A TG/DTA study on the effect of coal blending on ignition behaviour

Understanding the ignition behaviour of coal is of utmost importance for the design of boilers and control of the combustion process. In recent years there has been an increasing utilisation of coal blends for combustion, but information on the possible interactive effects during ignition of the individual components is scarce. In this work the ignition behaviour of a series of coal blends, made up from three coals of different rank, sub-bituminous, high volatile and low volatile bituminous, was studied. To this end a thermogravimetric analyser linked to a mass spectrometer for evolved gas analysis was used. Different ignition behaviour was observed for the coals studied; the sub-bituminous and low volatile bituminous coals ignited heterogeneously, while homogeneous ignition occurred for the high volatile bituminous coal. In the case of blends of the low and high volatile bituminous coals, different mechanisms of ignition were observed depending on the blends composition. This revised version was published online in July 2006 with corrections to the Cover Date.     

煤粉着火模式对再燃脱硝效率影响的实验研究

在一维携带流实验台上研究了烟煤煤粉着火模式,包括均相着火和非均相着火,对煤粉再燃还原NO的影响。实验结果表明,温度一定时,随着再燃区氧体积分数的增加,煤粉挥发分首先着火,脱硝效率明显下降;而非均相着火初期造成的颗粒高温有利于异相还原NO,脱硝效率得以回升;氧体积分数进一步提升,再燃区呈现富氧状态,脱硝效率再次下降。提高再燃区温度促进煤粉还原NO,脱硝效率更高,但是也促使挥发分在更低的氧体积分数下着火,着火后脱硝效率下降更多;粒径对煤粉着火以及还原NO的影响较为复杂,粒径在40μm以上,不同氧体积分数下脱硝效率基本上随粒径增大而下降。     

Fast co-pyrolysis of coal and biomass in a fluidized-bed reactor

Co-pyrolysis is one of the most promising options for the utilization of coal and biomass. Coal/biomass blends were prepared using Yilan subbituminous (YL) and corncob and the mass ratios of coal in mixtures varied between 0 and 100 %. Co-pyrolysis characteristics were investigated in a thermogravimetric analyzer from 303 to 973 K under the nitrogen flow of 100 mL min^?1. The co-pyrolysis residues were less than the sum simply added of the solid yields of individuals. With heating rate increased from 10 to 40 K min^?1, the residues decreased more severely compared to the expected under various blending ratios. For fast pyrolysis in fluidized-bed reactor, gas volumes and char yields of co-pyrolysis showed a significant linearity. But pyrolysis-oil yields were higher than the expected from the additive model when the YL blending ratios were less than 60 %. The co-pyrolysis evolved more H₂, CH₄, C₂ + C₃, and less CO than an additive pyrolysis process of individual fuel. The GC/MS results indicated that co-pyrolysis-oil contained more alcohols, ketones, aldehydes, or acids than that of individual fuel. All of that suggested the H/OH in volatiles produced from rapid pyrolysis of biomass transferred to the radicals of coal pyrolysis. The possible reaction mechanism also was provided in the paper.     

HCN and NH3 (NOx precursors) released under rapid pyrolysis of biomass/coal blends

