The combustion characteristics of high-heating-rate chars from untreated and torrefied biomass fuels

Torrefaction of biomass is of great interest at the present time, because of its potential to upgrade biomass into a fuel with improved properties. This study considers the fundamentals of combustion of two biomass woods: short rotation willow coppice and eucalyptus and their torrefied counterparts. Chars were prepared from the untreated and torrefied woods in a drop tube furnace at 1100 °C. Fuels and chars were characterised for proximate, ultimate and surface areas. Thermogravimetric analysis was used to derive pyrolysis and char combustion kinetics for the untreated and treated fuels and their chars. It was found that the untreated fuels devolatilise faster than their torrefied counterparts. Similarly, the chars from the untreated biomass were also found to be more reactive than chars from torrefied fuels, when comparing reaction rates. However, the activation energy value (Ea) for combustion of the untreated eucalyptus char was higher than that for the torrefied eucalyptus chars. Moreover, the eucalyptus chars were more reactive than the willow char analogues, although they had seen a lower extent of burn off, which is also a parameter indicative of reactivity. Similar trends in were also observed from their intrinsic reactivities; i.e. chars from the untreated fuel were more reactive than chars from the torrefied fuel and eucalyptus chars were more reactive than willow chars. Chars were also studied using scanning electron microscopy with energy-dispersive X-ray analysis. This latter method enabled a semi-quantitative analysis of char potassium contents, which led to an estimation of potassium partitioning during char formation and burnout. Results show a good correlation between potassium release and percent burnout. With respect to the effect of torrefaction on fuel-N, findings suggest that torrefaction would be beneficial for pf combustion in terms of nitrogen emissions, as it resulted in lower fuel-N contents and ∼72–92% of the fuel-nitrogen was released with the volatile fraction upon devolatilisation at 1100 °C.     

Experimental Study and Modelling of Char Combustion under Fluidized Bed Conditions

INTRODUCTIONMailyexperimentshavebeendonetostudytheconversionbehaviorofdifferentcoalsundervariousreactorsandconditions.Someauthorshaveproposeddetailedmodelsfromobservedresults,orfromthealreticalaspects.Twotypemodelsaredevelopedtopredicttheconcelltrationprofilesforthegaseousspeciesaroundaburningcharparticled].In'single--film'models,thecarbonreactdirectlywithoxygentoformCOorCOb.In'double--film'modelsitisassumedthattheoxygendiffusingtowardsthepaxticleisconsumedbeforeitreachesthesuxface.Thep…     

Combustion and gasification rates of lignocellulosic chars

This review critically examines the state of the art of rate laws and kinetic constants for the gasification, with carbon dioxide and steam, and the combustion of chars produced from lignocellulosic fuels, including a brief outline about yields and composition of pyrolysis products. The analysis also gives space to the role played by various factors, such as heating rate, temperature and pressure of the pyrolysis stage, feedstock and content/composition of the inorganic matter, on char reactivity. Finally, directions for future research are suggested.     

Physicochemical structure characteristics and intrinsic reactivity of demineralized coal char rapidly pyrolyzed at elevated pressure

This study aims to investigate the effect of pyrolysis pressure on the physical and chemical structure characteristics and reactivity of subbituminous demineralized coal char. The pyrolysis experiments were studied under different pressures using a pressurized drop tube reactor (PDTR). Structural properties of coal chars were investigated by the application of scanning electron microscopy (SEM), nitrogen adsorption analyzer, automatic mercury porosimeter, and Raman spectroscopy, respectively. The Random Pore Model was used to determine kinetic parameters and intrinsic reactivity of chars. The specific pore volume of chars pyrolyzed at 900–1000 °C increased first and then decreased with pyrolysis pressure increasing, and the maximum value of the specific pore volume of chars occurred at 1.0 MPa. The degree of graphitization of chars deepened with the increase of temperature or pressure. Intrinsic activation energy of char-O₂ was within the range of 126–134 kJ/mol. The intrinsic reactivity of char-O₂ reaction showed strong correlation the Raman parameters with the change of pyrolysis conditions, and it suggested that the intrinsic reactivity of char-O₂ reaction was mainly affected by aromatic ring structures rather than pore structures.     

