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.     

Examination of sorption and desorption of hydrogen on several samples of polish hard coals

Performed tests showed that at 298?K hard coals sorb relatively small amounts of hydrogen. Those amounts depend on carbon and oxygen content in tested coals. The most considerable amounts of hydrogen are sorbed by coals characterized by strong surface hydrophobicity and high content of aliphatic hydrocarbons. The hydrophilic nature of coal surface does not lead to higher sorption of hydrogen. It was found that the change in amount of sorbed hydrogen is closely related to the moisture. For high moisture coal a significant decrease in hydrogen sorption is observed. Also tests on hydrogen desorption on hard coals were carried out using method of lowering hydrogen pressure above the sorbent. Obtained results showed that tested coals desorb various amounts of hydrogen. Process of sorption is reversible only for some coals, while for the others the desorption isotherm partially lies beneath the sorption isotherm, which indicates that in addition to hydrogen some other chemical substances are emitted from coal.     

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.     

岩相及煤阶对煤的燃烧特性的影响

为了确定手选富显微组分煤及焦的燃烧特性，从显微组分和煤阶的角度用热天平的燃烧曲线研究反应性，并给出焦的活化能。煤和焦的比表面积由液氮等温吸附求得，并用扫描电镜观察了焦的表面形态。用灰色关联法分析各显微组分和煤阶对反应性和表面形态的影响。结果表明，镜质组对煤和焦反应性和表面形态均有重大影响，煤的反应性受显微组分的影响比煤焦更显著，若不考虑矿物质的影响，则各因素对煤及焦反应性影响次序为Ｖ＞Ｒ＞Ｉ＞Ｅ。     

Experimental study on interaction and kinetic characteristics during combustion of blended coals

The combustion behaviors and kinetic parameters of three parent coals (A1, A2, and A3) and their blends (A1/A2 and A2/A3) have been evaluated under oxidizing atmosphere (O₂ and N₂ mixtures), using a non-isothermal thermo-gravimetric analyzer. The aim of this study is to investigate the interaction between the blended components during the process of co-combustion, and the effects of blending ratio and oxygen concentration (10, 15, and 21%) on combustion performance of blended coals. When high reactivity and low reactivity coals are co-combusted, double peaks are observed in the DTG curves, and significant interaction occurs in the temperature range between the two peaks (T _p1 and T _p2). The activation energies obtained by Coats–Redfern method indicate that the activation energies of blended coals are lower than that of parent coals. The combustibility index S is used to evaluate the combustion performance of blended coals, and the results show the non-additive effects of the combustion characteristics of blended coals. The increased oxygen concentration results in a significant improvement of combustion performance of blended coals. In addition, as the blending ratio of high reactivity coal is increased, the oxygen can greatly enhance the combustion stability of blended coals.     

Thermal analysis study of the effect of coal-burning additives on the combustion of coals

Thermal analysis is widely used in combustion research for both fundamental and practical investigations. Efficient combustion of coals in cement industry is very important and necessary. In this research, the effects of three coal-burning additives on burning behaviour of bituminous coal and anthracite were studied with the help of thermogravimetry (TG) and differential scanning calorimetric (DSC) analysis. The kinetic study was carried out and the results were presented. The results showed that the coal-burning additives especially LSZ can reduce the ignition temperature, increase the ignition index D _i, combustion ending index D _f and affect the activation energy of the coal samples studied. The coal-burning additives especially LSZ can improve coal combustion effectiveness.     

煤燃烧过程中有害痕量元素形态分布的化学热力学平衡分析

采用化学热力学平衡分析方法,应用真实煤质数据预测了煤燃烧过程中国内六种具有代表性的煤种有害易挥发性痕量元素As和Se的化学形态分布。计算中考虑了痕量元素和卤素（如氯元素）的相互作用,也考虑了痕量元素与主量矿物元素之间的相互作用。研究结果表明,不同煤级、不同产地的煤中痕量元素As的化学形态分布有较大差异。As的热力学平衡计算中,数据库中是否忽略AsO形态对结果影响非常显著,忽略AsO形态的限制性模拟结果似乎更能反映真实煤燃烧过程中As的化学形态分布。煤级和煤的产地对Se的化学形态分布没有显著影响。     

