Gasification of porous carbon particle by carbon dioxide

The diffusive-kinetic model of porous carbon particles gasification is developed. The model considers the processes of heat and mass transfer both inside the porous particle and above it. Analysis of the model shows that heat and mass transfer have an influence to the gasification process to a marked degree. Gasification of carbon particle by carbon dioxide is impossible if particle temperature is lower about 850 K because concentration of carbon dioxide at the particle surface becomes lower than its equilibrium concentration. The rate of the carbon particle gasification is determined as a function of the porous particle internal surface area for different pressures and furnace temperatures.     

Kinetics of coal char gasification in a carbon dioxide medium

Solid fuel samples with different carbon contents are gasified by successively subjecting to pyrolysis in argon and oxidation in carbon dioxide at various temperatures to determine the rate of the chemical reactions and the activation energy required for simulating and optimizing the operation of gas generators. The samples were prepared from bituminous coal, lignite, and anthracite of the Kuznetsk and Kansk-Achinsk coal basins. The gasification of coal char samples in a carbon dioxide medium at 900–1200°C is analyzed by thermogravimetry. The temperature dependences of the weight change rate and gasification time of coal char samples are measured and used to calculate the preexponential factor and activation energy of the carbon oxidation reaction. It is found that, with increasing oxidizing medium temperature from 900 to 1200°C, the gasification time of the coal char samples obtained from anthracite and bituminous coal decrease 8- and 22-fold, respectively. A physicomathematical model of coal char gasification in a fixed bed, with the oxidizing gas diffusing through the ash layer formed, is proposed.     

A study of the gasification of carbon black with molten salt of Li2CO3 and K2CO3 for application in the external anode media of a direct carbon fuel cell

The characteristics of gasification reactions for carbon–carbonate mixtures were experimentally investigated at high temperatures up to 900 °C, considering the application of the mixtures to the external anode media of a direct carbon fuel cell. A thermo-gravimetric analysis (TGA) was conducted in either a nitrogen or carbon dioxide ambient environment for Li₂CO₃, K₂CO₃ and a mixture of these two substances with carbon black. Changes in the exit gas composition were also monitored during the heating process. It was shown that gasification in the mixture media occurs much more rapidly than carbonate decomposition at elevated temperatures, even for low concentrations of CO₂. It was also shown that the loading of carbonates to carbon significantly affects the global gasification reaction; it increased the reaction rate by an order of magnitude and decreased its activation energy. Based on the experimental observations, a simplified reaction model of gasification was suggested for the anode media of a DCFC, regarding carbonate-catalysed and metal-catalysed pathways of Boudouard reactions.     

Effect of gasification reactions on biomass char conversion under pulverized fuel combustion conditions

The effect of gasification reactions on biomass char conversion under pulverized fuel combustion conditions was studied by single particle experiments and modelling. Experiments of pine and beech wood char conversion were carried out in a single particle combustor under conditions of 1473-1723 K, 0.0-10.5% O₂, and 25-42% H₂O. A comprehensive progressive char conversion model, including heterogeneous reactions (char oxidation and char gasification with CO₂ and H₂O), homogeneous reactions (CO oxidation, water-gas shift reaction, and H₂ oxidation) in the particle boundary layer, particle shrinkage, and external and internal heat and mass transfer, was developed. The modelling results are in good agreement with both experimental char conversion time and particle size evolution in the presence of oxygen, while larger deviations are found for the gasification experiments. The modelling results show that the char oxidation is limited by mass transfer, while the char gasification is controlled by both mass transfer and gasification kinetics at the investigated conditions. A sensitivity analysis shows that the CO oxidation in the boundary layer and the gasification kinetics influence significantly the char conversion time, while the water-gas shift reaction and H₂ oxidation have only a small effect. Analysis of the sensitive parameters on the char conversion process under a typical pulverized biomass combustion condition (4% O₂, 13% CO₂, 13% H₂O), shows that the char gasification reactions contribute significantly to char conversion, especially for millimeter-sized biomass char particles at high temperatures.     

