负载型Ru催化剂的制备及其催化加氢性能  

Preparation and Hydrogenation Performance of Supported Ru Catalysts

作　　者：陈加利 李瑞利 邱国玉 CHEN Jia-li;LI Rui-li;QIU Guo-yu(School of Environment and Energy,Peking University Shenzhen Graduate School,Shenzhen 518055,Guangdong,China)

机构地区：[1]北京大学深圳研究生院环境与能源学院

出　　处：《精细化工》2019年第11期2243-2251,共9页Fine Chemicals

基　　金：深圳市创客专项个人创客（GRCK201708231614347)

摘　　要：通过Ru固载与水滑石修饰的Al2O3(HTc-Al2O3)合成同步化,制得Ru-HTc-Al2O3,对其进行了XRD、ICP-AES、SEM、HRTEM、BET、NH3-TPD和XPS表征,并将其用于对苯二甲酸二甲酯(DMT)催化加氢制取1,4-环己烷二甲酸二甲酯(DMCD)。以溶液浸渍法制得Ru/HTc-Al2O3和Ru/Al2O3进行对照。结果表明,相较于Ru/Al2O3和Ru/HTc-Al2O3,Ru-HTc-Al2O3具有更大的比表面积(105.4 m^2/g);其大粒径Ru粒子的形成和Ru的损失受到明显抑制,Ru粒子尺寸分布集聚区间向小尺寸方向偏移,并可提供更多的表面酸性位,尤其是中等强度的酸性位。通过考察催化剂质量与原料DMT初始物质的量比(CRR)、压力和温度的影响以及循环使用反应性能发现,催化反应活性顺序为:Ru-HTc-Al2O3> Ru/HTc-Al2O3> Ru/Al2O3;在CRR为100 g/mol、反应温度为180℃、反应压力为8 MPa时,Ru-HTc-Al2O3的催化性能达到最佳:DMT转化率为98.2%,DMCD选择性为96.9%。By immobilizing Ru and synthesizing hydrotalcite modified Al2 O3(HTc-Al2 O3) simultaneously, Ru-HTc-Al2 O3 was prepared and used as catalyst for the hydrogenation of dimethyl terephthalate(DMT) to dimethyl cyclohexane-1,4-dicarboxylate(DMCD). For comparison, Ru/HTc-Al2 O3 and Ru/Al2 O3 were prepared by solution impregnation method. The samples were characterized by XRD, ICP-AES, SEM, HRTEM, BET, NH3-TPD and XPS. The results showed that compared with Ru/HTc-Al2 O3 and Ru/Al2 O3, Ru-HTc-Al2 O3 had a larger specific surface area(105.4 m^2/g). Ru-HTc-Al2 O3 inhibited the formation of large Ru particles as well as Ru leaching. Moreover, for Ru-HTc-Al2 O3, the aggregation interval of Ru particle size distribution shifted to the direction of small size, which had more surface acid sites especially for the moderate ones. The effects of CRR(the ratio of catalyst mass to the initial feed molar of DMT), reaction temperature and reaction pressure on the catalytic performance of the catalysts were investigated. The stability of catalyst recycle reaction was evaluated. It was found that the order of catalytic activity was:Ru-HTc-Al2 O3 > Ru/HTc-Al2 O3> Ru/Al2 O3. Under the conditions of CRR=100 g/mol, reaction temperature 180 ℃ and reaction pressure 8 MPa, Ru-HTc-Al2 O3 behaved the best catalytic performance 98.2% for DMT conversion, 96.9% for DMCD selectivity were obtained.

关 键 词：RU 负载型催化剂 催化加氢 对苯二甲酸二甲酯 水滑石 

分 类 号：TQ612.1[化学工程—精细化工]