Combustion behaviour of some biodesulphurized coals assessed by TGA/DTA

Thermal analysis, i.e. TGA/DTA is used to study the changes in the combustion behaviour of microbially treated coals. In view of their high sulphur content and industrial significance three samples are under consideration, i.e. one lignite and two subbituminous from different region in Bulgaria. The differences in burning profiles can be related to structural changes resulted from biological treatments. The overall biological treatment generates these changes probably due to the oxidation process. Concerning organic sulphur biodesulphurization there is no change in any drastic manner of the thermal characteristic parameters. In general, applied biotreatments provoke a complex influence on combustion coal behaviour. From one side a better ignition performance, a minor decrease in higher heating value and diminishing peak temperature of maximum weight loss rate for all biotreated samples are observed. From other side some decrease in the combustibility indicated by an increase in the combustion time and the end of combustion temperature are obvious. Also well determined decrease of self-heating temperature after biotreatments evolves high risk of spontaneous unmanageable coal combustion.     

O2/CO2燃烧气氛对混煤灰中矿物质间反应影响研究

对蒙煤与平七煤两种单煤及其按照不同比例组成的混煤,分别在O₂/CO₂和O₂/N₂气氛下,采用管式炉燃烧制取灰样;对灰样进行灰熔点、XRD及同步热分析（TG/DSC）测试,并进行相关热力学计算,分析了O₂/CO₂燃烧方式对混煤灰中矿物质间反应的影响。结果表明,常规灰熔点测试方法测得的两种气氛下的混煤灰熔点没有明显差别。O₂/CO₂气氛促进了煤灰/混煤灰中钙的碳酸化,且明显抑制了高温下CaCO₃的分解。气氛的改变影响了含钙矿物的转化,进而影响了混煤中钙与莫来石反应生成低温共熔物;O₂/CO₂气氛下钙更易于与莫来石发生反应生成低温共熔物,从而会增加结渣倾向。当混煤中蒙煤比例达到或大于75%时,随着蒙煤比例的逐渐增加,莫来石含量减少,O₂/CO₂气氛对钙与莫来石之间的反应影响减弱,但对含铁矿物的影响更加明显,使其更易于生成含铁玻璃体,从而也会增加结渣倾向。     

Changes in coal char reactivity and texture during combustion in an entrained flow reactor

Char particle combustion is the slowest step in the combustion of coal, therefore char reactivity and texture have an important influence on this process. In this work, two coals were devolatilised in an entrained flow reactor and the chars obtained were burned under different experimental conditions in order to achieve various degrees of burnoff. Char reactivity was determined by means of non-isothermal thermogravimetric analysis, and the conversion-time data were evaluated by the random pore model proposed by Bhatia and Perlmutter. Char texture was characterised by means of N₂ and CO₂ adsorption isotherms. The surface areas obtained were used to calculate intrinsic reaction rate parameters. It was found that under chemical controlled conditions, the available surface area during combustion is best represented by the N₂ surface area.     

循环流化床燃煤过程NO、N2O和SO2的排放行为研究

在30kW循环流化床装置上进行了中国西部三种煤的燃烧实验，考查了燃烧温度、空气分级、空气过剩系数、固体颗粒循环料率和煤种等因素对NO、N2O、SO2污染物排放的影响。结果表明，强化空气分级可显著降低高挥发分煤种NO的生成量，但对N2O影响不大；增加空气过剩系数同时增加了NO与N2O的排放；增加固体循环料率显著降低NO生成量，但N2O排放略有增加；高阶煤燃烧生成较多N2O，低阶煤生成较多NO。燃烧温度1120K、过剩空气系数1.25下约85%燃料中N转化为N。实验范围内改变操作参数不影响SO2与CO排放量。     

Effect of chemical structure on combustion and thermal behaviour of polyurethane elastomer layered silicate nanocomposites

The effect of polyol molecular weight and functionality on nanodispersion of clay in PU/clay nanocomposites and the investigation of their thermal and combustion properties are reported and discussed. Lamellar elastomer polyurethane nanocomposites were synthesized using polyols with different molecular weight and functionality and according to these parameters they show several degrees of dispersion which affect their thermal and combustion behaviour. A barrier effect of clay layer is shown in TGA experiments by a delay of thermal degradation products release in nanocomposite materials compared to the virgin polymer; this barrier effect also leads to formation of char during combustion which lowers the peak of rate of heat release in cone calorimeter tests and eliminates fire-induced dripping of the nanocomposite sample during UL 94 test. However, in order to achieve non-burning behaviour nanocomposite technology must be combined with conventional flame retardant technology.     

