O2/CO2气氛下CO2和H2O气化反应对煤及煤焦燃烧特性的影响

利用热天平对比研究了大同煤及煤焦在O₂/N₂、O₂/CO₂和O₂/H₂O/CO₂中的燃烧行为,探讨CO₂和H₂O气化反应对其富氧燃烧特性的影响。结果表明,在5%氧气浓度下,煤粉在O₂/N₂、O₂/CO₂和O₂/H₂O/CO₂中的燃烧速率按顺序依次降低。氧气浓度降低到2%,由于CO₂和H₂O气化反应的作用,煤粉在高温区的整体反应速率按顺序依次增大。当氧气浓度为5%时,煤焦在O₂/CO₂中的燃烧速率要低于O₂/N₂中的燃烧速率,但燃烧反应推迟后气化反应的参与使得煤焦在O₂/H₂O/CO₂中的整体反应速率显著升高。当氧气浓度降低到2%后,随着温度的升高,在CO₂气化反应的作用下,煤焦在O₂/CO₂中的整体反应速率逐渐高于O₂/N₂中的燃烧速率。在O₂/H₂O/CO₂中,由于H₂O在共气化中起主要作用,煤焦在O₂/H₂O/CO₂高温区的整体反应速率进一步升高。动力学分析表明,在5%氧浓度时,煤焦在O₂/N₂、O₂/CO₂和O₂/H₂O/CO₂中的表观活化能依次升高。随着氧气浓度的降低,在不同反应气氛中的表观活化能均有所下降。     

O2/CO2煤粉燃烧时含铁矿物质转化行为的实验研究

通过乌兰木伦煤和哈拉沟煤在沉降炉中的燃烧实验,采用57Fe M(o)ssbauer谱仪,对煤中含铁矿物质及其在O2/N2和O2/CO2燃烧条件下生成的灰中含铁成分进行分析和比较,研究了O2/CO2煤粉燃烧时含铁矿物质的转化行为.结果表明,与O2/N2燃烧相比,O2/CO2燃烧对灰中生成的主要含铁矿物相种类没有影响,但显著地改变了灰中含铁矿物相的相对含量;O2/CO2燃烧更有利于内在黄铁矿和菱铁矿生成硅酸盐玻璃体而不是氧化成铁氧化物.灰中含铁矿物相的相对含量变化表明O2/CO2燃烧影响煤的结渣趋势,对于含内在含铁矿物较多的煤,O2/CO2燃烧会增加其结渣的趋势.     

Transformation of alkali and alkaline-earth metals during coal oxy-fuel combustion in the presence of SO_2 and H_2O

The occurrence modes of alkali and alkaline-earth metals(AAEMs) in coal relate to their release behavior and ash formation during combustion. To better understand the transformation of AAEMs,the release behavior of water-soluble,HCl-soluble,HCl-insoluble AAEMs during Shenmu coal(SM coal) oxy-fuel combustion in the presence of SO2 and H2O in a drop-tube reactor was investigated through serial dissolution using H2O and HCl solutions. The results show that the release rates of AAEMs increase with an increase in temperature under the three atmospheres studied. The high release rates of Mg and Ca from SM coal are dependent on the high content of soluble Mg and Ca in SM coal. SO2 inhibits the release rates of AAEMs,while H2O promotes them. The effects of SO2 and H2O on the Na and K species are more evident than those on Mg and Ca species. All three types of AAEMs in coal can volatilize in the gas phase during coal combustion. The W-type AAEMs release excessively,whereas the release rates of I-type AAEMs are relatively lower. Different types of AAEM may interconvert through different pathways under certain conditions. Both SO2 and H2O promote the transformation reactions. The effect of SO2 was related to sulfate formation and the promotion by H2O occurs because of a decrease in the melting point of the solid as well as the reaction of H2O.     

