铂表面H_2还原NO_x的详细反应机理

研究了柴油机NO_x存储还原技术(NSR)浓燃再生阶段中NO还原反应。发展了铂催化剂表面H_2还原NO的详细化学反应机理,包括6种气相组分、10种表面组分及28步基元反应,其中包含了主要含氮产物N_2及副产物N_2O和NH3的生成路径。此机理与CHEMKIN软件中的活塞流反应器(PFR)模型耦合进行数值模拟,反应器出口各组分体积分数预测结果与文献中实验数据吻合良好。在NO体积分数为500×10~-6、反应器入口温度为270℃的条件下分析了进气中H2体积分数((100~2500)×10~(-6))对含氮产物选择性的影响。结果表明,H_2体积分数小于500×10~(-6)时,N_2和N_2O为主要的含氮产物;随着H_2体积分数逐渐升高,当Φ(NO)/Φ(H_2)高于1.5时,NH_3成为主要产物。由敏感性分析结果可知,NH_3对H_2吸附反应的敏感性系数最大,提高该反应速率将促进NH_3的生成。     

CFB富氧燃烧中CO_2对煤焦与NO还原作用的影响

为了考察高浓度CO_2对煤焦与NO还原所带来的影响,本文在悬浮床反应器上开展了。N_2和CO_2气氛下煤焦与NO的还原实验。结果表明:在无煤焦或矿物组分催化下CO不与NO发生反应;900℃N_2气氛下,在煤焦与NO反应初期NO还原率保持不变,而在整个反应过程中碳比反应率和CO_2生成比例则持续增大;N_2气氛下,煤焦与NO反应的含碳产物在700℃时以CO_2为主,而随着温度升高CO的生成比例增大,900℃时CO的生成占主导地位;高浓度的CO_2对煤焦-NO还原反应有明显的抑制作用,且温度越高抑制作用越显著,这可能是因CO_2气化抢占碳活性位所致。     

NO在Ir(111)表面吸附与解离的第一性原理研究

本文系统研究了NO在Ir(111)表面的吸附,解离,以及可能的N_2生成机理.结果表明,顶位吸附的NO,其解离能垒较高(3.17 eV),不会发生解离,而三重Hcp和Fcc空位吸附的NO发生解离,能垒分别为1.23和1.28 eV.N_2是唯一的生成物,不会有副产物N_2O的产生.其最可能的反应路径为N和NO经过N_2O中间体而生成N_2,而不是直接N提取和N-N聚合产生N_2的机理.     

不同压力下对冲扩散火焰燃料型NO生成特性

采用NH3模拟燃料氮,数值预测了Ar稀释的CH_4/空气对冲扩散火焰在不同压力下NO的生成,并讨论了燃料型NO生成量的影响因素。结果表明:随着燃料氮含量的增加,燃料型NO反应路径逐渐成为NO生成的主要路径。其生成量随着压力的增加而减少。燃料中CH_4含量和气流出口速度对燃料型NO均有一定影响。CH基团同时参与NO的生成与还原反应,在本文工况下对NO还原反应影响更大,随着燃料中CH_4含量的增加,NO峰值会略有减小。气体出口速度增加,高温区变小,反应物在高温区的停留时间变短,对NO还原反应影响强于NO生成反应,因此随着出口速度增加,NO峰值略有增加。     

气体NO／SO2／N2／O2等离子体反应机理及动力学分析

本文研究了在低温等离子体条件下,电子碰撞NO/SO2/N2/O2气体引发离解反应的反应机理.应用碰撞理论和波尔兹曼方程分析,对能量分布函数及反应速率常数进行数值模拟,得到离解反应速率常数与温度的曲线,分析预报各反应过程及表现.最后将速率常数拟合为Arrhenius公式的形式.     

煤粉挥发份析出规律的研究

本文提出了粉煤挥发份析出的通用热解模型。该模型与现有的其他模型相比,主要特点是挥发份析出时的化学动力学参数E、K不随煤种变化,仅是颗粒最终温度T_∞的函数。这是一个新的结论。本文还得到了E(或K)和T_∞间的关系,它适用于所有的煤种。若在一定条件下得到粉煤挥发份的最终产量V_∞,则可用该模型预示任何煤种的挥发份析出过程。 本文报道了烟煤、褐煤、劣质烟煤、贫煤在高温下降炉中、加热气体为Ar、N_2和He的条件下,其挥发份的析出过程。煤颗粒的加热速率大于10~4K/s,直径从35μm—100μm,温度范围为973—1773K,取样时颗粒的冷却速率大于10~5K/s。确定挥发份的产量利用灰作示踪剂。气体在高温反应炉内的流动是层流运动,且颗粒在下降过程中弥散很小。     

