Effect of pyrolysis conditions on the char gasification with mixtures of CO2 and H2O

Two kinds of char were prepared from a lignite by fast pyrolysis using a drop tube furnace and by slow pyrolysis using a fixed-bed furnace at the temperature of 1273 K. Scanning electron microscopy, X-ray diffractometry and the BET method were employed to characterize char properties. The chars were gasified with CO₂, H₂O and their mixtures in a thermogravimetric analyzer (TGA) system to investigate gasification kinetics and derive the rate expression. To validate the gasification rate equation derived from TGA, a fluidized-bed gasification experiment was also carried out. The results showed that both fast-char and slow-char were mainly composed of dense char. The shrinking core model was applicable to predict both gasification of fast-char and slow-char. It was found that the char gasification rate in the mixtures of CO₂ and H₂O was obviously lower than the sum of the two rates of the char independently reacting with CO₂ and H₂O but higher than the rate of each independent reaction, for both the fast-char gasification and slow-char gasification. Both of the results from the TGA and the fluidized-bed reactor showed that char-H₂O reaction was independent on char-CO₂ reaction, while char-CO₂ reaction was inhibited by char-H₂O reaction.     

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.     

Effect of pyrolysis conditions on gasification reactivity of woody biomass-derived char

The effect of pyrolysis conditions on char reactivity has been studied using Raman spectroscopy. This paper reports on the relationship between the properties of biomass char and the gasification rate. The gasification kinetics of biomass char have been revealed by measuring the rate of weight loss during its reaction with CO₂ as a function of temperature. First-order kinetic rate constants are determined by fitting the weight loss data using a random pore model. The relationship between the char structure and CO₂ gasification reactivity was investigated in the range of 15–600 °C/min at a constant pyrolysis pressure (0.1 MPa), and 0.1–3.0 MPa at a constant heating rate (15 °C/min). The experimental results reveal that the reactivity of biomass char is determined by the pyrolysis condition. The CO₂ gasification rates in char generated at 0.1 MPa exhibited approximately twice the values as compared to those obtained at 3 MPa. This is because the uniformity of the carbonaceous structure increases with the pyrolysis pressure. The uniformity of carbonaceous structures would affect the CO₂ gasification reactivity, and the decreasing uniformity would lead to the progression of cavities on the char surface during the CO₂ gasification process. The gasification rate of biomass char increases with the heating rate at pyrolysis. This is due to the coarseness (surface morphology) of biomass char and rough texture, which increases with the heating rate.     

On the reaction mechanism of CO2 reforming of methane over a bed of coal char

CO₂ reforming of methane was studied over a bed of coal char in a fixed bed reactor at temperatures between 1073 and 1223 K and atmospheric pressure with a feed composition of CH₄/CO₂/N₂ in the ratio of 1:1:8. Experimental results showed that the char was an effective catalyst for the production of syngas with a maximum H₂/CO ratio of one. It was also found that high H₂/CO ratios were favoured by low pressures and moderate to high temperatures. These results are supported by thermodynamic calculations. A mechanism of seven overall reactions was studied and three catalytic reactions of CH₄ decomposition, char gasification and the Boudouard reaction was identified as being of major importance. The first reaction produces carbon and H₂, the second consumes carbon, and the third (the Boudouard reaction) converts CO₂ to CO while consuming carbon. Equilibrium calculations and experimental results showed that any water present reacts to form H₂ and carbon oxides in the range of temperatures and pressures studied. Carbon deposition over the char bed is the major cause of deactivation. The rate of carbon formation depends on the kinetic balance between the surface reaction of the adsorbed hydrocarbons with oxygen containing species and the further dissociation of the hydrocarbon.     

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.     

