Initial moisture effects on herbal biomass torrefaction behavior: Gaseous products evolution and char structure analysis

Initial moisture effects on biomass torrefaction were investigated by thermogravimetric (TG) and Fourier transform infrared spectrometer (FTIR) methods. Mass degradation properties, gaseous products’ evolution characteristics, and biomass char chemical structural features were studied. Results show that during torrefaction process, the evaporation of water will create a porous structure inside the solid particles, hence extend the mass loss time intervals. Gaseous products’ evolutions were favored, while tar was reduced because of enhanced secondary decomposition. Char structure analysis suggested that –OH stretch was slightly strengthened through water molecule decomposition and other radical reactions, which would increase the reactivity of char gasification and combustion.     

Ammonia chemistry in oxy-fuel combustion of methane

The oxidation of NH₃ during oxy-fuel combustion of methane, i.e., at high [CO₂], has been studied in a flow reactor. The experiments covered stoichiometries ranging from fuel rich to very fuel lean and temperatures from 973 to 1773 K. The results have been interpreted in terms of an updated detailed chemical kinetic model. A high CO₂ level enhanced formation of NO under reducing conditions while it inhibited NO under stoichiometric and lean conditions. The detailed chemical kinetic model captured fairly well all the experimental trends. According to the present study, the enhanced CO concentrations and alteration in the amount and partitioning of O/H radicals, rather than direct reactions between N-radicals and CO₂, are responsible for the effect of a high CO₂ concentration on ammonia conversion. When CO₂ is present as a bulk gas, formation of NO is facilitated by the increased OH/H ratio. Besides, the high CO levels enhance HNCO formation through NH₂+CO. However, reactions NH₂+O to form HNO and NH₂+H to form NH are inhibited due to the reduced concentration of O and H radicals. Instead reactions of NH₂ with species from the hydrocarbon/methylamine pool preserve reactive nitrogen as reduced species. These reactions reduce the NH₂ availability to form NO by other pathways like via HNO or NH and increase the probability of forming N₂ instead of NO.     

Simulation of dual firing of hydrogen-rich reformate and JP-8 surrogate in a swirling combustor

Flame control, particularly at very lean conditions, is a critical requirement for external combustion power sources such as thermoelectric and thermophotovoltaic generators. The availability of in-situ produced hydrogen from JP-8 fuel reforming presents a potential supply of hydrogen at the application site, such as the battlefield, without adding a second fuel to the logistics system. This research investigates the use of small amounts of hydrogen co-fired with JP-8 for improved energy efficiency, operational flexibility and environmental protection. Numerical simulations were conducted in a 6 kW (thermal) swirling flow combustor under different conditions. The simulations use hydrogen and a single hydrocarbon surrogate for JP-8 with a 4-step reaction mechanism. It also examined the effect of using hydrogen-rich reformate containing hydrogen, carbon monoxide and other gases dual-fired with JP-8. Results showed that at lean conditions, dual firing of hydrogen or reformate with JP-8 provided improved fuel conversion, better flame stability and higher fuel burnout. Dual firing hydrogen-rich reformate and JP-8 led to increased burner capacity, reduced system size and weight requirements. However, dual firing with hydrogen provided little benefit to JP-8 combustion under stoichiometric or fuel rich conditions because they were limited by mixing rather than chemical kinetics. These results indicate that dual firing of hydrogen with JP-8 is a promising method for improving lean flame stability and burner control. This has the potential to enable small scale power applications with specific temperature requirements such as thermoelectric and thermophotovoltaic generators.     