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。     

Combustion characteristics of cotton stalk in FBC

The present work reports studies on the mixing and combustion characteristics of cotton stalk with 10–100 mm in length in FBC. Experiments on a cold model show that cotton stalk cannot fluidize, and adding bed material can improve the fluidization condition. Cotton stalk can mix well with 0.6–1 mm alumina at fluidization number N = 3–7. However, when the fluidization number is higher more than 7, the mixing bed will exist a little segregation comparing with N = 3–7. Thermogravimetric experiments show that cotton stalk can be ignited easily at a lower temperature, and its devolatilization and combustion are quick. Fluidized-bed combustion of cotton stalk was tested in a 0.2 MW_th test facility. According to the temperature distribution along the bed height, when the primary and secondary air is adapted cotton stalk can be burned stably in the fluidized bed. During pure cotton stalk combustion tests, silica sand and alumina are used as bed material to compare their agglomeration characteristics. SEM/EDX analysis on agglomerate samples after combustion about 38 h suggests that the high alkali metals content causes the formation of the coating around silica sand particles. The coating consists of compounds with low-melting temperature results in agglomeration of silica sand particles. By contrast, alumina is difficult to react with alkali metals from biomass ash, and the agglomeration of alumina was not found at 910 °C. It is found that alumina is more favorable than silica sand particle for use in a fluidized bed in cotton stalk combustion.     

The devolatilization of coal and a comparison of chars produced in oxidizing and inert atmospheres in fluidized beds

This is a study of the devolatilization of coal in a laboratory-scale bed of silica sand, fluidized with either air or N₂ and electrically heated to 750 or 900°C. Coal particles (diameter 1.4–1.7 or 2.0–2.36 mm) were fed in batches to the surface of the bed and allowed to devolatilize in either an oxidizing atmosphere of air or inert N₂. In the first case, combustion of the volatiles occurred, but there was only thermal decomposition (pyrolysis) in the second situation. The resulting chars were recovered and analyzed for composition and structure, so that comparisons could be made between the effects of devolatilization with combustion and of pyrolysis in an inert atmosphere. It was found that the fractions of C and H in the char were only slightly sensitive to the type of fluidizing gas used. The amount of nitrogen in the recovered char and also the devolatilization time showed no dependence on the type of fluidizing gas, whereas BET areas were slightly larger after combustion in air. It is concluded that these effects are small relative to other errors, inherent in experiments on coal combustion, so that chars prepared in a bed fluidized by hot N₂ are very similar to those formed during coal combustion at nominally the same temperature. Equally, the overall composition of the volatile matter released during combustion in a fluidized bed is the same as in pyrolysis in nitrogen. The effects of other parameters, such as the temperature of the bed, the flow rate of the fluidizing gas and the size of the coal particles are also discussed in detail. It is concluded that most of the volatiles burn in a fluidized bed (at or less than 900°C) far away from the original coal particle. Also, NO_x is in effect a primary product of devolatilization, being produced in appreciable amounts when coal is heated in inert N₂. The ratio of C/N in the volatiles is found to be a constant during the latter stages of devolatilization, but beforehand at lower temperatures, carbon species are preferentially released. Overall, devolatilization of small particles (< 2.4 mm) in a fluidized bed at 900°C is kinetically controlled. The activation energy is small, being 15 ± 6 kJ/mol.     