煤燃烧过程中SO2,NO的逸出规律研究

研究了脱灰煤、负载ＦｅＣｌ３煤及几种没变质程度的原煤在程序升温燃烧过程中ＳＯ２、ＮＯ的逸出规律，结果表明：ＦｅＣｌ３对煤中某些有机硫的逸出有抑制作用，同时使ＮＯ的逸出总量大大降低；不同曙速率对ＳＯ２、ＮＯ的逸出峰型基本没有影响，但低的升温速度线下ＳＯ２、ＮＯ能够在较低的温度下逸出。     

Kinetic models comparison for steam gasification of different nature fuel chars

The reactivity in steam of five different types of solid fuels (two coals, two types of biomass and a petcoke) has been studied. The fuel chars were obtained by pyrolysis in a fixed-bed reactor at a temperature of 1373 K for 30 min. The gasification tests were carried out by thermogravimetric analysis (TG) at different temperatures and steam concentrations. The reactivity study was conducted in the kinetically controlled regime and three representative gas-solid models, volumetric model (VM), grain model (GM) and random pore model (RPM), were applied in order to describe the reactive behaviour of the chars during steam gasification. The kinetic parameters of these models were derived and the ability of the models to predict conversion and char reactivity during gasification was assessed. The best model for describing the behaviour of the samples was the RPM. The effect of the partial pressure of steam in gasification was studied, and the reaction order with respect to steam was determined. The reactivity of the chars was compared by means of a reactivity index. Biomass exhibited a higher reactivity than coals and petcoke. However, significant differences in reactivity were observed between the two types of biomass used, which could be due to catalytic effects.     

煤的吡啶吸附等温线及影响煤吸附行为因素的研究

采用四种标准煤样和模型化合物(WK11离子交换树脂及其Na和Ca类型),在30℃～60℃对比研究煤的吡啶气相吸附等温线和影响其吸附行为的因素。模型化合物结果表明:吡啶能断开WK11中的固有氢键,形成更强的吡啶-羧基官能团氢键,Na或Ca型WK11由于无法与吡啶形成氢键,因此吸附量很小,并几乎无溶胀现象。四种煤样的吡啶吸附结果表明:由于煤化程度和结构的不同,至少有两种类型的吡啶吸附等温线。同时,煤的吡啶吸附总量并不仅取决于在吸附过程中形成的氢键数量,而且也受其它特殊作用力的影响,这种影响对于高阶煤尤其显著。     

Thermolysis of Kansk-Achinsk Coals with Varied Extent of Oxidation and Combustion of Nonvolatile Thermolysis Products: A Study by Complex Thermal Analysis

Thermolysis of Berezovka coals with varied extent of oxidation and combustion of nonvolatile thermolysis products were studied by complex thermal analysis. The dynamics of thermochemical transforma- tion of the fuel in an inert medium was evaluated, with simultaneous determination of the kinetic parameters of evaporation of various kinds of moisture. The burn-out of nonvolatile thermolysis residues obtained from Berezovka coals at various pretreatment temperatures was studied, and a correlation was revealed between the kinetic parameters of combustion of nonvolatile residues and the extent of oxidation of the initial fuel.     

Structural properties of non-combustion-derived refractory organic matter which interfere with BC quantification

