O2/CO2气氛煤焦的燃烧及其孔隙结构变化

采用热力工况与实际煤粉炉相近的沉降炉实验装置,制备了不同环境气氛下(O2/N2及O2/CO2气氛)、不同燃尽率的煤焦试样,并采用低温氮吸附仪和扫描电子显微镜测定了其孔隙结构和表面形貌.结果表明,在相同的操作条件下,相同O2浓度的O2/CO2气氛下煤焦的燃烧速率较慢、燃尽率较低,各试样的孔比表面积和比孔容积均较小.两种气氛下燃尽过程孔结构参数(SBET和VBJH)均呈减小趋势,且在孔径变化较明显的区域内(<5 nm)在CO2气氛下煤焦的孔径分布较小且与煤种相关.SEM图像显示CO2气氛下的煤焦表面致密,孔隙较少,其定性结果与N2吸附法的定量测量结果吻合较好.     

高温下钙基吸附剂吸附CO2的研究

CaO基吸附剂是一种理想的CO2高温吸附剂。利用热重分析仪研究了由不同前体制备的CaO高温下对CO2的吸附性能。利用吸附仪测定了各吸附剂的比表面积等参数。实验发现CaO的最佳吸附温度范围为700—750℃;由CaC2O4.H2O制得的CaC2O4-CaO具有良好的吸附性能,在实验条件下,其吸附量为理论吸附量的89.1%;在较宽的CO2体积分数范围内,CaC2O4-CaO始终保持很高的吸附性能;吸收速率的大小受吸附剂比表面积、孔体积、孔结构等参数的共同影响。高温下,CaO基吸附剂吸附CO2的微观机理有待进一步研究。     

活性炭孔结构表征研究

N2吸附法是表征多孔材料孔结构的最常用的方法,具有操作简便、样品可回收的优点.N2吸附法测量结果通过不同的数学模型处理,获得微孔(＜2 nm)和中大孔(2 nm～100 nm)数据.应用N2吸附法和扫描电镜对煤基活性炭进行了系统的表征研究,从理论上对BJH法进行了探讨,归纳出了四种典型活性炭的吸附等温线.结合N2吸附法的吸附-脱附数据及扫描电镜表征结果,对其孔结构特点进行全面分析.     

O2/CO2气氛煤焦的燃烧及其孔隙结构变化

采用热力工况与实际煤粉炉相近的沉降炉实验装置,制备了不同环境气氛下（O₂/N₂及O₂/CO₂气氛）、不同燃尽率的煤焦试样,并采用低温氮吸附仪和扫描电子显微镜测定了其孔隙结构和表面形貌。结果表明,在相同的操作条件下,相同O₂浓度的O₂/CO₂气氛下煤焦的燃烧速率较慢、燃尽率较低,各试样的孔比表面积和比孔容积均较小。两种气氛下燃尽过程孔结构参数（SBET和VBJH）均呈减小趋势,且在孔径变化较明显的区域内（<5 nm）在CO₂气氛下煤焦的孔径分布较小且与煤种相关。SEM图像显示CO₂气氛下的煤焦表面致密,孔隙较少,其定性结果与N₂吸附法的定量测量结果吻合较好。     

气流床气化炉飞灰/CO2高温气化反应性

采用程序升温热重法研究了飞灰/CO2高温气化反应性。结果表明:随着升温速率的增加,不同飞灰炭气化反应性的变化程度有所不同;SCFA的气化反应性高于HLFA和NCFA。脱灰后飞灰炭的反应性变差;飞灰炭的气化反应性优于高温煤焦。     

热解条件对淮南煤焦孔隙结构的影响

用N2等温吸附(77 K)法考察了热解条件对淮南煤焦孔隙结构的影响.测量了淮南原煤、淮南快焦和淮南慢焦的BET比表面积,并由BJH模型计算得到了孔容积、平均孔径及孔径分布.结果表明,快速热解和慢速热解都可以使煤孔隙结构发达,加速孔的生成和发展,且热解温度越高,趋势越明显,但慢速热解对煤焦孔隙结构的影响更加显著.应用分形维数的概念,结合吸附/脱附曲线得到了煤焦的分形维数,结果表明快速热解和慢速热解都可以增加煤焦的分形维数.     