Quantifying the effect of CO2 gasification on pulverized coal char oxy-fuel combustion

Previous research has provided strong evidence that CO₂ and H₂O gasification reactions can provide non-negligible contributions to the consumption rates of pulverized coal (pc) char during combustion, particularly in oxy-fuel environments. Fully quantifying the contribution of these gasification reactions has proven to be difficult, due to the dearth of knowledge of gasification rates at the elevated particle temperatures associated with typical pc char combustion processes, as well as the complex interaction of oxidation and gasification reactions. Gasification reactions tend to become more important at higher char particle temperatures (because of their high activation energy) and they tend to reduce pc oxidation due to their endothermicity (i.e. cooling effect). The work reported here attempts to quantify the influence of the gasification reaction of CO₂ in a rigorous manner by combining experimental measurements of the particle temperatures and consumption rates of size-classified pc char particles in tailored oxy-fuel environments with simulations from a detailed reacting porous particle model. The results demonstrate that a specific gasification reaction rate relative to the oxidation rate (within an accuracy of approximately +/- 20% of the pre-exponential value), is consistent with the experimentally measured char particle temperatures and burnout rates in oxy-fuel combustion environments. Conversely, the results also show, in agreement with past calculations, that it is extremely difficult to construct a set of kinetics that does not substantially overpredict particle temperature increase in strongly oxygen-enriched N₂ environments. This latter result is believed to result from deficiencies in standard oxidation mechanisms that fail to account for falloff in char oxidation rates at high temperatures.     

Interrelation of anode and cathode processes in electrochemical carbon oxidation in a fuel cell with molten carbonate electrolyte

The object to be investigated is a fuel cell with a free molten carbonate electrolyte, which ensures direct electrochemical oxidation of solid hydrocarbons. The polarization characteristics of anode and cathode fuel cell assemblies, and also composition and gas release rate of gaseous products of anode reactions are studied. It is shown that the maximum voltages in the open cell circuit are obtained when the oxygen-carbon dioxide ratio in the cathode gas mixture corresponds to stoichiometric reaction coefficients that ensure replenishment of ions in electrolyte. However, the maximum current density values were obtained with a low carbon dioxide content. It is found that at high current values, anode potential fluctuations are observed. It is shown that carbon monoxide is the product of anode processes, along with carbon dioxide. The carbon monoxide content grows with temperature. The carbon dioxide content grows with increasing current in the fuel cell and with growing carbon dioxide content in cathode gases. The release rate of carbon oxidation products nonlinearly depends on the current value in the fuel cell. It is concluded that there is interrelation between the mass-exchange processes in the fuel cell, which is determined by the balance between cathode gas incoming into the reaction zone, the number of molecules generated during fuel oxidation, molecule dissolution and diffusion into the cathode region, and also the amount of gas released in the form of bubbles.     

基于MP-PIC模型的流化床煤气化过程三维数值模拟

本文以多相流质点网格模型(MP-PIC)为基础,采用欧拉-拉格朗日方法,建立了流化床煤气化过程的三维可压缩数理模型,该模型同时考虑了稠密气固流动,传热传质和相内、相间的化学反应。通过不同操作参数下模拟计算,获得反应器内的流型、气体组分分布、化学反应速率变化等规律。模型计算所得的出口气体组分与实验结果进行了比较,数值模拟与实验吻合。     

甲烷固体氧化物燃料电池多物理场模拟及积碳分析

建立了相关实验电池多物理场模型,该模型包括了电化学反应的电化学势平衡方程、甲烷水汽重整的通用速率方程和描述阳极复杂组分气体输运的菲克定律形式尘气模型. 该理论模型的电流～电压 曲线与实验数据很好地吻合,验证了理论模型的有效性. 理论分析发现,低水汽含量甲烷重整反应中水汽的反应级数为1. 理论模型的数值仿真计算还给出多个物理量的详细信息. 据此对碳沉积机制进行深入分析,清楚地描述了工作电流对抑制焦炭生成的机制. 分析比较了积碳活性的两个表达式,发现它们都可以正确地定性反映积碳活性变化趋势,但定量数值并不确切;阳极扩散层降低积碳临界电流的机制也获得了解释. 值得指出的是,虽然积碳活性模型只是定性正确,但分析表明积碳临界电流的降低却可以通过积碳活性模型进行定量解释.     

A novel single particle study of steam gasification kinetics of a coal-derived char at high temperatures and pressures

A novel single particle experiment was developed to allow for detailed char gasification measurements in pure steam at temperatures from 1000 °C to 1400  °C and pressures from 1  bar to 15  bar. A coal-derived activated carbon was thoroughly characterized with respect to its composition, physical structure, and reactivity revealing properties consistent with chars reported in the literature. The single particle approach allowed for the boundary and initial conditions to be well known and for the mass of the particle to be accurately measured before and after testing to provide high-quality conversion data. The resulting conversion data were analyzed using the random pore model and the shrinking core model, of which the random pore model provided the best fit. Apparent activation energies were calculated using the random pore model which provided values ranging from 57.1 kJ/mol to 129 kJ/mol which are nominally half of the magnitude of the values reported in the literature under kinetically controlled conditions, thus demonstrating that regime II conditions were present. Additionally, the activation energies decreased with increasing temperature further demonstrating the presence of regime II conditions. The calculated reaction order ranged from 0 to 0.5 and decreased with increasing pressure agreeing well with literature values and trends.     