Rapid pyrolysis of 6 biomass/coal blends (1:4, wt) including rice straw + bituminous (RS + B), rice straw + anthracite (RS + A), chinar leaves + bituminous (CL + B), chinar leaves + anthracite (CL + A), pine sawdust + bituminous (PS + B), and pine sawdust + anthracite (PS + A) was carried out in a high-frequency magnetic field based furnace at 600-1200 °C. The reactor could not only achieve high heating rates of fuel samples but also make biomass and coal particles contact well; secondary reactions of primary products during rapid pyrolysis can also be efficiently reduced. By comparing nitrogen distributions in products of blends (experimental values) with those of the sums of individual biomass and coal (weighted values), nitrogen conversion characteristics under rapid pyrolysis of biomass/coal blends were investigated. Results show that, biomass particles in blends lead to higher experimental char-N yields than the weighted values during rapid pyrolysis of biomass/anthracite blends. The decreased heating rates of both biomass and coal particles caused by the low packing densities of biomass may be the reason. For blends of CL + B in which packing density of chinar leaves is high, and for PS + B during pyrolysis of which melting and shrinkage happen to pine sawdust, both biomass and coal particles can obtain high heating rates, synergies can be found to promote nitrogen release from fuel samples and decrease char-N yields under all the conditions. But the low fluidity and not easily collapsed carbon skeletons of rice straw make the heating rates of rice straw and bituminous particles in RS + B lower than those of CL + B and PS + B, and weaker synergies can be found from char-N yields of RS + B. The synergies can obviously be found to decrease the (NH₃ + HCN)-N yields and make more nitrogen convert to N₂ except for those of several low-temperature conditions (600-700 °C). Under the low-temperature (600-700 °C) condition, synergies make molar ratios of HCN-N/NH₃-N higher than those of the weighted values.     

热解压力和升温速率对焦结构和氧化反应性的影响

以锡盟褐煤（L）、西山烟煤（B）和玉米秸秆（C）为原料考察了热解压力和升温速率对焦结构及氧化反应性的影响。利用两段式加压固定床反应器,在终温900℃,升温速率5℃/min和200℃/min以及压力0.1-2.0 MPa的热解条件下分别得到了慢速热解焦（SC）和快速热解焦（FC）,对焦进行了比表面积、表面形貌和芳香度表征,并且采用等温热重法对焦的氧化反应性进行了分析。结果表明,热解压力和升温速率影响挥发分的停留时间和释放速率,进而影响焦的产率和性质。三种原料的热解行为不同,热解压力和升温速率对焦的产率及焦结构和反应性的影响表现出不同的特点。三种原料快速热解焦产率都低于慢速热解焦产率,且焦产率都随着压力的升高而略微上升。L-FC和B-FC的比表面积分别大于L-SC和B-SC的比表面积。C-FC的比表面积却小于C-SC的比表面积。FC的表面要比SC的表面更为粗糙。B-FC的芳香度小于B-SC的芳香度,但是在加压热解条件下L-SC和C-SC的芳香度反而分别比L-FC和C-FC的低。高压慢速热解的焦氧化反应性较差。玉米秸秆焦的氧化反应性与矿物质的催化密切相关。热解过程中升温速率和压力会影响玉米秸秆焦中矿物质的含量和分布,这也是玉米秸秆焦的氧化反应性明显高于煤焦的氧化反应性的主要原因。     

Devolatilisation characteristics of coal and biomass blends

The characterisation of the initial devolatilisation products could provide important information for understanding synergistic effects and subsequently the formation routes leading to toxic organic compounds and soot during co-combustion. Initial devolatilisation characteristics of the fuels have been characterised following co-pyrolysis experiments. This paper investigates the devolatilisation behaviour during co-pyrolysis of pinewood together with one of three coals of different rank, lignite or high-volatile bituminous of different origin. A range of pyrolysis experiments has been performed over a temperature range from 400 to 900 °C using pyrolysis–GC–MS (py–GC–MS) and thermogravimetric analysis (TGA). Larger scale batch pyrolysis experiments of the hv bituminous coal–pine mixture have been performed enabling collection of the evolved tars. These tars have then been characterised by GC–MS and size exclusion chromatography (SEC). For these batch pyrolysis tests, synergy (non-additive behaviour) was observed and the blend pyrolysis oil contained a decrease in aromatics and an increase in phenols than would be expected for additive behaviour. The molecular weight distributions of the evolved tars also show non-additive behaviour. For the TGA experiments, additive behaviour was seen for all the coal–pine blends studied. Similarly, no obvious synergy was observed by py–GC–MS for the bituminous coal–pine blends, or for model compound–coal and coal–biomass component blends. Non-additive combustion behaviour is not easily explained by studying devolatilisation because of the difficulty in replicating the conditions of temperature profile and residence time experienced by the volatiles. Thus, conflicting behaviour is exhibited depending upon pyrolysis technique.     

