Ni-Fe合金催化剂制备及催化硬脂酸加氢脱氧性能  

Preparation of Ni-Fe alloy catalyst and catalytic hydrodeoxygenation of stearic acid

作　　者：郭效博 王玮[1] 赵佳平[2,3] 徐俊明 赵平 刘朋[1,2,3] GUO Xiaobo;WANG Wei;ZHAO Jiaping;XU Junming;ZHAO Ping;LIU Peng(Key Laboratory of Efficient Utilization of Forest Biomass Resources in Southwest China,National Forestry and Grassland Administration,Southwest Forestry University,Kunming 650233,China;Institute of Chemical Industry of Forest Products,CAF,Nanjing 210042,China;Key Lab of Chemical Engineering of Forest Products,National Forestry and Grassland Administration,Nanjing 210042,China)

机构地区：[1]西南林业大学西南地区林业生物质资源高效利用国家林业和草原局重点实验室,云南昆明650233 [2]中国林业科学研究院林产化学工业研究所,江苏南京210042 [3]国家林业和草原局林产化学工程重点实验室,江苏南京210042

出　　处：《煤炭学报》2023年第6期2315-2325,共11页Journal of China Coal Society

基　　金：中央级公益性科研院所基本科研业务费专项资金资助项目(CAFYBB2022ZC003)。

摘　　要：以油脂为原料通过加氢脱氧方式制备烃基生物柴油的研究具有重要现实意义和广阔应用前景。在烃基生物柴油的制备过程中,为降低油脂加氢脱氧过程中碳原子的损失,制备高活性、高选择性的催化剂至关重要。采用浸渍法制备了一系列Ni-Fe双金属催化剂,并将其应用于催化硬脂酸加氢脱氧反应;采用XRD、TEM、HRTEM、XPS、NH_(3)-TPD、H_(2)-TPR等手段对催化剂进行表征分析,探索了制备条件及金属Fe的加入对Ni基催化剂理化特性及加氢活性的影响,结果表明,在500℃还原、10%Ni金属负载量、Ni/Fe质量比=3∶1条件下制备的催化剂表现出较佳的加氢脱氧性能,Fe的加入与Ni形成了FeNi_(3)合金,Ni和Fe金属的内部相互作用还促进了Ni-Fe团簇的高分散性和形成了较小的粒径尺寸。此外,FeNi_(3)合金的形成还降低了Fe、Ni催化剂的还原温度,提升了Fe、Ni催化剂的中等酸活性和总酸度,这促进了催化剂的加氢脱氧活性。考察了反应温度、初始H_(2)压力、时间和催化剂用量等因素对硬脂酸加氢脱氧反应的影响。得出260℃、3.0 MPa、4 h、0.02 g催化剂用量为最优加氢脱氧反应条件,催化剂在该条件下实现催化硬脂酸加氢脱氧反应100%转化率和较高C_(18)选择性(93.5%)。最后,通过与商业催化剂进行催化性能对比,表明该催化剂在反应活性及C_(18)选择性方面均存在显著优势。这项研究为下一步油脂原料的选择性加氢脱氧提供数据支持及理论指导。The study of the preparation on hydrocarbon-based biodiesel from oils and fats by hydrodeoxygenation is of great practical importance and has a broad application potential.In the preparation of hydrocarbon-based biodiesel,the preparation of highly active and selective catalysts is essential to reduce the loss of carbon atoms during the hydrodeoxygenation of fats and oils.In this study,a series of Ni-Fe bimetallic catalysts were prepared by impregnation and applied to catalyze the hydrodeoxygenation reaction of stearic acid.The catalysts were characterized by XRD,TEM,HRTEM,XPS,NH_(3)-TPD,and H_(2)-TPR,and the effects of preparation conditions and the addition of metal Fe on the physicochemical properties and hydrogenation activity of Ni-based catalysts were explored. The results showed that the catalysts prepared at 500 ℃ reduction, 10% Ni metal loading and Ni:Fe = 3:1 showed a better hydrodeoxygenation performance, the Fe addi-tion formed FeNi_(3) alloy with Ni, and the internal interaction between Ni and Fe metal also promoted the high dispersion of Ni-Fe clusters and the formation of smaller particle size. In addition, the formation of the FeNi_(3) alloy also reduced the re-duction temperature of the Fe and Ni catalysts. It enhanced the moderate acid activity and total acidity of the Fe and Ni catalysts, which promoted the hydrodeoxygenation activity of the catalysts. The effects of reaction temperature, initial H_(2) pressure, time and catalyst dosage on the hydrodeoxygenation reaction of stearic acid were examined. The optimum hy-drodeoxygenation reaction conditions were obtained at 260 ℃, 3.0 MPa, 4 h, and 0.02 g catalyst dosage, under which the catalyst achieved 100% conversion and high C_(18) selectivity (93.5%) for the catalytic stearic acid hydrodeoxygenation reac-tion. Finally, a comparison of the catalytic performance with that of commercial catalysts showed that the catalyst had sig-nificant advantages in reactivity and C_(18) selectivity. This study provides data and theoretical guidance for the

关 键 词：硬脂酸 合金催化剂 加氢脱氧 C_(18)选择性 烃基生物柴油 

分 类 号：TK62[动力工程及工程热物理—生物能]