随机孔模型应用于煤焦燃烧的动力学研究

采用热重法研究煤焦在变温和等温条件下的燃烧过程,分析升温速率和温度对煤焦燃烧行为的影响,用随机孔模型(RPM)研究煤焦的燃烧失重过程,得到了煤焦燃烧变温和等温动力学方程. 实验结果表明,变温实验中,随着升温速率的增加,煤焦燃烧的失重曲线向高温方向移动,最大燃烧速率增加,升温速率由5℃/min增加到20℃/min时,最大燃烧速率由3.2%/min增加到11.3%/min;等温实验中,随着燃烧温度的提高,煤焦最大燃烧速率增加,燃烧温度由510℃增加到630℃时,最大燃烧速率由2.1%/min增加到8.3%/min,煤焦燃烧性能得到改善. 动力学计算结果表明,RPM能较好描述煤焦变温和等温燃烧过程中煤焦转化率与温度和时间的关系,煤焦变温和等温燃烧的表观活化能分别为84.27和64.16 kJ/mol.     

等温热重分析法对煤焦反应动力学特性研究

针对工业气化炉二级旋风分离器的气化后半焦,同时选取京能烟煤在1173K,1273K和1373K三个温度下快速热解焦炭作为比较,在TGA/SDTA851e型热重分析仪上,对四种经历不同热过程的焦炭进行等温热重实验,实验温度范围为773K～1023K,研究煤焦燃烧反应动力学特性及其影响因素.煤焦制取方式和热解温度的不同决定了煤焦反应性的不同,在这四种煤焦中,气化半焦JC的反应性最小,而京能烟煤三种热解煤焦的反应性随着热解温度的升高而减小.随着燃烧温度和氧含量的升高,煤焦的反应速率在增大.同时,用半转化率法确定了煤焦燃烧的转捩温度和各个反应区域的活化能,在化学反应动力区,JC,JN-1,JN-2和JN-3活化能分别为115kJ/mol,57kJ/mol,70kJ/mol和97kJ/mol,与等转化率法所求得的平均活化能相近.随着煤焦转化率的增大,反应越来越困难,活化能也在增大,而且煤焦燃烧反应离开化学反应动力区的转捩温度也在升高.     

单颗粒煤焦燃烧反应动力学研究方法

采用热天平研究了福建龙岩和加福的两种煤焦的单颗粒燃烧过程。探讨其燃烧过程中的气体扩散、灰层以及反应阻力的影响,建立了单颗粒煤焦燃烧过程分析方法,并由此建立了单颗粒煤焦热天平测定化学反应本征动力学常数的新方法。研究发现,随着单颗粒煤焦燃烧的进行,燃烧总阻力逐渐减小,当反应趋于结束时,燃烧阻力不再随反应时间变化,而是趋于稳定,此时燃烧阻力即为化学反应本征动力学的阻力,由此测定化学反应本征动力学常数。通过对不同温度、不同粒径煤焦以及不同空气流量下的实验与分析,表明该测定方法稳定性好,且测得的煤焦燃烧本征动力学常数和活化能与文献报道一致。     

基于非等温热重法的煤焦燃烧特性及反应动力学

利用非等温热重法研究了由津凯褐煤、万泰烟煤、冀中能源无烟煤和骊达宁无烟煤4种煤在不同变质情况下制备所得煤焦的燃烧特性,利用随机孔模型(RPM)、收缩核未反应芯模型和体积模型模拟了煤焦燃烧反应过程. 结果表明,煤焦燃烧性能与煤粉变质程度、灰分含量和升温速率有关;降低煤粉灰分含量、提高升温速率能够明显加快煤焦燃烧速率,缩短燃烧时间. 动力学计算表明,RPM模型表征煤焦燃烧效果最优,由其所计算的4种煤焦的表观活化能分别为55.74,88.26,84.27和101.30 kJ/mol.     

高温煤焦/CO2气化反应的动力学研究

对煤气化随机孔模型的动力学控制区的假设进行了改进,建立了高温煤焦/CO2气化反应碳转化率(X)与反应时间(t)的修正随机孔模型:X=1-exp[-kt(a+bkt+k2t2)],并在950℃～1 400℃气化温度范围内,用修正随机孔模型模拟淮南慢速热解煤焦和淮南快速热解煤焦/CO2气化反应,所得表观活化能范围分别为121.99kJ/mol～153.75kJ/mol和88.57kJ/mol～121.39kJ/mol.结果表明,修正随机孔模型的拟合效果优于随机孔模型和收缩未反应芯模型的拟合效果,能很好地体现煤焦气化反应的动力学特征,且该模型适用于不同煤焦的气化反应模拟.     