Pyrolysis volatiles and environmental impacts of printing paper in air

Pyrolysis volatiles and the environmental impact of printing paper in an air atmosphere were investigated using pyrolysis-gas chromatography/mass spectrometry and scanning electron microscopy. CO₂ and light-pollution products were found to be the major products from pyrolysis volatiles; furthermore, because oxygen participates in the chemical reaction, many of the pyrolysis volatiles emitted during the paper printing process were different from those formed under an N₂ atmosphere. Although a small number of the volatiles were moderately toxic products, the concentrations of these volatiles were low. Heat-induced inkless eco-printing (HIEP) was found to take less time than the pyrolysis experiment in this paper and thus resulted in fewer pyrolysis volatiles. Thus, fewer pyrolysis volatiles will be emitted within the practical temperature range; in particular, no carcinogens were emitted in the pyrolysis temperature range of 250–700 °C. Therefore, HIEP was found to be an ecologically and environmentally preferable technology.     

烟煤与生物质快速共热解产物特性分析

研究了烟煤(YL)分别与富含半纤维素的玉米芯(CB)和富含木质素的松木屑(SD)快速共热解产物产率和气体组成的变化规律。结果表明,烟煤与生物质共热解组分互相作用,造成共热解气、液、固相产率和气体组成的明显变化,且与生物质种类有关。相对于独立热解过程,玉米芯丰富的半纤维素造成热解水蒸气和CO₂浓度较高,且玉米芯中富含的K元素挥发迁移至煤焦表面,对热解半焦与水蒸气、CO₂的气化反应起到催化作用,反应生成的H₂和富氢组分易与热解生成的自由基结合,抑制自由基之间的缩聚反应,使得共热解气体和液体产率增加,而半焦产率减小。烟煤/松木屑共热解过程中,松木屑中富含的Ca元素在煤焦表面迁移,促进了松木屑热解液体在半焦表面裂解反应,生成CO₂、CO和富氢自由基等轻质组分,造成共热解半焦和液体产率降低而气体产率增加。热解产物半焦、焦油、水蒸气、CO₂之间的气化和裂解反应均产生富氢的次生组分,从而提高了共热解气体中CO和烃类气体产率,降低了H₂产率。     

Comparison of pulverized coal combustion in air and in O2/CO2 mixtures by thermo-gravimetric analysis

Thermo-gravimetric technique was used to study the combustion characteristics of pulverized coal in different O₂/CO₂ environments. The effects of combustion environment, oxygen concentration, particle size and heating rate were considered and the differences of pulverized coal pyrolysis, combustion and gaseous compounds release under two environments were analyzed. Results show that the coal pyrolysis in CO₂ environment can be divided into three stages: moisture release, devolatilization and char gasification by CO₂ in higher temperature zone. In the lower temperature zone, the mass loss rate of coal pyrolysis in CO₂ environment is lower than that in N₂ environment. The burning process of pulverized coal in O₂/CO₂ environment is delayed compared with that in O₂/N₂ environment for equivalent oxygen concentrations. With the oxygen concentration increase or the coal particle size decrease, the burning rate of coal increases and burnout time is shortened. As the heating rate increases, coal particles are faster heated in a short period of time and burnt in a higher temperature region, but the increase in heating rate has almost no obvious effect on the combustion mechanism of pulverized coal. During the programmed heating process, species in flue gas including H₂O, CO₂, CO, CH₄, SO₂ and NO were determined and analyzed using the Fourier-transform infrared (FTIR) spectrometer. Compared with pulverized coal combustion in O₂/N₂ environment, much more CO is produced in O₂/CO₂ coal combustion process, but the releases of SO₂ and NO are less than those released in O₂/N₂ environment. The present results might have important implications for understanding the intrinsic mechanics of pulverized coal combustion in O₂/CO₂ environment.     