煤焦的微观结构对N2O的生成与分解特性的影响

选取５种煤焦，在一个小型循环流床上进行燃烧，研究Ｎ２Ｏ的生成，并就这几种煤焦对Ｎ２Ｏ的分解特性进行了实验，用液氮吸附法对５种煤焦的微观结构进行了分析，就Ｎ２Ｏ在煤焦内部的扩散机理、煤焦的微观特性对煤焦燃烧生成Ｎ２Ｏ或分解Ｎ２Ｏ的特性的影响进行了分析和讨论。     

The effect of pressure on coal char combustion

A two-dimensional, two-phase combustion model of pulverized coal char at elevated pressures is presented in this paper. This is often encountered in furnaces used for power generation, industrial heating and steam production, and for conversion of solids to gas and liquid products. In pressurized circulating fluidized bed boilers, the effect of pressure on char combustion is significant. Of particular importance is to reveal the relative significance of the diffusion and chemical reaction, as controlling mechanisms, and to evaluate the effect of total pressure on the performance of the combustion chamber. The partial differential equations of conservation of mass, momentum and energy are solved taking into consideration turbulent flow, interphase mass- and heat-transfer, radiation and varying operational conditions (e.g. feed of coal and primary and secondary air). The equations are integrated with the finite volume method and are solved for the flow field, temperature field in the gaseous and solid phases and the concentration of reactants and products. The results show that both chemical reaction and diffusion mechanisms control the combustion at elevated pressure. Moreover, the effect of pressure on the reaction kinetics proves to be significant.     

Effect of CO2 and steam gasification reactions on the oxy-combustion of pulverized coal char

For oxy-combustion with flue gas recirculation, elevated levels of CO₂ and steam affect the heat capacity of the gas, radiant transport, and other gas transport properties. A topic of widespread speculation has concerned the effect of gasification reactions of coal char on the char burning rate. To asses the impact of these reactions on the oxy-fuel combustion of pulverized coal char, we computed the char consumption characteristics for a range of CO₂ and H₂O reaction rate coefficients for a 100 μm coal char particle reacting in environments of varying O₂, H₂O, and CO₂ concentrations using the kinetics code SKIPPY (Surface Kinetics in Porous Particles). Results indicate that gasification reactions reduce the char particle temperature significantly (because of the reaction endothermicity) and thereby reduce the rate of char oxidation and the radiant emission from burning char particles. However, the overall effect of the combined steam and CO₂ gasification reactions is to increase the carbon consumption rate by approximately 10% in typical oxy-fuel combustion environments. The gasification reactions have a greater influence on char combustion in oxygen-enriched environments, due to the higher char combustion temperature under these conditions. In addition, the gasification reactions have increasing influence as the gas temperature increases (for a given O₂ concentration) and as the particle size increases. Gasification reactions account for roughly 20% of the carbon consumption in low oxygen conditions, and for about 30% under oxygen-enriched conditions. An increase in the carbon consumption rate and a decrease in particle temperature are also evident under conventional air-blown combustion conditions when the gasification reactions are included in the model.     

Fundmental aspects of catalysed coal char gasification

A brief review of the basic aspects of catalysed coal char gasification is presented. Kinetics and mechanisms of catalysed and uncatalysed gasification reactions of coal char with steam, carbon dioxide and hydrogen are discussed. Mass transport effects and internal structure of coals are shown to be important in determining rates of these reactions. the importance of the type of catalyst used is also discussed. Such factors as catalyst cations and anions, the method by which the catalyst is contacted with the coal char, and physical and chemical states of the catalyst both prior to and during reaction are shown to be important in the gasification process. Finally, research instruments and equipment used recently for studies in catalysed gasification are reviewed. These include various types of reactor systems for following the course of these reactions and analytical instruments for assessing the physical and/or chemical state of the catalysts and/or coal char both prior to and during the gasification reactions.     

