O2含量对半焦燃烧动力学影响的热重研究

为了更进一步地清楚阐述半焦的燃烧过程,采用非等温热重法研究氧气体积分数对半焦燃烧动力学的影响。将半焦燃烧过程的第2次失重分为半焦热解脱挥发分(阶段1)、挥发分燃烧(阶段2)、挥发分燃烧且碳燃烧(阶段3)、碳单独燃烧(阶段4)4个阶段,采用Coats-Redfern法选取一级反应模型计算各个阶段的动力学参数。结果表明:24%φ(O_2)~30%φ(O_2)条件下,阶段3所需的表观活化能最小。24%φ(O_2)、26%φ(O2)、30%φ(O_2)条件下阶段4所需的表观活化能最大;28%φ(O_2)阶段2所需的表观活化能最大。     

褐煤半焦直接加氢制甲烷反应特性及其孔结构和表面形态变化

在高温高压(1 000 ℃、12 MPa)固定床反应器上对内蒙古褐煤半焦的加氢甲烷化反应特性进行了研究,采用氮吸附和扫描电镜(SEM)对甲烷化残渣比表面积、孔结构和表面形态进行了表征。结果表明,半焦加氢甲烷化可分为加氢热解、快速加氢和慢速加氢等三个反应阶段,每阶段分别发生含氧官能团和烷基侧链加氢反应、芳环结构加氢反应以及贫氢骨架碳结构加氢反应。半焦加氢甲烷化最优反应温度为800 ℃,反应压力为3.0~4.0 MPa;提高升温速率可以缩短前段(碳转化率低于46%)反应过程时间,对后段(碳转化率高于46%)反应过程影响较小。半焦甲烷化残渣的吸附-脱附等温线呈反S型,滞后环呈H3回线形状;在甲烷化反应过程中,半焦平均孔径先减小后增大,总孔容积和介孔容积逐渐增大,微孔容积和比表面积先增大后减小。     

煤粉与半焦的混合燃烧特性及动力学分析

为探究煤粉添加半焦后混合燃料的燃烧性能,通过热重分析研究煤、半焦及其混合物的燃烧过程,得到燃烧特性参数.由于不同温度区间的燃烧反应机理不同,利用分段法对燃烧过程进行动力学分析,对燃烧反应的前、后期分别使用缩核反应模型和缩核内扩散模型进行模拟,从而得到动力学参数.结果显示,随着混合燃料中半焦含量增加,其可燃性指数和燃烧特性指数都减少,燃烧前期活化能由76.79 kJ·mol-1增加到92.75 kJ·mol-1,后期活化能由102.62 kJ·mol-1增加到107.94 kJ·mol-1,说明半焦的添加会降低混合燃料的燃烧性能.对比不同半焦含量的混合燃料的燃烧特性参数和动力学参数,半焦的质量分数应控制在15%以内最适宜.     

Emission of Sulphur Dioxide During Thermal Treatment of Fossil Fuels

The dynamics of SO₂ emission during thermooxidation of Estonian oil shale, its semicoke, different samples of coal and their mixtures, as well as the influence of Estonian oil shale ash addition (for modelling the CFBC process) on the dynamics were studied. The experiments were carried out with thermogravimetric equipment under dynamic heating conditions (5 K min^-1) in the atmosphere of dried air, with simultaneous gastitrimetric EGA. It was established that SO₂ emission from the fuels started at 200-320°C. Depending on the form of sulphur (organic, pyritic, sulphate), the emission took place in two or three steps, and continued up to 580-650°C, during which 35-75% of the total sulphur was emitted into the gaseous phase. Regulating the mole ratio of free CaO/S in the mixtures of fuels with oil shale ash addition the emission of SO₂ ceased abruptly at 460-540°C and it was limited to the level of 7-30%. This revised version was published online in August 2006 with corrections to the Cover Date.     

