Formation of the structure of chars during devolatilization of pulverized coal and its thermoproperties: A review

The paper provides an overview of current studies on the behaviour of coal during devolatilization, especially the experimental studies and modelling efforts on the formation of char structure of bituminous coals in the open literature. Coal is the most abundant fossil fuel in the world. It dominates the energy supply in the future and plays an increasing role particularly in the developing countries. Coal utilization processes such as combustion or gasification generally involve several steps: i.e., the devolatilization of organic materials, homogeneous reactions of volatile matter with the reactant gases and heterogeneous reactions of chars with the reactant gases. The devolatilization process exerts its influence throughout the life of the solid particles from the injection to the burnout, therefore is the most important step which needs to be understood. When volatile matter is generated, the physical structure of a char changes significantly during the devolatilization, some accompanying a particle's swelling. The complexity of a char's structure lies in the facts that the structure of a char itself is highly heterogenous inside an individual particle and between different particles and the chemistry of a char is strongly dependent on the raw coal properties. A char's structure is strongly dependent on the heating conditions such as temperature, heating rate and pressure. Understanding the swelling of coal and the formation of char's pore structure during the devolatilization of pulverized coal is essential to the development of advanced coal utilization technologies. During combustion and gasification of pulverized coal, the behaviour of individual particles differs markedly due to the variation of their maceral composition. Particles with different maceral constituents generate different types of char structure. The structure of a char has a significant impact on its subsequent heterogeneous reactions and ash formation. The review also covers the most recent studies carried out by the authors, including the experimental observations of the thermoplastic behaviour of individual coal particles from the density fractions using a single-particle reactor, the experimental analysis on chars prepared in a drop tube furnace using the density-separated coal samples, the development of a mathematical model for the formation of char's pore structure based on a simplified multi-bubble mechanism and the investigation on the effect of pressure on char formation in a pressurized entrained-flow reactor.     

Effect of CO2 and steam gasification reactions on the oxy-combustion of pulverized coal char

For oxy-combustion with flue gas recirculation, elevated levels of CO₂ and steam affect the heat capacity of the gas, radiant transport, and other gas transport properties. A topic of widespread speculation has concerned the effect of gasification reactions of coal char on the char burning rate. To asses the impact of these reactions on the oxy-fuel combustion of pulverized coal char, we computed the char consumption characteristics for a range of CO₂ and H₂O reaction rate coefficients for a 100 μm coal char particle reacting in environments of varying O₂, H₂O, and CO₂ concentrations using the kinetics code SKIPPY (Surface Kinetics in Porous Particles). Results indicate that gasification reactions reduce the char particle temperature significantly (because of the reaction endothermicity) and thereby reduce the rate of char oxidation and the radiant emission from burning char particles. However, the overall effect of the combined steam and CO₂ gasification reactions is to increase the carbon consumption rate by approximately 10% in typical oxy-fuel combustion environments. The gasification reactions have a greater influence on char combustion in oxygen-enriched environments, due to the higher char combustion temperature under these conditions. In addition, the gasification reactions have increasing influence as the gas temperature increases (for a given O₂ concentration) and as the particle size increases. Gasification reactions account for roughly 20% of the carbon consumption in low oxygen conditions, and for about 30% under oxygen-enriched conditions. An increase in the carbon consumption rate and a decrease in particle temperature are also evident under conventional air-blown combustion conditions when the gasification reactions are included in the model.     

Kinetics of devolatilization and oxidation of a pulverized biomass in an entrained flow reactor under realistic combustion conditions

In this paper the results of a complete set of devolatilization and combustion experiments performed with pulverized (∼500 μm) biomass in an entrained flow reactor under realistic combustion conditions are presented. The data obtained are used to derive the kinetic parameters that best fit the observed behaviors, according to a simple model of particle combustion (one-step devolatilization, apparent oxidation kinetics, thermally thin particles). The model is found to adequately reproduce the experimental trends regarding both volatile release and char oxidation rates for the range of particle sizes and combustion conditions explored. The experimental and numerical procedures, similar to those recently proposed for the combustion of pulverized coal [J. Ballester, S. Jiménez, Combust. Flame 142 (2005) 210-222], have been designed to derive the parameters required for the analysis of biomass combustion in practical pulverized fuel configurations and allow a reliable characterization of any finely pulverized biomass. Additionally, the results of a limited study on the release rate of nitrogen from the biomass particle along combustion are shown.     

