Page 95 - 《精细化工》2019年第11期

第 36 卷第 11 期 精 细 化 工 Vol.36, No.11
2019 年 11 月 FINE CHEMICALS Nov. 2019

催化与分离提纯技术
负载型 Ru 催化剂的制备及其催化加氢性能

陈加利，李瑞利，邱国玉

（北京大学深圳研究生院 环境与能源学院，广东 深圳 518055）

摘要：通过 Ru 固载与水滑石修饰的 Al 2 O 3 （HTc-Al 2 O 3 ）合成同步化，制得 Ru-HTc-Al 2 O 3 ，对其进行了 XRD、
ICP-AES、SEM、HRTEM、BET、NH 3 -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-Al 2 O 3 和 Ru/Al 2 O 3 进行对照。结果表明，相较
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于 Ru/Al 2 O 3 和 Ru/HTc-Al 2 O 3 ，Ru-HTc-Al 2 O 3 具有更大的比表面积（105.4 m /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-Al 2 O 3 > Ru/HTc-Al 2 O 3 > Ru/Al 2 O 3 ；在 CRR 为 100 g/mol、反应温
度为 180 ℃、反应压力为 8 MPa 时，Ru-HTc-Al 2 O 3 的催化性能达到最佳：DMT 转化率为 98.2%，DMCD 选择
性为 96.9%。
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
中图分类号：TQ612.1 文献标识码：A 文章编号：1003-5214 (2019) 11-2243-09

Preparation and Hydrogenation Performance of Supported Ru Catalysts

CHEN Jia-li, LI Rui-li, QIU Guo-yu
（School of Environment and Energy, Peking University Shenzhen Graduate School, Shenzhen 518055, Guangdong,
China）

Abstract: By immobilizing Ru and synthesizing hydrotalcite modified Al 2O 3 (HTc-Al 2O 3) simultaneously,
Ru-HTc-Al 2O 3 was prepared and used as catalyst for the hydrogenation of dimethyl terephthalate (DMT) to
dimethyl cyclohexane-1,4-dicarboxylate (DMCD). For comparison, Ru/HTc-Al 2O 3 and Ru/Al 2O 3 were
prepared by solution impregnation method. The samples were characterized by XRD, ICP-AES, SEM,
HRTEM, BET, NH 3-TPD and XPS. The results showed that compared with Ru/HTc-Al 2O 3 and Ru/Al 2O 3,
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Ru-HTc-Al 2O 3 had a larger specific surface area (105.4 m /g). Ru-HTc-Al 2O 3 inhibited the formation of
large Ru particles as well as Ru leaching. Moreover, for Ru-HTc-Al 2O 3, 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-Al 2O 3 > Ru/HTc-Al 2O 3> Ru/Al 2O 3. Under the conditions of CRR=100 g/mol, reaction
temperature 180 ℃ and reaction pressure 8 MPa, Ru-HTc-Al 2O 3 behaved the best catalytic performance
98.2% for DMT conversion, 96.9% for DMCD selectivity were obtained.
Key words: Ru; supported catalyst; catalytic hydrogenation; dimethyl terephthalate; hydrotalcite

现代聚酯工业，尤其是涂料、合成纤维、合成 （CHDM）作为一种性能优异的交联分子，可明显提
橡胶等材料 的生产过程 中， 1,4- 环 己烷二甲醇 升产品的热稳定性、天气适应性以及物理强度 [1-2] 。

收稿日期：2019-03-25; 定用日期：2019-06-03; DOI: 10.13550/j.jxhg.20190235
基金项目：深圳市创客专项个人创客（GRCK201708231614347）
作者简介：陈加利（1986—），男，博士，工程师，E-mail：chenjia6420@163.com。