造纸污泥在回转窑中热解的试验研究

本文在自行设计的小型外热式回转窑试验装置上进行了污泥热解试验,考察了污泥在不同热解连温下三种形态热解产物的产率,分析了污泥在热解过程中热解气体的成分和热值的变化特性以及热解半焦的品质。采用表观动力学模型对热解气体的试验数据进行计算,结果表明用该模型描述热解气体的析出是合理的。     

SO2 binding into the solid phase during thermooxidation of blendsestonian oil shale semicoke

Approximately one million tons of semicoke (SC) is formed and stored in open air dumps every year in the production of shale oil by processing Estonian oil shale (OS). The content of different harmful compounds as sulphides, PAH, phenols, etc. in SC make these dumps one of the most serious sources of environmental contamination. The aim of this work was to study the behaviour of sulphur compounds in OS and its SC, formation of SO₂ and possibilities of binding it into the solid phase during thermooxidation of fuel blends based on SC. Blends modified with SC ash addition were studied as well. It was determined that SO₂ emission in thermooxidation of SC samples started at 280-300°C and proceeded with a steady speed up to 580-600°C and the amount of sulphur evolved was 5-10% from the total content of sulphur in the sample. The amount of SO₂ emitted decreased depending on the mass ratio of the composite fuels from 49-56 to 15-35% during thermooxidation of OS samples studied or their blends with SC, respectively, from 43-80% for coal samples to 13-60% for their blends with SC and to 2-13% during thermooxidation of these blends modified with SC ash addition. In the products of thermooxidation formed at 800-900°C the only sulphur containing phase was CaSO₄, at 650°C also traces of CaS and CaMg3(SO₄)₄ were fixed. This revised version was published online in July 2006 with corrections to the Cover Date.     

分段尝试法研究半焦/CO2气化反应过程动力学

为了深入了解半焦与CO2的气化反应过程动力学,本文通过不同升温速率下的非等温实验,确定在不同阶段下富鼎半焦与CO2的气化机理.采用分段尝试法研究富鼎半焦与CO2气化反应过程动力学,确定反应过程前期与后期的机理函数分别为f(α)=(1-α)[1-ψln(1-α)]1/2和f(α)=(3/2)[(1-α)-1/3-1]-1,从而建立相应动力学模型,计算反应过程不同阶段的动力学参数.通过对不同阶段的动力学模型进行数据拟合,实验数据与模型吻合较好,相关系数都大于0.98.最后,根据求得的动力学参数,确定不同升温速率下活化能的补偿效应,即活化能与指前因子的关系式.     

用热分析法研究半焦气化动力学

使用等温热重法，对鞍山钢铁公司高炉喷吹用的城子河烟煤制得的半焦气化动力学特性作了研究，并与焦炭的反应性作了比较。研究表明，半焦的反应性优于焦炭，半焦的气化反应是由气体的内扩散控制的，相应的表现内扩散活化能力为１３６．８３ｋｊ／ｍｏｌ，并得出了半焦气化的动力学模型。模型预测值与实测值有很好的一致性。     

半焦燃烧特性的热重试验研究

针对目前提倡的煤部分气化燃烧系统集成优化联合生产煤气和热能的新概念,在不同温度下制得四种煤的半焦,通过热天平燃烧试验研究了半焦的燃烧特性,考察了煤种和制备温度对半焦燃烧特性的影响.试验结果表明:煤种不同,所制得半焦燃烧特性不同;相同煤种制得半焦,随制备温度升高,半焦着火温度上升,燃烧活化能增加,燃烧反应活性降低.     

Study of the combustion mechanism of oil shale semicoke in a thermogravimetric analyzer

Oil shale semicoke, formed in retort furnaces, is a source of severe environmental pollution and is classified as a dangerous solid waste. For the industrial application of oil shale semicoke in combustion, this present work focused on the thermal analysis of its combustion characteristics. The pyrolysis and combustion experiments of semicoke were conducted in a Pyris thermogravimetric analyzer. From the comparison of pyrolysis curves with combustion curves, the ignition mechanism of semicoke samples prepared at different carbonization temperatures was deduced, and was found to be homogeneous for semicoke samples obtained at lower carbonization temperature, shifting to heterogeneous with an increase in the carbonization temperature. The effect of carbonization temperatures and heating rates on the combustion process was studied as well. At last, combustion kinetic parameters of semicoke were calculated with the binary linear regression method, showing that activation energy will increase with increasing the heating rate.