Experimental and modeling study on centimeter pine char combustion in fast-heating Macro TGA

Biomass energy is an important renewable resource, and thermochemical conversion, including pyrolysis and combustion, is one of the main methods of biomass energy utilization. In industrial reactors, the biomass particles will experience a fast heating (∼1000 °C/min) process during pyrolysis. The particle size of biomass applied in industry has a wide range (from millimeter to centimeter scale). The study of the reaction characteristics of biomass pyrolysis and combustion is helpful for optimizing furnace design and working condition selection. In this research, the combustion of centimeter-scale pine char was studied with a newly built fast-heating Macro Thermal Gravimetric Analyzer (Macro TGA). This Macro TGA is able to conduct the pyrolysis and combustion of large biomass samples (up to 40 mm) with a fast heating rate (∼1000 °C/min), which is able to reflect the working conditions in industrial-scale reactors such as grate furnaces and dual fluidized beds. This Macro TGA can measure the online sample weight, temperature and sample size simultaneously during pyrolysis and combustion experiments. The combustion characteristics of different sizes of pine chars were investigated at various temperatures and oxygen concentrations. A zero-dimensional model was established to predict the sample weight loss, temperature change and sample shrinkage during the pine char combustion process. Three kinetic parameters α, A and E were applied in the model, and the values of the kinetic parameters were optimized by a genetic algorithm. The model prediction and experimental results are consistent with each other. Compared with previous studies, this study developed a new experimental method to measure the reaction characteristics (including sample weight, temperature and size) of centimeter-scale biomass under similar pyrolysis and combustion reaction conditions compared to industrial reactors, and a zero-dimensional model was established to describe the pine char combustion process.     

Pressurized oxy-fuel combustion of a char particle in the fluidized bed combustor

Pressurized oxy-fuel combustion of coal in fluidized bed (FB) holds the potential to realize low-cost CO₂ capture. However, the fundamental study in this manner is still rare due to the difficult access to the pressurized oxy-FB combustion tests. In this work, the experimental study of single char combustion was firstly conducted in a visualized pressurized FB combustor under various operating conditions. Then an experimentally verified particle-scale char combustion model was developed to reveal the dependence of char combustion on parameters. Results showed that the char conversion was accelerated with the increase of pressure, mainly due to the high oxygen diffusion and char gasification. The gasification played a non-negligible role in pressurized oxy-fuel combustion, especially under high oxygen concentration and bed temperature. Increasing oxygen concentration and bed temperature not only promotes the char oxidation rate and particle temperature, but also increases the gasification rate and the share of char conversion via gasification, resulting in shortening the burnout time of char. In addition, a higher fluidization number lowered both the burnout time and peak temperature of char particle, due to the simultaneous improvement of mass and heat transfer. The influences of char size and fluidization number on char gasification conversion ratio are very weak. In addition, the quantitative analysis of the influence of different operating parameters on the combustion process was obtained by model sensitivity analysis.     

A detailed chemical kinetic model of high-temperature ethylene glycol gasification

In recent experimental investigations, ethylene glycol is used as a model substance for biomass-based pyrolysis oil in an entrained flow gasifier. In order to gain a deeper insight into process sequences and to conduct parametric analysis, this study describes the development and validation of a detailed chemical kinetic model of high-temperature ethylene glycol gasification. A detailed reaction mechanism based on elementary reactions has been developed considering 80 species and 1243 reactions for application in CFD software. In addition to mechanism validation based on ignition delay times, laminar flame speeds and concentration profiles, simulation results are compared to experimental data of ethylene glycol gasification under complex turbulent reactive flow conditions.     

基于简单碰撞理论煤粉燃烧动力学模型的研究 -PARTⅠ:理论建模与热重实验

本文根据反应动力学的简单碰撞理论(SCT),建立了气固两相反应通用模型,进一步研究了煤焦燃烧和燃尽的统一动力学模型;粉煤悬浮燃烧时挥发分的析出模型也可包含在该模型中;该模型充分考虑了粉煤在热天平中与在炉内燃烧条件下氧气浓度和氧气可达比表面积变化规律的差异,并给出了计算活化能函数和氧气可达比表面积的新方法,可提高利用热天平获取的动力学参数对炉内煤粉燃烧速率预报的准确性。通过热重分析和已经报道的试验数据对模型的合理性进行了检验。     

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.     

