煤与生物质的热解特性及动力学研究

作者利用TG/DTG曲线分析不同种类的生物质(桉树叶、橘皮)、煤分别热解,以及二者混合共同热解的基本热解特性,包括热解区间、最大热解速率的温度、不同加热速率对生物质热解进程的影响,比较不同种类生物质与煤按不同比例混合时对煤的热解特性的影响规律等。通过对热解动力学的分析,给出基本热解动力学方程,并研究了生物质、煤以及二者以不同比例掺混共热解时的热解动力学参数。探讨生物质之间、生物质与煤共热解过程中的协同作用和最佳混合比例,为生物质与煤能源的共同利用提供实验数据。     

共热解过程中煤与生物质相互作用的研究进展

煤炭与生物质共热解是实现煤炭高效清洁利用的重要途径之一。共热解可改善煤炭单独热解产生的污染问题和生物质单独利用时能源密度低、季节性供应不平衡的问题,不仅能提高煤炭转化效率,还能获得更高品质油品。本文从煤与生物质共热解的影响因素、研究方法和共热解过程中组分间相互作用等方面出发,对近期国内外煤与生物质共热解的研究进行综述。总结了生物质种类、热解工艺参数和热解反应器的类型对煤与生物质共热解过程的影响规律以及煤与生物质在共热解过程中的相互作用过程,即半焦与挥发分间的相互作用、挥发分间的相互作用、生物质中碱金属对共热解的催化作用,并针对如何进一步认识煤与生物质相互作用机理、提高共热解效率等问题和发展方向作了展望。     

煤和生物质共热解研究现状

煤和生物质共热解能够提高煤的利用效率,从而实现煤炭资源的综合、洁净和高效利用。生物质是富氢物质,煤和生物质共热解在某一温度发生同步热解,使生物质中富余的氢可能转移到煤中从而发生协同作用。本文综述了近年来国内外煤和生物质共热解的研究进展,考察升温速率对煤和生物质共热解协同作用影响研究及煤和生物质共热解对固、液、气体产物的影响研究。     

生物质与聚合物、煤共热解研究进展

综述了近几年来生物质与其它物质如煤和聚合物共热解的研究进展。通过对生物质、煤和聚合物的单独热解以及同煤和其它聚合物共热解的大量文献报道结果进行比较发现:生物质与许多聚合物共热解具有协同作用,可以降低液体产物的含氧量,提高热解液相产率等。显示出生物质与某些聚合物共热解比单独热解具有一定的优势;并比较了煤和生物质共热解产生的现象,得到煤和生物质共热解难以产生协同作用。本文作者结合现阶段的研究成果,提出生物质与煤采用两步法热解工艺的思路,使生物质材料的氢有可能转移到热解煤的产物中,以改善煤热解过程中液体的性质,对今后生物质与煤及聚合物共热解的研究方向提出了自己的建议。     

生物质与煤共热解研究现状

综述了近年来国内外煤与生物质共热解的研究现状。当生物质与煤共热解过程中存在协同反应时,能够将生物质中的氢有效地转移到煤热解过程中,改善煤热解过程中产物的性质,提高煤的热解效率。后续对生物质与煤共热解的研究可以考虑适当的方法,如添加合适的催化剂等来促进协同反应的发生。     

陕北油房梁煤与生物质共热解研究

在N2气氛下,利用热重分析仪对生物质与陕北油房梁煤混合热解特性进行研究,重点考察了生物质混掺比对煤热解的影响。结果表明:相同升温速率下,生物质与煤在热解过程中表现出明显不同的热解特征;生物质与煤以不同掺混比进行共热解时,得到的共热解曲线分段呈现出生物质与煤单独热解的特性,且热解残余固体量与掺混比呈线性关系;此外,对比混合物共热解的实际特征曲线与理论计算曲线,发现实际DTG曲线也与理论计算的DTG曲线基本重合。从上述结果可预测,在热重反应器同步升温情况下,生物质与煤在共热解过程中不存在协同作用。     

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.     

生物质与煤共热解气化行为特性及动力学研究（摘要）

在现有实验室条件下,全面分析了6种形式的生物质与煤共热解过程,考察其中的协同反应效应,利用分布活化能法（DAEM）研究生物质与煤的共热解动力学特性,得出共热解动力学相关参数,为实现生物质与煤高效协同共热解反应寻找更为有效的途径。主要内容和研究成果归纳如下：     