Sensitivity analysis of a biomass gasification model in fixed bed downdraft reactors: Effect of model and process parameters on reaction front

A detailed sensitivity analysis is performed on a one-dimensional fixed bed downdraft biomass gasification model. The aim of this work is to analyze how the heat transfer mechanisms and rates are affected as reaction front progresses along the bed with its main reactive stages (drying, pyrolysis, combustion and reduction) under auto-thermal conditions. To this end, a batch type fixed-bed gasifier was simulated and used to study process propagation velocity of biomass gasification. The previously proposed model was validated with experimental data as a function of particle size. The model was capable of predicting coherently the physicochemical processes of gasification allowing an agreement between experimental and calculated data with an average error of 8%. Model sensitivity to parametric changes in several model and process parameters was evaluated by analyzing their effect on heat transfer mechanisms of reaction front (solid–gas, bed–wall and radiative in the solid phase) and key response variables (temperature field, maximum solid and gas temperatures inside the bed, flame front velocity, biomass consumption and fuel/air ratio). The model coefficients analyzed were the solid–gas heat transfer, radiation absorption, bed–wall heat transfer, pyrolysis kinetic rates and reactor-environment heat transfer. On the other hand, particle size, bed void fraction, air intake temperature, gasifying agent composition and gasifier wall material were analyzed as process parameters. The solid–gas heat transfer coefficient (0.02 < correction factor < 1.0) and particle size (4 < diameter < 30 mm) were the most significant parameters affecting process behavior. They led to variations of 88% and 68% in process velocity, respectively.     

Steam gasification of energy crops of high cultivation potential in Poland to hydrogen-rich gas

In the paper energy crops of considerable cultivation potential in Poland, namely: Salix viminalis, Helianthus tuberosus, Sida hermaphrodita, Spartina pectinata, Andropogon gerardi and Miscanthus X giganteus were tested in terms of steam gasification reactivity of biomass chars, as well as yields and composition of product gas in steam gasification and lime-enhanced steam gasification in a laboratory scale fixed bed reactor at 650 °, 700 ° and 800 °C.The highest value of reactivity for 50% of carbon conversion, R₅₀, was observed for Sida hermaphrodita, regardless the process temperature.Application of CaO for in-situ CO₂ capture in steam gasification of biomass chars resulted in hydrogen content increase at 650 °C to the levels comparable with the ones reached at 800 °C without carbonation reaction. Also hydrogen and total gas yields increased in tests of lime-enhanced gasification.     

A weighted average global process model based on two−stage kinetic scheme for biomass combustion

This research study combustion kinetics of four biomass samples in China, red pine (Pinus tabulaeformis), corn straw (hybrid corn Zheng Dan-958), Bermuda grass and bamboo (Phyllostachys heterocycla var), using thermogravimetric analysis (TGA). Three stages of combustion process are identified as water evaporation, removal and combustion of volatile matters and combustion of char. Thermal kinetic parameters of each sample are calculated by using 1st order Coats–Redfern method based on the TGA data. It is found that the activation energy of the global process is in the range of 53.6–65.2 kJ mol⁻¹ with a poor linear correlation. The experimental data are then used to develop a two−stage reaction kinetic scheme with low temperature region (2nd stage) and high temperature region (3rd stage). The activation energy of the second stage is in the range of 123.5–140.5 kJ mol⁻¹, and that of the third stage was in the range of 59.4–93.4 kJ mol⁻¹, both of which were based on the 1st order Coats–Redfern method. Because the global process of actual combustion is different from the TGA, a modified weighted average model is proposed based on the two−stage reaction kinetic scheme. According to the modified model, the kinetic parameters of the global process for actual combustion are calculated and are all found a little smaller than that of the 2nd stages. That will benefit for the combustion simulation and the design of facility of biomass fuel.     

Oxidation of chars during smoldering combustion of cellulosic materials

In view of the significance of the properties and reactions of chars during the process of smoldering combustion, a series of cellulosic chars was prepared at temperatures ranging from 340 to 600°C and their pyrolysis and combustion properties were studied by thermal analysis. Correlation of the resulting data with the recently available quantitative information on the chemical composition of different chars indicates that solid-phase combustion of these materials proceeds in two distinct exothermic stages. The first exotherm, at ～360°C, is associated with combustion of the aliphatic components, and the second exotherm, at ～520°C, is due to oxidation of the aromatic components. The chars formed at lower temperatures have a high concentration of aliphatic groups and burn mainly in the first exotherm. As the temperature of the char formation increases, so does the aromaticity, and the combustion is shifted to the higher temperature range.     