混煤热解过程中的表面形态

以管式电炉为热解室,改变热解终温,在惰性气氛下对无烟煤与烟煤的混煤进行快速加热条件下的热解。采用低温氮气吸附方法研究混煤焦表面形态的变化规律。通过对吸附等温线的分析,表明煤焦具有连续、完整的孔隙结构,无定形孔的存在使得吸附迴线存在不闭合的状态。随着热解终温的升高,混煤焦的比表面积先增加后减小;随着烟煤掺混比例的增加,混煤焦的微孔容积和表面积也先增加后减小,A1B2混煤焦具有最大微孔容积和表面积。对煤焦孔隙的分形研究发现煤焦孔隙分形维数与微孔结构关系密切。混煤焦表面形态的变化规律体现了混煤热解的独立性以及相互作用。     

煤焦异相还原N2O的反应机理

采用两种不同的简化煤焦模型,利用量子化学密度泛函理论研究了煤焦异相还原N₂O的反应机理。通过计算反应物、中间体以及过渡态的结构和能量明确了反应的过程,并通过热力学分析和动力学分析深入分析煤焦异相还原N₂O的反应机理。研究结果表明：单个碳原子无法体现N₂O分子在煤焦表面的吸附和脱附过程,不适于作为煤焦模型研究煤焦异相还原N₂O的反应,六环苯环簇碳基模型可以成功地研究煤焦异相还原N₂O的反应。煤焦异相还原N₂O的反应共经历三个过渡态和两个中间体将N₂O还原成N₂,N₂O分子在煤焦表面的吸附反应的活化能为51.01 kJ·mol^-1,煤焦表面吸附N₂O的过程容易进行。煤焦异相还原N₂O的反应在所研究的温度范围（298.15~1500 K）内为放热反应,可以自发发生,反应平衡常数大于10⁵,可以完全进行,认为是单向反应。煤焦异相还原N₂O的反应在所研究的温度范围（298.15~1500 K）内反应速率较快,反应活化能为43.55 kJ·mol^-1,Arrhenius表达式为1.24×10¹⁰exp（-5238.15/T）。     

煤质成型活性炭的制备及其吸附性能研究

以神木烟煤为原料,煤沥青为黏结剂,在较低浸渍比下采用KOH和ZnCl_2活化法制备成型活性炭,利用低温(77 K)N_2吸附法对活性炭的比表面积及孔结构参数进行表征,考察浸渍比对活性炭孔结构的影响及其液相吸附性能,并对比分析两种化学活化法所制活性炭结构与性能的差异.结果表明,在相同浸渍比下,KOH活化法所制成型活性炭的比表面积、总孔容及碘吸附值均高于ZnCl_2活化法.当浸渍比为1.0时,采用KOH活化法可制备出表面积为811 m~2/g,总孔容为0.513 cm~3/g,中孔比例为23.6%,碘吸附值为1 125 mg/g的成型活性炭;采用ZnCl_2活化法可制备出表面积为472 m~2/g,总孔容为0.301 cm~3/g,中孔比例为30.6%,碘吸附值为527 mg/g的成型活性炭.两种活化法所制成型活性炭的孔径主要分布在1.2 nm~2.0 nm的微孔和3.6 nm~4.5 nm的中孔范围内.     

煤焦吸附NO特性与红外光谱分析

对煤焦与NO 的化学吸附过程进行了分析,研究了颗粒粒径和温度对煤焦吸附NO特性的影响; 得到了吸附平衡和动态数据, 利用漫反射红外光谱来研究煤焦经过表面吸附化学反应后官能团结构变化的信息,从而揭示煤表面吸附过程中发生的化学变化。结果表明,煤焦经化学吸附后表面增加了—NO2和—NO官能团,NO气体分子在煤焦表面主要发生的是二位吸附;并且随着煤样平均粒径的减小和温度的升高,—NO2和—NO官能团吸收峰强度明显增强,表明粒径减小和温度升高有利于煤焦化学吸附NO气体。     

秸秆灰对煤焦气化反应性的影响

钾、钙对煤焦气化反应性具有重要影响,秸秆灰中含有丰富的钾、钙。以神木煤为制焦原料,通过STA409PC同步热分析仪研究了秸秆灰对煤焦气化反应性的影响,并通过测定煤焦的碘吸附值对其比表面积及孔隙结构进行了分析。结果表明：煤与玉米秸秆共焦化所得煤焦的气化反应性明显优于单独煤焦,且与玉米秸秆的添加比例有关;采用脱灰玉米秸秆与煤共焦化所得煤焦的气化反应性与单纯煤焦相近;将与玉米秸秆等效的秸秆灰添加到煤焦中,煤焦的气化效果明显优于等效玉米秸秆与煤共焦化所得煤焦。煤焦碘吸附值测定结果表明,脱灰秸秆与煤共焦化所得煤焦的碘吸附值最大,单纯煤焦的碘吸附值最小,说明玉米秸秆及秸秆灰对煤焦的比表面积及孔隙结构具有重要的影响,与煤焦的气化反应性评价结果基本一致。     

Comparison of calculated mercury emissions from three Alberta power plants over a 33 week period - Influence of geological environment

