氮掺杂多孔炭负载镍纳米粒子对高温煤焦油的催化加氢转化  

Nitrogen-doped porous carbon supported nickel nanoparticles as catalyst for catalytic hydroconversion of high-temperature coal tar

作　　者：谢瑞伦 张侠 田誉娇 雷昭[1] 曹恩德 XIE Rui-lun;ZHANG Xia;TIAN Yu-jiao;LEI Zhao;CAO En-de(School of Chemistry&Chemical Engineering,Anhui Province Key Laboratory of Coal Clean Conversion&High Valued Utilization,Anhui University of Technology,Ma’anshan 243002,China)

机构地区：[1]安徽工业大学化学与化工学院,煤清洁转化与高值化利用安徽省重点实验室,安徽马鞍山243002

出　　处：《燃料化学学报》2021年第10期1402-1411,I0001-I0009,共19页Journal of Fuel Chemistry and Technology

基　　金：安徽省自然科学基金(1708085QB33);中国国际科技创新合作重点专项(2017YFE0124300)资助。

摘　　要：通过对生长在石墨相氮化碳两侧的镍基沸石咪唑酸盐骨架材料进行热分解,制备了一种新型的高活性氮掺杂多孔炭负载的镍基催化剂Ni@N-PC,并将其用于高温煤焦油异丙醇超声萃取物的催化加氢转化。催化剂的镍纳米颗粒主要包裹在碳纳米管的顶端,部分分散在碳纳米薄片表面。以1-萘酚为模型化合物,考察了催化剂在不同反应条件下的催化加氢转化活性,揭示了其催化反应机理。并利用GC/MS分析了高温煤焦油异丙醇超声萃取物及其加氢转化产物。结果表明,1-萘酚在120℃反应2 h有70%转化,在200℃反应2 h后完全转化,高温煤焦油异丙醇超声萃取物经加氢后得到大幅改质。高温煤焦油异丙醇超声萃取物中共检测到180种有机物,其中,含氮有机物33种,含硫有机物11种,含氧化合物39种,而经加氢转化后的产物中未检测到含氧、氮、硫等杂原子化合物,说明催化剂Ni@N-PC具有良好的去除杂原子的性能。经加氢后所有的烯烃、环烯和炔烃饱和,大部分芳烃转化为环烷烃,说明催化剂Ni@N-PC具有较高的催化加氢活性。A novel and highly active nitrogen-doped porous carbon-supported nickel catalyst Ni@N-PC was successfully developed by a thermolysis of nickel-based zeolitic imidazolate frameworks growing on both sides of graphitic carbon nitride and used for catalyzing hydroconversion of isopropanol soluble portion from ultrasonic extraction of high-temperature coal tar(ISP_(HTCT)).The active nickel nanoparticles were mainly encapsulated on the top of carbon nanotubes and partially dispersed on the surface of carbon nanosheets.Naphthalen-1-ol was used as a model compound to investigate the catalytic hydroconversion activity under different reaction conditions and reveal the mechanism for catalytic hydroconversion.The ISP_(HTCT)and catalytic hydroconversion products of ISP_(HTCT)(ISPCHCP)were analyzed with gas chromatograph/mass spectrometer.The results show that 70%of naphthalen-1-ol was converted at 160℃and completely converted at 200℃for 120 min,and the ISP_(HTCT)was greatly upgraded.A total of 180 organic compounds including 33 nitrogen-containing organic compounds,11 sulfur-containing organic compounds and 39 oxygenates were identified in ISP_(HTCT),while no obvious nitrogen-containing organic compounds,sulfur-containing organic compounds and oxygenates were detected in ISPCHCP,indicating the excellent performance of Ni@N-PC for heteroatom removal.All the alkenes,cyclenes and alkynes were saturated and the majority of arenes were converted to cyclanes by catalytic hydroconversion over Ni@N-PC,which exhibited high catalytic hydrogenation activity.

关 键 词：高温煤焦油 催化加氢转化 烃类 催化剂 

分 类 号：TQ529[化学工程—煤化学工程]