压汞法分析生物质焦孔隙结构

对于稻壳、树叶、棉花杆、玉米杆四种生物质焦,通过压汞法测量了其在大孔和部分中孔范围内的孔隙结构,发现热解温度、热解保持时间、热解快／慢速都会影响着焦样的比表面积和平均孔径。四种生物质中,树叶焦样的比表面积最大,玉米杆的比表面积最小;稻壳焦样的平均孔径最小,玉米杆的平均孔径最大。不同生物质焦样的孔径分布规律有很大不同。热解温度、热解速度和热解保持时间对孔径分布规律的影响不大,决定孔径分布规律的是生物质本身。在中孔和大孔的范围内,四种生物质焦样的孔径分布曲线都呈现出双峰结构。     

Characteristics of chars formed during rapid pyrolysis of biomass model components at high temperature

This paper reports char formation and inherent inorganic transformation during rapid pyrolysis of various biomass model components under simulated pulverized fuel (PF) conditions at 1300 °C. A drop-tube furnace with a novel double-tube configuration was deployed to achieve direct determination of char yield. The results show that rapid pyrolysis of xylan and water-washed lignin (W-L) under the conditions results in char yields of 3.4 wt.% and 12.6 wt.%, respectively, while no char was founded during rapid pyrolysis of water-washed cellulose (W-C). After loading K₂CO₃ into the W-C (i.e. KW-C) and W-L (i.e. KW-L), the char yields increase to 2.1 wt.% and 15.6 wt.%, respectively. The retentions of Na and S are low in chars after pyrolysis. After rapid pyrolysis, W-L and KW-L chars have higher retentions of AAEM species than xylan, W-C and KW-C chars. Micromorphology analysis shows char particles formed after rapid pyrolysis of all biomass components have a cenospheric structure and a rough surface with many bubbles and pores, demonstrating strong melting processes. For xylan and KW-L, the abundant inorganics accelerate char formation with swelling and reduce the extent of particle shrinkage, resulting in char particles with apparent sizes bigger than the parent feedstock particles. Oppositely, for KW-C and W-L that have low contents of inorganic species, the pyrolyzing particles experience significant shrinkage, resulting in formed char particles with apparent sizes that are much smaller than feedstock particles.     

Experimental and modeling study on centimeter pine char combustion in fast-heating Macro TGA

Biomass energy is an important renewable resource, and thermochemical conversion, including pyrolysis and combustion, is one of the main methods of biomass energy utilization. In industrial reactors, the biomass particles will experience a fast heating (∼1000 °C/min) process during pyrolysis. The particle size of biomass applied in industry has a wide range (from millimeter to centimeter scale). The study of the reaction characteristics of biomass pyrolysis and combustion is helpful for optimizing furnace design and working condition selection. In this research, the combustion of centimeter-scale pine char was studied with a newly built fast-heating Macro Thermal Gravimetric Analyzer (Macro TGA). This Macro TGA is able to conduct the pyrolysis and combustion of large biomass samples (up to 40 mm) with a fast heating rate (∼1000 °C/min), which is able to reflect the working conditions in industrial-scale reactors such as grate furnaces and dual fluidized beds. This Macro TGA can measure the online sample weight, temperature and sample size simultaneously during pyrolysis and combustion experiments. The combustion characteristics of different sizes of pine chars were investigated at various temperatures and oxygen concentrations. A zero-dimensional model was established to predict the sample weight loss, temperature change and sample shrinkage during the pine char combustion process. Three kinetic parameters α, A and E were applied in the model, and the values of the kinetic parameters were optimized by a genetic algorithm. The model prediction and experimental results are consistent with each other. Compared with previous studies, this study developed a new experimental method to measure the reaction characteristics (including sample weight, temperature and size) of centimeter-scale biomass under similar pyrolysis and combustion reaction conditions compared to industrial reactors, and a zero-dimensional model was established to describe the pine char combustion process.     