Effect of nitrogen and carbon dioxide as fuel impurities on PEM fuel cell performances

Polymer electrolyte membrane (PEM) fuel cells are considered to have the highest power density of all the fuel cells. They operate on hydrogen fuel, which is generally produced by reforming of hydrocarbons, and may contain large amounts of impurities such as carbon dioxide, nitrogen, and trace amounts of carbon monoxide. We studied the effect of dilution of hydrogen gas with carbon dioxide on PEM fuel cells by polarization studies. The polarization curves were different when hydrogen gas was diluted with same quantities of carbon dioxide and with nitrogen. It may be due to carbon monoxide formation by reverse shift reaction and poisoning of anode platinum catalyst. Use of Pt–Ru alloy catalyst was found to suppress the poisoning. The effects of hydrogen gas composition, temperature, current density, and anode catalyst on fuel cell performances were examined in this study.     

Influence of distributed solid-phase reactions on deflagrations in confined porous propellants

Combustion processes in energetic materials are often modeled by a surface gasification reaction followed by a distributed gaseous flame. However, under confinement, deflagrations in porous or granular propellants are generally accompanied by an increasing pressure difference, or overpressure, between the burned-gas region and the unburned reactants deep within the pores of the material. As the overpressure and/or the solid-phase reaction rate become sufficiently large, the gaseous and solid reaction zones tend to merge into a single multiphase reaction region. Furthermore, in certain parameter regimes, the gas flame penetrates into the porous solid, resulting in subsurface gaseous combustion. When the activation energies of the gaseous and solid-phase reactions are of the same order of magnitude and/or the overpressure becomes significant, gasification reactions may also become active within the solid, thus eliminating a distinct propellant surface and forming a distributed multiphase reaction layer. A large activation-energy analysis of this scenario is presented to study the effects of distributed solid reactions on the deflagration structure and the burning-rate response. The burning-rate eigenvalue is obtained from a numerical solution of the reaction-zone problem, and the results are calculated for various overpressures as well as different gas-to-solid activation-energy and thermal conductivity ratios. It is observed that increasing overpressure results in a more spatially distributed solid-phase reaction and a rapidly increasing flame-propagation speed.     

High-pressure shock tube studies on graphite oxidation reactions with carbon dioxide and water

Heterogeneous reactions involving graphite particles reacting with gaseous carbon dioxide and steam were studied under high-pressure and high-temperature conditions. The high-pressure shock tube facility at the University of Illinois at Chicago was utilized to perform the heterogeneous experiments with post-shock pressures ranging from 209 to 363 atm, temperatures ranging between 1546 and 2692 K, and nominal reaction times of 1 ms. Graphite particles were injected into the shock tube, by means of a particle injector, containing mixtures of varying concentrations of H₂O or CO₂ in Ar as balance. The overall reaction rate coefficients from these graphite experiments have been calculated and compared to previous work performed with carbon black particles as well as theoretical and experimental values from prior investigators.     

Experimental study of incomplete oxidation of methane in a ring channel

Chemical transformations at incomplete methane oxidation in the air medium were studied experimentally at reaction activation on the wall of an annular microchannel. Methane was oxidized incompletely on a rhodium catalyst deposited on an inner wall of the channel. Concentrations of the products of chemical transformations were measured in the outlet gas mixture for different reactor temperatures and stay times. We have determined the range of channel wall temperatures and stay times of the mixture corresponding to an increase in the portion of hydrogen and carbon dioxide indicating transition from predominant methane combustion to cascade chemical reactions with activation of steam and carbon dioxide methane conversions. It is shown that the kinetic model of chemical transformations of methane in the air medium depends significantly on the temperature of channel walls and stay time of the mixture. The effect of outer diffusion deceleration on the rate of chemical transformations at incomplete methane oxidation under the strained conditions is determined. The work was financially supported by the Russian Foundation for Basic Research (Grant No. 05-08-65526).     

