物理化学学报 >> 2012, Vol. 28 >> Issue (11): 2697-2704.doi: 10.3866/PKU.WHXB201207091

催化和表面科学 上一篇    下一篇

SBA-15负载高分散纳米NiO的丙烷氧化脱氢制丙烯催化性能

鲁怀乾, 石磊, 何冲, 翁维正, 黄传敬, 万惠霖   

  1. 厦门大学固体表面物理化学国家重点实验室, 醇醚酯化工清洁生产国家工程实验室, 化学化工学院化学系, 福建 厦门 361005
  • 收稿日期:2012-05-25 修回日期:2012-07-09 发布日期:2012-10-17
  • 通讯作者: 翁维正, 万惠霖 E-mail:wzweng@xmu.edu.cn; hlwan@xmu.edu.cn
  • 基金资助:

    国家重点基础研究发展计划(973) (2010CB732303); 国家自然科学基金(21173173, 21073148, 21033006); 教育部创新团队项目(IRT1036)和福建省重大科技专项(2009HZ0002-1)资助项目

Highly-Dispersed NiO Nanoparticles on SBA-15 for Oxidative Dehydrogenation of Propane to Propylene

LU Huai-Qian, SHI Lei, HE Chong, WENG Wei-Zheng, HUANG Chuan-Jing, WAN Hui-Lin   

  1. State Key Laboratory of Physical Chemistry of Solid Surfaces, National Engineering Labo-ratory for Green Chemical Productions of Alcohols, Ethers and Esters, Department of Chem-istry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, Fujian Province, P. R. China
  • Received:2012-05-25 Revised:2012-07-09 Published:2012-10-17
  • Contact: WENG Wei-Zheng, WAN Hui-Lin E-mail:wzweng@xmu.edu.cn; hlwan@xmu.edu.cn
  • Supported by:

    The project was supported by the National Key Basic Research Program of China (973) (2010CB732303), National Natural Science Foundation of China (21173173, 21073148, 21033006), Program for Innovative Research Team of the Ministry of Education of China (IRT1036), and Key Scientific Project of Fujian Province, China (2009HZ0002-1).

摘要:

采用浸渍法通过改变焙烧气氛制备了系列NiO/SBA-15 (wNiO=20%)催化剂, 并考察了催化剂的丙烷氧化脱氢(ODHP)反应性能. 实验结果表明, 与在静止和流动空气中焙烧的催化剂相比, 在1%NO/He (VNO/VHe=1:99)气氛中焙烧的NiO/SBA-15-NO具有优异的低温丙烷氧化脱氢制丙烯性能, 在350 ℃时, 丙烷的转化率和丙烯收率分别约达29%和13%. 反应温度升至450 ℃时, 丙烯的选择性仍保持在45%左右. X射线粉末衍射(XRD)和透射电镜(TEM)测试结果表明, 1%NO/He气氛可有效抑制焙烧过程中NiO纳米颗粒的团聚, 使NiO物种高分散于SBA-15 的孔道中. H2-程序升温还原(H2-TPR)和O2-程序升温脱附(O2-TPD)测试结果表明, 随着NiO在SBA-15上分散度的提高, 催化剂的抗还原性增强, ODHP活性氧物种O-的含量增加, 进而使1%NO/He气氛中焙烧的NiO/SBA-15-NO在较宽的温度范围内(350-450 ℃)均具有良好的丙烯选择性, 并显著提高了催化剂的低温活性.

关键词: NiO/SBA-15, 丙烷, 氧化脱氢, 丙烯, 焙烧气氛

Abstract:

A series of NiO/SBA-15 (wNiO=20%) catalysts were prepared by impregnating SBA-15 with an aqueous solution of nickel nitrate followed by calcining under three different atmospheres. The resulting materials were studied with regard to the oxidative dehydrogenation of propane (ODHP) to propylene. Compared to the catalysts calcined under either static or moving air, the NiO/SBA-15-NO catalyst calcined under flowing 1%NO/He (VNO/VHe=1:99) atmosphere demonstrated greater activity for this reaction at low temperature. Propylene yield of ~13% with propane conversion of ~29% was obtained at 350 ℃ and the propylene selectivity remained at about 45% even when the reaction temperature was raised to 450 ℃. X-ray diffraction (XRD), transmission electron microscopy (TEM), H2-temperature program reduction (H2-TPR), and O2-temperature program desorption (O2-TPD) characterizations were used to investigate the intrinsic differences between these NiO/SBA-15 catalysts. It was found that NiO species in the catalyst calcined under 1%NO/He atmosphere were highly dispersed inside the mesopores of SBA-15. With the increasing of NiO dispersion on the support, the quantity of NiO species with a reduction temperature above 450 ℃ increased significantly. In addition, the density of O-species on the catalyst calcined under 1%NO/He was much higher than that in the case of the other two samples. These factors are responsible for the superior performance of the NiO/SBA-15-NO catalyst for the ODHP reaction over the temperature range 350 to 450 ℃.

Key words: NiO/SBA-15, Propane, Oxidative dehydrogenation, Propylene, Calcination atmosphere

MSC2000: 

  • O643