制备温度对不同煤种半焦性质的影响

煤部分气化产物——半焦的制备方法与半焦的性质密切相关。本文研究了利用不同煤种在不同温度下制备的半焦的性质差异与各组分含量的变化趋势,并初步得出了关于制备半焦的一些经验与结论。

海拉尔褐煤半焦性质及冶炼75％硅铁研究

在实验室研究了海拉尔褐煤半焦的反应性能、比电阻等性质。通过冶炼硅铁的工业试验表明，该半焦具有降低硅铁电耗，提高产量等效果，是优质的炭质还原剂。

CO_2对褐煤热解行为的影响

利用热天平和快速升温固定床进行了CO2气氛下褐煤热解特性的研究,考察了CO2对半焦的产率和气体产物分布的影响。通过对半焦的比表面积、孔结构、官能团和元素含量的分析,确定了CO2对煤热解过程的影响机制。CO2对新生半焦的气化反应破坏了含氢的半焦结构,一方面,促进了羟基、甲基、亚甲基等基团的断裂和苯环的开裂;另一方面,减弱H与其依附本体的结合,增加了氢的流动性,引发了更多的氢自由基生成。这些氢自由基与煤大分子断裂生成的碎片自由基结合生成更多的挥发分,使半焦有较大的比表面积、孔容和开孔率。CO2的引入促进了煤的热解和挥发分的生成,增大了H2、CO、CH4和C2H6等小分子烃类物质逸出,降低了半焦的产率。

CO对褐煤快速热解行为的影响

利用快速升温固定床进行了霍林河褐煤在CO气氛下快速热解反应行为的研究,考察了热解半焦的产率、性质和气体产物的分布特点。半焦的红外光谱图、元素含量和表面结构性质分析表明,CO参与并改变了褐煤的热解行为。与N2气氛相比,热解温度低于600℃时,带孤对电子的极性CO容易诱发半焦结构中芳香环的开裂,侧链、醚键和脂肪链的断裂,促进小分子片段和自由基的生成,自由基稳定了煤热解生成的碎片,导致挥发分的生成和逸出量增加,H2、CH4、CO和CO2的产率增大,半焦产率降低,半焦的比表面积和孔容增大。热解温度高于700℃时,CO的歧化反应程度增大,产生的积碳附着于半焦的表面,阻塞了孔道,导致半焦的比表面积和孔容减小,从而抑制了CO在半焦孔隙结构内部的扩散,限制了CO与煤中有机大分子结构的接触和反应,导致H2、CH4和CO产率减小,而CO2产率因CO歧化反应而增大。

氧化钙对褐煤和无烟煤热解特性影响

为研究CaO对褐煤和无烟煤热解特性影响,采用实验室小型固定床反应器对锡林郭勒褐煤（X）和宁夏石嘴山无烟煤（SH）,进行热解实验,研究了CaO对热解三相产物分布规律影响。实验结果表明：在500~600℃时,添加2%CaO后褐煤热解生成CO_2的产率小于未添加CaO煤样热解生成CO_2的产率,添加CaO与否对其他3种气体H_2,CH_4,CO产率影响不大;与未加入CaO的褐煤煤样相比,加入CaO的褐煤煤样在相应温度下热解气相产物产率小幅度降低,且随着热解温度的升高,加入CaO的褐煤煤样气相产物产率增加速率大于未加入CaO的褐煤煤样。褐煤脱挥发分主要在600℃之前的热解阶段,而对于无烟煤来说,CaO在中温热解阶段对挥发分的脱除具有促进作用。对于褐煤半焦来说,加入2%CaO一直作为灰分存在半焦中,且随着热解温度的升高,褐煤半焦在高温时反应活性较高,发生热缩聚反应,导致半焦中有机质含量降低,以上2种原因直接导致褐煤半焦灰分升高;对于无烟煤来说,灰分增加主要是由于CaO的加入。

CO_2气氛对胜利褐煤热解过程的影响

以5-8 mm胜利褐煤为研究对象,利用固定床反应器,在400-700℃、CO_2气氛下进行热解实验,研究了CO_2气氛对煤热解气、液、固三相产物分布的影响,探讨了CO_2对煤焦结构作用的机理。研究表明,与N_2气氛相比,CO_2气氛热解提高焦油和热解水产率,降低热解气和半焦产率;400和500℃时,CO_2气氛下形成的半焦孔隙结构和总孔体积没有明显的变化,600和700℃时,CO_2气氛下所得半焦的比表面积及孔容较N2气氛下的大,是与煤焦内部挥发分大量释放以及CO_2进入孔道与活性位反应有关;煤热解过程中CO_2的引入能促进煤焦中3-5环芳香结构的消耗,导致煤焦结构芳香度的提高;600和700℃时,CO_2气氛下热解气中H_2和CH_4产率低,同时CO_2能与煤焦发生气化反应显著提高CO含量。