Effect of CO2 gasification reaction on oxy-combustion of pulverized coal char

For oxy-combustion with flue gas recirculation, as is commonly employed, it is recognized that elevated CO₂ levels affect radiant transport, the heat capacity of the gas, and other gas transport properties. A topic of widespread speculation has concerned the effect of the CO₂ gasification reaction with coal char on the char burning rate. To give clarity to the likely impact of this reaction on the oxy-fuel combustion of pulverized coal char, the Surface Kinetics in Porous Particles (SKIPPY) code was employed for a range of potential CO₂ reaction rates for a high-volatile bituminous coal char particle (130 μm diameter) reacting in several O₂ concentration environments. The effects of boundary layer chemistry are also examined in this analysis. Under oxygen-enriched conditions, boundary layer reactions (converting CO to CO₂, with concomitant heat release) are shown to increase the char particle temperature and burning rate, while decreasing the O₂ concentration at the particle surface. The CO₂ gasification reaction acts to reduce the char particle temperature (because of the reaction endothermicity) and thereby reduces the rate of char oxidation. Interestingly, the presence of the CO₂ gasification reaction increases the char conversion rate for combustion at low O₂ concentrations, but decreases char conversion for combustion at high O₂ concentrations. These calculations give new insight into the complexity of the effects from the CO₂ gasification reaction and should help improve the understanding of experimentally measured oxy-fuel char combustion and burnout trends in the literature.     

Simulation of front motion in a reacting condensed two phase mixture

The computational technique is developed in order to provide the scale capturing for numerical simulation of the thermal processes. The thermal front motion and gas flow dynamics as well as the rate of particle growth during the Carbon Combustion Synthesis of Oxides (CCSO) were predicted using the numerical simulation. In CCSO the exothermic oxidation of carbon nanoparticles generates a self-sustained thermal reaction front that propagates through the solid reactant mixture converting it to the desired complex oxides. The combusted carbon is emitted from the sample as carbon dioxide and its high rate of release increases the product porosity and friability. It was shown that the complicated finger front instability can be developed during the carbon combustion synthesis. This phenomenon results from a vortex gas flow in the reaction zone fed by the carbon dioxide co-flow and oxygen counter-flow filtration.     

炭/碳粒在CO_2/O_2气氛中燃烧速率的研究

１引言大量的研究表明,近一个世纪以来,大气中温室气体（主要是ＣＯ２）含量的迅速增加是引起全球气候变化的一个重要因素。而且,在今后若干年内,随着人类从矿物燃料中获取能源的进一步增加,ＣＯ２的排放量亦将持续增长。其中煤的利用量及在燃烧过程中ＣＯ２的排放量...     

生物质超临界水制氢的数值模拟

本文对生物质在超临界水环境下气化制氢过程提出简化的两相流物理化学模型,并利用该模型进行数值模拟.着重讨论了温度、颗粒半径对生成气体摩尔百分比、气化率的影响.数值结果表明,颗粒的半径主要影响生物质颗粒气化分解的速率,而温度主要影响颗粒气化产物进一步生成氢气的过程.颗粒越小,气化分解的速率越快.温度的影响主要集中在气相反应上,使得CO进一步转化为H2.本文的理论和数值结果对实际的制氢过程中的参数控制具有实用价值.     

An analysis of the transient combustion and burnout time of carbon particles

The various coupled and transient processes controlling the gasification mechanism and burnout time of carbon particles were analyzed, with emphasis on the influence of the initial particle size for the size range that is relevant to the firing of pulverized solid fuels. The formulation recognizes the suppression of the envelop gas-phase CO flame because of the small particle size, and allows for the three surface reactions of C + O₂, C + CO₂, and C + H₂O, as well as radiation heat transfer because of the potential high temperature attainable by the carbon particle. Results show that while the particle temperature continuously increases during the combustion of sufficiently large particles, the gasification actually consists of three phases: namely an initial particle heating period, an activation period for the surface reactions, and a diffusion-controlled, d²-law gasification period characterized by perpetually maximized surface reaction rates in spite of the continuously decreasing particle size. Radiation heat transfer is shown to have the same magnitude as those of reaction heat release and conduction, and actively affects the particle gasification response. For smaller particles, activation of the surface reactions is either substantially delayed subsequent to the initial heating period, or is completely suppressed, which respectively leads to either long burnout times or incomplete particle gasification. Influences due to the ambient oxygen concentration and the presence of CO₂ and H₂O as the oxidizer were also studied. Comparisons with literature experimental data show adequate agreement.     

循环床锅炉循环灰对焦油裂解的催化影响

以循环流化床锅炉循环灰为热载体、部分气化产生的半焦为锅炉燃料的煤的蒸汽－煤气联产技术中,降低焦油产率、提高煤气产率是一个努力方向．本文在固定床反应器实验台上以焦油的两种主要组份苯和甲苯为对象,实验研究了一种洗中煤形成的循环友对焦油裂解的催化影响,测定了裂解反应动力学参数,探讨了循环灰对焦油裂解的催化机理．实验结果表明,与热裂解相比,循环灰条件下焦油裂解活化能下降,气态裂解产物总量提高．