煤焦O_2/CO_2燃烧方式下NO_x生成与异相还原特性

在微型流化床反应器上,对几种典型煤焦在O2/CO2燃烧方式下不同燃烧气氛、氧气体积分数、初始循环NOx体积分数对NOx生成的影响以及煤焦/NO的异相还原进行了实验研究.实验结果表明,同一种气氛下CO2焦的N转化率大于N2气氛焦转化率;氧气体积分数提高对煤焦还原NOx既有促进也有抑制作用;初始NOx体积分数的提高对NOx还原量、还原速率均有提高.     

高体积分数CO_2气氛下NO-煤焦反应特性

以李家塔烟煤和锦界烟煤煤焦为研究对象,利用固定床反应器系统,研究了高体积分数CO2气氛下煤焦异相还原NO的反应特性,分析了反应气氛、CO2体积分数、O2体积分数、NO初始体积分数和热解温度等对煤焦还原NO的影响.结果表明:反应气氛中高体积分数CO2的存在不利于煤焦还原NO,且CO2体积分数越大,越不利于NO还原;当反应温度较低时,反应气氛中O2对煤焦还原NO具有一定的促进作用,但当反应温度较高时则不利于NO还原;随着NO初始体积分数增大,NO还原率降低;随着热解温度的升高,煤焦还原NO的能力下降.     

金属钙对煤焦异相还原NO催化机理的量子化学研究

从动力学和热力学角度,采用量子化学方法对金属钙催化煤焦异相还原NO的机理进行详细研究.采用QCISD(T)/6-311G(d,p)//UB3LYP/6-31G(d)方法,对煤焦及金属钙还原NO的各个基元反应进行动力学或热力学研究.结果表明,煤焦和金属钙还原NO的活化能分别为245.35 kJ/mol和109.82 kJ/mol,说明金属钙还原NO的活化能大大低于煤焦,金属钙对NO的还原能力显著高于煤焦.而另一方面,采用UB3LYP/6-31G(d)方法对CaO与煤焦的反应进行热力学分析.结果表明,该反应在高温下的相关吉布斯自由能差△G约为-1 000 kJ/mol,说明CaO在高温下很容易被煤焦迅速还原成Ca,从而使金属钙循环再生.     

煤粉再燃过程对煤焦异相还原NO的影响

利用高温携带流反应装置,研究了煤种(包括褐煤、烟煤和贫煤)、再燃区内反应温度、煤粉粒径、一次燃烧区空气过量系数SR1和再燃区空气过量系数SR2对煤焦异相还原NO作用的影响,探讨了煤焦异相还原NO的机理.结果表明:随着SR2和煤粉粒径的减小以及再燃区反应温度的提高,煤粉NO还原效率增加;在相同的SR2下,随着煤中挥发分含量的提高,煤粉粒径的增加和再燃区反应温度的降低,煤焦异相还原NO贡献上升;对于相同再燃燃料份额:SR1=1.0和SR1=1.2时煤焦异相还原NO的贡献均大于SR1=1.1时的异相还原NO的贡献.     

煤焦催化CO还原N2O的反应机理

为了研究燃烧过程中氮氧化物的转化特性,采用M06-2X/6-311G(d)密度泛函理论研究了CO还原N_2O的均相和异相反应过程,并通过计算热力学与动力学参数分析其反应机理。结果表明:CO均相还原N_2O的活化能为216.93 kJ/mol,煤焦异相催化CO还原N_2O反应的活化能为133.06 kJ/mol;CO还原N_2O的均相和异相反应过程差异较大,CO与N_2O的均相还原反应速率决定反应步是R→TS1,而异相还原反应速率决定反应步是IM→TS,在298.15～1 800 K内,异相还原的反应速率始终大于均相反应速率;煤焦表面可以为N_2O的还原提供反应位点,对气体之间的反应具有催化作用。     

煤粉再燃中煤焦异相还原NO机理的量化研究

采用armchair结构的焦炭模型,对焦炭异相还原NO的机理进行了分子水平上的模拟研究.在B3LYP/3-21G*计算水平上优化得到各反应路径上的反应物、产物、中间体和过渡态的几何构型.在B3LYP/6-31G(d)水平上计算优化所得结构的单点能.计算得到两个不同的反应路径,分别对应已提出的两个异相还原反应机理.NO分...     

