秸秆类生物质闪速热解规律

为了研究闪速加热条件下生物质的热解挥发特性，设计了等离子体加热高温层流炉作为实验设备。用有代表意义的玉米秸秆粉末，在该层流炉上进行了4个加热温度（800K，850K，900K，950K）的热解实验研究。得出了不同加热温度和停留时间下玉米秸秆粉末热解的实验数据；根据这些实验数据和Arrhenius一级反应动力学模型方程，分析得出相应的化学动力学参数：表观频率因子和表观活化能。研究发现，在闪速加热条件下，玉米秸秆粉末的热解化学动力学参数并不随工况的变化而改变，具有统一的公式。用这个模型进行了相应工况的理论计算，得到了挥发份随停留时间和反应温度变化的曲线，并与实验结果进行了比较。结果表明，实验值和模型计算预测值有很好的一致性，所得的模型和相应的动力学参数具有广泛适用性。本项研究结论对秸秆类生物质的闪速热解规律的研究和热解装置的优化设计有重要的指导意义。     

猪粪热解特性及其动力学研究

在程序控温热重分析仪上进行了不同升温速率(10,20,30,50℃/min)的猪粪热解失重试验,获得了猪粪热解特性参数;采用分布活化能模型(DAEM)进行动力学分析,计算得到整个热解过程的活化能和频率因子的分布规律。结果表明,猪粪热解过程呈现失水干燥段、热解过渡段、挥发分析出段和碳化段,升温速率对猪粪的热解有一定的影响,表现为随升温速率的升高,DTG曲线向高温侧移动;动力学分析表明,猪粪热解活化能在52~113 kJ/mol变化,低于锯末、稻壳、稻秆、椰壳热解的活化能,说明猪粪较其他生物质易受热分解;同时猪粪热解的活化能和频率因子之间存在动力学补偿关系,但整个热解过程中这种补偿关系呈分段趋势。     

秸秆类生物质热解特性及其动力学研究

该文对秸秆类生物质的热解行为进行了热重分析（TG）和差分热重分析（DTG）研究。加热速率分别为10K／min、20K／min和30K/min，加热终温为1173K；采用高纯氮气做保护气；样品粒径为250μm－1000μm。通过对TG、DTG曲线的分析，深入研究了加热速度、温度、加热时间等对热解过程的影响，建立了北方典型的秸秆类生物质的反应动力学方程，得出了该类物质热解反应动力学参数、表观活化能和频率因子，并提出了相应的热解机理。     

生物质加压热重分析研究

对两种生物质木屑和松针进行了不同压力和升温速率下的热重分析试验,通过生物质热重失重率（TG）和失重速率（DTG）曲线,获得了相关热解特性参数,提出了生物质的挥发分综合释放特性指数D．并通过热分析数学方法求取了生物质热解动力学参数．试验结果表明,氮气气氛中,木屑与松针常压和增压下主要热解阶段可认为两段一级反应;热解压力的提高,将延迟生物质挥发分初析温度和DTG峰值温度,降低最大析出率和DTG峰值,生物质的挥发分综合释放特性指数D也减小,增加了生物质挥发分的析出难度,并改变了热解反应活化能和频率因子．同一压力下,提高热解升温速率,生物质综合特性指数D将增加．     

非传统动力学分析法解析生物质热解过程

将一种新方法引入到生物质热解过程的分析中,该方法利用不同升温速率下的热重实验数据,基于合理的假设和非线性最小二乘法,确定出生物质热解过程中的反应分布,并最终计算得到对应的活化能、指前因子以及反应比率.在本研究中,首先将其用以计算模拟DTG数据,所得结果与预设数值非常吻合.同时,对纤维素热重实验数据进行分析,发现对于符合一级反应机理的脱挥发分过程,可以很好地计算各反应相关参数.最终将该方法应用到生物质热解过程研究中,结果表明不同生物质的热解过程是由具有不同特征的众多一级反应所组成.不同生物质单元反应的活化能、指前因子以及所对应的反应比率可分为3个部分.各部分的动力学参数以及分布状态与生物质的种类相关.     