再燃煤粉的NO还原特性研究

实验研究了原煤、煤焦以及煤在不同气氛下受热得到的气体产物对NO的还原特性。结果表明,原煤的NO还原能力不仅与其挥发分含量有关,还与煤中的矿物质有关;制焦气氛中的O2能改变煤焦对NO的还原能力,其改变与煤种有关。高挥发分煤所释放的挥发性产物对NO的还原率也高, 但Tongchuan(TC)煤除外。TC煤的挥发分含量不高,但由TC煤得到的挥发物对NO的还原率与高挥发分的Sanxie(SX)和Shenmu(SM)煤释放的挥发物相当。煤在N2环境下所释放的气体产物对NO的还原能力比CO2气氛下释放的气体产物对NO的还原能力强,但TC煤除外。同样,制气气氛中的氧对燃煤挥发物的NO还原能力的影响也很大,这种影响与煤种有关。     

增压O_2/CO_2气氛下煤燃烧特性实验研究

增压O2/CO2燃烧是一种可高效分离回收CO2的新兴燃烧技术,其燃烧机理与常压空气、常压O2/CO2燃烧存在较大差异。在加压热重分析仪上研究了增压条件下总压、氧浓度、气氛及粒径等反应参数对美国烟煤和淮北无烟煤燃烧特性的影响,确定了煤的着火温度,并对其进行燃烧动力学分析。结果表明,增压O2/CO2气氛下,随着压力或氧浓度的增加,DTG曲线向低温区移动,煤样整体燃烧速率加快。压力提升、氧浓度增加及煤粉细化均可改善O2/CO2气氛下煤样的着火特性。常压O2/CO2气氛下煤粉燃烧基本属于一级反应;增压O2/CO2气氛下,低温区属于0.5级反应,而高温区属于1.5级反应。     

High‐Temperature Study of 2‐Methyl Furan and 2‐Methyl Tetrahydrofuran Combustion

The ignition behavior of methyl furan (2‐MF) and methyl tetrahydrofuran (2‐MTHF) is investigated using the shock tube technique. Experiments are carried out using homogeneous gaseous mixtures of fuel, oxygen, and argon with equivalence ratios, ?, of 0.5, 1.0, and 2.0 at average pressures of 3 and 12 atm over a temperature range of 1060–1300 K. In addition to ignition delay time measurements, fuel concentration time histories during ignition and pyrolysis of 2‐MTHF are obtained by means of laser absorption spectroscopy using a He–Ne laser at a fixed wavelength of 3.39 µm. With respect to ignition delay times, it is observed that under similar conditions of equivalence ratio and argon/oxygen ratio (D), 2‐MTHF has longer ignition delay times than 2‐MF at 3 atm. In addition, 2‐MTHF has longer ignition delay times than 2‐MF at higher temperatures for the case of 12 atm and under the same conditions of ? and D. The higher reactivity of 2‐MF, as indicated by shorter ignition delay times, is attributed to differences in chemical structure, whereby weaker C–H bond sites are more readily susceptible to radical attack than in 2‐MTHF. It is observed that ignition delay times of 2‐MTHF decrease with increasing equivalence ratio at 12 atm for fixed argon/oxygen ratio. Ignition delay times are compared with model predictions using recent chemical kinetic models of both fuels, showing that both models generally predict shorter ignition delay times than measured. The relatively higher absorption cross section of 2‐MTHF at 3.39 µm allows for its concentration time histories to be determined and compared to model predictions. In line with the observed discrepancy in ignition predictions, predicted 2‐MTHF concentration profiles are such that the fuel is shown to be more rapidly consumed than observed in the experiments. The study advances understanding of the combustion chemistry of these cyclic ethers that are potential alternative fuels.     