Feed coals and fly ashes from two coal-fired power plants burning Alberta subbituminous coal were analyzed for C, Cl, Hg, and S and calorific values (for feed coal only), every week for a period of 33 weeks. The feed coals used in this study were deposited in brackish water and are compared to the coals deposited in a freshwater environment. The Hg and char (unburnt carbon) content of the fly ash was monitored to determine the variation of Hg and its possible relationship to the char types in the fly ash. The feed coals have Hg content of 0.026-0.089 mg/kg and their fly ash contains 0.02-0.243 mg/kg of Hg. The C content of the fly ashes ranges from 0.15% to 0.51%. The carbon/char was separated from the fly ash using HF and HCl. Reactive vitrinitic (formed from woody part of plants) and less reactive inertinitic (natural char) chars were separated by density separations of various specific gravities using ZnBr₂.The char is mostly reactive vitrinitic (67-80 vol.%). Both stations have similar range of C content for their respective fly ashes. However, station 2 shows a much wider range of Hg in fly ash compared to station 1. In general, the fly ash from coal deposited under brackish water environment (stations 1 and 2) appears to have same or higher Hg content for lower C content compared to the fly ash from coal deposited under fresh water environment.The calculated emitted Hg for the period of 33 weeks for station 1 is estimated to be 64-90% of the total input of Hg with an average of 74%. The calculated emitted Hg shows a more complex pattern for station 2 and falls into two groups; with group (a) showing higher enrichment index for both Hg and S. The calculated emitted Hg for this group is 43-74% with an average of 57%, indicative of more Hg being captured by fly ash, possibly due to interaction between Hg and S. In the second group (b) the emitted Hg is calculated to be 74-95% with an average of 85%. The relative enrichment of both Hg and S in group (b) is low compared to group (a), indicative of possible slight paleo-weathering of the feed coal.The present study indicates that geological parameters such as paleo weathering and also depositional environment of the feed coal may influence the Hg content of fly ash.     

水煤浆气化炉内飞灰的形成机理

基于实验室规模的多喷嘴对置式水煤浆气化炉,利用SEM、马尔文激光粒度仪和XRD表征气化炉内飞灰的粒径分布和组成,并分析了气化炉内飞灰的形成机理。结果表明,喷嘴平面处飞灰与气化炉出口处飞灰的粒径分布及化学组成存在显著差异,不同气化阶段飞灰的形成机理也不同。气化燃烧阶段飞灰的形成机理为部分固定碳燃烧和外在矿物转化,而在焦炭气化反应阶段,飞灰的形成机理为焦炭破碎和内在矿物释放及转化。     

Carbon content of fly ash and size distribution of unburnt char particles in fly ash

The type and size of unburnt char particles in 13 fly ash samples were determined microscopically. The samples were collected from a power station fired from an inertinite-rich coal seam. The carbon content of the ash samples ranged from 2.3 to 25.3 wt%. When the carbon content in a fly ash was high, the proportion of coarse char particles, in particular > 10⁶ μm³ particles, was also high. These results suggest that the size distribution of the feedstock coal has a major effect on the carbon content of the fly ash.     

Transformation of mineral and emission of particulate matters during co-combustion of coal with sewage sludge

Co-combustion of coal with sewage sludge was carried out in laboratory-scaled drop tube furnace to understand the interaction between different fuels. The combustion conditions were selected as follows: the raw material feeding rate was 0.2-0.3 g/min, temperature was 1200 °C, the atmosphere of 10% O₂ and N₂ being balance was used to guarantee an air ratio of 1.5, and the residence time varied from 0.6 to 2.4 s. The coal/sewage sludge is kept at 50:50 (wt% to wt%), four fuel pairs were selected with respect to the mineral association within individual fuel. The results showed the obvious interaction between coal and sewage sludge during their co-combustion. For the carbon conversion, the devolatilization of mixing fuel occurred quickly; the combustion of both char and evolved volatile progressed almost completely. As a result, the unburnt carbon was almost zero in the fly ash. In addition, the evolution of both mineral and PM varied with the association of minerals in raw fuels. For both coal and sewage sludge rich in included minerals, they combusted separately in the furnace, less interaction occurred accordingly. Conversely, for both them rich in excluded minerals, the minerals reacted with each other to form much agglomeration, and therefore, the particle size of the fly ash was increased, while the amount of PM was decreased, which changed as the coarse fly ash particles. Finally, for the case of coal rich in excluded mineral and sludge rich in included mineral, their co-combustion led to the interaction of their minerals. As a result, more the fine particles were formed, which in part changed into PM. For the vaporized trace elements, they were adsorbed by the melt CaPO₄/Al-Si in the ash and accordingly, their contents in the particulate matter were reduced whereas their particle size distribution shifted to the large value.     