Numerical study of further NOx emission reduction for coal MILD combustion by combining fuel‐rich/lean technology

This paper numerically examines the feasibility of further reducing NO_x emission from a semi‐industrial scale coal MILD (moderate and intense low‐oxygen dilution) combustion furnace by adopting fuel‐rich/lean technology. The implementation is achieved by separating the original fuel jet into two parallel jets which will be used as rich and lean streams. An effort has been made to develop a 13‐step reaction mechanism and NO_x evolution UDFs (user defined functions) for better understanding the interactions between MILD combustion and fuel‐rich/lean technology. The experiment of the reference case (Combustion and Flame 156.9 (2009): 1771‐1784) is well reproduced by the present numerical simulation, indicating high reliability of developed models. The validity of the further reduction of NO_x emission is assessed by the comparison among inner‐fuel‐rich (IFR), outer‐fuel‐rich (OFR), and reference cases resulting from the adjustment of the fuel supply through the two fuel‐rich/lean jets. The results show that both IFR and OFR configurations succeed in achieving further reduction of NO_x emission as compared with the reference case, which stems from both thermal and fuel paths. Specifically, the decrease of thermal‐NO emission originates from the contraction of high‐temperature regions (>1800 K), where nearly 94% reduction occurs within the temperature range of 1800 K and 1950 K while only 6% within 1950 K and 2030 K despite their high temperature sensitivity. The reduction of the fuel‐NO emission is mainly attributed to the promoted NO reduction on char surface and neutralization with HCN and NH₃. Generally, the NO_x emission can be minimized by enlarging the equivalence ratio difference between rich and lean jets, and the OFR configuration exhibits a higher potential than the IFR counterparts. However, since a relatively high temperature (1623 K) secondary air was used in the experiment, the maximum NO_x reduction potential was limited to only 2.5%.     

Effects of particle sizes on transport phenomena in single char combustion

A one-dimensional char combustion model including pore structure effects is used to numerically investigate single char particle combustion for several different types of char samples. Previously, it is expected that small char particles have less combustion time. However, the present work shows that this is true only if the combustion time is defined as that needed for a char particle diameter diminished below a certain value. If the combustion time is defined as time needed for the carbon conversion ratio higher than a certain value, there are optimal particle sizes in a limited combustion period. Just reducing the char particle sizes may not get high carbon conversion ratios. It has also been found that, in general, the larger particles have higher temperatures at the exterior surfaces.     

Effect of temperature on Lu’an bituminous char structure evolution in pyrolysis and combustion

In the process of pyrolysis and combustion of coal particles, coal structure evolution will be affected by the ash behavior, which will further affect the char reactivity, especially in the ash melting temperature zone. Lu’an bituminous char and ash samples were prepared at the N₂ and air atmospheres respectively across ash melting temperature. A scanning electron microscope (SEM) was used to observe the morphology of char and ash. The specific surface area (SSA) analyzer and thermogravimetric analyzer were respectively adopted to obtain the pore structure characteristics of the coal chars and combustion parameters. Besides, an X-ray diffractometer (XRD) was applied to investigate the graphitization degree of coal chars prepared at different pyrolysis temperatures. The SEM results indicated that the number density and physical dimension of ash spheres exuded from the char particles both gradually increased with the increasing temperature, thus the coalescence of ash spheres could be observed obviously above 1100°C. Some flocculent materials appeared on the surface of the char particles at 1300°C, and it could be speculated that β-Si₃N₄ was generated in the pyrolysis process under N₂. The SSA of the chars decreased with the increasing pyrolysis temperature. Inside the char particles, the micropore area and its proportion in the SSA also declined as the pyrolysis temperature increased. Furthermore, the constantly increasing pyrolysis temperature also caused the reactivity of char decrease, which is consistent with the results obtained by XRD. The higher combustion temperature resulted in the lower porosity and more fragments of the ash.     

Numerical studies on the combustion properties of char particle clusters

Particle clustering is an important phenomenon in dense particle–gas two-phase flow. One of the key problems worth studying is the reacting properties of particle clusters in coal particle combustion process in the dense particle region. In this paper, a two-dimensional mathematical model for the char cluster combustion in airflow field is established. This char cluster consists of several individual particles. The comprehensive model includes mass, momentum, and energy conservation equations for both gas and particle phases. Detailed results regarding velocity vector, mass component, and temperature distributions inside and around the cluster are obtained. The micro-scale mass and heat transfer occurred inside and around the char cluster are revealed. By contrastively studying the stable combustion of char particle clusters consisting of different particles, the combustion properties of char clusters in various particle concentrations are presented and discussed.     