高挥发分烟煤的热解、燃烧特性研究

采用固定床热解反应器、热解 红外联用仪 (Py FTIR)和热重分析仪 ,考察了高挥发分烟煤的热解、燃烧特性 ,实验结果表明 ,高挥发分烟煤在热解过程中放出大量烃类气体 ,从燃烧试验看 ,明显分为热解段和燃烧段 ,且热解段挥发分的释放非常迅速 ,从而揭示出高挥发分烟煤燃烧过程中产生大量黑烟的原因。     

加压下煤的着火特性的研究 Ⅰ.着火特性的影响因素

采用带程序升温控制的、可在加压下测定煤着火特性的装置,在程序升温速度(7.5℃/min)和加压条件下,测定了影响煤和煤焦着火特性(着火温度与燃烧时间)的各种因素,这些因素包括煤的粒度、试样质量、空气流量、系统压力和氧分压等。试验表明,这些因素的影响与煤中挥发份有一定的关系,着火温度和燃烧时间随总压或氧分压增加而下降。     

Fire safety evaluation of expanded polystyrene foam by multi-scale methods

Microscale thermal analysis, bench scale cone calorimetric and real scale burning tests were conducted to evaluated fire safety performance of expanded polystyrene (EPS) foam. Simultaneous thermal analysis was used to study the thermal degradation of the foam in nitrogen, air, and oxygen environments at four heating rates. An endothermic effect is observed only in nitrogen environment, while two exothermic effects are observed in oxygen and air environments. In the nitrogen environment, the onset temperature of the endothermic effect and the endothermic peak temperature are much higher than that of the exothermic processes observed in air and oxygen environments. The Flynn–Wall–Ozawa method is utilized to analyze the degradation kinetics of the non-isothermal thermogravimetry. The activation energies calculated for an air environment, in a conversion range α = 20–70 %, are lower than those for an oxygen environment. The temperature range for this conversion range is 275–371 °C. The enthalpies of the first exothermic effect exceed that of the oxygen environment by 10–45 %. Bench scale cone calorimetric tests were carried out at incident heat flux of 25, 35, and 50 kW m^?2 with two sets of cone equipment. Heat release rate, ignition time, effective heat of combustion, and critical heat flux required for ignition is obtained. In real scale burning tests, the EPS boards were ignited in sandwich structures. Fire spread speeds were derived from temperature measurement inside sandwich structure.     

典型烟煤热解机理的反应动力学模拟

建立合理有效的烟煤大分子模型，采用基于反应力场（Reactive Force Field，ReaxFF）的分子动力学方法模拟1400-2600 K典型烟煤的热解过程，得出产物分布和中间自由基的演变历程。研究表明，随着热解温度的升高，焦炭产量先增加后降低，焦油产量的变化趋势与焦炭相反，热解气产量单调增加。煤在低温下热解主要发生一次反应，生成焦油自由基碎片和小分子气体；高温下焦油碎片的二次反应显著，生成含量较多但数量较少的焦炭及含量与数量较多的小分子气体。2000 K是一次反应向二次反应的温度转折点。在高温热解时，煤中的C与H逐渐迁移到焦炭和焦油中，而含氧官能团较为活跃，O逐渐迁移到热解气中。二次反应阶段，O最活泼，H次之，C最稳定。热解过程中最先产生的气体是H₂O；NH₃主要来源于二次反应；H₂S在二次反应阶段被消耗转化为其他产物；H₂产量最多，且随热解温度升高而增加，尤其在二次反应中大量生成，主要源于裂解产生的氢自由基碰撞和芳香结构的缩合。基于ReaxFF模拟结果得到煤热解失重活化能为39.45 kJ/mol。     