Forest biomass waste combustion in a pilot-scale bubbling fluidised bed combustor

Combustion experiments of forest biomass waste in a pilot-scale bubbling fluidised bed combustor were performed under the following conditions: i) bed temperature in the range 750-800 °C, ii) excess air in the range 10-100%, and iii) air staging (80% primary air and 20% secondary air). Longitudinal pressure, temperature and gas composition profiles along the reactor were obtained.The combustion progress along the reactor, here defined as the biomass carbon conversion to CO₂, was calculated based on the measured CO₂ concentration at several locations. It was found that 75-80% of the biomass carbon was converted to CO₂ in the region located below the freeboard first centimetres, that is, the region that includes the bed and the splash zone.Based on the CO₂ and NO concentrations in the exit flue gas, it was found that the overall biomass carbon conversion to CO₂ was in the range 97.2-99.3%, indicating high combustion efficiency, whereas the biomass nitrogen conversion to NO was lower than 8%.Concerning the Portuguese regulation about gaseous emissions from industrial biomass combustion, namely, the accomplishment of CO, NO and volatile organic compounds (VOC) (expressed as carbon) emission limits, the set of adequate operating conditions includes bed temperatures in the range 750°C-800 °C, excess air levels in the range 20%-60%, and air staging with secondary air accounting for 20% of total combustion air.     

Multivariable optimization of reaction order and kinetic parameters for high temperature oxidation of 10 bituminous coal chars

In industrial pulverized fuel combustion, char oxidation is generally limited by the combined effects of chemical reactions and pore diffusion. Under such conditions, char oxidation is frequently predicted by power law models, which despite their simplicity, are widely used in the comprehensive CFD modeling of pulverized coal boilers. However, there is no consensus on the apparent reaction order given by such models. This study developed a systematic approach which gives consistent values over a range of conditions. Apparent reaction orders for 10 bituminous coal chars were investigated with three different oxygen concentrations, ranging from 4 to 12 vol.%, and a gas temperature of 1223 K for each char. Experimental burnout profiles of the chars were obtained by means of an Isothermal Plug Flow Reactor operating at industrially realistic heating rates (10⁴ K/s). For various reaction orders between 0.05 and 2.00, kinetic parameters were independently determined, following numerical procedures recently suggested in the literature. The resulting values were incorporated into an empirical power law model and compared to experimental data for the 10 chars, over a burnout range of 0–75%. The best fit to the experiments occurs with apparent reaction orders of around one for all the chars.     

The story of NCN as a key species in prompt-NO formation

The cyanonitrene radical, NCN, has been shown in the last two decades to play a crucial role in the formation of prompt-NO in combustion. This has stimulated a large number of experimental and theoretical studies on fundamental physico-chemical properties of NCN as well as on mechanistic and kinetic aspects of NCN reactions under combustion conditions. In this review, spectroscopic, thermodynamic, and kinetic data of NCN are collected and discussed. Methodic approaches for the detection of NCN in flames and in kinetic experiments are elucidated, and the suitability of cyanogen azide, NCN₃, as a precursor for NCN in kinetic experiments is examined. Kinetic and mechanistic aspects of a number of NCN elementary chemical steps are extensively reviewed. Regarding prompt-NO formation, the role of the reaction network initialized by the reaction CH + N₂ ⇌ NCN + H is examined by modeling measured flame profiles of NCN, HCN, and NO. In these simulations, the critical role of the product channel-branching of the NCN + H reaction, termed the prompt-NO switch, is confirmed. A particularly sensitive balance is observed between the product channels leading back to CH + N₂ or forward to HCN + N. The roles of spin conservation and intersystem crossing processes under flame conditions and in kinetic experiments with NCN₃ as NCN precursor are highlighted. A number of critical points and remaining open problems in NCN chemistry and prompt-NO formation are indicated.     