旋风炉内气相燃烧及两相流动的数值模拟

在有反应两相流动及煤粉燃烧的全双流体模型（ＰＴＦ模型,ｐｕｒｅ ｔｗｏ－ｆｌｕｉｄ ｍｏｄｅｌ）基础上,采用修正的ｋ－ε－ｋｐ两相湍流模型,对旋风炉内的湍流气相燃烧（甲烷和一氧化碳的燃烧）及在气相燃烧条件下的两相流动进行了数值模拟研究,模拟结果表明,在有燃烧的情况下,在旋风炉的底部存在近壁回流区,该回流区有利于火焰稳定,气粒两相切向速度分布具有类似的Ｒａｎｋｉｎｅ涡结构,该研究为煤粉燃烧的数值模拟     

Combustion and gasification of coals in fixed-beds

Fixed-bed processes are commercially used for the combustion and conversion of coal for generation of power or production of gaseous or liquid products. Coal particle sizes in fixed-bed processes are typically in the mm to cm diameter range, being much larger than in most other coal processes. This review provides a broad treatment of the technology and the science related to fixed-bed systems. Commercialized and developmental fixed-bed combustion and gasification processes are explored, including countercurrent, cocurrent, and crosscurrent configurations. Ongoing demonstrations in the U.S. Clean Coal Technology program are included. Physical and chemical rate processes occurring in fixed-bed combustion are summarized, with emphasis on coal devolatilization and char oxidation. Mechanisms, rate data and models of these steps are considered with emphasis on large particles. Heat and mass transfer processes, solid flows, bed voidage, tar production and gas phase reactions were also considered. Modeling of fixed-bed processes is also reviewed. Features and assumptions of a large number of one- and two-dimensional fixed-bed combustion and gasification models are summarized while the details of a recent model from this laboratory are presented and compared with data. Research needs are also discussed.     

Experimental studies of ash film fractions based on measurement of cenospheres geometry in pulverized coal combustion

In pulverized coal particle combustion, part of the ash forms the ash film and exerts an inhibitory influence on combustion by impeding the diffusion of oxygen to the encapsulated char core, while part of the ash diffuses toward the char core. Despite the considerable ash effects on combustion, the fraction of ash film still remains unclear. However, the research of the properties of cenospheres can be an appropriate choice for the fraction determination, being aware that the formation of cenospheres is based on the model of coal particles with the visco-plastic ash film and a solid core. The fraction of ash film X is the ratio of the measuring mass of ash film and the total ash in coal particle. In this paper, the Huangling bituminous coal with different sizes was burnt in a drop-tube furnace at 1273, 1473, and 1673 K with air as oxidizer. A scanning electron microscope (SEM) and cross-section analysis have been used to study the geometry of the collected cenospheres and the effects of combustion parameters on the fraction of ash film. The results show that the ash film fraction increases with increasing temperature and carbon conversion ratio but decreases with larger sizes of coal particles. The high fraction of ash film provides a reasonable explanation for the extinction event at the late burnout stage. The varied values of ash film fractions under different conditions during the dynamic combustion process are necessary for further development of kinetic models.     

炉内煤粉燃烧一维数学模型及其仿真

为了准确计算炉内煤粉的燃尽率,从研究煤粉粒子的燃烧机理入手,以炉膛内最复杂的燃烧器区域的煤粉燃烧过程为研究对象,通过合理简化煤粉中挥发分和焦炭的燃烧过程,建立了炉内煤粉燃烧沿高度方向上的一维宏观模型,在模型中考虑了煤粉燃烧过程中氧含量的变化,以单个煤粉颗粒燃烧的等密度模型为基础,通过多种煤粉粒径的燃烧过程反映煤粉燃烧的整体过程,推导出计算炉内煤粉燃尽率的显示公式,满足了实时仿真计算的要求。计算结果与实测数据和现有的文献相符,并对结果进行了分析。     

