-atom scrambling is the major channel in O⁻ + N₂O.The experimental results also point out cases where the reaction proceeds by more than one mechanism as, for example, in the reaction system H₂O⁺ + H₂O.     

On the reaction mechanism of CO2 reforming of methane over a bed of coal char

CO₂ reforming of methane was studied over a bed of coal char in a fixed bed reactor at temperatures between 1073 and 1223 K and atmospheric pressure with a feed composition of CH₄/CO₂/N₂ in the ratio of 1:1:8. Experimental results showed that the char was an effective catalyst for the production of syngas with a maximum H₂/CO ratio of one. It was also found that high H₂/CO ratios were favoured by low pressures and moderate to high temperatures. These results are supported by thermodynamic calculations. A mechanism of seven overall reactions was studied and three catalytic reactions of CH₄ decomposition, char gasification and the Boudouard reaction was identified as being of major importance. The first reaction produces carbon and H₂, the second consumes carbon, and the third (the Boudouard reaction) converts CO₂ to CO while consuming carbon. Equilibrium calculations and experimental results showed that any water present reacts to form H₂ and carbon oxides in the range of temperatures and pressures studied. Carbon deposition over the char bed is the major cause of deactivation. The rate of carbon formation depends on the kinetic balance between the surface reaction of the adsorbed hydrocarbons with oxygen containing species and the further dissociation of the hydrocarbon.     

Theoretical study on the catalytic properties of single-atom catalyst stabilised on silicon-doped graphene sheets

ABSTRACT

The stable configurations, electronic structures and catalytic activities of single-atom metal catalyst anchored silicon-doped graphene sheets (3Si-graphene-M, M?=?Ni and Pd) are investigated by using density functional theory calculations. Firstly, the adsorption stability and electronic property of different gas reactants (O₂, CO, 2CO, CO/O₂) on 3Si-graphene-M substrates are comparably analysed. It is found that the coadsorption of O₂/CO or 2CO molecules is more stable than that of the isolated O₂ or CO molecule. Meanwhile, the adsorbed species on 3Si-graphene-Ni sheet are more stable than those on the 3Si-graphene-Pd sheet. Secondly, the possible CO oxidation reactions on the 3Si-graphene-M are investigated through Eley–Rideal (ER), Langmuir–Hinshelwood (LH) and new termolecular Eley–Rideal (TER) mechanisms. Compared with the LH and TER mechanisms, the interaction between 2CO and O₂ molecules (O₂?+?CO → CO₃, CO₃?+?CO → 2CO₂) through ER reactions (< 0.2?eV) are an energetically more favourable. These results provide important reference for understanding the catalytic mechanism for CO oxidation on graphene-based catalyst.     

The effect of CO on CO2-char gasification

The effect of CO on the gasification of a Polish coal-derived char was investigated in a fluidised bed from 1123 to 1248 K. Rate expressions developed from Ergun's mechanism or a modified three-step reaction mechanism, coupled with Cylindrical Pore Interpolation Model (CPIM) to account for the intra-particle mass transfer, were developed to predict gasification and the effect of CO. Compared to the Ergun's rate expression, the three-step expression has an extra term for p_co, making the inhibition effect of CO more pronounced. The agreement between experimental and numerical results was satisfactory for both models simulating gasification by CO₂/N₂. Then, when CO (1% or 3%) was intentionally introduced in the feed gas (CO₂/N₂), the gasification rates significantly decreased. It was found that the model based on Ergun's mechanism over-estimated the gasification rate, while the results from the model with the three-step mechanism agreed with the experimental data.     