煤催化热解过程动力学的研究

由ＷＲＴ－２型热天平测定上海市工业用煤在添加不同类型催化剂（或氧化剂）时的热解曲线，由此确定不同催化剂添加量时的热解动力学参数（表观活化能Ｅ，频率因子Ｋ０，反应级数ｎ），并根据动力学参数的变化规律建立催化热解模型。试验结果表明：催化剂可促进煤热解过程的发生，但不能使挥发份产量提高；氧化剂的效果不如催化剂；热解过程中，热重微分曲线上的峰值点所对应的温度Ｔｍａｘ可作为判断催化剂效能的特征参数；Ｔｍａｘ     

植物化工醇废液热解动力学研究

为了研究植物化工醇废液的热解反应机理,将废液置于氮气气氛下进行加热反应。利用热重分析仪考察了不同升温速率对废液热解反应影响,得到了TG/DTG曲线。实验结果表明废液热解反应有五个波动峰,以及蒸发、热解和无机盐反应三个过程,利用Coats-Redfern法计算了动力学参数,热解过程活化能和频率因子均最小,无机盐反应过程最大,活化能大小与升温速率和反应阶段有关。改变升温速率并不会明显改变热解反应特性,热解过程主要是挥发分析出,失重比和失重速率均最大。     

木质纤维热解的热重和反应动力学研究

试验研究了木质纤维素的热解特性,并对其热解过程进行了分析.结果表明,纤维素在不同升温速率下的热解分为3个阶段:水分的析出、挥发分的析出以及固定炭的生成.纤维素热解是一级反应过程,根据积分法中的Coats和Redfern法对试验数据处理可得到反应的动力学参数(活化能E,频率因子A).     

生物质成型燃料热解特性及动力学研究

利用NETZSCH STA409PC型热重-差热分析仪对生物质成型燃料在以10℃/min、20℃/min及30℃/min升温速率下的热解过程进行了热重分析。对TG-T、DTG-T曲线分析,结果表明生物质成型燃料热解过程分为干燥、热解预热、热解与炭化4个阶段,热解过程随着升温速率升高出现热滞后现象。对剧烈失重区间建立了反应动力学模型,求解出此温度区间的表观活化能、频率因子等动力学参数。     

活化能与频率因子的相关分析

本文在简要叙述了表观活化能和频率因子这两个反应动力学参数的概念后，用公式关系和实验数据论述了两者间的相关性，目的是了解燃料反应在学参数之间的规律、简化反应动力学参数的测定和计算，并将繁琐的反应动力学参数的简单的工业分析沟通，用工业分析数据推断煤质表观活化能的大小，判断煤质热解反应的难易，分析燃料反应动力学特性，分析实际炉内燃烧特性，予示炉内燃烧过程，为定量地描工粉的燃烧过程，建立炉内数学模型打基础     

Kinetic modelling of the first step of Mn2O3/MnO thermochemical cycle for solar hydrogen production

This work reports the kinetic study of the first step of the Mn₂O₃/MnO thermochemical cycle for hydrogen production by water splitting. The reaction kinetics of Mn (III) oxide thermal reduction has been evaluated using dynamic thermogravimetric analysis at constant heating rate under nitrogen flow. This way the reaction rate can be described as a function of temperature and different kinetic models were fitted to the experimental data obtained from thermogravimetric experiments. A good fitting can be observed for each experiment, although a significant disparity in the values estimated for the Arrhenius parameters has been found (activation energies and pre-exponential factors). Unique values for the kinetic parameters have been calculated by application of a multivariate non-linear regression method for the simultaneous fitting of data from all the experiments carried out at different heating ramps. However, also in this case the values of the Arrhenius parameters are significantly different depending on the chosen kinetic equation. Optimal kinetic parameters have been finally calculated through the estimation of activation energy values by model-free isoconversional methods and using a rigorous multivariate nonlinear regression for the calculation of the model-dependant pre-exponential factors.     

热解条件对生物质焦气化活性的影响及等温气化动力学参数求解方法

生物质气化是生物质利用研究的一个重点。生物质气化包含生物质的热解和热解所得焦炭的气化两个过程。不同的热解条件将得到具有不同气化活性的生物质焦炭,不同热解条件制取的焦炭的动力学参数也不相同。本文主要概述了热解条件对生物质焦气化活性的影响。同时基于阿伦尼乌斯公式介绍了生物质焦等温气化动力学参数的两种获取方法,非等转化率法是通过选择动力学模型中的结构因子f(x) 来获取动力学参数,而等转化率法是通过避开选择动力学模型中的结构因子f(x) 来获取动力学参数。基于简单碰撞理论提出了获取等温气化动力学参数的新方法,对阿伦尼乌斯公式中的指数项、指前因子A提出了明确的物理意义。基于简单碰撞理论的等温求解气化动力学参数方法类似于基于阿伦尼乌斯公式的等温求解气化动力学参数方法。     

Comparative study on pyrolysis characteristics and kinetics of oleaginous yeast and algae

The pyrolysis processes of oleaginous yeast and algae were studied and compared using a non-isothermal thermogravimetric analyzer at heating rates of 10–50 °C/min, and the most probable mechanism function and kinetic analyses of the main stage of pyrolysis were carried out by the Popuse method, Starink method, and Fridemen method. The main pyrolysis stage of the samples could be described by the Jander equation and Z–L–T equation and the activation energy of the three biomass was 108–117, 107–121 and 93–108 kJ/mol, respectively. For the three kinds of biomass, the DTG curves were divided based on the four pseudo-components by performing Gaussian fitting which are carbohydrates, proteins, lipids, others, and the weight coefficients of them could be identified. The activation energy of each pseudo-component was obtained in the range of 58.36–140.44 kJ/mol by the Kissinger method. The four-pseudo-component model based on Gaussian fitting provides effective data for the design of oleaginous yeast and algae thermal decomposition systems and the kinetic analysis of the pyrolysis process.     