Black carbon (BC), presenting the residue from incomplete combustion processes of fossil fuels and vegetation, has received special interest as a possible carbon sink in soils and sediments. In spite of this, there is still a need to develop accurate and comparable analytical protocols to determine the amount of BC stored in different environmental matrices and to characterise potentially interfering materials in the analysis of BC. Therefore in this study a melanoidin, a sample from the Green River Shale, a lignite and a bituminous coal were characterised by means of elemental analysis, thermogravimetry–differential scanning calorimetry (TG–DSC), pyrolysis coupled with gas chromatography–mass spectrometry (Py-GC/MS) and ¹³C NMR spectroscopy. Thermal analysis (TG–DSC) indicated larger contributions of labile OM in the melanoidin and in the shale samples than in the lignite and the bituminous coal, although the coals showed an intense exothermal peak at temperatures higher than 550 °C. This behaviour is in agreement with high thermal recalcitrance of the latter and was also found in earlier studies of BC-rich material. Comparable to the latter, Py-GC/MS of the coals reveals considerable amounts of lignin-derived products. This and the similar thermal behaviour of both refractory materials aggravate their discrimination during BC-analysis. The pyrogram of the melanoidin reveals an important contribution of furanes and pyrane-like structures that derive from carbohydrates. NMR spectroscopy supports that those compounds are original constituents of the melanoidin rather than solely pyrolysis products. Considering that those compounds are typically formed during charring of N-containing biomass, their contribution to the BC structure should not be neglected if one seeks for a better understanding of BC structural properties. For the shale sample, both analytical pyrolysis and ¹³C NMR spectroscopy confirm a high contribution of long alkyl-C chains. Due to their high hydrophobicity such structures can stand chemical oxidation and their presence in soil and sediment samples can obscure BC quantification by those methods. This study indicates that present approaches for BC-identification that are based on the assumption of BC being mostly a highly condensed polyaromatic network, have to be taken with caution and modified in accordance with a more heterogeneous composition of BC containing considerable fractions of only partly charred biopolymers.     

水热污泥与煤在混燃过程中的协同效应特性研究

以城市污泥衍生的水热污泥(SS-derived hydrochar)为对象,结合傅里叶红外光谱分析(FT-IR)、X射线荧光光谱分析(XRF)和X射线衍射分析(XRD)等对比研究了水热污泥与三种不同品阶煤(褐煤、烟煤和无烟煤)在有机/无机结构与燃料特性上的异同;同时,通过热重(TG)与偏差分析(Deviation)考察水热污泥与各阶煤在不同混合比例条件下的协同燃烧行为及其作用机制。结果表明,污泥经过水热处理后其有机结构和燃烧行为均提升至与煤相似的水平,该过程不仅改善污泥的燃烧特性,并增强其与煤之间的协同燃烧效应。水热污泥中适量的轻质组分与(碱)碱土金属能在混合燃烧过程中加速煤的失重速率,其对三种煤的促进作用可达4.4%-16.1%(褐煤)、1.9%-9.4%(烟煤)和4.8%-12.1%(无烟煤)。总体而言,水热污泥与褐煤混合而成的燃料在燃料性能上具有较大的优势,并且其混合比例以30%(水热污泥):70%(褐煤)与50%(水热污泥):50%(褐煤)为宜。     

新疆高钠煤中钠的赋存形态及其对燃烧过程的影响

采用不同萃取液对中国新疆高钠煤进行逐级萃取实验,利用离子色谱仪和电感耦合等离子体原子发射光谱仪对萃取制得的滤液和固体煤样进行相应的元素分析,并通过逐级萃取后煤样的着火温度、燃尽温度和综合燃烧特性指数来分析高钠煤中不同存在形式钠对其燃烧特性的影响.结果表明,中国新疆高钠煤中的钠主要以水溶钠为主,有机钠和不可溶钠含量较少.影响高钠煤中水溶钠含量的主要因素有煤颗粒内部孔隙结构和颗粒粒径,且高钠煤中有机钠在各个粒径范围都保持了相对稳定的含量.煤种不同会导致煤中水溶钠与水溶氯的存在形式不同.煤中水溶钠的存在不利于高钠煤的着火温度和燃尽温度的降低与燃烧特性的提高,相反煤中的有机钠却对其具有促进作用.     

原位漫反射红外光谱中采用新的实验手段研究煤岩显微组分中的氢键

首次提出采用小瓷片反应器,结合增大载气流量的方法进行产生挥发组分固体的原位漫反射红外光谱实验,研究了两种煤的镜质组和丝质组中的氢键分布及热稳定性.两种显微组分间氢键分布的规律相似;镜质组中SH-N、羧酸二聚体和自缔合羟基等的热稳定性比丝质组中的高.但对OH-N、羟基四聚体和OH-OR₂的热稳定性随煤岩组分的变化无明显规律;随着温度的升高,OH-π含量先升高后降低,于350～380℃达最大值,其中镜质组OH-π的含量增加较快.显微组分中氢键的变化规律反映了其结构上的差异.