随机孔模型研究煤焦O2/CO2燃烧动力学特征

在热重分析仪上对焦作无烟煤焦和云浮烟煤焦O₂/CO₂条件下燃烧特性进行研究。确定在不同温度下不同煤焦O₂/CO₂燃烧的特征。利用随机孔模型(RPM)表征两种煤焦反应速率与碳转化率的关系,同时与未反应缩核模型(Model Ⅰ)和混合模型(Model Ⅱ)的拟合结果进行比较。研究表明,在不同反应条件下,随机孔模型具有最佳的拟合效果,相关系数都在0.986以上。比较RPM、ModelⅠ和Model Ⅱ计算结果发现,焦作无烟煤焦的O₂/CO₂等温燃烧的活化能比云浮烟煤焦的高,且同一煤种燃烧反应温度越高反应速率常数越大。由于随机孔模型的结构参数ψ可以很好地表现孔结构变化对煤焦燃烧反应的影响,因此随机孔模型能更加准确地描述煤焦O₂/CO₂燃烧特征。     

油砂燃烧特性与动力学的分布活化能模型

采用美国Pyris1TGA热重分析仪对印度尼西亚油砂进行了燃烧特性实验,并分析了升温速率等因素对油砂燃烧反应特性的影响,求得了着火温度、燃烧稳定性判别指数和燃烧反应性能参数等值。通过数据分析,利用分布活化能模型确定了印度尼西亚油砂在整个燃烧过程中活化能随着转化率的变化关系,反应初始阶段,2种油砂的活化能在50—90 kJ/mol之间;STB与STC转化率在0.28和0.27时活化能最大,分别为226 kJ/mol和103 kJ/mol。转化率大于0.6时,STB活化能为200 kJ/mol,STC活化能为160 kJ/mol。还分析了活化能和频率因子之间的补偿效应,为油砂的有效开发与经济利用提供了理论依据。     

油砂燃烧特性与动力学的分布活化能模型

采用美国Pyris1TGA热重分析仪对印度尼西亚油砂进行了燃烧特性实验,并分析了升温速率等因素对油砂燃烧反应特性的影响,求得了着火温度、燃烧稳定性判别指数和燃烧反应性能参数等值。通过数据分析,利用分布活化能模型确定了印度尼西亚油砂在整个燃烧过程中活化能随着转化率的变化关系,反应初始阶段,2种油砂的活化能在50—90 kJ/mol之间;STB与STC转化率在0.28和0.27时活化能最大,分别为226 kJ/mol和103 kJ/mol。转化率大于0.6时,STB活化能为200 kJ/mol,STC活化能为160 kJ/mol。还分析了活化能和频率因子之间的补偿效应,为油砂的有效开发与经济利用提供了理论依据。     

不同煤焦微观表征及其对燃烧反应性的影响

从时间尺度和放热量来看,焦炭的反应在煤的整个燃烧过程中占有主导地位,而煤焦的微观结构与燃烧反应性有很大的关系,因此有必要进一步研究其影响因素和关系.本次研究选取了22种样品(涵盖了无烟煤、烟煤、贫煤、褐煤、煤泥和气化细渣)进行实验,用XRD对煤焦的微观晶体结构进行测量,用TGA对煤焦的燃烧反应性进行测量,从统计上研究不...     

煤焦直接还原脱除烟道气氮氧化物

选用3种不同煤焦,采用程序升温和恒温实验方法,在固定床上考察了不同实验条件下的NO转化率和C对NO选择性,分析了煤焦脱硝的机理和影响因素。实验结果表明：NO和O₂在煤焦表面发生化学吸附所形成的络合物在脱硝过程中起着关键作用,影响C-NO反应和C-O₂反应的竞争与协作关系。在所考察的煤焦中锡林浩特褐煤焦脱硝效果最好,当温度为723 K时烟道气中NO还原率可达99%;在温度623～923 K、O₂浓度0～5%范围内,提高温度和O₂浓度均有利于提高NO转化率,而降低O₂浓度有利于提高C对NO选择性;烟道气中NO浓度越高,其转化率越低,但C对NO选择性越高。     

A comprehensive fractal char combustion model☆

The char combustion mechanisms were analyzed and a comprehensive fractal char combustion model was developed to give a better understanding and better predictions of the char combustion characteristics. Most of the complex factors affecting the char combustion were included, such as the coupling effects between the pore diffusion and the chemical reactions, the evolution of the char pore structures and the variation of the apparent reaction order during combustion, the CO/CO2 ratio in the combustion products and the correction for oxy-char combustion. Eleven different chars were then combusted in two drop tube furnaces with the conversions of the partly burned char samples measured by thermogravimetric analysis. The combustion processes of these chars were simulated with the predicted char conversions matching very well with the measured data which shows that this char combustion model has good accuracy. The apparent reaction order of the char combustion decreases, stabilizes and then increases during the combustion process. The combustion rates in the oxy-mode are general y slower than in the air-mode and the effect of the char-CO2 gasification reac-tion becomes obvious only when the temperature is relatively high and the O2 concentration is relatively low.     

