煤直接液化残渣及其萃取产物的热重分析

第40卷第6期燃料化学学报Vol 40 No 6ournal of Fuel Chemistry and TechnologyJun,2012文章编号:0253-2409(2012)060655405煤直接液化残渣及其萃取产物的热重分析刘朋飞12,张永奇,房倚天(1.中国科学院山西煤炭化学研究所,山西太原03001;2.中国科学院研究生院,北京10009)摘要:利用热天平考察了神华和胜利两种典型中国煤直接液化残渣及其萃取产物的失重曲线。实验表明神华残渣和胜利残渣的轻质组分含量相近其失重率也相近但轻质组分组成不同使得失重过程并不一致。升温速率增加热解最大失重速率增加,最大失重速率温度升高。以残渣各组分失重曲线拟合得到的残渣失重曲线可近似表示残渣的失重曲线。动力学分析表明,由实验数据拟合的活化能和指前因子计算得到的失重曲线,与实际实验得到的失重曲线较为一致。液化残渣在低温区失重率很高,而且这部分失重产物可以通过溶剂萃取的方式得到。关键词:煤直接液化;残渣;热重;萃取;活化能;指前因子中图分类号:0643文献标识码:ATG analysis of coal direct liquefaction residue and its solvent extractsLIU Peng-fei, ZHANG Yong-qi, FANG Yi-tian(1. Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, China;2. Graduate University of Chinese Academy of Sciences, Bejing 100049, China)Abstract: Pyrolysis of two typical Chinese coal liquefaction residues( Shenhua and Shengli)and their solventextracts was carried out by TG. The results show that Shenhua and Shengli residue contain similar content oflight component, and their weight losses in TGA are similar. However, the different composition of lightcomponent in the two residues leads to their difference in TG curves. As increasing of heating rate, the maximumweight loss rate and its corresponding temperature increase. The calculated weight loss calculated from theconstitutes is approximately the actual value of the residue. From the kinetic analysis, it is found that the weightloss calculated by the experimental E and k, agree well with that obtained from the experiment. The weight lossis mainly caused by evaporation of volatile matter which can be extracted by solventKey words: coal direct liquefaction; residue; thermogravimetric analysis; extract; activation energy; frequency煤直接液化技术是解决中国未来能源紧张问题1实验部分的关键技术之一。煤直接液化残渣是煤加氢直接液1.1实验物料及分析方法本实验所用神华煤液化过程产生的副产品,其产量约占直接液化原煤质化残渣(SHR)取自上海6t/d直接液化中试装置量的30%左右,残渣的高效利用直接影响着煤直接胜利煤液化残渣(SLR)取自煤科总院0.ItUd直接液化工艺过程的经济性。神华直接液化工厂的液化装置。两种残渣粒径均小于100目,并在恒温建成投产,标志着中国成为世界上掌握百万吨级直干燥箱中70℃下干燥24h。接液化技术的国家,但因此产生的大量液化残渣也利用索氏抽提装置将液化残渣分别依次用正己使得液化残渣的有效处理成为紧迫的问题。烷、甲苯、四氢呋喃萃取,得到的萃取物和最终不溶液化残渣中含有大量较高经济价值的重质液物在常温下都为固体索氏提取流程见图体(2),通常情况下可以采用热解23的方式将这部热重分析在 SETARAM热天平上进行。热解分重质液体提取出来加以利用。而萃取是提取残渣条件为样品质量为6~8mg,N2流量120mL/min重质液体的重要手段之一,相比热解方法其条件也升温速率为5、10、20、40K/min,终温为80℃。更加温和。本实验将对残渣及残渣萃取物进行热重残渣的工业、元素分析及溶剂萃取组成见表1。行为研究探讨萃取工艺利用残渣重质液体的可行1.2反应速率分析性,并得到残渣的热解动力学参数。E热重转化率x由式(1)定义中国煤化工CNMHG收稿日期:201140812;修回日期:201114联系作者:张永奇,Tel/Fax:0351-2021137,E-mal:zhangye@sice.ac.cn。燃料化学学报第40卷其中,α为一定温度下残渣挥发性物质的失重对式(6)两边取自然对数,且由通常情况下RT