高碱煤含钠矿物沉积层的高温熔融及多相反应过程分析

采用纯矿物试剂模拟燃用高碱煤时炉内受热面典型的灰沉积层化学组成,利用热机械分析（TMA）、TG-DSC分析、高温煅烧实验结合XRD、SEM-EDS表征方法研究了不同Na₂SO₄含量灰沉积层的高温熔融过程及矿物间的多相反应机理。结果表明,掺混Na₂SO₄后沉积层熔化特征温度显著降低,Na₂SO₄的主要反应途径与掺混比例有关,当掺混比低于20%时,Na₂SO₄与SiO₂、CaO、Al₂O₃反应主要转变为CaSO₄和钠的硅铝酸盐;掺混比大于40%时则主要与CaSO₄生成低熔点的钠钙复合硫酸盐。富Na₂SO₄沉积层颗粒在800℃时开始黏结;900-950℃时,霞石、钠长石等钠的硅铝酸盐发生低温共熔,同时Na₂SO₄和CaSO₄生成的复合硫酸盐开始熔融,逐渐形成液相;1200-1250℃时,镁黄长石与含钙矿物发生强烈共熔,温度超过1300℃后矿物完全熔融成为自由液相。     

混煤燃烧过程中砷/硒与飞灰中矿物质之间的高温原位反应

为了研究混煤燃烧过程中痕量元素与飞灰中矿物质的原位反应，选取烟煤（HLH）、无烟煤（ZW）及其混煤在1150 ℃时的沉降炉中进行燃烧，并分别收集和分析了高温段灰分（HTA）和低温段灰分（LTA）中砷和硒残留率。结果表明，砷在高温段灰分中的残留率低于低温段灰，说明在烟气冷却过程中砷会被灰重新吸附。ZW、Z3H1、Z1H1、Z1H3、HLH的高温段灰中砷的残留率分别为60.31%、26.85%、13.29%、20.23%、36.11%，说明混煤的高温段灰比原煤更难捕获砷。同时，硒在五种煤样的高温段灰中的残留率分别为24.68%、23.60%、20.58%、15.19%和38.13%，其残留规律与砷相同。此外，X射线衍射（XRD）分析结果表明，混煤燃烧过程中矿物形态发生了明显变化。与原煤不同的是，混煤的HTA中出现了莫来石，且莫来石的峰值随着混煤中ZW比例的增加而增强。这与HTA中砷和硒的残留趋势一致。说明在混煤燃烧过程中，矿物质种类的变化以及矿物质与痕量元素的原位反应对砷和硒的排放有显著影响。     

The gas-phase reaction of O3 with H2CO

Explosions occur when O₃ and H₂CO are mixed in a fresh vessel, even in the presence of several hundred torr of N₂ or O₂. However, in an aged vessel the reaction is well behaved. The reaction between O₃ and H₂CO was studied at room temperature in an aged vessel in the presence of about 400 torr of either N₂ or O₂. The initial rate of O₃ decay in the presence of N₂ is about 10³ times faster than in the presence of O₂, and very small amounts of O₂ quickly reduce the initial rate of O₃ decay in the N₂ case. A chain mechanism is postulated to account for the results in which chain initiation can occur both by thermal decomposition of O₃, followed by reaction of O(³P) with H₂CO to produce HO and HCO, as well as by which may occur both homogeneously and heterogeneously. The rate coefficient k₁ ? 2.1 × 10^?24 cm³/molec · sec represents an upper limit (to within a factor of 2 uncertainty) to the direct gas-phase reaction between O₃ and H₂CO.     

片状煤焦颗粒CO2气化过程中形态及结构演变特性研究

采用高温热台显微镜观测了片状煤焦颗粒CO₂气化过程中的形态演变,并通过拉曼光谱分析了气化半焦的碳微晶结构,同时研究了气化温度（1000-1200℃）和煤焦初始当量直径（1.00-1.60 mm）对其CO₂气化过程中的形态及结构演变的影响规律。结果表明,与反应前期相比,反应后期的颗粒收缩（面积、体积、当量直径）更加剧烈。在所研究的气化温度范围内,随着气化温度的升高,煤焦颗粒的面积收缩率和体积收缩率逐渐减小。煤焦初始粒径显著影响颗粒收缩,1100℃气化温度下,颗粒的收缩趋势在初始粒径1.30 mm处出现转折。煤焦气化过程中碳消耗主导着表观密度的变化,在所研究的温度和粒径范围内,当碳转化率达到80%时,表观密度比线性减小到0.4以下。在相同气化温度下,随着碳转化率的增加,煤焦的石墨化程度先减小后增加,无定形碳含量先增加再减小。     