低阶煤低温热解半焦在模拟高炉喷吹条件下的燃烧性能

采用自制固定床热解装置在隔绝空气的条件下制备神木长焰煤热解终温分别为400℃、450℃、500℃及550℃的热解半焦,利用管式沉降炉模拟高炉喷吹条件研究神木长焰煤低温热解半焦的燃烧性能,并考察了热解终温、半焦喷吹粒径以及燃烧反应温度对半焦燃烧性能的影响。研究表明：低温热解半焦的燃烧性能优于实验所选用无烟煤的燃烧性能,半焦的燃烧性能与其燃料比之间存在负相关关系,即燃料比越高,燃烧性能越差;降低热解终温、减小半焦喷吹粒径以及提高燃烧反应温度均能改善半焦的燃烧性能,当热解终温为400℃、喷吹粒径100～200目、燃烧反应温度为1100℃时半焦的燃尽度最佳为96%。本实验半焦制备及燃烧条件与现有低温热解和高炉喷吹工艺相符,且热解半焦各项性能均符合喷吹用煤指标。     

The estimation of char reactivity from coal reflectogram

Measurements of the intrinsic reactivity of chars to oxygen are increasingly being sought as an indicator of the combustion potential of fuels. The coal reflectogram has been used to characterize the chemical properties of coal and its resultant char structure. In this study, six Australian coals varying in rank were separated using density separation technique to obtain vitrinite and inertinite rich fractions. Chars were obtained from these density fraction samples in a Drop Tube Furnace (DTF) at 1673 K. The reactivity of the chars was measured non-isothermally in a Thermal Gravimetric Analysis (TGA) in the temperature range of 573–1073 K. The results suggested that with the increase in the coal rank, the maximum reactivity of chars derived from vitrinite rich fractions decreases, while the reactivity of chars derived from inertinite rich fractions decreases with the increase in the inertinite content in samples and has no obvious relationship with rank. The kinetic parameters were derived using data from non-isothermal TGA after accounting for changing in surface area with conversion. The frequency factor is found to decrease with increasing coal FMR, defined as the summation of each reflectance value multiplied by its frequency, for a constant activation energy (E=146 kJ/mol). This suggests that the behavior of a maceral is characterized primarily by its reflectance distribution instead of the type of its parent coal.     

O2/CO2气氛下多种碳基随机孔模型的建立

传统随机孔模型基于简单一步反应建立,不适用于处理O₂/CO₂气氛下焦炭颗粒复杂气固反应。针对此问题,基于焦炭本身具有多种碳基的特点,以及焦炭颗粒在O₂/CO₂气氛下燃烧的特性,建立复杂气固反应下的多种碳基随机孔模型和孔隙结构模型。模拟直径为100 μm的焦炭颗粒在O₂/CO₂气氛下燃烧的过程,使用FORTRAN语言自主编程计算并分析结果。研究表明,燃烧初期颗粒呈现竞争效应,孔隙内部气体浓度产生剧烈波动。波动的生成原因是化学反应与物理扩散之间的竞争,可以通过增加环境氧浓度和减小焦炭颗粒粒径来改善。所提出的多种碳基随机孔模型对于表征O₂/CO₂气氛下焦炭颗粒的燃烧特性有着良好的适应性。     

Char characterization and DTF assays as tools to predict burnout of coal blends in power plants

The aim of this study is to predict efficiency deviations in the combustion of coal blends in power plants. Combustion of blends, as compared to its single coals, shows that for some blends the behavior is non-additive in nature. Samples of coal feed and fly ashes from combustion of blends at two power plants, plus chars of the parent coals generated in a drop-tube furnace (DTF) at temperatures and heating rates similar to those found in the industrial boilers were used. Intrinsic kinetic parameters, burning profiles and petrographic characteristics of these chars correlated well with the burnout in power plants and DTF experiments. The blend combustion in a DTF reproduces both positive and negative burnout deviations from the expected weighted average. These burnout deviations have been previously attributed to parallel or parallel-series pathways of competition for oxygen. No deviations were found for blends of low rank coals of similar characteristics yielding chars close in morphology, optical texture and reactivity. Negative deviations were found for blends of coals differing moderately in rank and were interpreted as associated with long periods of competition. In this case, fly-ashes were enriched in material derived from the least reactive char, but also unburnt material attributed to the most reactive char was identified. Improved burnout compared to the weighted average was observed for blends of coals very different in rank, and interpreted as the result of a short interaction period, followed by a period where the less reactive char burns under conditions that are more favorable to its combustion. In this case, only unburned material from the least reactive char was identified in the fly-ashes.     