生物质和煤共热解特性及催化剂对热解的影响

为研究生物质和煤程序升温共热解特性及相互作用,利用热天平和管式炉反应器对白松木屑和五彩湾烟煤的共热解特性及催化剂对生物质和煤共热解的影响进行了研究,并考察了共热解半焦的孔结构特性。结果表明：不同比例的生物质和煤在共热解过程中,两者基本保持了各自的热解特性,由于生物质和煤的主要热解阶段温度相差较大,共热解过程中没有发生明显的协同作用。生物质和煤共热解半焦产率实验值大于计算值,当生物质质量分数从75%减少至25%时,半焦产率实验值与计算值之间的差值从0.81个百分点增加到1.07个百分点。橄榄石和载镍橄榄石（NiO/olivine）的添加促进了共热解反应发生的深度。载镍橄榄石催化剂添加（原料和催化剂质量比1：1）的条件下,共热解碳转化率提高了0.5%~5.1%,随着混合物中生物质比例的增加,催化剂的催化效果更加明显。     

生物质与塑料催化共热解技术研究进展

生物质是唯一一种可再生碳源，其高效利用是解决能源与环境问题的纽带。近年来，基于化石能源的塑料制品使用和废弃量快速增加，其难于自然降解，对环境造成严重威胁。生物质与塑料的催化共热解技术能够得到选择性更高的产品，进而提升高附加值产物的产率和品质，是生物质与塑料规模化利用的重要方向。本文从生物质与塑料高效转化的角度出发，梳理了生物质与塑料催化共热解技术研究进展，对生物质与塑料共热解机理、ZSM-5基催化剂共热解、过渡金属基催化剂共热解、碱/碱土金属催化剂共热解、多催化剂共热解等不同种类的催化共热解研究前沿进行了综述，并对比了原位催化和非原位催化的共热解方式，展望了生物质与塑料催化共热解的主要技术和发展方向，以期为生物质与塑料的高效协同转化提供方法参考和研究思路。     

Thermogravimetric study of interactions in the pyrolysis of blends of coal with radiata pine sawdust

The co-pyrolysis of coal-biomass blends were studied by using thermogravimetric analysis to look for thermal events indicating interactions that could cause synergic or inhibitory effects during the first stage in the co-combustion of these materials. Two coals from different rank were selected for the study and combined with radiata pine sawdust, the selected biomass compound. Pyrolysis assays were carried out on the individual components and the binary coal-sawdust blends (50% p/p) at different heating rates (10, 30, 50 °C/min) until reaching a maximum temperature of 1200 °C. The individual components behaved as expected and as is widely described in the specialized literature. Interactions detected in the blends resulted in greater-than-expected volatile yield values. These interactions were produced at pyrolysis temperatures over 400 °C, when most of the components in the blend are devolatilized, and are attributed to secondary reactions that inhibit the formation of char.     

Devolatilization rate of biomasses and coal-biomass blends: an experimental investigation

Devolatilization behavior of different coals and biomasses under heating conditions typical of conventional pyrolysis processes was investigated. Thermogravimetric analyses were performed on coals (with high and low volatile matter), biomasses (pine sawdust and dried sewage sludge) and coal-biomass blends with different weight ratios. The different behavior of coals and biomass fuels in the devolatilization process (different amount and nature of volatile species released, different rate of devolatilization and different reactivity of produced chars) was analyzed for abstracting kinetic data. In addition, analyses of coal-biomass blends revealed that in the operative conditions used (i.e. low heating rate 20 °C/min and high nitrogen flowrate), primary reactions of the thermal decomposition of biomass fuels are not significantly affected by the presence of coal, and also coal does not seem to be influenced by the release of volatile matter from biomass. This led to the first conclusion that the weight loss of a blend can be obtained from the weighted sum of reference materials.Further, a kinetic analysis was performed in order to fit the experimental results and verify simple sub-models (namely, distribution activation energy model and lumped model) to be used in comprehensive combustion codes (computational fluid dynamic) assuring a major accuracy compared with SFOR model, but maintaining both simplicity and computational velocity. A quite good fitting was obtained for all materials and blends studied.     

低阶煤与浒苔低温共热解过程分析及动力学

采用自行设计低温干馏装置对不同配比的低阶煤（LRC）和浒苔（EN）进行低温干馏实验,发现在浒苔配入量为30%时,焦油的产率达到最大值11.39%,比煤单独热解提高了28.61%,比理论加权值提高了8.87%。对低阶煤、浒苔及浒苔配入量为30%的混合样进行热重分析,发现低阶煤与浒苔共热解时在240～750℃段存在明显的协同效应,且其相对最大值达18.5%。动力学分析表明,混合热解时活化能与指前因子之间存在补偿效应,两者混合使反应活性增大,反应速率降低,协同作用主要表现在使共热解反应活性增大。     

生物质与煤共热解时COS的析出特性研究

采用热重分析和色谱、质谱偶联技术,对三种秸秆类生物质与煤混合热解过程中产生的含硫气体进行了在线检测,研究生物质对煤热解析出的COS气体的影响.研究表明:生物质与煤混合热解时,对析出的含硫气体有明显影响.生物质的加入对COS的释放有明显的促进作用,随着生物质比例的增加,促进作用增强.     