Mechanism for sonochemical reduction of Au(III) in aqueous butanol solution under Ar based on the analysis of gaseous and water-soluble products

When an aqueous Au(III) solution containing 1-butanol was sonicated under Ar, Au(III) was reduced to Au(0) to form Au particles. This is because various reducing species are formed during sonication, but the reactivity of these species has not yet been evaluated in detail. Therefore, in this study, we analyzed the effects of Au(III) on the rates of the formation of gaseous and water-soluble compounds (CH₄, C₂H₆, C₂H₄, C₂H₂, CO, CO₂, H₂, H₂O₂, and aldehydes), and the rate of Au(III) reduction as a function of 1-butanol concentration. The following facts were recognized: 1) for Au(III) reduction, the contribution of the radicals formed by the pyrolysis of 1-butanol was higher than that of the secondary radicals formed by the abstraction reactions of 1-butanol with ·OH, 2) ·CH₃ and CO acted as reductants, 3) the contribution of ·H to Au(III) reduction was small in the presence of 1-butanol, 4) aldehydes and H₂ did not act as reductants, and 5) the types of species that reduced Au(III) changed with 1-butanol concentration.     

Nitric oxide reduction by CO ON Rh(111): Temperature programmed reaction

The reaction of NO with CO on Rh(111) has been studied with temperature programmed reaction (TPR). Comparisons are made with the reaction of O₂ with CO and the reaction of NO with H₂. The rate-determining step for both CO oxidation reactions is CO(a) + O(a) → CO₂(g). Repulsive interactions between adsorbed CO and adsorbed nitrogen atoms lead to desorption of CO in a peak at 415 K which is in the temperature range where the reaction between CO(a) and O(a) produces CO₂(g). Thus the extent of reaction of CO(a) with NO(a) is less than that between CO(a) and O(a) due to the lower coverage of CO caused by adsorbed N atoms and NO. A similar repulsive interaction between NO(a) and H(a) suppresses the NO + H₂ reaction. CO + NO reaction behavior on Rh(111) is compared to that observed on Pt(111).     

The absorption cross sections of N2, O2, CO,NO, CO2, N2O,CH4, C2H4, C2H6 and C4H10 from 180 to 700Å

The absorption cross sections of N₂, O₂, CO, NO, CO₂, N₂O, CH₄, C₂H₄, C₂H₆, C₄H₁₀ have been measured photoelectrically in the 180–700 Å region using synchrotron radiation. The absorption cross sections in the region λ ≥ 500 Å was found to be structureless and to increase monotonically with wavelength for all gases. The positions of the structure observed in the 520–720 Å region for N₂, O₂, CO₂ and N₂O are consistent with the various Rydberg series reported by previous authors.     

Oxidation of H2/CO2 mixtures and effect of hydrogen initial concentration on the combustion of CH4 and CH4/CO2 mixtures: Experiments and modeling

An experimental investigation of the oxidation of hydrogen diluted by nitrogen in presence of CO₂ was performed in a fused silica jet-stirred reactor (JSR) over the temperature range 800-1050 K, from fuel-lean to fuel-rich conditions and at atmospheric pressure. The mean residence time was kept constant in the experiments: 120 ms at 1 atm and 250 ms at 10 atm. The effect of variable initial concentrations of hydrogen on the combustion of methane and methane/carbon dioxide mixtures diluted by nitrogen was also experimentally studied. Concentration profiles for O₂, H₂, H₂O, CO, CO₂, CH₂O, CH₄, C₂H₆, C₂H₄, and C₂H₂ were measured by sonic probe sampling followed by chemical analyses (FT-IR, gas chromatography). A detailed chemical kinetic modeling of the present experiments and of the literature data (flame speed and ignition delays) was performed using a recently proposed kinetic scheme showing good agreement between the data and this modeling, and providing further validation of the kinetic model (128 species and 924 reversible reactions). Sensitivity and reaction paths analyses were used to delineate the important reactions influencing the kinetic of oxidation of the fuels in absence and in presence of additives (CO₂ and H₂). The kinetic reaction scheme proposed helps understanding the inhibiting effect of CO₂ on the oxidation of hydrogen and methane and should be useful for gas turbine modeling.     