水泥回转窑内NO生成及其分布规律研究

本文在气固流动、煤粉燃烧和NO生成数学模型的基础上,对水泥回转窑内物料烧成过程的物理化学反应热效应采用分区段拟合的方法,建立了一套描述水泥回转窑窑内过程的数学模型。并对某3000吨／天生产能力的带四通道燃烧器的水泥回转窑进行了数值模拟,得到了回转窑内气体速度场、气体温度和组分浓度沿窑长的变化规律,对窑内NO生成进行了深入研究。研究结果表明:水泥回转窑内NO生成按机理可分为热力型NO和燃料型NO,由于窑内存在着高温、富氧环境,热力型NO为主要生成方式;热力型NO和燃料型NO生成过程存在着相互抑制作用。     

水合肼还原的氧化石墨烯吸附NO_2的实验研究

还原氧化石墨烯由于独特的原子结构,作为气体检测领域有潜力的候选者引起了研究者们的广泛兴趣.本文采用水合肼作为还原剂来制备还原氧化石墨烯,并以此作为叉指电极的气体敏感层,研究了其对NO2气体的响应特性.结果表明,水合肼还原的氧化石墨烯可以实现在室温下对浓度为1—40 ppm (1 ppm=10–6)的NO2气体的检测,具有较好的响应性和重复性,恢复率可以达到71%以上,但是灵敏度只有0.00201 ppm–1,还有较大的提升空间.此外,对浓度5 ppm的NO2的响应和恢复时间分别是319 s和776 s.水合肼还原的氧化石墨烯气体传感器的传感机制可归因于NO2分子和传感材料之间的电荷转移.还原氧化石墨烯的突出电学特性促进了电子转移过程,这使得传感器在室温下表现出优异的气体传感性能.本实验研究可为石墨烯基传感器件的应用奠定一定的基础.     

气体NO/N2系统等离子体反应NO还原机理研究

首先建立了气体放电等离子体发射光谱测量系统,获得了NO/N2和纯N2气体放电的发射光谱,然后用自洽场分子轨道从头计算法得到了N2基态和激发态分子轨道模型.发现NO/N2气体放电等离子体脱除NO主要是通过包括反应速度非常快的N+NO→N2+O以及e+N2(A3∑u+)→2N+e和e+N2→N2(A3∑u+)+e在内的一系列基元反应进行的,活性N原子是NO还原的基础.     

热解温度对酚醛树脂焦的微观结构和还原NO反应性的影响

利用傅立叶变换红外光谱(FTIR)、X射线衍射(XRD)和Raman光谱研究了热解温度(500～900℃)对酚醛树脂焦炭微观结构的影响.使用热重分析仪(TGA)研究了酚醛树脂焦还原NO的反应性.结果表明,随着热解温度升高,苯环、酚羟基、脂肪亚甲基等官能团含量降低.衍射实验表明存在(002)峰、(10)峰和(11)峰.随着热解温度升高,焦炭微晶尺寸增大,微晶结构逐渐趋向有序.酚醛树脂焦的Raman光谱分析与XRD分析存在较好的关联性.反应性实验表明焦炭还原NO的反应性没有随热解温度呈现规律性的变化.     

A reactive molecular dynamics study of NO removal by nitrogen-containing species in coal pyrolysis gas

Coal splitting and staging is a promising technology to reduce nitrogen oxides (NOx) emissions from coal combustion through transforming nitrogenous pollutants into environmentally friendly gasses such as nitrogen (N₂). During this process, the nitrogenous species in pyrolysis gas play a dominant role in NOx reduction. In this research, a series of reactive force field (ReaxFF) molecular dynamics (MD) simulations are conducted to investigate the fundamental reaction mechanisms of NO removal by nitrogen-containing species (HCN and NH₃) in coal pyrolysis gas under various temperatures. The effects of temperature on the process and mechanisms of NO consumption and N₂ formation are illustrated during NO reduction with HCN and NH₃, respectively. Additionally, we compare the performance of NO reduction by HCN and NH₃ and propose control strategies for the pyrolysis and reburn processes. The study provides new insights into the mechanisms of the NO reduction with nitrogen-containing species in coal pyrolysis gas, which may help optimize the operating parameters of the splitting and staging processes to decrease NOx emissions during coal combustion.     

Laser pyrolysis of coal

A laser pyrolysis study was performed on No. 6 high volatile bituminous Illinois (USA) coal. Possible relationships between the elemental surface composition of solid samples and the variable output power and wavelength of the argon ion laser were observed. For wavelengths of 5017 Å and 5145 Å and incident powers of 0·24 and 0·54 watts, scanning electron microscopy coupled with X-ray energy spectral analysis indicated the highest content reduction in both organic and mineral sulfur.Mass spectroscopy was employed to analyze the composition of the evolved gases from laser pyrolysis of pulverized coal. Coal pyrolysis utilizing a 2·5 watt argon ion laser produced hydrogen sulfide through decomposition of pyritic sulfur FeS₂, or organic sulfur upon irradiation of the coal. Other gases such as methane and ethane were created with solid residues (tars and ash). Pulsed CO₂ laser irradiation of coal samples produced a solid residue having a different elemental composition than that of the original coal sample.     

