热分析获取锅炉内煤着火特性——Part Ⅱ:本征反应动力学

Thermal analysis for obtaining coal ignition characteristics in boilers——Part 2: Intrinsic reaction kinetics

  • 摘要: 煤焦的本征反应动力学模型是计算流体力学(CFD)模拟锅炉内煤着火燃烧速率所需的关键子模型,通常可由热分析获得。热分析反应动力学的研究虽然已发展了数十年,但仍然存在3个问题:① 非等温和等温动力学参数的不统一;② 定值动力学参数和变动力学参数均值的不统一;③ 缺乏不含不确定参数的通用动力学模型,如常用的n级动力学模型、随机孔模型和自催化模型分别含有不确定性参数,如反应级数n、结构参数ψ、反应指数ac。为解决上述问题,提出了通用表面活化函数模型GSAFM,其反应机理函数f(X) = 1 − X(X为转化率),且活化能EX和指前因子AX是随转化率变化的。采用4种等转化率法(变动力学参数模型)包括等温(ISO)GSAFM、非等温(NON)GSAFM、Flynn-Wall-Ozawa(FWO)和Kissinger-Akahira-Sunose(KAS),以及一种定值动力学模型ISAFM,对将军庙(JJM)和红沙泉(HSQ)煤焦的非等温和等温燃烧的本征反应速率进行了预测。结果表明,ISO GSAFM具有最好的预测效果;FWO和KAS的预测效果很差,主要由于这2种模型涉及的温度积分近似处理给EX的求取带来了一定的误差,该误差在求取AX时呈指数级放大。ISO GSAFM获取的煤焦等温燃烧的EX均值为141 kJ/mol,与ISAFM获取的146 kJ/mol接近,从而解决了问题②;其获取的动力学参数可以很好地预测煤焦非等温燃烧的本征反应速率,表明非等温和等温试验可以共用ISO GSAFM获取的动力学参数,即解决了问题①;其f(X) = 1 – X,具有不含不确定参数的通用性,即解决了问题③。ISO GSAFM得到的煤焦的EX在着火区间达到最大值,这一现象表明,煤在锅炉内的着火过程是其燃烧过程中最困难的环节;随后,EX由于煤焦燃烧进入稳定阶段而逐渐减小,但在反应后期会转变为快速增大的趋势,这符合煤焦在反应后期存在失活现象的事实。因此,ISO GSAFM在解决问题①~③的同时还能解释试验现象,有望为以基于定值动力学模型的CFD模拟提供新的本征反应动力学子模型。同种煤阶的JJM和HSQ煤焦存在理化结构上的差异,但两者的EX随转化率变化的趋势相似且大小差异小于5%,采用各自变动力学参数的算数平均可对其本征反应速率进行准确预测,表明同种煤阶的不同煤焦的本征反应速率可以用基于GSAFM的均值动力学参数进行预测,即有望实现同一种煤阶的煤焦反应速率采用同一种变动力学参数(多样本的均值)进行预测。此外,GSAFM表明煤焦的EX只与其化学结构相关,利用变活化能的特征值可精细化地研究煤焦的化学结构对其本征反应性影响的内在机理,如前述的着火困难和失活机理等;用煤焦的化学结构预测出EX后,可通过GSAFM直接预测出煤焦的本征反应速率;上述关联方法为煤焦结构与反应性的研究提供了新的思路。

     

    Abstract: The intrinsic reaction kinetic model of coal char is a key submodel required for computational fluid mechanics (CFD) simulation of coal ignition combustion rates in boilers, typically obtainable from thermal analysis. Although the study of thermal analysis reaction kinetics has been developed for decades, three main issues persist: ① Inconsistency between nonisothermal and isothermal kinetic parameters; ② Inconsistency between fixed kinetic parameters and mean variable kinetic parameters; ③ Lack of a universal kinetic model without uncertain parameters, such as the commonly used nth-order kinetic model, random pore model, and autocatalytic model, each containing uncertain parameters like reaction order n, structural parameter ψ, and reaction index a and c. To address these issues, a generalized surface activation function model (GSAFM) was proposed. Its reaction mechanism function f(X) = 1 − X (where X is the conversion ratio), with activation energy EX and pre-exponential factor AX varying with conversion ratio. Four isoconversional methods (variable kinetic parameter models) were employed, including isothermal (ISO) GSAFM, nonisothermal (NON) GSAFM, Flynn-Wall-Ozawa (FWO), and Kissinger-Akahira-Sunose (KAS), alongside a fixed kinetic parameter model (ISAFM) to predict the intrinsic reaction rates of nonisothermal and isothermal combustion of Jiangjunmiao (JJM) and Hongshaquan (HSQ) coal chars. Results indicated that ISO GSAFM had the best predictive performance; FWO and KAS had poor predictive performance, primarily due to the approximation error introduced in EX determination by temperature integration in these models, which exponentially amplified when determining AX. The mean EX of coal char for isothermal combustion obtained by ISO GSAFM was 141 kJ/mol, close to the 146 kJ/mol obtained by ISAFM, thus resolving issue ②; its kinetic parameters could effectively predict the intrinsic reaction rates of coal char for nonisothermal combustion, indicating that ISO GSAFM parameters could be shared between nonisothermal and isothermal experiments, resolving issue ①; its f(X) = 1 − X demonstrated generality without uncertain parameters, addressing issue ③. The EX of coal char reached its maximum value in the ignition zone, explaining the fact that coal ignition in the boiler is the most difficult segment in the combustion process; subsequent EX gradually decreased as coal char combustion entered a stable combustion stage but showed a rapid increase in the late reaction stage, consistent with the deactivation phenomenon in the later stages of coal char combustion. Therefore, ISO GSAFM simultaneously solves issues ①‒③ while explaining experimental phenomena, potentially providing new intrinsic reaction kinetics submodels for CFD simulation based on fixed kinetic models. Although JJM and HSQ coal chars of the same rank exhibit differences in physicochemical structure, the trend of EX variation with conversion ratio is similar, with differences of values less than 5%. Accurate prediction of their intrinsic reaction rates can be achieved by arithmetically averaging their respective variable kinetic parameters, indicating that the intrinsic reaction rates of different coal chars of the same rank can be predicted using mean kinetic parameters based on GSAFM, thus potentially realizing the use of the same variable kinetic parameters (mean of multiple samples) for predicting the reaction rates of coal chars of the same rank. Furthermore, GSAFM indicates that the EX of coal char is only related to its chemical structure; the use of characteristic values of variable activation energy can provide insight into the underlying mechanism of the influence of coal char chemical structure on its intrinsic reactivity, such as ignition difficulty and deactivation mechanism. Once EX of coal char is predicted based on its chemical structure, its intrinsic reaction rates can be directly predicted using GSAFM. This correlation method provides a new perspective for studying the relationship between coal char structure and reactivity.

     

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