油页岩有机质热解特性及其与煤共炭化过程中的传氢和粘结机理研究

Coal is the essential material base for the survival and development of coking industry. Strongly caking coal is one of the significant factors in the production of high quality coke. Coking coal in our country is in short supply, especially the strongly caking coal, while oil shale is in the rich resource. To improve the caking ability of coking process, organic matter in oil shale can be added into coking coal due to its rich in hydrogen and hydrogen transfer effect. However, the content of mineral in oil shale is high. If oil shale be added into coal to coking directly that would result in the deterioration of coke quality. Therefore, the separation and enrichment of organic matter in oil shale, the investigation on pyrolysis characteristics of the organic matter and its coking mechanism of co-carbonization with coal of different degree of coalification have a theoretical and practical significance to apply the addition of oil shale organic matter into coking coal, expand the source of coking coal, reduce the use of strong caking coal and improve the quality of coke. The aims of this work are to investigate the structures of organic matter in oil shale, change rules of functional groups during pyrolysis process, plastic characteristics of colloid, mechanisms of pyrolysis rules of organic matter in oil shale of low mineral content co-carbonization with coal of different degree of coalification, hydrogen transferring and coking mechanisms, technological conditions and relationship with coke quality based on the separation and enrichment of organic matter from oil matter., which can provide a theoretical basis for application of oil shale organic matter adding into coking coal.

煤炭是炼焦业赖以生存和发展的重要物质基础，强粘煤是生产优质焦炭的重要因素之一。我国炼焦煤、尤其是强粘煤资源紧缺, 但油页岩资源丰富，如能在炼焦配煤中配加油页岩中的有机质，则可以借助有机质的富氢和传氢作用，改善炼焦过程中的粘结性。但油页岩矿物含量高，如果直接进行配煤炼焦，会导致焦炭质量恶化。因此，对油页岩有机质进行分离富集，进而对富集后的有机质进行高温热解特性及其与不同煤化度煤共炭化时的传氢和粘结成焦机理进行研究，对应用油页岩有机质配煤炼焦、扩大炼焦煤源、减少强粘煤用量或改善焦炭质量具有重要的理论和实践意义。本课题旨在通过对油页岩有机质分离富集基础上，对油页岩有机质的结构组成及其热解过程中的官能团变化规律和胶质体塑性特征、以及低矿物含量油页岩有机质与不同煤化度煤共炭化过程中的热解变化规律、传氢与粘结成焦机理、工艺条件及其与焦炭质量关系进行研究，为科学应用油页岩有机质进行配煤炼焦提供理论依据。

我国炼焦煤资源紧缺，但油页岩资源丰富，如能在炼焦配煤中配加油页岩有机质，则可以借助有机质的富氢和传氢作用，改善炼焦过程中的粘结性，同时扩大炼焦煤源。本项目采用酸洗法对桦甸油页（OS）岩进行分离和富集，记为酸洗油页岩（OSA），利用低温热解对OSA的粘结性进行改性，借助TG-DTG、XPS、XRD、Raman、13C-NMR、顺磁（ESR）、粘结力指数G、原位红外等分析仪器对OSA热解改质机理进行了研究。在此基础上，选取粘结性最优提质OSA代替青龙山瘦煤进行配煤炼焦，对所得焦炭进行反应性和反应后强度分析测试。. （1）OS及OSA的干燥基灰分分别为70.8%及5.4%。. （2）XRD结果表明，热解温度300-450℃范围内，OSA与瘦煤以3：7质量混合制备的混合物（MS）的晶格面间距从0.357 nm减小到0.346 nm，平均堆积高度从1.509 nm增加到1.980 nm，表明热解处理增加了其变质程度。此外，随着热解温度的升高，MS的含氧官能团和孔体积减小。TG和ESR结果表明，共热解过程中存在协同效应。OSA热解生成的富氢自由基被煤热解生成的中间产物——胶质体中的贫氢较大分子自由基捕获，因此，共热解固体产物增加。. （3）400℃处理后的OSA的粘结性指数较好。. （4）13C-NMR实验结果表明，脂肪性从OSA的91.1%逐渐下降到500℃处理后OSA的24.8%，芳香性相应的增加。. （5）利用基准混煤和替换混煤（400℃处理后的OSA替代基准煤中的瘦煤）方案制备的焦炭CO2反应性分别为50.8%和52.2%、焦炭反应后强度分别为43.9%和45.3%， 表明两种配煤方案下制备的焦炭性能指标接近。. （6）500℃时，褐煤（HM）的固体产率为48.20%、焦油产率为3.17%，OSA的固体产率为38.90%、焦油产率为7.60%；HMOSA的固体产率为46.71%、焦油产率为10.58%，大于其理论值4.50%，说明OSA的加入提高了低阶煤焦油的产率。. （7）原位红外光谱分峰结果表明，随温度的升高，CYM、HM及CYMOSA中–OH的含量单调下降，OSA中–OH的含量先增大后减小，HMOSA的自由羟基–OH先减小后增大，缔合羟基–OH逐渐增大；CYM、HM、HMOSA中的脂肪族–CH3/–CH2–逐渐下降