煤粉炉和循环流化床锅炉飞灰吸附汞动力学及其吸附机制

在固定床吸附反应器内对两台300MW等级燃煤发电机组循环流化床锅炉和煤粉锅炉飞灰样品进行气相零价汞吸附实验,通过改变实验工况研究温度、入口汞浓度和入口气体流量对飞灰汞吸附能力的影响。采用颗粒内扩散模型、准一阶和准二阶动力学模型、耶洛维奇（Elovich）模型对实验数据分别进行拟合,从动力学的角度探讨两种锅炉飞灰对气相零价汞吸附的影响机制以及两种锅炉飞灰与气相零价汞之间吸附动力学行为差异。结果表明：相同工况下循环流化床锅炉飞灰汞吸附过程的穿透时间和平衡吸附量远大于煤粉锅炉飞灰。吸附温度为150℃时,两种锅炉飞灰对气相零价汞的平衡吸附量最大。由于外扩散阻力随气体入口流量的增加而减小,入口汞浓度的增加可提高传质推动力,飞灰对汞的吸附得以增强。动力学分析表明飞灰的零价汞吸附由外扩散、内扩散和表面化学吸附共同控制,其中表面化学吸附是该吸附过程中的控制步骤;准二阶动力学模型和Elovich动力学模型更适合于描述该吸附过程。相同实验条件下,循环流化床锅炉飞灰吸附过程拟合所得的颗粒内扩散系数、准一阶动力学常数和初始吸附速率均大于煤粉锅炉飞灰。     

平顶山高灰熔融性温度煤的气化反应性研究

介绍了平顶山地区有代表性的7种煤样在800℃～1 200℃下,其脱灰煤焦-CO2气化反应活性的实验,主要考察了煤种、灰含量及粒径对煤焦反应性的影响,实验结果表明:煤种对煤焦-CO2气化反应有明显影响;煤中灰分对煤焦气化反应的影响主要表现在两个方面,一是灰成分对煤焦气化反应的催化作用,二是灰熔融性影响煤焦气化排渣行为。脱灰既可以除去煤焦中具有催化作用的矿物质,又可以增大煤焦的内表面积。     

超低排放燃煤机组硒的迁移转化及飞灰对其富集特性

采用微波消解法和氢化物发生-原子荧光光谱法考察了9台超低排放在役机组硒迁移转化规律,探究了循环流化床（CFB）和煤粉炉（PC）机组飞灰特性差异对硒吸附能力的影响。燃烧后煤中硒几乎全部呈现挥发态,底渣中残留量极低。与浓度归一化和质量分布法相比较,相对富集系数法可以客观地评价燃煤副产物中硒的富集能力,两类机组中硒均主要富集于飞灰中。CFB较低炉膛温度和添加CaO可以降低入炉煤中硒释放比例并增强飞灰对硒的吸附能力,故其底渣和飞灰中硒的富集程度均高于PC,导致脱硫石膏中硒富集程度低于PC。飞灰对硒的吸附量随比表面积或孔容积增大而增大,但随粒径或孔径增大而减小。CFB飞灰中未燃尽碳含量高、形状不规则、表面粗糙且存在较多蜂窝状孔隙,导致其对硒的富集程度高于PC飞灰。     

粉煤灰多元复杂体系锂资源提取的研究及发展

随着锂资源供需关系的紧张和需求量日益增大,从海水、废旧锂电池以及粉煤灰等低品位或者二次资源中回收锂受到重视。综述了煤及粉煤灰中锂资源的含量及分布、粉煤灰多元复杂体系中锂资源提取的技术现状,回顾了当前国内外从其他低品位资源中提锂的技术方法、材料和反应机制,分别从碱性、中性、酸性三种不同的提锂环境进行总结和阐述,对其用于粉煤灰提锂的可行性进行了评估,并对其存在问题和发展方向进行了分析和讨论,从其他低品位资源中提锂的方法可为粉煤灰提锂提供借鉴和参考。文章结尾对粉煤灰中锂资源的提取进行了展望,提出了粉煤灰中伴生资源协同提取的重要性和发展方向。     

Research and development of lithium recovery from multi-component complex system of coal fly ash

With the tight supply and demand of lithium resources and the increasing demand, the recovery of lithium from low-grade or secondary resources such as seawater, waste lithium batteries and fly ash has attracted attention. This review summarized the concentration and distribution of lithium resources in coal and coal fly ash, the technological progress of recovering lithium from multi-component complex system of coal fly ash. This paper also summarized the current methods, materials and reaction mechanisms for recovering lithium from other low-grade resources, which we elaborated from alkaline, neutral and acidic systems. Their feasibility for extracting lithium from coal fly ash was evaluated. The problems and development directions were also analyzed and discussed. The above methods can provide technological reference for recovering lithium from coal fly ash. Finally, we gave a prospect on the recovery of lithium resources from coal fly ash. The synergetic recovery of multi elements from coal fly ash has been highlighted.