煤粉MILD燃烧NOx生成和还原机理的数值分析

采用计算流体动力学(CFD)软件分析了国际火焰研究基金会(IFRF)试验系统上煤粉低氧稀释(MILD)燃烧特性和NO_x排放特性。比较了不同的湍流与化学反应相互作用模型、挥发分气相反应机理和焦炭燃烧模型对煤粉MILD燃烧特性预测的影响,通过对比烟气速度场、温度场、组分浓度场的模型预报结果与试验结果,得到了能够准确预测煤粉MILD燃烧特性的模型组合,即EDC-WD-MSR模型。采用此模型对煤粉MILD燃烧NO_x生成和还原路径进行分析,结果表明：煤粉MILD燃烧中燃料型NO占主导地位,热力型NO、N₂O中间体路径和快速型NO之和对NO总排放的贡献小于10%。煤粉MILD燃烧存在强烈的NO均相和异相还原反应,其中NO异相还原反应使燃料型NO的排放量占单独计算的焦炭NO和挥发分NO排放量之和的71.1%。     

O_2/CO_2气氛下甲烷燃烧中NO_x转化过程的CHEMKIN模拟

采用CHEMKIN中的PFR模型对CH4在不同气氛(O2/CO2和O2/N2)下的燃烧过程进行单程模拟来研究NH3的转化和NOx生成过程,并引入烟气再循环对其进一步模拟来研究实际富氧甲烷燃烧NOx排放机理。结果表明:富燃料燃烧时CO2气氛下的NOx排放比N2气氛高,贫燃料燃烧时2种气氛的NOx排放相当。CO2气氛下,引入烟气再循环后,过氧系数λ=0.7时,NOx排放比单程时降低95%;λ=1.2时比单程降低18%。烟气再循环是导致富氧甲烷燃烧低NOx排放的主要因素。     

混合气的氧燃比和温度对富氧燃烧柴油机PAH、碳烟和NO_x排放和燃烧路径的影响

构建了包含PAH和NOx反应的正庚烷氧化反应动力学详细组合模型,并对其进行了验证.以该组合模型为基础,开展了混合气的氧燃比(R)和温度(T)对富氧燃烧柴油机排放和燃烧路径影响的理论计算工作.结果表明,所构建的组合模型是可信的,可以用来对柴油机的燃烧和排放特性进行预测.富氧燃烧柴油机有害排放物PAH、碳烟和NOx受混合气的氧燃比和温度的影响显著,其生成规律在R-T图中呈"半岛"型分布.在R-T图中,富氧柴油机的燃烧路径有别于传统柴油机,导致其PAH和碳烟排放降低,而NOx排放增加.最后,为了降低富氧燃烧柴油机的NOx排放,提出了两种富氧燃烧路径的控制策略.     

分解炉内贫氧高CO2燃烧条件下挥发分NO生成机理

基于GRI3.0详细动力学反应机理数据库,采用生成速率分析方法,从化学反应动力学角度分析水泥分解炉内煤粉挥发分贫氧燃烧时低温、高浓度CO2条件下挥发分NO生成机理及挥发分中HCN转化生成NO的主要转化路径.分析结果表明,煤粉在过量空气系数为0.8的贫氧燃烧条件下,分解炉内高浓度CO2气氛会促进NO生成,增大NO的排放浓度;850～950℃温度范围内,CO2体积分数为0%～35%条件下挥发分NO生成的主要机理反应式为N+O2(→)NO+O、HNO+H(→)H2+NO和N+CO2(→)NO+CO;高体积分数CO2通过推进反应FINO+H(→)H2+NO和N+CO2(→)NO+CO促进NO生成;其中HNO是NO生成过程中最重要的活性含氮中间产物,对NO生成起主要的贡献作用;HCN氧化生成NO的主要反应路径为HCN先转化生成NHi,再进一步转化生成HNO活性含氮中间体,最终生成NO.     

反应气氛对燃料氮析出规律的影响研究

在自行设计的试验装置上研究了HT、LC煤在不气氛下氮的析出特性.结果表明在混有CO的还原性气氛中NOx析出时间延迟,挥发分析与焦氮析出时间有融合的趋势,NOx生成量减少;在高氧浓度混有CO2的气氛中,氮析出时间提前,且在燃烧前期聚集释放,析出量大;在低氧浓度下挥发分氮与焦氮分阶段析出,NOx生成量减少.     