烟煤焦在H2O和CO2气氛下的结构演变与气化反应性关联

本研究以烟煤在1000 ℃热解所制得的焦样为研究对象,考察了其在H₂O、CO₂及两者混合气氛下的结构演变,以及气化反应性的影响。为了探究焦样在气化过程中的结构演变,利用氮吸附、SEM和拉曼光谱等表征手段分析不同碳转化率下的焦样结构。结果表明,H₂O气氛对焦样结构的演变明显不同于CO₂气氛,揭示了焦样在两种气氛下的反应路径不同。因结构演变的不同,随碳转化率的增加,焦样在两种气氛下表现出不同的气化反应性能。在CO₂气氛下,焦样的气化反应速率随碳转化率的增加而逐渐降低,与H₂O气氛存在下变化趋势相反。在H₂O和CO₂共气化条件下,煤焦在H₂O和CO₂混合气氛下的反应速率高于单气氛下的反应速率的计算值,表现出一定的协同作用。这是因为焦样与H₂O反应能够产生较大的比表面积,为焦样与CO₂反应提供更多的反应场所,促进了焦样与CO₂的反应。     

分解炉内CO2浓度对煤焦燃烧NO释放的影响

利用高温气固悬浮实验台对水泥行业中两种典型煤焦在不同CO₂浓度下燃烧时NO的释放特性进行了实验研究,考察了不同CO₂浓度气氛下,温度变化和添加生料对煤焦炭氮向NO转化的影响。研究结果表明,随着气氛中CO₂浓度的升高,煤焦燃烧时NO的释放速率减小,体积浓度的峰值降低,焦炭氮转化为NO的转化率下降。水泥生料对焦炭氮向NO的转化具有正催化作用;温度升高也会促进焦炭氮向NO的转化。但随着气氛中CO₂浓度的升高,升高温度和添加生料对焦炭氮向NO转化的促进作用相对减弱。     

Modeling and experimental studies on combustion characteristics of porous coal char: Volume reaction model

A generalized single‐particle model for the prediction of combustion dynamics of a porous coal char in a fluidized bed is analyzed in the present work using a volume reaction model (VRM). A fully transient nonisothermal model involving both heterogeneous and homogeneous chemical reactions, multicomponent mass transfer, heat transfer with intraparticle resistances, as well as char structure evolution is developed. The model takes into account convection and diffusion inside the particle pores, as well as in the boundary layer. By addressing the Stefan flow originated due to nonequimolar mass transfer and chemical reactions, this work enables a more realistic analysis of the combustion process. The model, characterized by a set of partial differential equations coupled with nonlinear boundary conditions, is solved numerically using the implicit finite volume method (FVM) with a FORTRAN code developed in‐house. The use of a FVM for solving such an elaborate char combustion model, based on the VRM, was not reported earlier. Experiments consisting of fluidized‐bed combustion of a single char particle were carried out to determine the internal surface area of a partially burned char particle and to enable model validation. Predicted results are found to compare well with the reported experimental results for porous coal char combustion. The effects of various parameters (i.e., bulk temperature and initial particle radius) are examined on the dynamics of combustion of coal char. The phenomena of ignition and extinction are also investigated. © 2010 Wiley Periodicals, Inc. Int J Chem Kinet 42: 299–315, 2010     

高温环境下灰中矿物质对长广煤燃烧固硫行为的影响

针对煤粉炉及层燃炉中煤灰固硫特性,以高温固硫物相硫铝酸钙为固硫产物,对掺混不同比例煤灰的三种煤和添加设定比例CaO和Al2O3后煤的高温固硫特性进行了分析。结合XRD晶相分析和SEM表面形态分析发现,相对低比例煤灰而言,高比例煤灰更能提高煤的固硫率,渣样中硫铝酸钙含量明显增多。煤中添加CaO和Al2O3添加剂后,1300℃下的固硫率为24%,此时产物中有固硫物相硫铝酸钙生成。     

Strongly cluster size dependent reaction behavior of CO with O2 on free silver cluster anions

Reactions of free silver anions Agn- (n = 1 - 13) with O2, CO, and their mixtures are investigated in a temperature controlled radio frequency ion trap setup. Cluster anions Agn- (n = 1 - 11) readily react with molecular oxygen to yield AgnOm- (m = 2, 4, or 6) oxide products. In contrast, no reaction of the silver cluster anions with carbon monoxide is detected. However, if silver cluster anions are exposed to the mixture of O2 and CO, new reaction products and a pronounced, discontinuous size dependence in the reaction behavior is observed. In particular, coadsorption complexes Agn(CO)O2- are detected for cluster sizes with n = 4 and 6 and, the most striking observation, in the case of the larger odd atom number clusters Ag7-, Ag9-, and Ag11-, the oxide product concentration decreases while a reappearance of the bare metal cluster signal is observed. This leads to the conclusion that carbon monoxide reacts with the activated oxygen on these silver clusters and indicates the prevalence of a catalytic reaction cycle.     