一类煤与天然气互补利用的新型发电系统

提出一种新型发电系统,通过煤和天然气的互补利用来减少能量转化过程的不可逆损失。煤气化炉采用空气和水蒸气做氧化剂,碳转化率约为60%,未转化部分形成半焦,半焦燃烧释放的热量驱动天然气重整反应,制取合成气。煤部分气化所得气化煤气和半焦燃烧驱动天然气重整所得合成气混合,作为联合循环的燃料。结果显示,新系统的热效率为51.5%,效率为50.3%,天然气折合发电效率为61%。新系统为高效合理利用煤和天然气提供了一种新途径。     

原煤与煤焦热解气化过程氮转化特性研究

采用热重红外联用的方法,在线检测实验煤种在常压热重分析仪上气化时气体产物的释放过程.实验主要考察无烟煤的挥发分的析出、孔隙比表面积和孔容积对 N 析出与转化的影响,从反应机理上分析含 N 热解气化产物的转化规律.研究发现挥发分的析出速度对煤焦气化影响很明显,在原煤慢焦气化过程中,由于挥发分析出速度慢,形成的孔隙和孔容积较小,而且挥发分中含N量减少会导致焦炭 N 含量增加,从而使得 NH3 和 NO 的析出量增大.在快焦气化过程中,挥发分快速析出,形成的孔隙比表面积和孔容积都较大,导致活性 H 较快释放生成,所以仍然有一定浓度的 HCN 和 NH3.     

Attrition of lignite char under fluidized bed gasification conditions: The effect of carbon conversion

The effect of carbon conversion on the attrition of lignite char particles during fluidized bed gasification by CO₂ was studied in a lab-scale apparatus. The influence of bed temperature and inlet CO₂ concentration on carbon conversion and, consequently, on attrition was studied. The mechanical resistance of the char particles was also characterized at different stages of char conversion by specific attrition experiments. A predictive kinetic model for CO₂ gasification of the lignite char was developed from the experimental results, that was able to correctly predict the evolution of carbon conversion versus time. On this basis a semi-empirical model was developed in order to simulate the evolution of carbon elutriation rate with carbon conversion degree, i.e. the gasification-assisted attrition enhancement effect.     

生物质洁净能源研究中的流化床动力学模型

分别对最小流化床、鼓泡流化床和腾涌流化床及相应的全混模型、鼓泡模型、气泡汇集模型等加以综述 ,分析其优缺点 ,并在此基础上提出动力学模拟研究的新思路 .根据流化床内在的本质———流化态的不同 ,将流化床分为最小流化床、鼓泡流化床和腾涌流化床三种 .总结了前人针对各种流化床提出的全混模型、鼓泡模型、气泡汇集模型等思想 ,建议今后可以在以下几个方面进行深入研究 :⑴使得模型更有普适性 .⑵由于气泡有效直径尚不能在理论上求得 ,可以在理想气泡直径变化公式的基础上 ,加入非线性化学的计算 .⑶确定不同情况下的参数 ,使得工作更有延续性 ,也使得模型更加具有生命力 .⑷从高压的角度去进行模型的计算 ,并得到相应的试验数据支持 .     

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.     

High-temperature pyrolysis of petroleum coke and its correlation to in-situ char-CO2 gasification reactivity

The understanding of the pyrolysis behavior of petroleum coke (PC), a by-product of oil refining, is very critical to its energy utilization. Different from most previous work, this investigation particularly focused on PC pyrolysis at high temperatures > 1273 K. The CO₂ gasification reactivity of in-situ char, rather than quenched char, was evaluated and correlated to PC pyrolysis behavior at different temperatures. A Chinese PC with sizes below 100 μm was tested on a high-temperature thermogravimetric analyser (TGA). Three sets of tests were carried out for different purposes. The first set was to simultaneously obtain sample mass loss and gas evolution data during pyrolysis through thermogravimetry-mass spectrometry (TG-MS). The second set aimed to collect char samples for subsequent analyses by scanning electron microscopy (SEM) and Raman spectrometry. The third set was to evaluate in-situ char-CO₂ gasification reactivity through the TGA. The results showed that, in addition to the commonly-observed primary pyrolysis stage at low temperatures, there was a secondary PC pyrolysis stage at high temperatures > 1300 K. In this process, the gases such as HCN, CO₂ and SO₂ were significantly released. The observed changes of char morphology suggested a four-staged thermoplastic transformation of the PC during pyrolysis, which has little been discussed previously. At different stages, i.e. softening, plasticizing, resolidification and graphitization, the rate of carbon ordering was different. The in-situ char-CO₂ gasification reactivity was found to first increase, then decrease and finally increase again with increasing temperature. Such changes coincided with the thermoplastic state of the pyrolyzed char, but not with the changes of char surface area or carbon ordering. The obtained knowledge is new and highlights the potentially important roles of char thermoplastic state in determining its reactivity towards CO₂.     