Combustion behavior in air of single particles from three different coal ranks and from sugarcane bagasse

Comparative combustion studies were performed on particles of pulverized coal samples from three different ranks: a high-volatile bituminous coal, a sub-bituminous coal, and two lignite coals. The study was augmented to include observations on burning pulverized woody biomass residues, in the form of sugarcane bagasse. Fuel particles, in the range of 75–90 μm, were injected in a bench-scale, transparent drop-tube furnace, electrically-heated to 1400 K, where they experienced high-heating rates, ignited and burned. The combustion of individual particles in air was observed with three-color pyrometry and high-speed high-resolution cinematography to obtain temperature–time–size histories. Based on combined observations from these techniques, in conjunction to morphological examinations of particles, a comprehensive understanding of the combustion behaviors of these fuels was developed. Observed differences among the coals have been striking. Upon pyrolysis, the bituminous coal chars experienced the phenomena of softening, melting, swelling and formation of large blowholes through which volatile matter escaped. Combustion of the volatile matter was sooty and very luminous with large co-tails forming in the wake of the particle trajectories. Only after the volatile matter flames extinguished, the char combustion commenced and was also very luminous. In contrast, upon pyrolysis, lignite coals became fragile and experienced extensive fragmentation, immediately followed by ignition of the char fragments (numbering in the order of 10–100, depending on the origin of the lignite coal) spread apart into a relatively large volume. As no separate volatile matter combustion period was evident, it is likely that volatiles burned on the surface of the chars. The combustion of the sub-bituminous coal was also different. Most particles experienced limited fragmentation, upon pyrolysis, to several char fragments, with or without the presence of brief and low-luminosity volatile flames; other particles did not fragment and directly proceeded to char combustion. Finally combustion of bagasse was once again very distinctive. Upon pyrolysis, long-lasting, low-luminosity, nearly-transparent spherical flames formed around slowly-settling devolatilizing particles. They were followed by bright, short-lived combustion of the chars. Both volatiles and chars experienced shrinking core mode of burning. For all fuels, flame and char temperature profiles were deduced from pyrometric data and burnout times were measured. Combustion rates were calculated from luminous carbon disappearance measurements, and were compared with predictions based on published kinetic expressions.     

Porous structure and morphology of granular chars from flash and conventional pyrolysis of grape seeds

This work studies the influence of the operating conditions used in the pyrolysis of grape seeds on the morphology and textural properties of the chars resulting. Flash and conventional (283 K min⁻¹ heating rate) pyrolysis have been used within a wide range of temperature (300–1000 °C). The effect of a pretreatment for oil extraction has also been studied. The porous structure of the chars was characterized by adsorption of N₂ at 77 K, Ar at 77 K and 87 K, and CO₂ at 273 K and mercury intrusion porosimetry. The morphology was analyzed by scanning electron microscopy. All the materials prepared revealed an essentially microporous structure, with a poor or even negligible contribution of mesopores. Increasing pyrolysis temperature led to higher specific surface areas and lower pore size. The highest specific surface area values occurred within 700–800 °C, reaching up to 500 m² g⁻¹ with pore sizes in the 0.4–1.1 nm range. No significant morphological changes were observed upon carbonization so that the resulting chars were granular materials of similar size than the starting grape seeds. The hollow core structure of the chars, with most of the material allocated at the periphery of the granules can help to overcome the mass transfer limitations of most common (solid or massive) granular activated carbons. The chars showed a good mechanical strength during attrition tests. These chars can be potential candidates for the preparation of granular carbons molecular sieve or activated carbons raw materials.     