Effect of pyrolysis conditions on gasification reactivity of woody biomass-derived char

The effect of pyrolysis conditions on char reactivity has been studied using Raman spectroscopy. This paper reports on the relationship between the properties of biomass char and the gasification rate. The gasification kinetics of biomass char have been revealed by measuring the rate of weight loss during its reaction with CO₂ as a function of temperature. First-order kinetic rate constants are determined by fitting the weight loss data using a random pore model. The relationship between the char structure and CO₂ gasification reactivity was investigated in the range of 15–600 °C/min at a constant pyrolysis pressure (0.1 MPa), and 0.1–3.0 MPa at a constant heating rate (15 °C/min). The experimental results reveal that the reactivity of biomass char is determined by the pyrolysis condition. The CO₂ gasification rates in char generated at 0.1 MPa exhibited approximately twice the values as compared to those obtained at 3 MPa. This is because the uniformity of the carbonaceous structure increases with the pyrolysis pressure. The uniformity of carbonaceous structures would affect the CO₂ gasification reactivity, and the decreasing uniformity would lead to the progression of cavities on the char surface during the CO₂ gasification process. The gasification rate of biomass char increases with the heating rate at pyrolysis. This is due to the coarseness (surface morphology) of biomass char and rough texture, which increases with the heating rate.     

Rapid pyrolysis of biochar prepared from slow and fast pyrolysis: The effects of particle residence time on char properties

This paper investigates the evolution of char properties with particle residence time during rapid pyrolysis of biochar under conditions pertinent to pulverized fuel (PF) applications. Two biochar samples were considered, prepared via slow (S-BC) and fast (F-BC) pyrolysis of mallee wood (150–250 µm) at 500 °C and two different heating rates (10 °C/s and ∼400 °C/s), respectively. The biochar samples were then subjected to rapid pyrolysis at 1300 °C using a novel drop-tube furnace (DTF), which enables direct determination of char yield experimentally. The evolution of char yield, the release of alkali and alkaline earth metallic (AAEM) species, and particle size and shape during rapid pyrolysis are investigated as a function of particle residence time (0.45 s to 1.4 s). The results show that char yields decrease from ∼77% to 75% when particle residence time increases from 0.45 s to 1.4 s. Rapid pyrolysis of F-BC has slightly higher char yields, due to the higher ash content of F-BC. More Cl in F-BC facilitates the release of Na during rapid pyrolysis, leading to the lower retention of Na in FC than in SC. Nevertheless, the retentions of K (∼90%), Mg (∼85%), and Ca (∼90%) are higher in FC, which can be ascribed to its higher contents of oxygen after rapid pyrolysis. The investigation of particle size and shape shows that biochar particles exhibit little changes after rapid pyrolysis, indicating their strong resistance to shrinkage and deformation even at high temperature.     

Effect of phosphorus (P) on the structure and reactivity of biochars produced from the pyrolysis of acid-washed biomass loaded with P of various forms

This paper investigates the effect of phosphorus (P) on char structure and reactivity of char prepared from the fast pyrolysis of purposely-prepared P-loaded biomass samples at 1000 °C in absence of other inorganic species. Biomass was first acid-washed then loaded with P of three different occurrence forms (one organic P i.e. phytic acid, and two inorganic P i.e. orthophosphoric acid and polyphosphoric acid) at the same P content of 0.8 wt%. Experimental results show that both organic and inorganic P substantially increase char yields during pyrolysis from 6.2% for the biomass sample without P to 23.0–26.0% for P-loaded samples due to the enhanced crosslinking by P-containing structures in char, leading to increases in the char C and H contents and decrease in O content. The presence of P in biochars from fast pyrolysis of various P-loaded biomass samples plays important role in the evolution of char structure and intrinsic reactivity measured during low-temperature oxidation at 500 °C in air under chemical-reaction-controlled regime. After pyrolysis and subsequent char oxidation, all P in biomass either as organic or inorganic P are found to be present in forms of acid-insoluble organic structures. For char prepared from acid-washed wood, char reactivity increases with char conversion due to the increasing pore surface area at higher conversion. Comparatively, for char prepared from acid-washed wood loaded with various P at char conversion below 60%, the presence of P increases char intrinsic reactivity due to the enhanced crosslinking of reactive carbon structures and reduced condensation of char structures. However, at conversions above 60%, P-containing species in char lead to a significant decrease in char reactivity, due to the formation of abundant CO-P bonds, that is highly resistant to the oxidation in air, in the reacting chars.     