On the rank-dependence of coal tar secondary reactions

The secondary reactions of volatile compounds, including coal tar and light gases, accounts for a great portion of soot formation and the subsequent heat release and pollutant emissions in the combustion zone. While coal primary pyrolysis has been extensively studied over the last few decades and several network pyrolysis models has been developed to describe this process, coal secondary pyrolysis is still not well understood. The Babcock and Wilcox Company has been investigating coal secondary pyrolysis in order to develop a comprehensive mechanism for inclusion in predictive computational fluid dynamics and coal combustion models. Supportive experiments were carried out in an entrained-flow reactor. Tar was extracted from the pyrolysis byproducts of seven coals of widely-distributed rank at temperatures ranging from 923 to 1473 K, and analyzed by ¹³C NMR. Tars formed from higher rank coals generally demonstrated higher sooting propensities. This rank-dependent sooting propensity is associated with tar’s chemical structure properties. With increased heat treatment severity, tar molecules lose a substantial amount of aliphatic attachments, and the average size of substitution per cluster decreases. Compared to tars formed from high-rank bituminous coals, those formed from low-rank sub-bituminous coals have a larger attachment portion, higher averaged substitution, and higher oxygen-containing functional groups. These differences contribute to the higher cracking propensity observed for low-rank coal tars.     

Experimental study of influence of temperature on fuel-N conversion and recycle NO reduction in oxyfuel combustion

Coal combustion in O₂/CO₂ environment was examined with a bituminous coal in which the gas-phase and char combustion stages were considered separately. The effects of temperature (1000–1300 °C) and the excess oxygen ratio λ (0.6–1.4) on the conversion of volatile-N and char-N to NOx were studied. Also, the reduction of recycle NOx by fuel-N was investigated under various conditions. The results show that fuel-N conversion to NO in O₂/CO₂ is lower than that in O₂/N₂. In O₂/CO₂ atmosphere, the volatile-N conversion ratios vary from 1–7% to 15–24% under fuel-rich and fuel-lean conditions, respectively. The char-N conversion ratios are 11–28% and 30–50% under fuel-rich and fuel-lean conditions, respectively. The influences of temperature on the conversion of volatile-N to NO under fuel-rich and fuel-lean conditions are contrary. A significant difference for char-N conversion in fuel-rich and fuel-lean conditions is observed. The experimental data of recycle NO reduction indicate that the reduction of recycle NO by gas-phase reaction can be enhanced by volatile-N addition in fuel-lean condition at high temperature, while in fuel-rich condition, the volatile-N influence cancelled out and the overall impact is small. NO/char reaction competes with the conversion of fuel-N to NO at higher 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.     

Insight into the calcium carboxylate release behavior during Zhundong coal pyrolysis and combustion

In this paper, the dynamic behavior of calcium carboxylate release during Zhundong coal pyrolysis and combustion is studied via reactive molecular dynamics (ReaxFF MD) simulation. The molecular structure model of Zhundong coal is constructed based on the combination of the classic Hatcher coal model and experimental characterizations. Pyrolysis simulations on the coal model are performed at different temperatures ranging from 2000 K to 2800 K. The pyrolysis experiments are also carried out to validate the ReaxFF simulation. The results show that most of the calcium are released into the volatiles by the thermal decomposition of CM-Ca (coal/char matrix with calcium bonded) after releasing CO₂. The distributions of the calcium bonded to gas, tar and inorganics as well as the atomic calcium in the volatiles are quantitatively classified. The thermal cracking of tar fragments are significant at high temperatures leading to the conversion of calcium from tar into the organic gas. Furthermore, the nascent char model is constructed to study the release behavior of calcium in char combustion stage. The calcium is initially released in the form of oxidized calcium and atomic calcium. With increasing temperature, the oxidized calcium trends to convert to the organically bonded calcium. By using the Arrhenius expression, the kinetic parameters for the release of calcium into various species during pyrolysis and char combustion stages are quantitatively determined.     

