南宁褐煤固体热载体快速热解研究

在实验室１０ｋｇ／ｈ处理量的连续实验装置上,以南宁褐煤为原料,进行了快速热解实验。实验结果表明,利用劣质的南宁褐煤,可以生产符合城市煤气标准的中热值煤气、轻质焦油和活性半焦。重点分析和讨论了工艺特点、原料煤热解特性、产品分布、组成、性状及加工利用等问题。     

固体热载体法褐煤热解过程中的传质传热特性

为揭示在固定床反应器中固体热载体法快速热解褐煤工艺过程中的热、质传递机理,建立了固体热载体法褐煤热解过程中的传质传热模型。模型包括球型颗粒的一维非稳态导热方程和基于分布活化能模型的动力学模块,分别采用有限容积法与Matlab软件中遗传算法工具箱对二者进行数值计算。通过呼伦贝尔褐煤热重实验数据与温度测定实验数据分别验证了预测的动力学参数及颗粒传热模型结果。研究发现,热、质变化在固体热载体法褐煤热解工艺中呈现复杂的耦合特性。此外,考察了在不同初始温度、热载体进料比与煤颗粒半径条件下,褐煤在热解过程中颗粒内部温度场在径向上随时间的变化规律,并分析了产物释放速率与温度场的关联性,结果表明热历程改变是工艺条件对热解产物分布造成影响的根本原因。     

褐煤低温热解分级利用现状分析及展望

我国"富煤,贫油,少气"的能源现状,决定了很长时间我国仍将以煤炭为主。其中中低阶煤占目前煤炭总探明储量的50%以上,为高效利用褐煤等中低阶煤炭资源,笔者对我国褐煤资源的分布特点、物理特性及其干燥脱水、压缩成型和低温热解加工利用现状进行了分析,重点综述了褐煤低温热解技术研究现状,对目前广泛应用的固体热载体热解技术、气体热载体和气-固热载体进行了总结,并从反应器类型、热载体类型、适用范围、进料粒度、目标产品、工业化程度等方面对热解工艺进行了对比,指出了现阶段褐煤分级利用过程中存在的产品附加值不高、焦油收率低、余热回收和粉尘处理等关键技术问题,并对未来褐煤热解分级炼制工艺进行了展望,提出了通过提高焦油等热解产物的附加值来延伸产品链、开发与其他物质的共热解工艺、完善现有反应器并开发新的热解反应器、通过工艺调整提高褐煤中氧等元素利用率及大型化发展的必要性。提出未来褐煤等中低阶煤综合利用的建议,将褐煤热解提质技术与现有的煤气化、液化、MTO、MTP等煤化工技术集成,并通过设置适宜的产品目标和设计合理的工艺路线,得到多种高附加值清洁燃料、化工原料以及热能、电力等产品,有效延长褐煤产业链,实现低阶煤分级分质利用,促进我国煤炭转化产业结构调整和优化升级。     

褐煤成型技术研究现状

中国褐煤资源丰富,由于其煤质特点,利用褐煤时需要进行提质加工。褐煤提质加工技术众多,国内外的褐煤提质加工技术主要包括热解提质加工工艺、脱水提质加工工艺及成型提质加工工艺等。褐煤成型技术可根据用户的不同需求,通过特殊的工艺,克服原煤存在的缺陷,生产出质量优良的产品;解决了褐煤易自燃、水分含量高等对长距离运输及储存不利的问题,具有明显的经济效益和环境效益。综述国内外褐煤众多提质工艺中的成型技术现状,介绍具有代表性工艺技术的主要特点,对比分析了国内外褐煤成型工艺技术的主要指标,总结了褐煤成型工艺技术在中国今后的发展。     