生物质在闪速加热条件下的挥发特性研究

生物质快速热裂解技术是实现生物质液化的重要手段。研究在闪速加热条件下(达到104K／s)生物质的热挥发特性对于热裂解装置的设计非常重要。在等离子体加热的层流炉上对于几种典型的生物质材料,包括玉米秸秆、麦秸、稻壳、椰子壳等,进行了实验研究,获得了它们热挥发的活化能、反应频率因子等。研究发现,在闪速加热条件下,生物质热挥发的动力学参数与升温速率无关。     

Characterization of high heating-rate chars from alternative fuels using an electrodynamic balance

Important advantages in the use of alternative and renewable fuels (CO₂ reduction in the atmosphere, recovery of energy from wastes, limited SO_x, NO_x and heavy metal emissions) can be obtained only by solving technological and economical problems that make direct combustion of such fuels impractical. This is possible after a detailed investigation to determine the most important features of these materials in all steps of the thermal process. At present, few data can actually be found for the char properties of these fuels. Nevertheless, the knowledge of properties of chars (especially after severe devolatilization) is crucial for both modeling purposes (reactivity, kinetics of combustion and gasification, morphology variations, composition, and fate of pollutant precursors) and practical applications (boiler efficiency, ash deposition, and condensation causing fouling and slagging problems).This work deals with the characterization of chars from different classes of materials (biomasses, waste, and low and high volatile matter (VM) coals) obtained after a devolatilization performed in severe thermal conditions, i.e., high temperature and high heating rate. A methodological approach is developed, applied, and discussed, using an electrodynamic balance that is a versatile analyzer for the study of properties of single levitated particles. The specific heat, size, and shape distribution, and density variation between the char and the parent material are evaluated for all materials. Scanning electron microscopy (SEM) analysis is also carried out to investigate morphological variations and support the major results obtained with the electrodynamic analyzer.     

Particle temperature and potassium release during combustion of single pulverized biomass char particles

This work investigated the combustion characteristics of single pulverized biomass-derived char particles. The char particles, in the size range 224–250 µm, were prepared in a drop tube furnace at pyrolysis temperatures of 1273 or 1473 K from four types of biomass particles – wheat straw, grape pomace, kiwi branches and rice husk. Subsequently, the char particles were injected upward into a confined region of hot combustion products produced by flat flames stabilized on a McKenna burner, with mean temperatures of 1460, 1580 and 1670 K and mean O₂ concentrations of 4.5, 6.5 and 8.5 vol%. The data reported include particle temperature, obtained using a two-color pyrometry technique, and potassium release rate, measured using a laser-induced photofragmentation fluorescence imaging technique. In addition, particle ignition delay time and burning time, obtained from the temporal evolution of the thermal radiation intensity of the burning char particles, are also reported. The results indicated that ignition of the char particles occurs simultaneously with the starting of the potassium release, then the particle burning intensity increases rapidly until it reaches a maximum, after which both the particle temperature and the potassium release rate remain approximately constant until the end of the char oxidation process. The char ignition process is temperature controlled, and the char oxidation process is oxygen diffusion controlled, with the total potassium release being independent of the oxygen concentration and the temperature of the combustion products. The combustion behavior of the chars studied is more affected by the char type than by the conditions used to prepare them.     

Effect of high CO2 concentration on char formation through mineral reaction during biomass pyrolysis