Formation and O2/CO2 combustion characteristics of real-environment coal char in high-temperature oxy-fuel conditions

Oxygen-fuel combustion is a promising technology for CO₂ emission reduction. The high-temperature entrained flow reactor and high-temperature drop tube furnace were used to analyses the formation and O₂/CO₂ combustion characteristics of real-environment coal char in high-temperature oxy-fuel conditions. It proposed “inflection point standard” of high-temperature flame method for the preparation of real-environmental oxy-fuel coal char according to the flame method. The results show that the ratios of C=O/C-O and C=O/C_ar increase in the coal char compared with the raw coals. The trend of C=O/C_ar in oxy-fuel condition is opposite to that in the inert atmosphere, due to the effect of high-concentration CO₂. To achieve the burnout rate similar to air combustion for coal char, with the increase of coal rank, the O₂ concentration should be enhanced. The optimal O₂ concentration for the oxy-fuel combustion of JC anthracite is 30%, while that of other low-rank coals could be lower than 30%. The combustion characteristic of JC anthracite is with the highest sensitivity to temperature and O₂ concentration.     

Experimental study on effects of combustion atmosphere and coal char on NO2 reduction under oxy-fuel condition

Nitrogen oxides (NO_x) as the principal air pollutants are mainly from the combustion of fossil fuels. Oxy-fuel combustion is a promising clean coal technology, by which carbon dioxide (CO₂) can be captured in large-scale and NO_x emission can be reduced significantly. The formation of nitrogen dioxide (NO₂) in oxy-fuel combustion exceeds that under traditional air condition. However, the specific studies on NO₂ chemistry under oxy-fuel condition are still insufficient and the functional mechanisms of minerals and combustion atmosphere on NO₂ reduction have yet to be fully understood. The objective of present study is to experimentally clarify the effects of combustion atmosphere and coal char on NO₂ reduction in oxy-fuel combustion using a fixed-bed reactor. Experimental results showed that the decomposition of NO₂ had a strong temperature dependence and the NO₂ reduction rate showed a positive variation with temperature. The strength of catalytic activity in NO₂ reduction to nitric oxide (NO) was Fe₂O₃ > MgO > CaO > Al₂O₃ > Na₂CO₃ > K₂CO₃ > SiO₂. In addition, the increased concentrations of carbon monoxide (CO) and CO₂ could promote the reduction of NO₂, while the low content of CO₂ only established a slight impact on NO₂ reduction. However, the increase of oxygen (O₂) concentration displayed an inhibition effect on NO₂ reduction to a certain extent. The variation of atmosphere in oxy-fuel combustion generated a substantial influence on the creation and reduction of NO₂. The char prepared in lower temperature exhibited a higher promotion effect on the consumption of NO₂. Higher contents of fixed carbon and basic oxides had more obvious stimulation effects on NO₂ reduction. Fixed carbon had a superior activity in NO₂ reduction than ash. The kinetic analysis indicated that high content of CO and the presence of char could reduce the apparent activation energy of NO₂ reduction. The present study can be helpful to improve the understanding of NO₂ chemistry in oxy-fuel combustion.     

Numerical simulation of pulverized coal MILD-oxy combustion under different oxygen concentrations

As an emerging clean coal combustion technology, Moderate or Intense Low-Oxygen Dilution (MILD) combustion or oxy-fuel combustion, compared with traditional coal combustion, has many advantages. However, compared with MILD combustion and oxy-fuel combustion, MILD-oxy combustion is believed more attractive. In this work, MILD-oxy combustion characteristics with oxygen concentrations from 10% to 50% are studied numerically. The results show that within a certain range, increasing the oxygen concentration is in favor of MILD-oxy combustion performance close to that of MILD-air combustion. When the oxygen concentration is higher enough, the momentum reduced by the increase of oxygen concentration has a great influence on the furnace temperature. With the increase of oxygen concentration, the radiation heat transfer is enhanced and the convective heat transfer is weakened. The increase of oxygen concentration can promote the occurrence of char gasification reaction with CO₂. In addition, MILD-oxy combustion has a large impact on CO emission.     

Thermal analysis and kinetics of coal during oxy-fuel combustion

The pyrolysis and oxy-fuel combustion characteristics of Polish bituminous coal were studied using non-isothermal thermogravimetric analysis. Pyrolysis tests showed that the mass loss profiles were almost similar up to 870℃ in both N_2 and CO_2 atmospheres, while further mass loss occurred in CO_2 atmosphere at higher temperatures due to char-CO_2 gasification. Replacement of N_2 in the combustion environment by CO_2 delayed the combustion of bituminous coal. At elevated oxygen levels, TG/DTG profiles shifted through lower temperature zone, ignition and burnout temperatures decreased and mass loss rate significantly increased and complete combustion was achieved at lower temperatures and shorter times. Kinetic analysis for the tested coal was performed using Kissinger-Akahira-Sunose(KAS) method. The activation energies of bituminous coal combustion at the similar oxygen content in oxy-fuel with that of air were higher than that in air atmosphere. The results indicated that, with O_2 concentration increasing, the activation energies decreased.     