挥发分火焰对碳粒燃烧的影响

建立了球坐标系下传热、传质、化学反应全耦合的煤粉燃烧数值模拟程序．通过煤粉与事先脱除挥发分的焦炭的对比实验及数值模拟,研究了挥发分火焰对碳粒表面一次产物CO火焰的点燃及碳粒燃烧的影响．傅里叶变换红外光谱仪(FTIR)测温实验及煤粉燃烧动态过程的数值模拟结果不仅进一步验证了碳粒着火初期CO火焰所引起的颗粒高温现象,而且给出了挥发分引燃表面反应一次产物CO的直接证据．由于挥发分火焰的引燃作用,碳粒可以在较其非均相着火温度为低的温度下被点燃,阐明了Juntgen提出的联合着火方式的物理本质．     

颗粒轨道模型对粉煤湍流燃烧计算结果影响的研究

本文对炉内粉煤两相湍流燃烧过程作数值模拟，着重研究了不同颗粒轨道模型对数值模拟结果的影响。研究结果表明，随机轨道模型能较好地模拟粉煤的运动规律，并得到较好的计算结果。     

Numerical Simulation of Pressure Effects on the Gasification of Australian and Indian Coals in a Tubular Gasifier

This article presents a numerical study on the effect of pressure on the gasification performance of an entrained flow tubular gasifier for Australian and Indian coals. Gasification using a substoichiometric amount of air, with or without steam addition, is considered. The model takes into account phenomena such as devolatilization, combustion of volatiles, char combustion, and gasification. Continuous-phase conservation equations are solved in an Eulerian frame and those of the particle phase are solved in a Lagrangian frame, with coupling between the two phases carried out through interactive source terms. The numerical results obtained show that the gasification performance increases for both types of coal when the pressure is increased. Locations of devolatilization, combustion, and gasification zones inside the gasifier are analyzed using the temperature plots, devolatilization plots, and mass depletion histories of coal particles. With increase in pressure, the temperature inside the gasifier increases and also the position of maximum temperature shifts upstream. For the high-ash Indian coal, the combustion of volatiles and char and the gasification process are relatively slower than those for the low-ash Australian coal. The mole fractions of CO and H₂ are found to increase with increase in pressure, in all the cases considered. Further, the effects of pressure on overall gasification performance parameters such as carbon conversion, product gas heating value, and cold gas efficiency are also discussed for both types of coals.     

Numerical investigation of influence of homogeneous/heterogeneous ignition/combustion mechanisms on ignition point position during pulverized coal combustion in oxygen enriched and recycled flue gases atmosphere

It is expected that pulverized coal combustion will continue to play a major role in electricity generation for the foreseeable future. Oxy-fuel coal combustion is actively being investigated, as alternative to conventional pulverized-coal combustion, due to its potential to easier carbon dioxide sequestration. This paper presents experimental and numerical analysis of ignition phenomena in oxy-fuel conditions. A modification of standard sequential coal combustion model is proposed. The new model is developed following the criteria for the particle ignition mechanism as the function of surrounding conditions. The implemented model was validated based on ignition point position obtained from the drop tube facility experiments in various O₂-N₂ and O₂-CO₂ conditions. The obtained numerical results showed a much better agreement with the experimental results when compared with the simulations performed with the default FLUENT sub-models for coal particle ignition/combustion, thus enabling a quantitative determination of pulverized coal flame ignition point position using numerical analysis.     

Influence of biomass blends on the particle temperature and burnout characteristics during oxy-fuel co-combustion of coal

The difference in combustion performance between brown coal and black coal blended with Eucalyptus woodchip and woodchar in varying blending ratios were examined in the air and oxy firing conditions. On top of the experimental investigation using a drop tube furnace (DTF), a computational fluid dynamics (CFD) model was further developed to interpret these results, validated using the experimental data. The CFD model incorporates a comprehensive reaction for devolatilisation reaction to predict the gas release utilising predictions based on chemical percolation devolatilisation (CPD) model. The heterogeneous reactions are defined based on the intrinsic reaction model that accounts for the influence of char properties in chemical and pore diffusion reactions using a user-defined function (UDF). Moreover, the C–CO₂ gasification reaction rate which is critical in an oxy-firing mode was further studied using the CFD tool to determine how the role of gasification varied for various fuel blends. Based on carbon burnout and average particle temperature profiles, the blending of woodchips is highly beneficial to the overall combustion performance in particular for low reactive black coal while its effect on brown coal is marginal. Woodchar and black coal are comparable with similar temperature plots and relatively constant burnout but it behaves relatively inert with a highly reactive brown coal. During oxy firing, increasing the woodchip content enhanced the effect of C–CO₂ gasification due to its extremely large pre-exponential factor for the CO₂ gasification reactivity which explains the improved burnout. The blending of woodchar caused a gradual reduction in the gasification extent for both coals explained by the low heating rates under which woodchar was pyrolysed and also due to the decrease in the peak particle temperature. However, the observed gasification was found to be less than the expected value based on the linear addition of the two single fuels for both biomass blends.     