褐煤热解分质清洁利用研究进展

介绍了褐煤热解技术,对比研究了典型热解工艺,分析了褐煤热解的影响因素,探讨了分质产品的利用途径及现状,并对实现褐煤大规模高效利用应开展的研究工作进行了展望。     

油页岩开发利用技术进展

在介绍油页岩性质的基础上,系统总结了国内外油页岩热解开发利用的最新研究进展,主要包括油页岩热解化学、热解工艺、页岩灰利用以及油页岩开发利用的技术分析等。油页岩资源的开发利用对缓解石油资源供应紧张和保障能源安全供应具有重要意义。油页岩资源的开发利用必须结合油页岩资源赋存、地质结构和油页岩的性质选择合适的工艺和技术,实现油页岩资源的高效清洁利用。     

我国褐煤热解技术现状及发展趋势

褐煤水分高,氧含量高,易风化自燃,不利于长途运输,要大规模开发利用必须对其加工提质。本文主要介绍了国内典型的几种褐煤热解技术,如大工DG工艺、多段回转炉工艺、BT工艺等,并对其工作原理、操作条件、原料、热解产品等方面进行了分析对比。阐述了褐煤热解的应用现状,并对其发展趋势进行了分析。     

煤系共伴生油页岩热解残渣利用技术

油页岩残渣是油页岩热解过程中排放的固体废物,约占油页岩的80%~90%。中国油页岩残渣利用率较低,残渣堆积量日益增多,后续问题十分突出。煤系油页岩残渣的资源化利用成为油页岩热解提油产业发展的瓶颈。介绍了油页岩热解加工利用现状及其残渣在废水处理和废气吸附方面的应用,分析了当前页岩热解残渣利用过程中存在利用方式单一的问题,并结合油页岩热解残渣结构和组成的特殊性,提出了油页岩残渣用作环保材料如吸附剂的发展方向。     

褐煤热解特性及热解动力学研究

采用非等温热重法对白音华褐煤热解特性进行了实验研究,考察了升温速率和粒度对白音华褐煤热解特性的影响,同时对其热解动力学进行了分析。结果表明：升温速率是影响褐煤热解的主要因素,粒度对褐煤的热解也有一定的影响。利用Coats-Redferm积分法确定了褐煤热解低温段的动力学参数。     

多噬香鞘氨醇单胞菌降解陕西神府褐煤的工艺条件及产物研究

利用多噬香鞘氨醇单胞菌对陕西神府褐煤进行降解实验,通过单因素和正交实验确定了多噬香鞘氨醇单胞菌降解陕西神府褐煤的最佳工艺条件.煤样预处理采用10 mol/L硝酸氧化,煤样粒度为0.074 mm～0.125 mm,菌液量为8 mL/50 mL(培养基),降解时间为14 d,培养温度为35℃,培养方式为摇床培养,此时最大降...     

Upgrading of flash pyrolysis tars to synthetic crude oil: 4. Hydrotreatment with iron catalyst in a slurry-phase reactor

Flash pyrolysis tars, produced from Millmerran (Queensland subbituminous) and Piercefield (New South Wales bituminous) coals, have been hydrogenated in a slurry-phase bubble-column reactor using red mud and sulphur as catalyst. Oils of low coking propensity and high volatility were produced from both coal tars. The slurry-phase reactor successfully overcame the severe coking problems previously encountered when hydrogenating flash pyrolysis tars in fixed-bed reactors, completely eliminating coke formation. For Millmerran coal tar the effect of reaction temperature on reactor performance was investigated in the range 420–460 °C. The major effects of increasing temperature were to reduce the coking propensity of the product oil and to increase its volatility. Product oils from both tars were high in aromatics and heteroatoms, and the distillate fractions derived from these oils would require further refining to produce finished products (i.e., gasoline and diesel). It should be possible to achieve this using conventional refining technology.     