O₂/CO₂ combustion has attracted considerable attention as a promising technology for CO₂ capture. Using biomass for fuel is considered carbon neutral, and O₂/CO₂ biomass combustion can mitigate the deleterious environmental effect of greenhouse. In this study, the effect of CO₂, the main component gas in O₂/CO₂ combustion, on the pyrolysis characteristics of biomass is investigated. Cellulose, lignin, and metal-depleted lignin pyrolysis experiments were performed using a thermobalance. Information on the surface chemistry of the chars was obtained by Fourier transform infrared (FTIR) spectroscopy to investigate changes in the surface chemistry during pyrolysis under different surrounding gasses. When the temperature increased to 1073 K at heating rate of 1 K s^?1, the char yield of lignin in the presence of CO₂ increased by about 10% compared with that under Ar. However, for cellulose and metal-depleted lignin, no significant difference appeared between pyrolysis under CO₂ and that under Ar. FT-IR showed that a strong peak corresponding to carbonate ions appeared in the char derived from lignin under CO₂. Therefore, salts such as Na₂CO₃ or K₂CO₃ formed during the lignin pyrolysis under CO₂. At around 1650–1770 cm^?1, a significant difference appeared in the FTIR spectra of chars formed under CO₂ and those formed under Ar. C=O groups not associated with an aromatic ring were found only in chars formed under CO₂. It was suggested that these salts affected the char formation reaction, in that the char formed during lignin pyrolysis under CO₂ had unique chemical bands that did not appear in the lignin-derived char prepared under Ar.     

Biomass pyrolysis in pulverized-fuel boilers: Derivation of apparent kinetic parameters for inclusion in CFD codes

Biomass combustion in pulverized-fuel boilers is a growing way to produce electricity from a renewable source of energy. Slagging and fouling limit however the reliability of the units that were initially designed for coal combustion. Computational Fluid Dynamics (CFD) codes aiming at studying those phenomena include simplified models of biomass particle pyrolysis, of which the pertinence has already been questioned for the typical conditions of interest. A comprehensive model has been developed to investigate pyrolysis of particles in pulverized-fuel boilers, with sizes ranging from 17 μm to 2.5 mm. The detailed model accounts for internal heat conduction, internal gaseous convection, moisture evaporation and particle shrinkage. It includes a competitive, multi-component kinetic scheme, improved for high temperatures. The discrepancy between the simplified models integrated in most CFD applications and the detailed simulations is highlighted. The simplified isothermal models underestimate pyrolysis time for the largest particles. Moreover, such models delay and shorten the volatiles release. The flame lengths, the local temperature fields and the pollutant emissions might be importantly impacted in global combustion simulations. Apparent kinetic parameters have been derived from the detailed simulations. Their use in existing simplified models improves the behavior of the biomass particles during pyrolysis, and offers therefore an efficient alternative to the integration of complex pyrolysis models in CFD codes.     

Simultaneous in-situ measurements of gas temperature and pyrolysis of biomass smoldering via X-ray computed tomography

In-situ X-ray computed tomography (XCT) imaging is employed to investigate the smoldering dynamics of biomass at the sub-millimeter scale. This technique provides simultaneous and spatially-resolved information about the gas temperature and the biomass density, thereby enabling tracking of the pyrolysis and char oxidation fronts. To achieve well-controlled heating and flow conditioning, oak biomass samples are instrumented above a diffusion flame inside a tube, with total oxygen concentrations of 6% and 11% per volume. Experiments are performed on a laboratory XCT system. The flow is diluted with Kr to increase X-ray attenuation in the gas phase thus allowing for simultaneous 3D measurements of sample density and surrounding temperature. XCT scans are acquired every 90 s at a spatial resolution of 135 µm. The high spatial resolution enables the volumetric visualization of the smoldering process that is associated with pyrolysis and char oxidation. These measurements show how the grain structure affects flame stabilization and induces fingering of the pyrolysis front, while crack formation accelerates the char oxidation locally. Evaluations of the sample mass via XCT are compared with load cell measurements, showing good agreement. A low-order model is developed to evaluate the propagation speeds of pyrolysis and oxidation fronts from the X-ray data over time, and comparisons are made with the surface recess speed.     

Characterization of Synthetic-Coal Char Particles using fractal dimension analysis

The development and change of surface ruggedness in chars was studied at conditions typical in a pulverized coal furnace. The fractal dimension, a measure of surface ruggedness, of chars was measured using physisorption techniques. By adjusting the temperature encountered (1173 to 1773 K) and residence time (0.1 to 1.5 s) of the synthetic coal (sized to 46–106 μm diameter), chars at different stages of combustion were prepared in a laminar flow (drop-tube) furnace. The particles were quickly cooled and quenched in an inert atmosphere. The samples were examined using a scanning electron microprobe, and their fractal dimensions were determined using gas physisorption. The adsorption data were used to test if the char surface was fractal on a molecular scale, to determine the fractal dimension, and to quantify changes in the fractal dimension during combustion. The fractal dimension of the unburned synthetic coal was approximately 2. The fractal dimension increased as high as 2.85 as the carbon matrix burned away and exposed mineral moieties. However, as combustion continued the carbon burned completely away leaving a mineral fly ash particle with a fractal dimension as low as 2.47.     