A simplified fuel‐NOx model based on regression analysis

The mechanism of detailed chemical reactions in combustion is very complicated, especially when the formation of a pollutant such as NO_x is considered. Based on regression analysis, a simplified fuel–NO_x model is developed for premixed flame. The new model is available for a wider range of temeperature and fuel–air ratios compared with De Soete's (1975) fuel NO model. The reduction CHi species on NO is considered so that the model can be used in both fuel‐lean and fuel‐rich combustion systems. After a great simulation of a one‐dimensional premixed flame system using Miller and Bowman's (1989, Prog. Energy Combust. Sci., 15, 287) detailed elementary reaction model, the calculation of all the reaction rates is presented based on regression analysis. Copyright © 1999 John Wiley & Sons, Ltd.     

Influence of reactive species on the lean blowout limit of an industrial DLE gas turbine burner

In order to achieve ultra-low emissions of both NO_X and CO it is imperative to use a homogeneous premixed combustor. To lower the emissions further, the equivalence ratio can be lowered. By doing so, combustion is moved towards the lean blowout (LBO) limit. To improve the blowout characteristics of a burner, heat and radicals can be supplied to the flame zone. This can be achieved using a pre-chamber combustor. In this study, a central body burner, called the RPL (rich-pilot-lean) section, was used as a pre-chamber combustor to supply heat and radicals to a downscaled industrial burner. The flue gas from the RPL is mixed with the surrounding fresh mixture and form a second flame zone. This zone acts as a stabilizer for the investigated burner. The LBO limit was modeled using two perfectly stirred reactors (PSRs) in series, which allows the chemical influence on the LBO limit to be isolated. The resulting trends for the modeled LBO limit were in agreement with measured data. Increasing the equivalence ratio in the RPL section, thus increasing the energy supplied by the fuel, is a major contributor to combustion stability up to a limit where the temperature decrease is too large support combustion. For lean RPL combustion, the reactive species O, H and OH in combination affect the stability to a greater extent than the temperature alone. At rich equivalence ratios, the conversion of methane to hydrogen and carbon monoxide in the RPL section is a factor influencing the LBO limit. The results are compared with emission probe measurements that were used to investigate the LBO limit for methane and a generic syngas (10% CH₄, 67.5% H₂, and 22.5% CO). The syngas was also investigated after being diluted with nitrogen to a Wobbe index of 15 MJ/m³.     

Measurements of combustion efficiency in nonequilibrium RF plasma-ignited flows

The paper presents results of combustion efficiency measurements using Fourier transform infrared absorption spectroscopy in premixed hydrocarbon-air and CO-air flows excited by a low-temperature transverse radiofrequency (RF) discharge plasma. The results demonstrate that significant fractions of these fuels are burned in RF plasma-generated and -stabilized flames (up to 100% of ethylene, 70% of methane, and 40% of CO). The results also show that fuel oxidation in the RF plasma-excited flows is most efficient in lean mixtures. Measurements of reaction product concentrations in hydrocarbon-air and CO-air mixtures show that significant amounts of fuel react under conditions when there is no flame detected in the test section. Under these conditions, fuel species oxidation occurs in plasma chemical reactions, without producing ignition. Also, experiments in CO-air flows demonstrated ignition and combustion at the equivalence ratios well below the lean flammability limit for CO. Finally, experiments in higher power RF discharges (500 W) showed that nonequilibrium plasma ignition occurs at flow velocities up to at least u=60 m/s and at flow residence times exceeding ∼1 s. The effect of significant fuel oxidation, which is observed for lean fuel-air mixtures outside the flammable range, before the ignition occurs, provides additional evidence for the nonthermal fuel oxidation triggered by plasma-generated radicals. The present results, combined with previous experiments in which RF plasma ignition was demonstrated to occur in a low-temperature plasma, suggest the following nonequilibrium plasma ignition mechanism: (i) active radical species generation by the nonequilibrium plasma, (ii) plasma chemical reactions of fuel species oxidation with participation of these radicals, (iii) flow heating due to net exothermal plasma chemical fuel oxidation process, and (iv) subsequent thermal ignition and combustion.     

