不同钼源改性煤直接液化铁基催化剂的研究  

Study on Modification of Iron-based Catalysts with Different Molybdenum Sources for Direct Liquefaction

作　　者：李导 舒歌平[1] 高山松 王洪学 谢晶[1,2] LI Dao;SHU Geping;GAO Shansong;WANG Hongxue;XIE Jing(National Engineering Research Center for Direct Coal Liquefaction,201108 Shanghai,China;Shanghai Research Institute,China Shenhua Coal to Liquid and Chemical Company Limited,201108 Shanghai,China)

机构地区：[1]煤炭直接液化国家工程研究中心,上海201108 [2]中国神华煤制油化工有限公司上海研究院,上海201108

出　　处：《煤炭转化》2022年第6期54-61,共8页Coal Conversion

摘　　要：为了研究在铁基催化剂的基础上,添加少量的高活性有色金属钼元素是否可以提高催化剂活性、改善直接液化反应性能,在煤粉负载的FeOOH催化剂上,分别引入粉末状钼化合物、油溶性钼化合物和水溶性钼化合物三种不同形态的钼源,在氢初压为6 MPa、反应温度为455℃的条件下进行催化剂的高压釜性能评价实验。结果表明:添加粉体类形态的含钼催化剂并不能改变煤的转化率,而仅能较小幅度地提高沥青烯向油的转化率,其主要原因是活性金属钼没有在煤浆中高度分散。添加油溶性钼和水溶性钼均为有效的添加形式。油溶性钼化合物的油溶性可以使活性组元钼高度分散于煤液化溶剂中,在液化条件下转化为高分散的MoS_(2)活性相与煤紧密接触并反应,并有效防止反应过程中大分子的团聚。以共沉淀和浸渍两种方式引入的水溶性钼源高度分散在了反应物煤粉上,形成纳米级颗粒并与煤粉充分有效地接触,显著提高了煤转化率及油产率。其中,铁钼共沉淀的方式使铁与钼两种活性组元形成高度结合的固溶体形态,使用的钼源价格适中,且制备流程简单,在钼的添加量为m Mo∶m干煤=0.2%时,与基准FeOOH催化剂相比,煤转化率提高了1.77%,萃取油收率提高了8.76%,液化反应性能有较大幅度的提升。The objective of this research is to study whether adding a small amount of highly active molybdenum on the basis of iron-base catalysts can increase the activity of the catalyst and improve the performance of a direct liquefaction reaction.Three kinds of molybdenum sources,i.e.,powder molybdenum compounds,oil-soluble molybdenum compounds,and water-soluble molybdenum compounds,were introduced into the FeOOH catalyst supported on coal powders.The performance of the catalysts was evaluated in the autoclave at the initial hydrogen pressure of 6 MPa and the reaction temperature of 455℃.The experimental results show that the Mo-containing catalysts with powder morphology can not change the conversion of coal but only slightly increase the conversion of asphaltene to oil.The main reason is that the active metal molybdenum is not highly dispersed in the coal slurry.Adding oil-soluble molybdenum and water-soluble molybdenum are effective addition forms.The oil solubility of molybdenum highly disperses active molybdenum in coal liquefaction solvent.The active molybdenum is converted to a highly dispersed MoS 2 active phase and then closely contacts and reacts with coal under liquefaction conditions,and the agglomeration of macromolecules is effectively prevented.The water-soluble molybdenum source introduced by co-precipitation and impregnation is highly dispersed on the reactant coal powder and forms nano-sized particles to ensure effective contact with the coal powders,resulting in significant improvements of the coal conversion and oil yield.The method of Fe-Mo co-precipitation creates a highly combined Fe-Mo solid solution form.The molybdenum source used is moderate in price and easy to prepare.Compared with the benchmark FeOOH catalyst,the performance of the liquefaction reaction is significantly improved when the molybdenum addition amount is m Mo∶m dry coal=0.2%.The coal conversion rate increases by 1.77%,and the oil extraction yield increases by 8.76%.

关 键 词：煤直接液化 铁基催化剂 有机钼 共沉淀 改性性能 

分 类 号：TQ529.1[化学工程—煤化学工程] TQ426