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。     

富氧燃烧条件下煤焦的燃尽特性

本文利用平面火焰携带流反应器研究了DT烟煤在富氧燃烧条件下的燃烧实验。采用灰示踪法分析煤焦的燃尽和元素释放特性,并采用等密度模型计算了基于氧化反应C+0.5O_2→CO的表观反应动力学参数。研究结果表明;煤粉在富氧燃烧条件下的燃尽慢于空气燃烧;富氧燃烧条件下,煤焦与CO_2的气化反应会导致煤焦表面对O的化学吸附,进而导致氧元素释放速率减慢;高氧浓度条件下,高浓度CO_2对煤焦燃尽的抑制作用大于CO_2气化反应对煤焦燃尽的促进作用,降低环境氧浓度可以逐步提高CO_2气化反应对煤焦燃尽的贡献。     

荧光熄灭法测定前列腺素E1

本文研究了前列腺素Ｅ１（简称ＰＧＥ１）对甲醇荧光峰的熄灭作用，且其熄灭程度与ＰＧＥ１浓度间有较好的定量关系，线性回归方程为ΔＦ＝０．２２２ｃ＋９．３３×１０－２（ΔＦ为荧光熄灭值；ｃ为ＰＧＥ１浓度，单位为μｇ／ｍＬ），回归系数ｒ＝０．９９９３０。实验表明，用该法所得结果与紫外分光光度法所得结果较相吻合。     

煤焦着火温度预测

分别计算两种不同的煤焦(ZCY和SLH)的表面氧化反应动力学参数,从而计算煤焦表面氧化反应热流。因煤焦颗粒的直径很小,假设煤焦的表面和内部温度变化是一致的,根据煤焦的升温速率与热流的关系,计算出煤焦在炉膛中温度与进入炉膛时间的关系,利用Semenov着火判据,从而预测两种不同煤焦的着火温度以及着火所需时间。ZCY和SLH的着火温度分别为705 K、685 K;着火所需时间与炉膛的环境温度有关,温度越高,时间越短。     

低氧浓度下煤燃烧特性的热重实验研究

煤燃烧的部分过程是在低氧浓度下进行的,本文利用热重实验研究煤在低氧浓度下燃烧特性的变化,重点研究着火特性、燃尽特性和燃烧速率的变化;同时计算分析低氧浓度下,煤燃烧反应动力学参数的变化。实验结果表明,低氧浓度下煤燃烧反应的TG和DTG曲线均向高温区靠近,着火温度基本不变,燃尽温度提高,燃烧速率下降;低氧浓度下燃烧反应的动力学参数活化能E和频率因子k_0之间存在着补偿效应。     

η－配对超导体的临界温度

本文研究具有非零中心动量的η－配对超导系统．用吸引的Ｈｕｂｂａｒｄ模型描述传导电子（或空穴），并认为其能量被限制在化学势范围内．利用平均场方法求出了零温度能隙△（０）和临界温度Ｔｃ同掺杂浓度δ的关系以及２△（０）／ｋＢＴｃ的值．我们的结果在相当宽的掺杂浓度范围内同有关的高Ｔｃ实验相符合．     

催化动力学光度法测定水中痕量铁

本文研究了ｐｈ５．０的ＨＡｃ－ＮａＡｃ介质中，痕量铁催化过氧化氢氧化紫脲酸的褪色反应，建立了催化动力学光度法测定痕量铁的新方法，方法的线性范围０－０．４０，０．４０－２．０μｇ／２５ｍＬ，检出限为８×１０＾－１１ｇ／ｍＬ，用于水样中痕量铁的测定，结果满意。     