Characterizing char particle fragmentation during pulverized coal combustion

A particle population balance model was developed to predict the oxidation characteristics of an ensemble of char particles exposed to an environment in which their overall burning rates are controlled by the combined effects of oxygen diffusion through particle pores and chemical reactions (the zone II burning regime). The model allows for changes in particle size due to burning at the external surface, changes in particle apparent density due to internal burning at pore walls, and changes in the sizes and apparent densities of particles due to percolation type fragmentation. In percolation type fragmentation, fragments of all sizes less than that of the fragmenting particle are produced. The model follows the conversion of particles burning in a gaseous environment of specified temperature and oxygen content. The extent of conversion and particle size, apparent density, and temperature distributions are predicted in time.Experiments were performed in an entrained flow reactor to obtain the size and apparent density data needed to adjust model parameters. Pulverized Wyodak coal particles were injected into the reactor and char samples were extracted at selected residence times. The particle size distributions and apparent densities were measured for each sample extracted. The intrinsic chemical reactivity of the char to oxygen was also measured in experiments performed in a thermogravimetric analyzer. Data were used to adjust rate coefficients in a six-step reaction mechanism used to describe the oxidation process.Calculations made allowing for fragmentation with variations in the apparent densities of fragments yield the type of size, apparent density, and temperature distributions observed experimentally. These distributions broaden with increased char conversion in a manner that can only be predicted when fragmentation is accounted for with variations in fragment apparent density as well as size. The model also yields the type of ash size distributions observed experimentally.     

A mechanistic char oxidation model consistent with observed CO2/CO production ratios

Reliable prediction of char conversion, heat release, and particle temperature during heterogeneous char oxidation relies upon quantitative calculation of the CO₂/CO production ratio. This ratio depends strongly on the surface temperature, but also on the local partial pressure of oxygen and thus becomes more important in simulations of oxy-fuel or pressurized combustion systems. Existing semi-empirical intrinsic kinetic models of char combustion have been calibrated against the temperature-dependence of the CO₂/CO production ratio, but have neglected the effect of the local oxygen concentration. In this study we employ steady-state analysis to demonstrate the limitations of the existing 3-step semi-global kinetics models and to show the necessity of using a 5-step model to adequately capture the temperature- and oxygen-dependence of the CO₂/CO production ratio. A suitable 5-step heterogeneous reaction mechanism is developed and its rate parameters fit to match CO₂/CO production data, global reaction orders, and activation energies reported in the literature. The model predictions are interrogated for a broad range of conditions characteristic of pressurized, oxy-fuel, and conventional high-temperature char combustion, for which essentially no experimental information on the CO₂/CO production ratio is available. The results suggest that the CO₂/CO production ratio may be considerably lower than that estimated with existing power-law correlations for oxygen partial pressures less than 10 kPa and surface temperatures higher than 1600 K. To assist with implementation of the mechanistic CO₂/CO production ratio results, an analytical procedure for calculating the CO₂/CO production ratio is presented.     

Bistable kinetics of simple reactions on solid surfaces: lateral interactions, chemical waves, and the equistability criterion

In heterogeneous reactions, the rate constants of desorption, diffusion and elementary reaction steps are usually strongly dependent on reactant coverages due to adsorbate-adsorbate lateral interactions. We analyze the effect of this factor on the bistable regime of the reaction kinetics. As an example, we consider CO oxidation on Pt(111). The equistability lines in the bistable region for this reaction are calculated by analyzing propagation of chemical waves and taking into account the coverage dependence of the CO diffusion coefficient. The results of simulations are compared with the available experimental data. We show that it is possible to obtain the relationship between various kinetic parameters, for example, between CO and oxygen sticking probabilities, by studying special features of the bistable kinetics.