LEED and thermal desorption studies of small molecules (H2, O2, CO,CO2, NO,C2H4, C2H2 and C) chemisorbed on the stepped rhodium (755) and (331) surfaces

The chemisorption of H₂, O₂, CO, CO₂, NO, C₂H₂, C₂H₄ and C has been studied on the clean stepped Rh(755) and (331) surfaces. Low energy electron diffraction (LEED), Auger electron spectroscopy (AES) and thermal desorption spectroscopy (TDS) were used to determine the size and orientation of the unit cells, desorption temperatures and decomposition characteristics for each adsorbate. All of the molecules studied readily chemisorbed on both stepped surfaces and several ordered surface structures were observed. The LEED patterns seen on the (755) surface were due to the formation of surface structures on the (111) terraces, while on the (331) surface the step periodicity played an important role in the determination of the unit cells of the observed structures. When heated in O₂ or C₂H₄ the (331) surface was more stable than the (755) surface which readily formed (111) and (100) facets. In the CO and CO₂ TDS spectra a peak due to dissociated CO was observed on both surfaces. NO adsorption was dissociative at low exposures and associative at high exposures. C₂H₄ and C₂H₂ had similar adsorption and desorption properties and it is likely that the same adsorbed species was formed by both molecules.     

Combustion rates of graphite rods in the forward stagnation field of the high-temperature, humid airflow

Relevant to High-Temperature Air Combustion, an experiment has been conducted to study carbon combustion in the high-temperature oxidizer-flow, by use of a graphite rod set in the forward stagnation field. Effects of humid air and O₂-reduced oxidizer have been examined, after re-confirming that the combustion rate in the high-temperature oxidizer-flow is enhanced, because of elevated transport properties when the mass flow rate of oxidizer is the same, and that it is suppressed, because of reduced mass transfer rates through the thickened boundary layer when the velocity gradient is the same. It is found that high H₂O mass-fraction is favorable for the enhancement of combustion rate at high surface temperatures (>2000 K), because of its participation in the surface C–H₂O reaction, while it is not the case at medium surface temperatures (1400–1700 K), because of the suppressing effect, caused by the establishment of CO flame. As for O₂ and CO₂ concentrations in the high-temperature oxidizer-flow, it is found that O₂ mass-fraction can be reduced without reducing combustion rate in the room-temperature airflow, and that it can further be reduced in existence of enough CO₂ that can be an oxidizer in carbon combustion. Theoretical works have also been conducted for the system with three surface reactions and two global gas-phase reactions. It is found that the Frozen mode without CO flame and the Flame-detached mode with infinitely fast gas-phase reaction can fairly represents combustion behavior before and after the establishment of CO flame, respectively, as far as the trend and the approximate magnitude are concerned. It is also shown that a new mode with suppressing H₂ ejection from the surface can fairly represent the combustion rate, experimentally obtained in humid airflow with relatively low velocity gradient when the surface temperature is high.     

Sonolysis of an oxalic acid solution under xenon lamp irradiation

The photosonolysis of oxalic acid was carried out in an Ar atmosphere. The detectable products of sonolysis were CO₂, CO, H₂, and H₂O₂. The yield of CO₂ was higher than that for the sum of sonolysis and photolysis reactions. Namely, a synergistic effect was observed during simultaneous irradiations of 200 kHz ultrasound and Xe lamp. The degradation of oxalic acid was promoted by active species such as H₂O₂ produced from water by sonolysis. An oxalic acid–H₂O₂ complex is likely to be present in the solution, but could not be detected. The effects of not only the photo-irradiation but also the thermal or incident energy during Xe lamp illumination were also considered.     

Analysis of the product gas from biomass gasification by means of laser spectroscopy

The use of biomass and waste for decentralised combined heat and power production (CHP) requires highly efficient gasification processes. In the Technische Universität München (TUM), an innovative gasification technology has been developed. This allothermal gasifier is producing a hydrogen- rich, high-calorific gas, that can be further used in a microturbine or a fuel cell producing energy. For the operation of such a system, the online analysis of the composition of the product gas is of high importance, since the efficient working of the machines is linked with the gas quality. For this purpose an optical measurement system based on laser spectroscopy has been applied. This system can measure not only the basic components of the product gas (H₂, CH₄, CO, CO₂, H₂O), but it also gives information concerning the content of high hydrocarbons, the so-called tars, in the product gas.     