Pb(Zr0.52Ti0.48)O3陶瓷畴界粘滞运动的介电损耗模拟

对不同频率下（１ —１０ ｋ Ｈｚ） Ｐｂ（ Ｚｒ０５２ Ｔｉ０４８） Ｏ３ 多晶陶瓷的介电性能的测量表明：在接近铁电相变温度 Ｔｃ 以下存在一介电损耗峰,该峰具有弛豫特征但不满足 Ａｒｒｈｅｎｉｕｓ 关系．这一损耗峰被认为是由于畴界与晶格、缺陷钉扎的互作用引起的．用畴界粘滞运动的动力学方程,考虑陶瓷样品中 Ｔｃ 离散分布的情况,模拟了该介电损耗峰在不同频率下的行为,得到了与实验数据一致的结果．并由拟合参数计算了畴界运动的粘滞系数和缺陷钉扎引起的回复力常量．     

燃煤火电机组碳氧化因子分析与案例研究

研究碳减排的前提之一即需要计算碳排放量,目前国际上普遍使用IPCC给出的碳排放计量方法进行计算。但对于燃煤火电行业,IPCC方法过于简化,导致碳氧化因子偏离实际值。本文以某300MW亚临界燃煤火电机组为例,研究燃煤火电机组碳氧化因子受机组负荷、煤质等因素的影响规律,通过将煤质的工业分析简化为煤质因子,揭示了碳氧化因子与煤质的关联关系。此外,本文利用工程数据计算了该机组年度CO_2排放量,指出了与IPCC默认计算结果的差异所在。     

共价和极化对119Sn、129I 穆斯堡尔谱位移的影响

利用化学键的介电理论研究了＾１１９Ｓｎ、＾１２９Ｉ穆斯堡谱同质异能位移,发现由共价性ｆ＾μｃ和极化率α＾μＬ定义的化学环境因子ｈ与穆斯堡尔谱同质异能位移δ存在线性关系：δ＝δ０＋ｂｈ,ｈ＝（∑／μαＬ＾μｆ＾μｃ）＾１／２。     

煤中矿物质对其半焦反应活性的影响

本工作考察了大同煤、神木煤、蔚县煤镜质组酸洗前后半焦反应活性的变化。煤酸洗后灰分的失去导致了半焦反应活性的降低。煤种不同,制焦条件不同,矿物质在半焦中的分布形式及存在状态不同,对半焦反应的催化能力也不同。煤种不同,煤中矿物质对半焦活化能的影响彼此不同。在整个反应历程中,具有催化作用的矿物质对半焦活化能的影响并不是恒定的。煤酸洗后半焦反应活性的降低是活化能和指前因子共同变化的结果。     

The influence of char surface oxidation on thermal annealing and loss of combustion reactivity

Thermal annealing associated with heat treatment of coal chars affects gasification reactivity and levels of unburned carbon in residual ash from coal-fired furnaces. The present study addresses the effect of char surface oxidation, occurring upon exposure to oxygen, on the course of thermal annealing, and related loss of combustion reactivity. This goal is pursued by comparing the extent of thermal annealing suffered by coal char upon heat treatment in a nitrogen atmosphere with that of chars that underwent oxidation prior to or during heat treatment. Oxidation of char was accomplished by supplying single or multiple pulses of air during the heat treatment, which were sufficient to oxidize the char surface but small enough to limit carbon gasification to less than 5%. The extent of thermal annealing was characterized both in terms of the loss of combustion reactivity and of the development of structural anisotropy of char samples, investigated by HRTEM. Results of the present study confirm that heat treatment reduces oxyreactivity of char samples, the effect being more pronounced at temperatures exceeding 1200 °C. Oxidation of samples mitigates the effects of heat treatment, as demonstrated by the smaller loss of gasification reactivity and by the more limited development of structural anisotropy of oxidized samples. Correspondingly, elemental analysis of samples indicates the formation of stable surface oxides upon oxidation, that are subsequently desorbed upon heat treatment. At temperatures exceeding 1200 °C, the effect of oxidation vanishes. Results are analysed and discussed in the light of the possible hindrance of thermal annealing due to the formation of stable surface oxides and of the parallel modifications occurring to the ash constituents.     

