Critical evaluation of global mechanisms of wood devolatilization

Thermogravimetric data on the devolatilization rate of beech wood are re-examined with the aim of incorporating the effects of high heating rates (up to 108 K min⁻¹) in the global kinetics. The mechanism consisting of three independent parallel reactions, first-order in the amount of volatiles released from pseudo-components with chief contributions from hemicellulose, cellulose and lignin, is considered first. It is found that the set of activation energies estimated by Gronli et al. [M.G. Gronli, G. Varhegyi, C. Di Blasi, Ind. Eng. Chem. Res. 41 (2002) 4201-4208] (100, 236 and 46 kJ mol⁻¹, respectively) for one slow heating rate results in very high deviations between predicted and measured rate curves. The agreement is significantly improved by a new set of data consisting of activation energies of 147, 193 and 181 kJ mol⁻¹, respectively. In this case, the overlap is reduced between the reaction rates of the three pseudo-components whose chemical composition is also modified. In particular, instead of a slow decomposition rate over a broad range of temperatures, the activity of the third reaction is mainly explicated along the high-temperature (tail) region of the weight loss curves. The performances of more simplified mechanisms are also evaluated. One-step mechanisms, using literature values for the kinetic constants, produce large errors on either the conversion time (activation energy of 103 kJ mol⁻¹) or the maximum devolatilization rate (activation energy of 149 kJ mol⁻¹). On the other hand, these parameters are well predicted by two parallel reactions, with activation energies of 147 and 149 kJ mol⁻¹.     

电动态平衡技术在研究单颗粒煤燃烧中的应用

利用电动态平衡技术,将单个带电煤颗粒悬浮在样品池中,可以实现煤颗粒燃烧过程的原位微观研究。本文简要介绍了电动态平衡技术的原理和相关的操作方法,总结了该技术应用于煤燃烧研究的进展,进一步探讨了结合时间分辨光谱技术研究煤燃烧物理化学过程细节的可行性与发展前景。目的在于向国内研究者介绍这一新技术并激发更多的研究兴趣。     

Particle imaging of ignition and devolatilization of pulverized coal during oxy-fuel combustion

Oxy-fuel combustion of coal is a promising technology for cost-effective power production with carbon capture and sequestration that has ancillary benefits of emission reductions and lower flue gas cleanup costs. To fully understand the results of pilot-scale tests of oxy-fuel combustion and to accurately predict scale-up performance through CFD modeling, fundamental data are needed concerning coal and coal char combustion properties under these unconventional conditions. In the work reported here, the ignition and devolatilization characteristics of both a high-volatile bituminous coal and a Powder River Basin subbituminous coal were analyzed in detail through single-particle imaging at a gas temperature of 1700 K over a range of 12–36 vol % O₂ in both N₂ and CO₂ diluent gases. The bituminous coal images show large, hot soot cloud radiation whose size and shape vary with oxygen concentration and, to a lesser extent, with the use of N₂ versus CO₂ diluent gas. Subbituminous coal images show cooler, smaller emission signals during devolatilization that have the same characteristic size as the coal particles introduced into the flow (nominally 100 μm). The measurements also demonstrate that the use of CO₂ diluent retards the onset of ignition and increases the duration of devolatilization, once initiated. For a given diluent gas, a higher oxygen concentration yields shorter ignition delay and devolatilization times. The effect of CO₂ on coal particle ignition is explained by its higher molar specific heat and its tendency to reduce the local radical pool. The effect of O₂ on coal particle ignition results from its effect on the local mixture reactivity. CO₂ decreases the rate of devolatilization because of the lower mass diffusivity of volatiles in CO₂ mixtures, whereas higher O₂ concentrations increase the mass flux of oxygen to the volatiles flame and thereby increase the rate of devolatilization.     

Ignition and devolatilization of pulverized bituminous coal particles during oxygen/carbon dioxide coal combustion

Oxygen/carbon dioxide recycle coal combustion is actively being investigated because of its potential to facilitate CO₂ sequestration and to achieve emission reductions. In the work reported here, the effect of enhanced oxygen levels and CO₂ bath gas is independently analyzed for their influence on single-particle pulverized coal ignition of a U.S. eastern bituminous coal. The experiments show that the presence of CO₂ and a lower O₂ concentration increase the ignition delay time but have no measurable effect on the time required to complete volatile combustion, once initiated. For the ignition process observed in the experiments, the CO₂ results are explained by its higher molar specific heat and the O₂ results are explained by the effect of O₂ concentration on the local mixture reactivity. Particle ignition and devolatilization properties in a mixture of 30% O₂ in CO₂ are very similar to those in air.     

