催化学报

催化学报 ›› 2013, Vol. 34 ›› Issue (5): 1020-1026.DOI: 10.1016/S1872-2067(12)60543-9

• 研究论文 • 上一篇    下一篇

ZnO与骨架NiMo物理混合用于丙三醇催化重整-氢解制1,2-丙二醇

胡基业a, 刘晓钰a, 范义秋a, 谢颂海a, 裴燕a, 乔明华a, 范康年a, 张晓昕b, 宗保宁b   

  1. a 复旦大学化学系上海市分子催化和功能材料重点实验室, 上海 200433;<;
    b r>;
    b 中国石油化工股份有限公司石油化工科学研究院催化材料和反应工程国家重点实验室, 北京 100083
  • 收稿日期:2012-12-20 修回日期:2013-05-20 出版日期:2013-05-06 发布日期:2013-05-06
  • 通讯作者: 乔明华,宗保宁
  • 基金资助:

    新世纪优秀人才支持计划(NCET-08-0126);国家重点基础研究发展计划(973计划,?2012CB224804);国家自然科学基金(21073043);上海市科委项目(10JC1401800,08DZ2270500);上师大上海市稀土功能材料重点实验室开放课题.

Physically mixed ZnO and skeletal NiMo for one-pot reforming-hydrogenolysis of glycerol to 1,2-propanediol

HU Jiyea, LIU Xiaoyua, FAN Yiqiua, XIE Songhaia, PEI Yana, QIAO Minghuaa, FAN Kangniana, ZHANG Xiaoxinb, ZONG Baoningb   

  1. a Department of Chemistry and Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University, Shanghai 200433, China;
    b State Key Laboratory of Catalytic Materials and Reaction Engineering, Research Institute of Petroleum Processing, Beijing 100083, China
  • Received:2012-12-20 Revised:2013-05-20 Online:2013-05-06 Published:2013-05-06
  • Supported by:

    This work was supported by the Program for New Century Excellent Talents in Universities (NCET-08-0126), the National Basic Research Program of China (973 Program, 2012CB224804), the National Natural Science Foundation of China (21073043), Shanghai Science and Technology Committee (10JC1401800, 08DZ2270500), and Shanghai Key Laboratory of Rare Earth Functional Materials, Shanghai Normal University.

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摘要：

以骨架NiMo以及与氧化物物理混合, 考察了其在连续固定床反应器中无外加氢气条件下的丙三醇一锅法重整-氢解制1,2-丙二醇(1,2-PDO)的性能.研究发现, 骨架NiMo自身催化活性高, 但对1,2-PDO的选择性一般.当将其与MgO, SiO2, Al2O3, HZSM-5, TiO2, ZrO2或CeO2机械混合时, 丙三醇转化率和1,2-PDO选择性均发生下降.但当与ZnO物理混合时, 催化活性和选择性均有所提高, 1,2-PDO得率可达52.0%, 优于贵金属催化剂在该一锅法反应中得到的结果.物理混合的ZnO与骨架NiMo之间这种独特的协同作用, 归因于重整过程中产生的CO2在ZnO上发生化学吸附, 原位增强了ZnO的路易斯酸性.这不仅促进了丙三醇在ZnO上脱水生成中间产物丙酮醇, 也促进了丙酮醇在骨架NiMo上加氢生成1,2-PDO.

关键词: 丙三醇, 氢解, 氧化锌, 镍, 钼, 协同效应

Abstract:

The one-pot aqueous phase reforming (APR) and hydrogenolysis of glycerol to 1,2-propanediol (PDO) was catalyzed by physically mixed skeletal NiMo and zinc oxide catalysts in a continuous flow fixed-bed reactor without the aid of added H2. The skeletal NiMo catalyst alone is highly active towards glycerol but the selectivity for 1,2-PDO is only moderate. Physically mixing of MgO, SiO2, Al2O3, HZSM-5, TiO2, ZrO2, or CeO2 as a cocatalyst with skeletal NiMo was detrimental to the conversion of glycerol and yield of 1,2-PDO. However, physically mixing with ZnO gave an advantageous promoting effect on both the catalytic activity and selectivity for 1,2-PDO, and gave a 1,2-PDO yield of 52.0%, which is higher than that obtained with noble metal catalysts for the APR-hydrogenolysis of glycerol. The synergistic effect between physically mixed ZnO and skeletal NiMo was attributed to in situ enhancement of the Lewis acidity of ZnO by chemisorbed CO2 from the APR of glycerol on skeletal NiMo, which benefited both the dehydration of glycerol to acetol on ZnO and the hydrogenation of acetol to 1,2-PDO on skeletal NiMo.

Key words: Glycerol, Hydrogenolysis, Zinc oxide, Nickel, Molybdenum, Synergistic effect