School of Chemical Engineering, Northwest University, International Science and Technology Cooperation Base of MOST for Clean Utilization of Hydrocarbon Resources, Chemical Engineering Research Center of the Ministry of Education for Advanced Use Technology of Shanbei Energy, Shaanxi Research Center of Engineering Technology for Clean Coal Conversion, Collaborative Innovation Center for Shanbei Energy and Chemical Industry Development

高温煤焦油的高温馏分中含有丰富的多环芳烃化合物,通过催化加氢可将多环芳烃转化成燃料油加以高值、多元利用。首次利用泡沫镍为载体制备了硫掺杂的钼基催化剂,应用于煤焦油高温馏分中多环芳烃芘的催化加氢反应,揭示了硫化钼催化剂的构效关系。通过SEM和XRD表征,考察了负载在泡沫镍上的活性金属钼的结构、分布与分散性,实验结果表明,金属钼的活性物种呈现超薄的纳米片状结构,具有良好的分散性,在载体上均匀分布,有效提高了催化加氢反应的性能;通过XPS和TEM表征,表明了硫掺杂催化剂的活性物种为MoS2,并产生了高价态的氧化钼,共同作用于芘的催化加氢反应;硫的掺杂提供了硫空位,产生了更多活性位点,从而提高了催化剂活性;通过催化加氢反应,系统地考察了反应温度、氢气压力、反应时间、催化剂质量、硫脲添加量对催化加氢反应性的影响,实验结果表明,在反应温度为300℃,氢气压力为6MPa,反应时间为2h,催化剂质量为0.5g,硫脲添加量为2mmol时,MoS2-2/NF催化剂的芘转化率是未掺杂硫的MoOx/NF催化剂的芘转化率的2.43倍,并且通过再生反应,转化率可以提升至再生前的6.14倍。

The high temperature fraction of coal tar contains abundant polycyclic aromatic compounds (PAHs), which can be converted into fuel oil for high-value and diversified utilization through catalytic hydrogenation. In this study, molybdenum-based catalysts doped with sulfur were prepared for the first time using nickel foam as a carrier and applied to the catalytic hydro-genation of PAHs pyrene in the high temperature fraction of coal tar, revealing the structure-ac-tivity relationship of molybdenum sulfide catalysts. The structure, distribution and dispersity of the active metallic molybdenum loaded on nickel foam were investigated by SEM and XRD char-acterization. The results show that the active species of metallic molybdenum presentes an ultra-thin nano sheet structure with good dispersity, which is uniformly distributed on the carrier, ef-fectively improving the performance of the catalytic hydrogenation reaction. Through XPS and TEM characterization, it is clarified that the active species of sulfur doped catalyst is MoS2, and high valence molybdenum oxide is produced, which acts together in the catalytic hydrogenation reaction of pyrene. The sulfur doping provides the vacancies on the surface of molybdenum-based catalyst and generates more active sites, which effectively improves the catalytic performance of the catalysts. The effects of reaction temperature, hydrogen pressure, reaction time, catalyst quality, and thiourea addition on the catalytic hydrogenation reactivity were systematically inves-tigated by the catalytic hydrogenation reaction. The experimental results show that the conver-sion of PAHs pyrene by the MoS2-2/NF catalyst is 2.43 times higher than that of the MoOx/NF catalyst without sulfur doping at a reaction temperature of 300 ℃, a hydrogen pressure of 6 MPa, a catalyst quality of 0.5 g, and a thiourea addition of 2 mmol. Furthermore, the conver-sion can be enhanced to 6.14 times higher through the regeneration reaction.

国家自然科学基金项目(22078266).

王悦燚,王 婧,贾永梁,等.硫化钼催化剂用于催化多环芳烃芘的加氢反应[J].煤炭转化,2023,46(6):1-11

DOI:10.19726/j.cnki.eb-cc.202306001.WANG Yueyi,WANG Jing,JIA Yongliang,et al.Molybdenum sulfide catalyst for hydrogenation of PAHs pyrene[J].Coal Conversion,2023,46(6):1-11