Evaluation of char combustion models: measurement and analysis of variability in char particle size and density

Char samples representing a range of combustion conditions and extents of burnout were obtained from a well-characterized laminar flow combustion experiment. Individual particles from the parent coal and char samples were characterized to determine distributions in particle volume, mass, and density at different extent of burnout. The data were then compared with predictions from a comprehensive char combustion model referred to as the char burnout kinetics model (CBK). The data clearly reflect the particle-to-particle heterogeneity of the parent coal and show a significant broadening in the size and density distributions of the chars resulting from both devolatilization and combustion. Data for chars prepared in a lower oxygen content environment (6% oxygen by vol.) are consistent with zone II type combustion behavior where most of the combustion is occurring near the particle surface. At higher oxygen contents (12% by vol.), the data show indications of more burning occurring in the particle interior. The CBK model does a good job of predicting the general nature of the development of size and density distributions during burning but the input distribution of particle size and density is critical to obtaining good predictions. A significant reduction in particle size was observed to occur as a result of devolatilization. For comprehensive combustion models to provide accurate predictions, this size reduction phenomenon needs to be included in devolatilization models so that representative char distributions are carried through the calculations.     

Particle temperature and potassium release during combustion of single pulverized biomass char particles

This work investigated the combustion characteristics of single pulverized biomass-derived char particles. The char particles, in the size range 224–250 µm, were prepared in a drop tube furnace at pyrolysis temperatures of 1273 or 1473 K from four types of biomass particles – wheat straw, grape pomace, kiwi branches and rice husk. Subsequently, the char particles were injected upward into a confined region of hot combustion products produced by flat flames stabilized on a McKenna burner, with mean temperatures of 1460, 1580 and 1670 K and mean O₂ concentrations of 4.5, 6.5 and 8.5 vol%. The data reported include particle temperature, obtained using a two-color pyrometry technique, and potassium release rate, measured using a laser-induced photofragmentation fluorescence imaging technique. In addition, particle ignition delay time and burning time, obtained from the temporal evolution of the thermal radiation intensity of the burning char particles, are also reported. The results indicated that ignition of the char particles occurs simultaneously with the starting of the potassium release, then the particle burning intensity increases rapidly until it reaches a maximum, after which both the particle temperature and the potassium release rate remain approximately constant until the end of the char oxidation process. The char ignition process is temperature controlled, and the char oxidation process is oxygen diffusion controlled, with the total potassium release being independent of the oxygen concentration and the temperature of the combustion products. The combustion behavior of the chars studied is more affected by the char type than by the conditions used to prepare them.     

The role of porosity in char combustion

A detailed study has been conducted on the nature of porosity developed during the combustion of chars prepared from different coals, and how this relates to the apparent reactivity of the char towards oxygen. An Illinois No. 6 coal char and a Wyodak coal char have been examined in both Zone I and Zone II conditions (intrinsic rate control and diffusional mass transfer zones, respectively). These results strongly suggest that there exists some amount of free volume in a char that has not been burned off. Such an unburned char does not reveal much porosity when standard nitrogen adsorption is applied, but rapidly develops such porosity upon burnoff. The free volume opens, but is not truly accessible to reactant gases. It appears likely, based upon the present results, that the only truly available surface for reaction exists in pores larger than 10–15 Å.     