煤与生物质共热解的TGA-FTIR研究

利用热重分析仪和傅里叶红外光谱仪对煤与木屑混合物在惰性气氛中进行了共热解研究,考察煤阶及煤与生物质掺混比例对热解过程的影响.结果表明,煤与木屑共热解特性并不是单独煤和单独木屑热解特性的简单叠加;高阶煤与生物质共热解更有利于协同反应的发生.通过对红外吸收光谱的分析发现,木屑与不同煤化程度煤共热解析出气体的成分和含量也不同,说明煤阶对煤与生物质共热解的气态产物有明显影响,也从侧面揭示了混合物热解过程中煤与木屑之间发生了相互作用.     

基于过程强化与反应调控的煤定向热解制高品质油气产物基础研究及中试验证

对比了现有煤热解制油气技术的特点,从反应工程“三传一反”的角度系统分析和概括了煤热解过程中挥发分在颗粒内生成和释放、颗粒间扩散和反应器中停留等关键步骤中的热量、质量传递和挥发分二次反应对油气品质的影响,揭示了目前碎煤热解制油气技术普遍存在的目标产品产率低、品质差、含尘量高等技术难题的根源,并总结出煤定向热解调控的有效措施,即在挥发分生成和半焦缩聚段采用高温加热和快速传递的传热方式,在挥发分扩散过程中利用半焦床层重整焦油和过滤灰尘,在反应器中设置气体通道导流挥发分的定向溢出。针对研究团队前期开发的内构件移动床定向热解理念,介绍了导热板和集气腔等内构件的作用机制,即通过导热板和中心集气腔等内构件进行传热强化、热解气流动的有序引导,实现热量和挥发分的同向扩散和传递;通过移动床中颗粒的缓慢运动和床层的过滤作用除尘;概述了1~5 kg/次基础实验、反应器结构内传热和流动模拟,100 kg/次模试分析和1000 t/a中试验证的研究结果,充分证实了该技术在同步提高油气质量与品质、降低油中尘含量等方面的优势和对碎煤原料的适用性;基于上述研究形成了内构件定向热解技术及基于该技术的热/电-油-气联产技术。     

煤炭低温干馏微波加热技术的研究进展

随着石油能源储量的日趋减少,清洁煤转化技术得到越来越多的重视。如何将现有的低阶煤炭资源进行高效转化及利用,对缓解我国能源危机和带动当地经济迅速发展具有重要作用。论述了国内外传统煤加热技术现状及微波热解煤的技术进展,微波热解的工艺特点和反应机理,最后对微波热解应用于煤炭低温干馏的前景进行了展望,为煤热解技术日后的研究提供有效的参考。     

煤气化化学与技术进展

阐述了煤气化化学及气化过程,说明煤气化过程主要包括煤的热裂解、部分氧化燃烧、炭的气化、炉渣的生成和排出4个转化步骤。论述了固定床气化技术、流化床气化技术、气流床气化技术3种煤气化技术的工艺、设备、优缺点和适用范围。从煤灰液渣对耐火衬里的腐蚀机理、煤灰化学组成、灰熔融性和灰熔融温度、液渣黏度四方面分析了气流床灰/渣特性。最后阐述了美国煤气化技术进展及发展方向,提出应重点开展IGCC煤气化、低阶煤(褐煤和次烟煤)气化技术研究,开展以提高气化炉可靠性、气化效率和煤种适应性为目标的气化炉优化研究,控制多种污染物排放至极低水平的合成气净化技术研究,低成本高效率的O2分离技术及H2和CO2的分离技术研究等。     

Acidic groups in coal and coal-derived materials

The application of non-aqueous titrations to coal and coal-derived liquids is described to distinguish and determine carboxylic and phenolic groups in these materials. Such titrations have been applied to two coals, a subbituminous and a bituminous coal. For the subbituminous coal the amount of phenolic groups estimated from non-aqueous titrations is only about 30% of that estimated from acetylation studies, whereas both these methods give similar results for the bituminous coal. The lower values obtained by non-aqueous titrations, for the subbituminous coal, are due to proximal phenolic groups which are only partially titratable and alcohol groups which are non-titratable.     