Combustion of hydrogen in a bubbling fluidized bed

The combustion of hydrogen in a hot, bubbling bed of quartz sand fluidized by air has been studied for the first time, by injecting hydrogen just above the distributor, via six horizontal fine tubes of Cr/Ni. Overall the fluidizing gas was oxygen-rich, with the composition varying from nearly stoichiometric to very lean mixtures. With the bed initially fluidized at room temperature, combustion (after ignition by a pilot flame) occurs in a premixed flame sitting on top of the bed. When the sand warms up, combustion becomes explosive in bubbles leaving the bed, exactly as with a hydrocarbon as fuel. However, in contrast to hydrocarbons, it is clear that when the bed reaches 500-600 °C, heat is produced both above the top of the bed (because of H₂ bypassing the bed) and very low down in the bed. In fact, with hydrogen as fuel, the location of where bubbles ignite descends abruptly to low in the sand; furthermore, the descent occurs at ∼500 °C, which is ∼100 K below the ignition temperature predicted by well-established kinetic models. However, the kinetic models do reproduce the observations, if it is assumed that the Cr/Ni hypodermic tubes, through which the fuel was injected, exert a catalytic effect, producing free H atoms, which then give rise to HO₂ radicals. In this situation, kinetic modeling indicates that bubbles ignite when they become sufficiently large and few enough to have a lifetime (i.e. the interval between their collisions) longer than the ignition delay for the temperature of the sand. The amounts of NO found in the off-gases were at a maximum (24 ppm), when the bed was at ∼500 °C for λ=[O₂]/stoich[O₂]=1.05. The variations of [NO] with [air]/[H₂] and also temperature indicate that NO is produced, at least partly, via the intermediate N₂H. In addition, the air-afterglow emission of green light (from NO+O→NO₂+hν) was observed in the freeboard, indicating the presence there of both NO and free atoms of oxygen for 1.05<λ<1.1.     

Reactivity of pulverized coals during combustion catalyzed by CeO2 and Fe2O3

Effects of CeO₂ and Fe₂O₃ on combustion reactivity of several fuels, including three ranks of coals, graphite and anthracite chars, were investigated using thermo-gravimetric analyzer. The results indicated that the combustion reactivity of all the samples except lignite was improved with CeO₂ or Fe₂O₃ addition. It was interesting to note that the ignition temperatures of anthracite were decreased by 50 °C and 53 °C, respectively, with CeO₂ and Fe₂O₃ addition and that its combustion rates were increased to 15.4%/min and 12.2%/min. Ignition temperatures of lignite with CeO₂ and Fe₂O₃ addition were 250 °C and 226 °C, and the combustion rates were 12.8% and 19.3%/min, respectively. When compared with those of lignite without catalysts, no obvious catalytic effects of the two catalysts on its combustion reactivity were revealed. The results from the combustion of the three rank pulverized coals catalyzed by CeO₂ and Fe₂O₃ indicated significant effects of the two catalysts on fixed carbon combustion. And it was found that the higher the fuel rank, the better the catalytic effect. The results of combustion from two kinds of anthracite chars showed obvious effects of anthracite pyrolysis catalyzed by CeO₂ and Fe₂O₃ on its combustion reactivity.     

Syngas production from wood pellet using filtration combustion of lean natural gas–air mixtures

A common method for the production of hydrogen and syngas is solid fuel gasification. This paper discusses the experimental results obtained from the combustion of lean natural gas–air mixtures in a porous medium composed of aleatory alumina spheres and wood pellets, called hybrid bed. Temperature, velocity, and chemical products (H₂, CO, CO₂, CH₄) of the combustion waves were recorded experimentally in an inert bed (baseline) and hybrid bed (with a volume wood fraction of 50%), for equivalence ratios (φ) from 0.3 to 1.0, and a constant filtration velocity of 15 cm/s. Upstream, downstream and standing combustion waves were observed for inert and hybrid bed. The maximum hydrogen conversion in hybrid filtration combustion is found to be ∼99% at φ = 0.3. Results demonstrate that wood gasification process occurs with high temperature (1188 K) and oxygen available, and the lean hybrid filtration process can be used to reform solid fuels into hydrogen and syngas.