Combustion characteristics of semicokes derived from pyrolysis of low rank bituminous coal

Various semicokes were obtained from medium-low temperature pyrolysis of Dongrong long flame coal.The proximate analysis,calorific value and Hardgrove grindability index(HGI) of semicokes were determined,and the ignition temperature,burnout temperature,ignition index,burnout index,burnout ratio,combustion characteristic index of semicokes were measured and analyzed using thermogravimetry analysis(TGA).The effects of pyrolysis temperature,heating rate,and pyrolysis time on yield,composition and calorific value of long flame coal derived semicokes were investigated,especially the influence of pyrolysis temperature on combustion characteristics and grindability of the semicokes was studied combined with X-ray diffraction(XRD) analysis of semicokes.The results show that the volatile content,ash content and calorific value of semicokes pyrolyzed at all process parameters studied meet the technical specifications of the pulverized coal-fired furnaces(PCFF) referring to China Standards GB/T 7562-1998.The pyrolysis temperature is the most influential factor among pyrolysis process parameters.As pyrolysis temperature increases,the yield,ignition index,combustion reactivity and burnout index of semicokes show a decreasing tend,but the ash content increases.In the range of 400 and 450 °C,the grindability of semicokes is rational,especially the grindability of semicokes pyrolyzed at 450 °C is suitable.Except for the decrease of volatile content and increase of ash content,the decrease of combustion performance of semicokes pyrolyzed at higher temperature should be attributed to the improvement of the degree of structural ordering and the increase of aromaticity and average crystallite size of char.It is concluded that the semicokes pyrolyzed at the temperature of 450 °C is the proper fuel for PCFF.

Characterization of semi-coke generated by coal-based direct reduction process of siderite

Solid wastes derived from metallurgical industries pose a significant threat to environment. The utilization and disposal of these solid wastes are the major concern in the world. Semi-coke generated in coal-based direct reduction process of iron ore is a by-product and its suitable utilization is not available so far. In order to handle it properly, the characteristics of this by-product were comprehensively investigated. A series of analysis methods were used to demonstrate its mineral compositions, petrography and physico-chemical properties. The results reveal that the semi-coke has poor washability. The fixed carbon content of semi-coke reaches 76.11% and the gross calorific value is 28.10 MJ/kg, both of which are similar to those of traditional sinter coke breeze. Also, semi-coke ash possesses lower content of SiO2, Al2O3, S and higher content of CaO and MgO, which could improve the strength of sinter ore when partially substituting for coke breeze in sintering. Semi-coke features well-development porous structure and higher reaction activity, which predicts that the sintering speed could be elevated to some extent when employing it as a partial replacement of coke breeze, so the studies further suggest that the potential adverse effect of the high reactivity on sintering process could be weakened by adequately coarsening the semi-coke's particle size.

Physicochemical Properties and Gasification Reactivity of the Ultrafine Semi-char derived from a Bench-scale Fluidized Bed Gasifier

Zhtmdong coalfield is the largest intact coalfield worldwide and fluidized bed gasification has been considered as a promising way to achieve its clean and efficient utilization. The purpose of this study is to investigate the phy- sicochemical properties and gasification reactivity of the ultrafme semi-char, derived from a bench-scale fluidized bed gasifier, using Zhundong coal as fuel. The results obtained are as follows. In comparison to the raw coal, the carbon and ash content of the semi-char increase after partial gasification, but the ash fusion temperatures of them show no significant difference. Particularly, 76.53% of the sodium in the feed coal has released to the gas phase after fluidized bed gasification. The chemical compositions of the semi-char are closely related to its particle size, attributable to the distinctly different natures of diverse elements. The semi-char exhibits a higher graphitization degree, higher BET surface area, and richer meso- and macropores, which results in superior gasification reactiv- ity than the coal char. The chemical reactivity of the semi-char is significantly improved by an increased gasifica- tion temperature, which suggests the necessity of regasification of the semi-char at a higher temperature. Conse- quently, it will be considered feasible that these carbons in the semi-char from fluidized bed gasitiers are rec- laimed and reused for the gasification process.