高温再热对依兰煤低温干馏产物及结焦行为的影响

研究了依兰六级煤低温干馏气在高温二次加热过程中的裂解和结焦行为,分析了干馏气体产率、焦油产率的变化和加热器内的结焦情况。煤低温干馏终温600℃,干馏气二次加热温度600℃～750℃。研究表明,二次加热造成干馏产物中气体产率显著增大,焦油产率降低,加热器内存在结焦现象。提高二次加热的温度和延长气体在加热器内的停留时间,加剧了干馏气中烃类分子的裂解、缩聚和结焦,进一步降低了油品收率,并造成油品密度增大。温度对干馏产物中有机大分子裂解行为的影响更为显著,而停留时间和干馏气中烃类产物的浓度对缩聚反应的影响更大。     

N2O emissions from fluidised bed combustion. The effect of fuel characteristics and operating conditions☆

Fluidised bed combustion (FBC) is a versatile and relative clean technology except with respect to nitrous oxide (N₂O) emissions. The emissions of N₂O from FBCs are very dependent on a number of operating conditions (temperature, sorbent addition, excess oxygen, etc.), fuel characteristics and many homogeneous and heterogeneous reactions that take place.This paper describes the results obtained during the study of the effect of coal type on N₂O emissions from FBC. The combustion tests were performed in a circulating fluidised bed pilot plant, using two coals: a Spanish subbituminous (Puertollano) and a bituminous coal from Colombia (Carbocol). Using supporting laboratory-scale fluidised bed pyrolysis experimental data with these fuels the partitioning of fuel-N and the formation of the most important N₂O precursors, NH₃, HCN and char was followed. The pyrolysis tests results showed that the major part of the nitrogen remained in the char. Both coals a produced similar amount of HCN, but the amount of char-N was lower with Carbocol coal that with Puertollano coal. The combustion results showed that the conversion of fuel-N to N₂O was higher on the tests with Puertollano coal than with Carbocol coal. For this it was concluded that the formation of N₂O via char-N oxidation was the most important pathway. The temperature profile of the combustor and the sorbent addition strongly influence N₂O emissions.     

Effect of inorganic matter on reactivity and kinetics of coal pyrolysis

Two Chinese coals, Shenfu subbituminous coal and Huolingele lignite, were used to investigate the effect of mineral matter in coal on reactivity and kinetic characteristics of coal pyrolysis. The experiments were carried out by using thermogravimetry to check the pyrolysis behavior of raw coal, HCl/HF demineralized coal and demineralized coal with inorganic matter (CaO, K₂CO₃ and Al₂O₃) added, respectively. The results showed that inherent mineral in coal had no evident effect on the reactivity and kinetics of coal pyrolysis. CaO, K₂CO₃ and Al₂O₃ all had a catalytic effect on the reactivity of coal pyrolysis, their effects were closely related to temperature region and coal types. The pyrolysis process of all the samples studied can be described by three independent first order kinetic model. Addition of inorganic matter the activation energy decreased and the characteristic temperature of coal changed.     

Experimental studies on pyrolysis of Datong coal with solid heat carrier in a fixed bed

An experimental apparatus was set up for batch simulation of coal pyrolysis with solid heat carrier in a fixed bed. Quartz sand as heat carrier preheated to about 700–800°C was mixed with Datong bituminous coal by an agitator. The thermal history of the coal particle has been followed by a K-type thermocouple. The effects of particle size, pyrolysis time and temperature on the gas yield during pyrolysis of coal with solid heat carrier were examined for different conditions. The experimental results showed that a dominant percentage of the gas product is produced during the first 1–3 min, although gas evolution would last for as long as 10 min. The total gas yield, insensitive to particle size of the heat carrier, depends on carrier temperature and coal particle size under tested conditions. The contact heat transfer of cold and hot particles was analyzed.