The influence of thermal annealing on oxygen uptake and combustion rates of a bituminous coal char

The effect of thermal annealing on the combustion reactivity of a bituminous coal char has been investigated with a focus on the role of the formation of surface oxides by oxygen chemisorption. The combined use of thermogravimetric analysis and of analysis of the off-gas during isothermal combustion of char samples enabled the determination of the rate and extent of oxygen uptake along burn-off. Combustion was carried out at temperatures between 350 and 510 °C. Char samples were prepared by controlled isothermal heat treatment of coal for different times (in the range between 1 s and 30 min) at different temperatures (in the range 900–2000 °C). Results indicate that oxygen uptake is extensive along burn off of chars prepared under mild heat treatment conditions. The maximum oxygen uptake is barely affected by the combustion temperature within the range of combustion conditions investigated. The severity of heat treatment has a pronounced effect on char combustion rate as well as on the extent and rate at which surface oxides are built up by oxygen chemisorption. Chars prepared under severe heat treatment conditions show negligible oxygen uptake and strongly reduced combustion rates. Altogether it appears that a close correlation can be established between the extent and the accessibility of active sites on the carbon surface and the combustion rate. Despite the investigation has been carried out at temperatures well below those of practical interest, results provide useful insight into the relationship existing between thermal annealing, formation of surface oxide and combustion reactivity which is relevant to the proper formulation of detailed kinetic models of char combustion.     

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.     

The effect of bulk gas diffusivity on apparent pulverized coal char combustion kinetics

Apparent char kinetic rates are commonly used to predict pulverized coal char burning rates. These kinetic rates quantify the char burning rate based on the temperature of the particle and the oxygen concentration at the external particle surface, inherently neglecting the impact of variations in the internal diffusion rate and penetration of oxygen. To investigate the impact of bulk gas diffusivity on these phenomena during Zone II burning conditions, experimental measurements were performed of char particle combustion temperature and burnout for a subbituminous coal burning in an optical entrained flow reactor with helium and nitrogen diluents. The combination of much higher thermal conductivity and mass diffusivity in the helium environments resulted in cooler char combustion temperatures than in equivalent N₂ environments. Measured char burnout was similar in the two environments for a given bulk oxygen concentration but was approximately 60% higher in helium environments for a given char combustion temperature. To augment the experimental measurements, detailed particle simulations of the experimental conditions were conducted with the SKIPPY code. These simulations also showed a 60% higher burning rate in the helium environments for a given char particle combustion temperature. To differentiate the effect of enhanced diffusion through the external boundary layer from the effect of enhanced diffusion through the particle, additional SKIPPY simulations were conducted under selected conditions in N₂ and He environments for which the temperature and concentrations of reactants (oxygen and steam) were identical on the external char surface. Under these conditions, which yield matching apparent char burning rates, the computed char burning rate for He was 50% larger, demonstrating the potential for significant errors with the apparent kinetics approach. However, for specific application to oxy-fuel combustion in CO₂ environments, these results suggest the error to be as low as 3% when applying apparent char burning rates from nitrogen environments.     

A mechanistic study on kinetic compensation effect during low-temperature oxidation of coal chars

This paper provides mechanistic insights into the low-temperature oxidation of a range of carbon materials (graphite, a sub-bituminous coal char, and a brown coal char). Kinetic analysis was carried out on oxidation of the chars, prepared from fast-heating pyrolysis, under chemical-reaction-controlled regime. FT-Raman spectroscopic analysis was adopted to provide direct structural information on the carbon structure of reacting carbon materials throughout oxidation. The results demonstrate the significance of selective oxidation under the conditions, and parallel to this, the kinetic compensation effect of carbon oxidation reaction throughout conversion for all samples. Supported by the results from FT-Raman spectroscopy, the kinetic compensation effect seems to be a result of the selective oxidation of these carbon materials with heterogeneous carbon structures. Oxidation of all samples, with or without catalysts, appears to be similar in terms of the ‘nature’ of carbon structural condensation during low-temperature oxidation, suggesting a similar increase in apparent active sites population with respect to increase of apparent energy barrier. Under the current experimental conditions, a general kinetic compensation effect correlation has been deduced for various materials, requiring only the initial char kinetic parameters. The inherent inorganic species in chars also seem to alter the ‘degree/extent’ of carbon structural condensation as results of selective oxidation. In this case, the use of the compensation effect correlation will require more information on the catalysis during oxidation, apart from the initial char kinetic parameters.