Toluene combustion: reaction paths, thermochemical properties, and kinetic analysis for the methylphenyl radical + O2 reaction

Aromatic compounds such as toluene and xylene are major components of many fuels. Accurate kinetic mechanisms for the combustion of toluene are, however, incomplete, as they do not accurately model experimental results such as strain rates and ignition times and consistently underpredict conversion. Current kinetic mechanisms for toluene combustion neglect the reactions of the methylphenyl radicals, and we believe that this is responsible, in part, for the shortcomings of these models. We also demonstrate how methylphenyl radical formation is important in the combustion and pyrolysis of other alkyl-substituted aromatic compounds such as xylene and trimethylbenzene. We have studied the oxidation reactions of the methylphenyl radicals with O2 using computational ab initio and density functional theory methods. A detailed reaction submechanism is presented for the 2-methylphenyl radical + O2 system, with 16 intermediates and products. For each species, enthalpies of formation are calculated using the computational methods G3 and G3B3, with isodesmic work reactions used to minimize computational errors. Transition states are calculated at the G3B3 level, yielding high-pressure limit elementary rate constants as a function of temperature. For the barrierless methylphenyl + O2 and methylphenoxy + O association reactions, rate constants are determined from variational transition state theory. Multichannel, multifrequency quantum Rice-Ramsperger-Kassel (qRRK) theory, with master equation analysis for falloff, provides rate constants as a function of temperature and pressure from 800 to 2400 K and 1 x 10(-4) to 1 x 10(3) atm. Analysis of our results shows that the dominant pathways for reaction of the three isomeric methylphenyl radicals is formation of methyloxepinoxy radicals and subsequent ring opening to methyl-dioxo-hexadienyl radicals. The next most important reaction pathway involves formation of methylphenoxy radicals + O in a chain branching process. At lower temperatures, the formation of stabilized methylphenylperoxy radicals becomes significant. A further important reaction channel is available only to the 2-methylphenyl isomer, where 6-methylene-2,4-cyclohexadiene-1-one (ortho-quinone methide, o-QM) is produced via an intramolecular hydrogen transfer from the methyl group to the peroxy radical in 2-methylphenylperoxy, with subsequent loss of OH. The decomposition of o-QM to benzene + CO reveals a potentially important new pathway for the conversion of toluene to benzene during combustion. A number of the important products of toluene combustion proposed in this study are known to be precursors of polyaromatic hydrocarbons that are involved in soot formation. Reactions leading to the important unsaturated oxygenated intermediates identified in this study, and the further reactions of these intermediates, are not included in current aromatic oxidation mechanisms.     

O_2/CO_2气氛添加高岭石对燃煤PM_(2.5)排放的影响

采用管式炉研究了在O2/CO2气氛下添加高岭石对PM2.5(空气动力学直径小于2.5μm的颗粒物)排放特性的影响。实验采用荷电低压撞击器(ELPI)采集和分析燃烧后的PM2.5。结果表明,添加高岭石是燃烧过程中影响PM2.5生成的重要因素。添加高岭石后,生成PM1的数量和质量浓度均降低,而PM1-2.5的数量和质量浓度均略有增加,PM2.5粒径分布均呈双峰分布,峰值点分别出现在0.2μm和2.0μm左右。随着高岭石添加质量比的增加,PM2.5中的S、Pb、Cu、Na和K五种元素的浓度呈下降趋势。粒径小于0.317μm的亚微米颗粒通过气化-凝结机理形成,而超微米颗粒则是通过亚微米颗粒凝聚、聚结和矿物质熔融、破碎、聚结形成。     

The comparative study of CO2 + Hads reaction on platinum electrode in H2O and D2O

The observed isotopic effect in CO₂ + H_ads reaction showed that at 0.05 V the rate determining step is

formation whereas at 0.2 V the reorientation of adsorbed intermediate:

is probably the slowest step of reaction. The oxidation of adsorbed product is slower in D₂SO₄ than H₂SO₄ solution like the surface oxidation of platinum. The rate determining step of COOH_ads oxidation is a reaction with OH_ads.