热解温度对酚醛树脂焦的微观结构和还原NO反应性的影响

利用傅立叶变换红外光谱(FTIR)、X射线衍射(XRD)和Raman光谱研究了热解温度(500～900℃)对酚醛树脂焦炭微观结构的影响.使用热重分析仪(TGA)研究了酚醛树脂焦还原NO的反应性.结果表明,随着热解温度升高,苯环、酚羟基、脂肪亚甲基等官能团含量降低.衍射实验表明存在(002)峰、(10)峰和(11)峰.随着热解温度升高,焦炭微晶尺寸增大,微晶结构逐渐趋向有序.酚醛树脂焦的Raman光谱分析与XRD分析存在较好的关联性.反应性实验表明焦炭还原NO的反应性没有随热解温度呈现规律性的变化.     

Swelling properties and intrinsic reactivities of coal chars produced at elevated pressures and high heating rates

A high-temperature, high-pressure flat-flame burner reactor was developed to prepare char at different pressures. This system achieves particle heating rates of 10⁵ K/s, which better mimics industrial conditions than conventional drop tube or radiative flow reactors. Previous data at atmospheric pressure demonstrated a significant decrease in particle swelling during devolatilization as heating rates increased from 10⁴ K/s (the typical drop tube heating rate) to 10⁵ K/s. Pyrolysis experiments were performed at pressures from 1 to 15 atm at 1300 °C for two bituminous coals and a lignite. Average swelling was determined from a combination of the mass release and the average density. The results indicate significantly lower swelling ratios at elevated pressures than reported in the literature. Scanning electron micrographs show that the bubbles in the bituminous coal particles popped before significant swelling at these elevated heating rates. Lignite particles exhibited shrinkage rather than swelling, but still showed a small effect of pressure. TGA oxidation reactivities were determined for the Pitt #8 and Knife River lignite char samples at their respective char preparation pressures. The oxidation reactivities of both the bituminous and lignite chars decreased with increasing pressure.     

干凝胶粒子物性对空心玻璃微球炉内成球过程的影响

为实现干凝胶法制备惯性约束聚变靶用空心玻璃微球(HGM)炉内成球工艺过程的有效控制,从数值模拟和工艺实验两个方面研究了干凝胶粒子直径、比热容、发泡剂质量分数和辐射吸收系数对干凝胶粒子炉内成球过程及最终HGM性能参数的影响。结果表明,随着干凝胶粒子直径和/或比热容的增大,干凝胶粒子在吸热封装阶段的升温速率显著降低,在炉内成球过程各工艺阶段的停留时间快速下降,尤其是在精炼阶段的停留时间急剧缩短。降低干凝胶粒子的比热容和/或提高干凝胶粒子的发泡剂质量分数,HGM的直径和壁厚均匀性增大,高质量空心球的比例也相应提高。干凝胶粒子的辐射吸收系数变化对炉内成球过程几乎没有影响。     

煤中矿物质对其半焦反应活性的影响

本工作考察了大同煤、神木煤、蔚县煤镜质组酸洗前后半焦反应活性的变化。煤酸洗后灰分的失去导致了半焦反应活性的降低。煤种不同,制焦条件不同,矿物质在半焦中的分布形式及存在状态不同,对半焦反应的催化能力也不同。煤种不同,煤中矿物质对半焦活化能的影响彼此不同。在整个反应历程中,具有催化作用的矿物质对半焦活化能的影响并不是恒定的。煤酸洗后半焦反应活性的降低是活化能和指前因子共同变化的结果。     