煤粉燃烧过程中NOx生成的数值模拟

本文提出用有限反应速率２阶矩封闭模型来模拟湍流对煤燃烧过程中ＮＯｘ生成的影响。     

Mechanism analysis on the pulverized coal combustion flame stability and NOx emission in a swirl burner with deep air staging

Low NOx burner and air staged combustion are widely applied to control NOx emission in coal-fired power plants. The gas-solid two-phase flow, pulverized coal combustion and NOx emission characteristics of a single low NOx swirl burner in an existing coal-fired boiler was numerically simulated to analyze the mechanisms of flame stability and in-flame NOx reduction. And the detailed NOx formation and reduction model under fuel rich conditions was employed to optimize NOx emissions for the low NOx burner with air staged combustion of different burner stoichiometric ratios. The results show that the specially-designed swirl burner structures including the pulverized coal concentrator, flame stabilizing ring and baffle plate create an ignition region of high gas temperature, proper oxygen concentration and high pulverized coal concentration near the annular recirculation zone at the burner outlet for flame stability. At the same time, the annular recirculation zone is generated between the primary and secondary air jets to promote the rapid ignition and combustion of pulverized coal particles to consume oxygen, and then a reducing region is formed as fuel-rich environment to contribute to in-flame NO_X reduction. Moreover, the NOx concentration at the outlet of the combustion chamber is greatly reduced when the deep air staged combustion with the burner stoichiometric ratio of 0.75 is adopted, and the CO concentration at the outlet of the combustion chamber can be maintained simultaneously at a low level through the over-fired air injection of high velocity to enhance the mixing of the fresh air with the flue gas, which can provide the optimal solution for lower NOx emission in the existing coal-fired boilers.     

Gasification of a pulverized sub-bituminous coal in CO2 at atmospheric pressure in an entrained flow reactor

Char gasification by CO₂ may play an important role in oxy-fuel applications and affect particle temperature histories and overall reaction rates during combustion. This paper presents the results of a complete set of experiments of char gasification in CO₂ performed with a pulverized Indonesian sub-bituminous coal in an entrained flow reactor under realistic conditions; series of burnout curves at different reactor temperatures (1040–1300 °C) and CO₂ concentrations (0.7–100%) reveal consistent trends in the gasification rates. The study included also devolatilization and oxidation tests with this coal in the same experimental facility. The data are used to derive apparent kinetics for the three processes, in a manner similar to that followed in a previous work for the oxidation of a pulverized coal. The gasification kinetic parameters and reaction rates measured are then compared with values taken or derived from previous works by others, obtained by thermogravimetric analysis or experiments in entrained flow reactors. Finally, the relevance of char gasification in the overall reaction rate under conditions representative of those in an industrial boiler is explored, in particular for the case of oxy-coal combustion.     

煤粉颗粒群着火和燃烧过程的数值模拟

建立了一维非稳态球形煤粉颗粒团的群燃烧模型.数值模拟煤粉颗粒团的着火和燃烧过程,获得了颗粒团燃烧火焰随时间的变迁.分析了煤粉颗粒团内部参数和外部环境参数对颗粒团着火和燃烧的影响.随着颗粒团内煤粉浓度的增加,颗粒团的均相着火延迟先减小后增加.增加煤粉颗粒尺寸和降低外部温度都会明显延迟均相着火.环境氧气含量的增加会减小着火延迟,同时增加颗粒团的燃烧速率.模拟计算和文献试验结果的变化趋势相吻合.     