Fragmentation of pulverized coal in a laminar drop tube reactor: Experiments and model

Fragmentation during pulverized coal particles conversion shifts the particle size distribution of the fuel towards smaller particle sizes, affecting both conversion rates and heat release. After pyrolysis of a high volatiles Colombian coal in CO₂ atmosphere in a drop tube reactor at 1573?K, solid carbonaceous particles of different size, from 100?µm of the particle feed down to the nanometric size, have been observed. A fragmentation model has been used to predict the fate of Colombian coal particles under the experimental conditions of the drop tube experiment and predict the particle size distribution (PSD). Model and experimental results are in very good agreement and indicate that in the DTR experiment the coal underwent almost complete pyrolysis and that fragmentation generated a 36?wt% population of particles with size close to 30?µm. The close match between the PSDs obtained from experiments and from the fragmentation model is an important novelty. It demonstrates that fragmentation occurs not only under fluidized bed conditions but also under the conditions of pulverized coal combustion. Experimentalists are warned against the fact that the fine particulate sampled at the outlet of laminar flow reactors and boilers is not always composed of soot only. Char fragments can be misidentified as soot. The implementation of fragmentation submodels in pulverized fuel combustion and gasification codes is highly recommended.     

Particle imaging of ignition and devolatilization of pulverized coal during oxy-fuel combustion

Oxy-fuel combustion of coal is a promising technology for cost-effective power production with carbon capture and sequestration that has ancillary benefits of emission reductions and lower flue gas cleanup costs. To fully understand the results of pilot-scale tests of oxy-fuel combustion and to accurately predict scale-up performance through CFD modeling, fundamental data are needed concerning coal and coal char combustion properties under these unconventional conditions. In the work reported here, the ignition and devolatilization characteristics of both a high-volatile bituminous coal and a Powder River Basin subbituminous coal were analyzed in detail through single-particle imaging at a gas temperature of 1700 K over a range of 12–36 vol % O₂ in both N₂ and CO₂ diluent gases. The bituminous coal images show large, hot soot cloud radiation whose size and shape vary with oxygen concentration and, to a lesser extent, with the use of N₂ versus CO₂ diluent gas. Subbituminous coal images show cooler, smaller emission signals during devolatilization that have the same characteristic size as the coal particles introduced into the flow (nominally 100 μm). The measurements also demonstrate that the use of CO₂ diluent retards the onset of ignition and increases the duration of devolatilization, once initiated. For a given diluent gas, a higher oxygen concentration yields shorter ignition delay and devolatilization times. The effect of CO₂ on coal particle ignition is explained by its higher molar specific heat and its tendency to reduce the local radical pool. The effect of O₂ on coal particle ignition results from its effect on the local mixture reactivity. CO₂ decreases the rate of devolatilization because of the lower mass diffusivity of volatiles in CO₂ mixtures, whereas higher O₂ concentrations increase the mass flux of oxygen to the volatiles flame and thereby increase the rate of devolatilization.     

Experimental study on electrostatic removal of high-carbon particle in high temperature coal pyrolysis gas

A high-temperature electrostatic precipitator (ESP) presents a good solution for hot gas cleaning, which can remove fly ash from pyrolysis gas at temperatures higher than the tar dew point. In this paper, the characteristics of negative DC corona discharge in air and simulated coal pyrolysis gas were studied. The removal of coal pyrolysis furnace fly ash (ash A) was investigated and compared with that of coal-fired power plant fly ash (ash B) in ESP with a temperature ranging from 300?K to 900?K. The current density of simulated gas was higher than that of air under the same discharge voltage and at different temperatures. The simulated gas also had a higher spark voltage and a lower onset voltage compared with air. The fractional collection efficiency of ash A was lower for particles with diameters of larger than 0.1?µm at high temperature, compared with ash B. A lower collection efficiency in simulated gas was obtained for particles with diameters of less than 0.1?µm compared with air. The collection efficiency of submicron particles in simulated gas was usually higher than it in air, especially for particles with diameters of less than 0.04?µm. In simulated gas, the overall collection efficiency of ash A was obviously lower than that of ash B, especially at high temperature. From 300?K to 700?K, the collection efficiencies of both ash samples were as high as above 93%, but the collection efficiency of ash A in simulated gas decreased to 78.7% at 900?K.     

A DNS study on temporally evolving jet flames of pulverized coal/biomass co-firing with different blending ratios

Biomass co-firing within the existing pulverized coal boiler is thought as a practical near-term way of biomass utilization, while its detailed combustion characteristics and pollutant formation have not yet been fully understood. In the present study, we report a Carrier-phase Direct Numerical Simulation study coupled with detailed mechanism to provide a deep insight into the coal/biomass co-firing (CBCF) jet flames under different blending ratios. It is found that compared with the pure coal flame, the CBCF could (i) prompt the volatiles ignition, produce higher H₂O and similar CO₂ mass fractions at blending ratios of 20% and 40%, and obviously reduce the gas temperature and CO₂ mass fraction at the blending ratio of 50%; (ii) prompt the coal devolatilization and char burnout at blending ratios of 20% and 40%, while the char burnout is reduced when blending ratio is 50% due to the local enrichment of large particles and lack of oxygen; (iii) reduce the thermal, prompt, NNH and N₂O-intermediate routes of NO formation, but show limited effect on the NO-reburning route of NO destruction, therefore, resulting in an obvious NO reduction.