Si或P改性Pd/Al_(2)O_(3)催化剂的水热稳定性和耐磨性及其催化戊基蒽醌加氢性能  

Hydrothermal Stability,Abrasion Resistance and 2-Amyl-anthraquinone Hydrogenation Performance for Si,P Modified Pd/Al_(2)O_(3)Catalysts

作　　者：邓明杨 张晓昕[1] 宗保宁[1] DENG Mingyang;ZHANG Xiaoxin;ZONG Baoning(State Key Laboratory of Catalytic Materials and Reaction Engineering for Petrochemical Industry,Research Institute of Petroleum Processing,SINOPEC,Beijing 100083,China)

机构地区：[1]中国石化石油化工科学研究院石油化工催化材料与反应工程国家重点实验室,北京100083

出　　处：《石油学报（石油加工）》2022年第5期1001-1009,共9页Acta Petrolei Sinica(Petroleum Processing Section)

基　　金：国家自然科学基金项目(22072182)资助。

摘　　要：采用等体积浸渍法向γ-Al_(2)O_(3)中引入Pd,Si或P元素,制备了系列2%Pd/X-Al_(2)O_(3)(X=Si或P)催化剂。采用XRD、NH_(3)-TPD、CO化学吸附、XRF、TEM、XPS等测试手段对催化剂进行表征,并评价了其催化戊基蒽醌加氢性能。结果表明,Si或P的掺杂未改变原始γ-Al_(2)O_(3)载体的晶型结构,Si或P嫁接在γ-Al_(2)O_(3)表面,减少了其四面体和八面体空穴,形成了Al—O—Si或Al—O—P键,使催化剂的表面酸性有所降低,金属与载体的锚固作用减弱从而分散性降低,Pd^(2+)/Pd^(0)的摩尔比增大。水热实验结果表明,由于γ-Al_(2)O_(3)表面空穴的减少,改性催化剂的水热稳定性和耐磨性均显著提高。在蒽醌加氢反应实验中,改性后催化剂的蒽醌加氢效率达到了17~20 g/L,选择性提高到了94%,这可能是因为Pd^(2+)的比例增大使催化剂表面的缺电子吸附位增加,蒽醌分子更易活化,且催化剂表面强酸量的减少调节了蒽醌分子的吸附强度,从而加氢活性和选择性均有所提高。2%Pd/X-Al_(2)O_(3)(X=Si or P)catalysts were synthesized by isometric impregnation method to introduce non-metallic elements(Si or P)and Pd toγ-Al_(2)O_(3).The samples were characterized by various testing methods including XRD,NH_(3)-TPD,CO chemical adsorption,XRF,TEM and XPS,and the 2-amyl-anthraquinone hydrogenation performance was evaluated.The results showed that the original crystal structure ofγ-Al_(2)O_(3)still remained even by the doping of Si and P,Si or P was grafted on the surface ofγ-Al_(2)O_(3)forming Al—O—Si or Al—O—P linkage,thus reducing its tetrahedral and octahedra cavities,so that the surface strong acidity was reduced and the dispersion of Pd decreased by the weakened interaction between Pd and carrier.Besides,the molar ratio of Pd^(2+)/Pd^(0)increased.Hydrothermal experiments showed that the hydrothermal stability and abrasion resistance of the modified catalysts were significantly enhanced due to the reduction of surface cavities ofγ-Al_(2)O_(3).In the anthraquinone hydrogenation reaction,the modified catalysts exhibited hydrogen efficiency of 17—20 g/L and a high selectivity of 94%.Increase of Pd^(2+)ratio may have added the electron-deficient adsorption sites of the catalyst and more vitalized the anthraquinone molecules.And the decrease of strong acidity on the catalyst surface adjusted the adsorption strength of the anthraquinone molecules,thereby improving the hydrogenation activity and selectivity.

关 键 词：蒽醌加氢 PD催化剂 水热稳定性 非金属 

分 类 号：TQ426.63[化学工程] TQ123.6