Influence of pyrolysis pressure on structure and combustion reactivity of Zhundong demineralized coal char

The investigation on evolution of coal char structure during pressurized pyrolysis can reveal the combustion reactivity of coal char in thermal utilization at elevated pressure. In this study, Zhundong subbituminous coal was demineralized and a pressurized drop tube reactor (PDTR) was used to prepare coal char under different temperature and pressure conditions. The physicochemical structures of raw and demineralized coal chars were characterized by the application of nitrogen adsorption analyzer, automatic mercury porosimeter, and Fourier transform infrared spectroscopy (FTIR). The change mechanism of char infrared structure with pyrolysis pressure is revealed on the molecular level in this paper. The results show that the N₂ adsorption quantity of raw coal char increases with the increase of pyrolysis temperature, while that of demineralized coal char decreases. Because of the difference in molecular volume and steric hindrance between aliphatic and aromatic structure in char, the increasing pressure has less inhibition effect on the escape of the former than the latter. With the increase of pyrolysis pressure, the combustion reactivity of char is related to the infrared structure at 700 and 800 °C while to macropore structure at 900 and 1000 °C.     

Impacts of char structure evolution and inherent alkali and alkaline earth metallic species catalysis on reactivity during the coal char gasification with CO2/H2O

In this work, we studied the effects of char structural evolution and alkali and alkaline earth metallic species (AAEMs) catalysis on the reactivity during the char gasification with CO₂, H₂O, and their mixture. The gasified chars with different carbon conversion levels were prepared, and their physicochemical structures were characterized via nitrogen adsorption and FT‐Raman techniques. The concentrations of AAEMs in different modes were obtained by the sequential chemical extraction method. The reactivities of the raw and gasified chars were analyzed by the thermogravimetric analysis. The gasification atmospheres had varied effects on the physicochemical structure of coal char. The gasified char obtained in the CO₂ atmosphere had a lower aromatic condensation degree compared with that obtained in the H₂O atmosphere, irrespective of the temperature. The impact of the atmospheres on the specific surface area of the char varied with the temperature because H₂O and CO₂ have different routes of development of pore structure with coal char. A large specific surface area facilitates the exposure and dispersion of more AAEMs on the surface of the channel, which is conducive to their contact with the gasification agent to play the catalytic role. Thus, the reactivity of the gasified char is well correlated with its specific surface area at different gasification temperatures. In the absence of AAEMs, the chemical structure of coal char becomes the dominant factor affecting the reactivity.     

A consistent flamelet formulation for a reacting char particle considering curvature effects

In the present work, the combustion of a single char particle in quiescent and convective environments is investigated numerically. Fully resolved CFD calculations are carried out considering heterogeneous reactions at the particle surface and detailed homogeneous reactions in the gas phase. Unity and non-unity Lewis number diffusion modeling approaches are employed and compared to each other. The flame shape of the particle in a quiescent atmosphere shows full symmetry whereas the particle in the convective environment exhibits a stagnation region upstream of the particle and a wake region downstream of the particle. The detailed CFD results are used to analyze the flame structure around the char particle and corresponding flamelet simulations are carried out. For the presently investigated case, curvature effects of mixture fraction, species and temperature are found to be significant in almost all the cases. These curvature effects correspond to diffusion tangential to iso-surfaces of mixture fraction. To describe these processes, new extended flamelet equations are derived. The individual terms in the flamelet equations are analyzed for both the quiescent and the convective environment based on the CFD data and the results confirm the importance of tangential diffusion. Except for the quiescent environment and unity Lewis numbers, curvature cannot be neglected for the investigated char combustion case. For all other cases, significant differences between the standard flamelet model and the detailed CFD results are found. On the other hand, applying the extended flamelet equations yields very good agreement with the CFD results.