Leed and thermal desorption studies of small molecules (H2, O2, CO,CO2, NO,C2H4, C2H2 AND C) chemisorbed on the rhodium (111) and (100) surfaces

The chemisorption of H₂, O₂, CO, CO₂, NO, C₂H₄, C₂H₂ and C has been studied on the clean Rh(111) and (100) surfaces. LEED, AES and thermal desorption were used to determine the surface structures, disordering and desorption temperatures, displacement and decomposition characteristics for each species. All of the molecules studied readily chemisorbed on both surfaces. A large variety of ordered structures was observed, especially on the (111) surface. The disordering temperatures of most ordered surface structures on the (111) surface were below 100°C. It was necessary to adsorb the gases at 25° C or below in order to obtain well-ordered surface structures. Chemisorbed oxygen was readily removed from the surface by H₂ or CO gas at crystal temperatures above 50°C. CO₂ appears to dissociate to CO upon adsorption on both rhodium surfaces as indicated by the identical ordering and desorption characteristics of these two molecules. C₂H₄ and C₂H₂ also had very similar ordering and desorption characteristics and it is likely that the adsorbed species formed by both molecules is the same. Decomposition of ethylene produced a sequence of ordered carbon surface structures on the (111) face as a result of a bulk-surface carbon equilibrium. The chemisorption properties of rhodium appear to be generally similar to those of iridium, nickel and palladium.     

Largeurs des raies spectrales de CO autoperturbe et perturbe par N2, O2, H2, HCI,NO et CO2

Linewidths of CO self-broadening and broadened by N₂, O₂, H₂, HCI, NO, and CO₂ have been calculated using different contributions in the intermolecular dispersion potential.The quadrupole moment of some perturbers has been determined by comparison between calculated and observed linewidths. The values obtained for the quadrupole moments may depend on the dispersion potential, especially when it is low (as is the case for N₂, O₂ and H₂). For CO-CO and CO-NO, the electrostatic interactions including the octupole moment yield good results for the linewidths for high |m|-values.     

Interaction of O2, CO2, CO,C2H4 and C2H4O with Ag(110)

The interaction of O₂, CO₂, CO, C₂H₄ AND C₂H₄O with Ag(110) has been studied by low energy electron diffraction (LEED), temperature programmed desorption (TPD) and electron energy loss spectroscopy (EELS). For adsorbed oxygen the EELS and TPD signals are measured as a function of coverage (θ). Up to θ = 0.25 the EELS signal is proportional to coverage; above 0.25 evidence is found for dipole-dipole interaction as the EELS signal is no longer proportional to coverage. The TPD signal is not directly proportional to the oxygen coverage, which is explained by diffusion of part of the adsorbed oxygen into the bulk. Oxygen has been adsorbed both at pressures of less than 10^-4 Pa in an ultrahigh vacuum chamber and at pressures up to 10³ Pa in a preparation chamber. After desorption at 10³ Pa a new type of weakly bound subsurface oxygen is identified, which can be transferred to the surface by heating the crystal to 470 K. CO₂ is not adsorbed as such on clean silver at 300 K. However, it is adsorbed in the form of a carbonate ion if the surface is first exposed to oxygen. If the crystal is heated this complex decomposes into O_ad and CO₂ with an activation energy of 27 kcal/mol(1 kcal = 4.187 kJ). Up to an oxygen coverage of 0.25 one CO₂ molecule is adsorbed per two oxygen atoms on the surface. At higher oxygen coverages the amount of CO₂ adsorbed becomes smaller. CO readily reacts with O_ad at room temperature to form CO₂. This reaction has been used to measure the number of O atoms present on the surface at 300 K relative to the amount of CO₂ that is adsorbed at 300 K by the formation of a carbonate ion. Weakly bound subsurface oxygen does not react with CO at 300 K. Adsorption of C₂H₄O at 110 K is promoted by the presence of atomic oxygen. The activation energy for desorption of C₂H₄O from clean silver is ～ 9 kcal/mol, whereas on the oxygen-precovered surface two states are found with activation energies of 8.5 and 12.5 kcal/mol. The results are discussed in terms of the mechanism of ethylene epoxidation over unpromoted and unmoderated silver.