A model of the combustion of a single small coal particle using kinetic parameters based on thermogravimetric analysis

A mathematical model for the combustion in air of a single entrained spherical coal particle, 30 μm in diameter, has been developed incorporating thermogravimetric analysis data of Whitwick coal. The model is based on a set of ordinary differential equations, describing the reaction rates and the mass and heat transport processes. The system of equations was solved numerically. The combustion mechanism of the particle was described by locating the reaction zone at the solid surface, where gas-phase combustion of volatiles and heterogeneous reaction between gaseous oxygen and the carbon and hydrogen in the solid occurred in parallel. The combustion process was chemical-reaction-rate-controlled, with the oxygen partial pressure at the surface almost that of the surrounding bulk gas. The simulation results using this model, with the kinetic parameters for devolatilization and combustion derived from the experimental thermogravimetric data, are consistent with previously reported combustion lifetimes of approximately 1 s, for particles of this size and rank. They are also consistent with the anticipation that higher ambient gas temperatures should result in shorter burn-out times. The use of thermogravimetric data in the modelling of the combustion of small particles of these low-rank coals is a potentially valuable method for characterization of feedstocks for pulverized coal-fired boilers. © 1998 John Wiley & Sons, Ltd.     

Combustion Characteristics and Kinetics of Partial Gasified Coal Char

Abstract

Combustion characteristics and kinetics of partial gasified coal char (PGC-char) were investigated in this article. Two-stage distributed activation energy model (TS-DAEM) and simple model were used to model the combustion kinetics. The experimental results showed that the combustion characteristics of PGC-chars varied with coal types and percentage of gasification. Modeling results showed that TS-DAEM could suitably describe the combustion of PGC-char. The activation energy and preexponential factor increased with the increasing of PGC-char gasification percentage, but the percent of high reactivity part decreased. This indicated that the difficulty reactive part in the partial gasified coal char became more and more with the gasification conversion. However, simple model wasn't fit to describe the combustion of PGC-char, especially for PGC-chars with obvious second peak in combustion DTG curves.     

Interactive processes in gasification and combustion—Part III: Coal/char particle arrays, streams and clouds

A comprehensive review is presented on the interactive transport processes in the gasification and combustion of a cloud of drops and solid particles. The review is divided into three parts. Part I is concerned with the interactive processes for arrays, streams and clouds of drops, Part II presents a review of isolated coal, carbon and porous char particles pertaining to interactive processes, and finally Part III deals with the interactive processes for solid particle arrays, streams and clouds. Isolated particle gasification (pyrolysis and heterogeneous) and combustion were briefly reviewed in Part II. Because of strong analogy of the group ignition and combustion, to porous char ignition and combustion, the literature on porous char combustion was also included in Part II and new results were presented on the internal ignition of porous char particle using Frank-Kamanetsky type of analysis. Part III presents an integrated approach starting from arrays to clouds and gasification to combustion. The interactions occur through processes ranging from pure diffusive to convective transport processes. Approximate criteria for interactive processes are given.

As opposed to liquid drop arrays and clouds, there is no systematic study for arrays of char or coal particles. Due to the similarity between droplet evaporation and char combustion, new results are presented for the combustion of char arrays in quiescent atmosphere. Convective effects are also briefly discussed. Expanding the Frank-Kamenetsky analysis to ignition of clouds, simple solutions are presented for cloud ignition temperatures. A comparison of results between different techniques and between theory and experiment is given.

Interesting results for the ignition characteristics of coal dispersions are obtained in that the particles with relatively small or low volatile matter which ignite heterogeneously when isolated are found to ignite homogeneously under cloud conditions. The minimum ignition temperature is found to increase with decrease in size under isolated mode while the opposite is true under interactions. The problems of the gasification, ignition, and combustion of clouds in confined and unconfined volumes are reviewed.

Experiments conducted with streams (laminar flow reactors, LFR) and clouds (TGA, heated grids, shock tubes, batch of particles in LFR, Hertzberg Ignition apparatus) are reviewed. Following the drop literature, the relation between array and group combustion is presented. Finally, the relevance of the reviewed literature to pollutants' formation and destruction and spray combustion modeling is briefly discussed.