逆向复式射流预燃室燃烧器煤粉颗粒行为预报

1引言预燃室燃烧技术是近十多年来开发研究的一种高燃烧效率低NO。的燃烧技术门．它是一种分级燃烧技术。燃料在预燃室内只是部分地燃烧,在贫氧的一次火焰区内脱挥发分,从而减少了NO。的形成。自1982年以来,我国开发研究了很多种类的预燃室,如旋流、大速差l‘］、偏置射流预燃室等。工程热物理研究所研究开发了逆向复式射流预燃室燃烧器l‘,‘］。经实验室和工业实验证明,该预燃室有极优良的火焰稳定性能和煤种适应性,能够实现较低的NOx排放。本文针对逆向射流预燃室内这一独特的流场结构,利用数值模拟来预报煤粉颗粒在其内的运…     

Experimental and modeling assessment of sulfur release from coal under low and high heating rates

Coal combustion releases elevated amounts of pollutants to the atmosphere including SO_X. During the pyrolysis step, sulfur present in the coal is released to the gas phase as many different chemical species such as H₂S, COS, SO₂, CS₂, thiols and larger tars, also called SO_X precursors, as they form SO_X during combustion. Understanding the sulfur release process is crucial to the development of reliable kinetic models, which support the design of improved reactors for cleaner coal conversion processes. Sulfur release from two bituminous coals, Colombian hard coal (K1) and American high sulfur coal (U2), were studied in the present work. Low heating rate (LHR) experiments were performed in a thermogravimetric analyzer coupled with mass spectrometry (TG-MS), allowing to track the mass loss and the evolution of many volatile species (CO, CO₂, CH₄, SO₂, H₂S, COS, HCl and H₂O). High heating rate (HHR) experiments were performed in an entrained flow reactor (drop-tube reactor – DTR), coupled with MS and nondispersive infrared sensor (NDIR). HHR experiments were complemented with CFD simulation of the multidimentional reacting flow field. A kinetic model of coal pyrolysis is employed to reproduce the experiments allowing a comprehensive assessment of the process. The suitability of this model is confirmed for LHR. The combination of HHR experiments with CFD simulations and kinetic modeling revealed the complexity of sulfur chemistry in coal combustion and allowed to better understand of the individual phenomena resulting in the formation of the different SO_X precursors. LHR and HHR operating conditions lead to different distribution of sulfur species released, highly-dependent on the gas-phase temperature and residence time. Higher retention of total sulfur in char is observed at LHR (63%) when compared to HHR (37–44%), at 1273 K. These data support the development of reliable models with improved predictability.     

Pore-Resolving Simulations of Biomass Char Particle Combustion

Biomass char morphology affects combustion behavior at the particle scale for zone II conditions, in which both heterogeneous reaction and intra-particle diffusion govern the overall rate. Furthermore, particle-scale processes affect reactor-scale outputs, and reactor-scale simulations are sensitive to particle-scale models. However, most char particle combustion models employ coarse-grained, effective-continuum approaches, which treat all porosity at the subgrid-scale. Effective-continuum approaches are not valid or accurate in the presence of large, irregular pores which can approach the size of the particle. A 3-D, pore-resolving CFD simulation approach using real biomass char particle geometries obtained from X-ray micro-computed tomography (micro-CT) is therefore used to examine the impact of morphology on zone II combustion for pulverized (∼100 µm) biomass char particles for the first time. In contrast to larger, millimeter to centimeter sized particles, the sub-millimeter, high aspect ratio biomass char particles exhibited localized reactant penetration into the innermost regions of the particles, facilitated by the presence of large pores connected to the external surface. The oxygen mole fraction distributions were governed by the large pore morphology, were non-monotonic with distance from the surface, and achieved minima in thick microporous char regions surrounding the large pores. A comparison between the pore-resolving simulation and an equivalent, spatially resolved, effective-continuum simulation revealed that even in the microporous char, the effective-continuum model underpredicted reactant penetration. A careful comparison was then performed between 30 pore-resolving particle simulations and several effectiveness factor models that employed particle-specific parameters. Commonly used uniform cylinder models significantly underpredicted effectiveness factors for these real pulverized pine char particles, while accessible hollow cylinder models achieved less than 10% relative error when averaged over all 30 particles.