Effects of High-temperature Char Layer and Pyrolysis Gas on NOx Reduction in a Typical Decoupling Combustion Coal-fired Stove

The suppression of nitrogen oxides(NO_x) is the key to reducing pollutant emission of a domestic coal-fired stove due to the limitation of technology condition and economic cost. The decoupling combustion(DC) technology invented by Institute of Process Engineering(IPE), Chinese Academy of Sciences(CAS) is characterized by that a traditional stove is separated into a pyrolysis and a combustion chamber as well as a bottom passage between them. In this study, the combustion of briquette from bituminous coal in different operation modes in a typical decoupling stove is tested and simulated to validate the advantage of DC technology over so-called reverse combustion. The smokeless and high-efficiency combustion of bituminous briquette with low emissions of NO_x and CO can be implemented by utilizing low NO_x combustion under low temperature and reduction atmosphere in the pyrolysis chamber as well as after-combustion of char and pyrolysis gas under high temperature and oxidation atmosphere in the combustion chamber. The effects of the main reducing components in pyrolysis gas as well as char on NO_x reduction were numerically investigated in this study, which shows that the reducing ability increases gradually from CH_4, CO to char, but the combined reducing ability of them cannot be determined by a simple addition.     

燃尽风率对四角切圆锅炉燃烧及NOx生成特性的影响

对某电厂一台300 MW四角切圆锅炉低氮改造后的NOx生成特性进行了数值模拟计算,分析了燃尽风率对NOx生成特性的影响。分析结果表明:燃尽风率增大时,在主燃烧区喷入空气量减少,导致煤粉燃烧不完全、温度降低;燃尽区的富氧氛围使未燃尽的煤粉进一步完全燃烧;主燃烧区的还原性氛围使得该区域NOx会随着燃尽风率的增大而减少;燃尽区的高温以及较低的CO浓度降低了该区域的还原性氛围,使NOx排放量增加。综合考虑NOx排放和消旋效果,该炉型锅炉采用30%的燃尽风率是比较合理的。     

Combustion characteristics of Turkish lignites at oxygen-enriched and oxy-fuel combustion conditions

Combustion and oxy-fuel combustion characteristics of two Turkish lignites (Orhaneli and Soma) were investigated by Thermogravimetric Analysis (TGA) method. Experiments were carried out under oxygen-enriched air and oxy-fuel combustion conditions with 21, 30, 40% oxygen concentrations. Three heating rates of 5, 10, and 20 °C/min were considered and the isoconversional kinetic methods of FWO, KAS, and Friedman were employed to estimate activation energies. The uncertainty assessment in obtaining the activation energy values was also considered. The obtained results indicated that the combustion of volatiles at both air and oxy-fuel conditions were approximately identical. However, at air combustion conditions, the decomposition of CaCO₃ took place at temperatures above 700 °C. This decomposition process was independent of the oxygen concentration and took place when the temperature reached to a certain threshold. The decomposition of CaCO₃ did not accomplish in oxy-fuel conditions as far as the temperature was higher than 900 °C. Combustion in oxy-fuel conditions had higher activation energy values comparing to conventional combustion atmosphere. The activation energy values were approximately unchanged at the start of combustion regardless of oxygen concentration or combustion atmosphere at about 165 kJ/mol and 150 kJ/mol for Orhaneli and Soma lignites, respectively. The apparent activation energies were higher at elevated oxygen concentrations. The uncertainties values related to FWO method were lower than KAS and Friedman methods. The calculated average uncertainty values were found to be at the range of 5–15% for most of the cases.     

全氧燃烧技术在钢包烘烤上的应用

主要介绍全氧燃烧技术以及在钢包烘烤上的应用实践,全氧燃烧时用纯氧代替空气作为燃料的助燃剂,79%的氮气不再参与燃烧,烟气中不存在氮气,烟气量大幅下降。钢包烘烤采用全氧燃烧技术,具有如下优点:燃烧过程完全,无CO外溢,减少NO_x和废气排放,减少对大气的污染,减少热量损失,提高热量利用率,并且降低能源消耗。     

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.