Large eddy simulation of a pulverized coal jet flame ignited by a preheated gas flow

Large eddy simulation (LES) is applied to a pulverized coal jet flame ignited by a preheated gas flow. The simulation results are compared to experimental data obtained for the inlet stoichiometric ratios of 0.14, 0.22, and 0.36. An accurate and computationally inexpensive devolatilization model suitable for combustion simulation in LES is proposed and incorporated into the LES. The numerical results of gas temperature and coal burnout on the centerline show good agreement with the experimental data. Two kinds of lift-off heights are introduced to verify the combustion simulation. One is the height from the primary nozzle exit to the starting point of the growing flame region. The other is the height from the primary nozzle exit to the starting point of the continuous flame region. The calculated results of the two lift-off heights show good agreement with the experimental data. In contrast to LES, the standard k–ε model overestimates the lift-off heights because it calculates time-averaged temperature which does not contain information about local flame structure. The stoichiometric ratio in the gas phase at the starting point of the growing flame region is found to be independent of the inlet stoichiometric ratio in the range from 0.14 to 0.36.     

Biomass pyrolysis in a heated-grid reactor: Visualization of carbon monoxide and formaldehyde using Laser-Induced Fluorescence

The development of improved biomass pyrolysis models is vital for more accurate modelling and design of biomass conversion equipment. Such improved models must be based on reliable experimental data: biomass should be pyrolyzed at high heating rates and the reaction products should be measured using an on-line, non-intrusive method. Therefore, a heated grid reactor with heating rate of 300-600 K/s was used to study pyrolysis of biomass at temperatures in the range of 500-700 °C. The formation of formaldehyde and carbon monoxide from wood at high heating rates was successfully visualized using Laser-Induced Fluorescence (LIF). A thin vertical laser line or sheet was present directly above the biomass lying on the heated grid. Two-photon excitation at 230 nm was applied to induce fluorescence of carbon monoxide present in the volatiles, whereas excitation of formaldehyde was done at 355 nm. Visualization of these compounds shows that the release rises strongly with temperature; this typically happens on a timescale in the order of seconds. In principle, the method described allows for the determination of truly primary products. Future research is recommended, aimed at quantifying the concentrations measured by LIF. Care must be taken to calibrate for quenching of the fluorescence signal. Avoiding secondary reactions taking place in the gas phase is another experimental challenge.     

Experimental investigation of the effect of initial fuel particle shape, size and bed temperature on devolatilization of single wood particle in a hot fluidized bed

Considerable amount of investigation on the subject of devolatilization of wood is found in the open literature. However, a systematic study of the effect of initial particle size and shape, and bed temperature on devolatilization time and char yield of wood in a hot fluidized bed is still missing. This paper attempts to fill this gap through a systematic experimental investigation to determine the devolatilization time and char yield of a typical woody biomass, “Casuarina equisetifolia” particles of different initial sizes and shapes at various fluidized bed temperatures. Experiments are conducted using 10, 15, 20, and 25 mm Casuarina wood particles of three shapes, namely, cube, cylinder, and sphere at bed temperatures of 1023, 1123, and 1223 K.It is found that the initial wood particle size has the strongest influence on devolatilization time followed by the shape of initial wood particle and the bed temperature. Correlation for devolatilization time (τ_d) as a function of initial wood particle size (d_eq), sphericity (?), and bed temperature (T_b), is developed using 573 experimental data points exhibiting a correlation coefficient of 0.96 and predictions falling well within a deviation band of ±20%. The predictions of the present correlation are compared with the predictions of the existing correlations in literature for conditions also out of the present study and the deviation is found to be ±30%.Char yield, defined as the ratio of the residual mass at the end of devolatilization process to the initial mass of the wood particle is found to be in the range of 9-14% for all sizes, shapes, and bed temperatures. Char yield does not depict any definite trend with the variation of initial particle size, shape and bed temperature.