石油焦与煤混合燃料热重分析研究

石油焦与煤混合燃烧是高效处理石油焦的有效方法，作者对选用的石油焦和煤不同配比的混合燃料进行了热重分析研究。使用常压高温热天平研究、分析了各配比混合燃料的热解特性和燃烧特性。并根据化学动力学方法计算了各过程的化学动力学参数，即活化能E和频率因子A0。结果表明，各混合燃料热解起始温度大致相同，随煤焦比减小，挥发分析出速率变缓，最大释放速度所对应的温度升高，最终失重率减小，挥发分释放特性指数减小；随煤焦比增大，混合燃料着火温度和燃尽温度逐渐降低，最大燃烧速率所对应的温度降低，燃烧特性指数增大；随煤焦比减小，活化能和频率因子增大。     

Experimental and kinetic investigation of the pyrolysis,combustion, and gasification of deoiled asphalt

The pyrolysis, combustion, and gasification behaviors of deoiled asphalt were studied by a thermogravimetric analyzer and the kinetics were also analyzed using a multi-stage first-order integral model. All the experiments were conducted at non-isothermal conditions with heating rates range of 10–40 K min^?1 under N₂ (pyrolysis), air (combustion), or CO₂ (gasification) atmosphere, respectively. The results showed that, for pyrolysis, the reaction mainly occurred between 498 and 798 K and could be divided into two stages: the first was caused by the volatilization of small molecules and the second probably due to the cracking reactions. For combustion, the mass loss process could be divided into three stages: the devolatilization and oxidation first, the ignition and combustion of the volatiles second, and finally the combustion of the formed char. Under CO₂ atmosphere, the mass loss behavior was similar with that of the N₂ atmosphere at lower temperatures, but when the temperature was higher than 1,233 K, the gasification reaction obviously happened. The results of kinetic investigation showed that the multi-stage first-order integral method agreed well with the above experiments.     

不同煤阶热解半焦的FT-Raman光谱研究

在热天平上采用慢速升温制备了褐煤、高挥发分烟煤和低挥发分烟煤的半焦。采用FT-Raman光谱对半焦进行了分析。半焦800cm^-1至1800cm^-1的Raman光谱可分解为10个谱带,以表征高度无序炭材料中的典型结构。光谱和谱带的强度比都可用来描述半焦的结构特征。在600℃低温热解时,三种煤半焦的结构差异明显。随热解温度升至800℃或900℃,这种差别消失。褐煤中可交换的钠离子影响热解过程中的成焦反应。     

Study on the kinetics and reactivity at the ignition temperature of Jurassic coal in North Shaanxi

Thermal analysis of seven Jurassic coal samples from North Shaanxi in West China and three permo-carboniferous coal samples from East China was studied to identify ignition temperatures in the process of the oxidation and spontaneous combustion. The experiments were carried out under non-isothermal heating conditions up to 700 °C at the heating rates of 5, 10, 15, and 20 °C min^?1 in an air atmosphere. Through the FTIR spectrometer experiments, the absorbance peaks of functional groups of coal samples were analyzed at the ignition temperatures, pre-ignition of the 10 °C, post-ignition of the 10 °C at the heating rate of 10 °C min^?1. By the differential spectrum method, the changes of functional groups were discussed with the aim to determine characteristics and reactivity of the ignition temperature around. The results showed that ignition temperatures of experimental coal samples increased with the rising heating rates, and ignition temperatures of Jurassic coals were lower than that of the permo-carboniferous coal samples at the same heating rate. Apparent activation energy of experimental Jurassic coals at the ignition temperatures was calculated by Ozawa method based on the non-isothermal and differential heating rates, ranging from 80 to 105 kJ mol^?1, which were lower than that of the eastern permo-carboniferous samples. On the basis of Pearson correlation coefficient method which can signify the degree of correlations ranging from ?1 to 1, the correlation analyses were conducted between activation energy and functional groups variation within 10 °C before and after ignition temperature. It was concluded that the key functional groups of Jurassic coals in the oxidation and ignition reaction were methyl and alkyl ether within 10 °C before ignition temperature, and carboxyl and carbonyl within 10 °C after ignition temperature.