Flash co-pyrolysis of biomass with polylactic acid. Part 1: Influence on bio-oil yield and heating value

High amounts of water present in bio-oil are one of the major drawbacks for its utilisation as a fuel. One technology that shows the potential to satisfy the demand for bio-oil with a reduced water content is the flash co-pyrolysis of biomass with polylactic acid, PLA. The influence of PLA on the pyrolysis of willow is investigated with a semi-continuous home-built pyrolysis reactor. Flash co-pyrolysis of willow/PLA blends (10:1, 3:1, 1:1 and 1:2) show synergetic interaction. A higher bio-oil yield and a lower water content as a function of the willow/PLA ratios are obtained. Among the tested blends, the 1:2 willow/PLA blend shows the most pronounced synergy: a reduction in the production of pyrolytic water of almost 28%, accompanied by an increase of more than 37% in the production of water-free bio-oil. Additionally, PLA shows to have a positive influence on the energetic value of the bio-oil produced and on the resulting energy recuperation.     

固定床反应器中生物质/废塑料共热解制备燃料油

通过热重分析不同生物质（木屑和秸秆）单独热解以及与塑料（PP和dcPVC）共热解时的热解行为,研究了生物质与塑料共热解过程中的协同作用。在固定床反应器中考察了塑料的含量对生物质/塑料共热解的影响,最后通过元素分析和GC-MS对所得生物油进行了分析。研究结果表明：生物质和塑料共热解过程中存在明显的协同作用。木屑和PP共热解过程中的协同作用最为显著,当PP含量为80%时,所得生物油的产率最高,明显高于两者单独热解得到的生物油。元素分析和GC-MS分析结果表明：木屑和PP所得生物油的含氢量较高,所得到生物油的热值与石化燃油的相近。     

TG-FTIR characterization of coal and biomass single fuels and blends under slow heating rate conditions: Partitioning of the fuel-bound nitrogen

The devolatilization behavior of a bituminous coal and different biomass fuels currently applied in the Dutch power sector for co-firing was experimentally investigated. The volatile composition during single fuel pyrolysis as well as during co-pyrolysis was studied using TG-FTIR characterization with the focus on the release patterns and quantitative analysis of the gaseous bound nitrogen species. It was shown that all investigated biomass fuels present more or less similar pyrolysis behavior, with a maximum weight loss between 300 and 380 °C. Woody and agricultural biomass materials show higher devolatilization rates than animal waste. When comparing different fuels, the percentage of fuel-bound nitrogen converted to volatile bound-N species (NH₃, HCN, HNCO) does not correlate with the initial fuel-N content. Biomass pyrolysis resulted in higher volatile-N yields than coal, which potentially indicates that NO_x control during co-firing might be favored. No significant interactions occurred during the pyrolysis of coal/biomass blends at conditions typical of TG analysis (slow heating rate). Evolved gas analysis of volatile species confirmed the absence of mutual interactions during woody biomass co-pyrolysis. However, non-additive behavior of selected gas species was found during slaughter and poultry litter co-pyrolysis. Higher CH₄ yields between 450 and 750 °C and higher ammonia and CO yields between 550 and 900 °C were measured. Such a result is likely to be attributed to catalytic effects of alkali and alkaline earth metals present in high quantity in animal waste ash. The fact that the co-pyrolysis of woody and agricultural biomass is well modeled by simple addition of the individual behavior of its components permits to predict the mixture's behavior based on experimental data available for single fuels. On the other hand, animal waste co-pyrolysis presented in some cases synergistic effects in gas products although additive behavior occurred for the solid phase.     

微型流化床内松木屑和煤泥等温混合热解特性

采用微型流化床反应器对松木屑和煤泥的等温混合热解气体释放行为进行实验研究。探讨不同温度和掺混比例对CH₄、CO、CO₂与H₂释放特性的影响,并通过模型配合法求解其动力学参数,研究松木屑和煤泥混合热解过程的相互作用。通过FT-IR检测发现煤泥的主要成分为含有C-O和C==O键的芳香化合物,松木屑则以带-OH键的长链脂肪烃为主。在等温稳定反应阶段,松木屑热解气体生成速率高于煤泥,随着生物质掺入比例的不断提高,混合原料气体生成反应速率亦呈现不同程度的增加。利用模型积分法求解了松木屑、煤泥及其混合物热解气体生成动力学参数,并通过实验值和计算值对比筛选出了最概然机理函数。通过活化能对比发现,混合热解对4种气体组分生成具有不同的影响作用,其中CO实验活化能明显低于计算值,表现为二者协同作用利于CO的生成释放;对H₂而言,在75%混合比例条件下,混合反应导致其生成活化能呈现协同负效应,使得活化能实验值明显高于计算值;相较而言,CH₄在混合热解过程影响相对较弱,并呈现小幅度的协同负效应,而CO₂的生成特性则受混合比例的影响较为明显。