Pyrolysis rates of biomass materials

A method is proposed by which pyrolysis rates of biomass materials can be predicted from the species compositions in terms of the basic constituents (cellulose, hemicellulose and lignin) and their individual kinetic parameters. The activation energies, frequency factors and reaction orders for cellulose, hemicellulose and lignin have been determined in a conventional manner. The measured rates of pyrolysis of different biomass species (hazelnut, wood, olive husk and rice husk) compare well with literature data.     

Liquefaction of palm kernel shell to bio-oil using sub- and supercritical water: An overall kinetic study

Palm kernel shell was liquefied using sub- and supercritical water at 330–390 °C and 25 MPa for different reaction times. The overall kinetics of the liquefaction based on the conversion of biomass was analyzed using kinetic equation adopted from the literature, and the kinetic parameters were estimated from the evaluation of the kinetic equation. In this study, the rate constant (k) increased from 0.43 to 0.49 s^?1 with reaction temperature from 330 to 390 °C. The relationship of rate constant (k) and temperature agreed reasonably well with the Arrhenius equation. The activation energy (E) and pre-exponential factor (A) values for the liquefaction process were estimated to be 6.70 kJ/mol and 1.65 s^?1, respectively. In addition, the experimental bio-oil yields with respect to reaction time were well-fitted using the modified Reverchon-Sesti Osseo equation.     

Non-isothermal kinetics of pyrolysis of Turkish petroleum pitches

Non-isothermal thermogravimetric data of two Turkish petroleum pitches were used to evaluate kinetic parameters of pyrolysis reactions. The article reports the application of Ozawa–Flynn–Wall model to deal with non-isothermal TG data for the evaluation of the activation energy corresponding to the pyrolysis of two different petroleum pitches. Non-isothermal kinetic studies of pyrolysis of the pitches based on the TGA measurements at different heating rates resulted that average activation energy of pyrolysis of pitch B (213 kJ/mol) was higher than that of average activation energy of pitch A (186 kJ/mol). Reaction orders of pitch A and pitch B were calculated as 0.6 and 0.9, respectively.     

Experimental investigation on the kinetics of catalytic recombination of hydrogen with oxygen in air

Catalytic recombination of hydrogen with oxygen is one of the most attractive options to control the hydrogen concentration in air. The basic pre-requisite for the process design of any catalytic reactor is the knowledge of kinetic data. In the present study, the kinetic data for the catalytic recombination of hydrogen in presence of 0.5% Pd on alumina catalyst were generated using a packed bed reactor with complete recycle. The experiments were conducted using low concentration of hydrogen in air at different temperatures and the apparent rate constants were estimated assuming a first order reaction with respect to hydrogen. The resistances due to internal and external mass transfer were decoupled from the apparent kinetics and estimated separately. The activation energy and frequency factor were found out using the slope and intercept of the Arrhenius plot. The effect of different process parameters such as temperature, superficial velocity and the catalyst particle size on the overall reaction rate was also studied. The knowledge of the intrinsic kinetics along with the mass transfer can be easily extended for the design of catalytic recombination reactors during scale up.     

Kinetic study on pyrolytic process of oil-palm solid waste using two-step consecutive reaction model

Pyrolysis of oil-palm (Elaeis guineensis Jacq.) shell, a cheap and abundantly available solid waste from palm oil producing process, was carried out using thermogravimetric analysis. The effects of raw material particle size and heating rate on the pyrolytic properties and kinetic parameters (activation energy, frequency factor and reaction order) were investigated. A one-step global model and a two-step consecutive reaction model were used to simulate the pyrolytic process and predict the weight loss during pyrolysis. The two-step model fitted the experimental data much better than the one-step model as the softening effect and formation of an intermediate during the pyrolytic process were taken into account. This two-stage reaction characteristic was confirmed by two obvious maxima in the derivative thermogram for pyrolysis of palm shells under different heating rates. The pyrolytic reactions at the low- and high-temperature regimes were found to be based on a first-order reaction mechanism and a contracting volume mechanism, respectively.