基于Langmuir-Hinshelwood动力学解析O2/CO2/H2O气氛下烟煤焦反应机理

流化床富氧燃烧湿烟气循环兼具经济与环保优势。湿烟气循环（O₂/CO₂/H₂O）条件下煤焦与O₂、CO₂及H₂O的反应同时发生。为探究O₂/CO₂/H₂O气氛下煤焦-O₂、煤焦-CO₂、煤焦-H₂O反应间的相互作用机制,在自制高精度热重实验装置上系统考察了O₂、CO₂、H₂O及其混合气氛下,典型烟煤焦在900℃的反应特性。基于吸附和脱附原理的Langmuir-Hinshelwood（L-H）机理性模型分别计算了烟煤焦与O₂、CO₂和H₂O反应的动力学参数。通过采用单独活性位点与竞争活性位点两种假设分析了O₂/CO₂、O₂/H₂O和CO₂/H₂O气氛下烟煤焦-O₂、烟煤焦-CO₂和烟煤焦-H₂O两两反应间的作用机制,揭示了H₂O分子优先吸附于烟煤焦表面活性位点,O₂分子次之,而CO₂分子相对滞后。O₂/CO₂/H₂O气氛下烟煤焦-O₂、烟煤焦-CO₂、烟煤焦-H₂O反应表现出部分竞争反应活性位点,传统的单独活性位点与竞争活性位点假设均无法准确描述其反应速率特性。基于H₂O分子优先,O₂分子次优先吸附的原理,建立了O₂、CO₂、H₂O混合气氛下煤焦反应速率L-H动力学方程,方程计算结果与实验值良好吻合。研究结果为深入分析煤焦颗粒流化床富氧燃烧特性及构建可靠、准确的燃烧反应模型提供了理论支撑。     

Study on CO2 gasification reactivity of chars obtained from Soma-Isıklar lignite (Turkey) at various coking temperatures

A kinetic study on the gasification of char with CO₂ is presented in this paper. The chars from different coking temperatures show a different reactivity, which can be mostly attributed to kinetic parameters (E_A, k_m, η) and the specific surface area values. The kinetic analysis results with CO₂ gasification of chars from the Soma-Isıklar lignite present that CO₂ gasification rates for chars are controlled by chemical reaction at experimental gasification temperature range. Therefore, the specific surface area and kinetic parameters of prepared chars from Soma-Isıklar lignite should be considered as a very important factor for the gasification reactivity and rates.     

A comparative reactivity and kinetic study on the combustion of coal-biomass char blends

The combustion behavior and kinetics of various biomass chars, a lignite and a hard coal char and their blends were investigated. Pure fuel chars were compared to blended chars with respect to their performance during combustion. Non-isothermal thermogravimetry experiments were performed in air atmosphere, over a temperature range of 25-850 °C and at a heating rate of 10 °C/min. Kinetic evaluation was performed using a power law model. Reaction kinetic parameters were obtained by modeling the combustion of biomass and coal chars as a single reaction, with the exception of lignite and olive kernel chars, the combustion of which was modeled by two partial reactions. A single reaction model was used in the case of coal-wood char blends, while for the lignite-biomass char blends two partial reactions were used. Reactivity was assessed using the specific reaction rate, as a function of conversion. Biomass chars were generally more reactive than those of hard coal and lignite. The combustion behavior of the blends was greatly influenced by the rank of each coal (hard coal or lignite) and the proportion of each component in the blend. Combustion performance of the blends showed some deviation from the expected weighted average of the constituent chars. An attempt was made to estimate the kinetics of the blends using, as a basis, the parameters estimated for the individual components. In this case, because of the interactions between the components of the blends, the kinetic parameters needed to be slightly modified. Alteration in reactivity was more pronounced in the case of lignite-biomass chars than coal-wood chars.     

INFLUENCE OF CHAR PROPERTIES ON REACTION RATES

The reaction of coal char is affected by the char morphology, which is dependent on the temperature and pressure at which the char is prepared. Char properties, such as surface area (by CO₂ adsorption) and diffusion coefficients of CO₂ in char have been measured for chars prepared at 900-1200°C and at pressure to 16 atm at 900°C. The diffusion coefficient results strongly indicate Knudsen or activated surface diffusion. The surface areas and diffusion coefficients decrease in general at higher preparation temperatures, but have a maximum at 1000°C. There is an apparent relationship between these observations and the reactivity results which demonstrate unusual behavior above 1000°C.