Citation: WU Yi-min, LI Shuo, LI Chun-yi. Influence of Li loading on the catalytic performance of Li/MgO in the oxidative dehydrogenation of propane to olefins[J]. Journal of Fuel Chemistry and Technology, ;2016, 44(11): 1334-1340. shu

Influence of Li loading on the catalytic performance of Li/MgO in the oxidative dehydrogenation of propane to olefins

State Key Laboratory of Heavy Oil Processing, China University of Petroleum (East China), Qingdao 266580, China

Corresponding author: LI Chun-yi, chyli@upc.edu.cn
Received Date: 23 June 2016
Revised Date: 21 July 2016

Fund Project: The project was supported by the Key Project of National Nature Science Foundation of China Petroleum and Chemical Joint Funds U1362201

Figures(6)

A series of Li/MgO catalysts with different Li loadings were prepared by incipient wetness impregnation method and characterized by TG-DTA, N₂ sorption and XRD; two modes for propane adsorption on Li/MgO were considered by calculation with Material Studio and the influence of Li loading on the catalytic performance of Li/MgO in the oxidative dehydrogenation of propane to olefins was investigated. The result indicated that with the increase of Li loading, the conversion of propane and the selectivity to C₂H₄, C₂H₆, CH₄, CO_x increases at first, reaches the highest values at a Li loading of 3% and then decreases with further increasing the Li loading, whereas the selectivity to propene changes in an opposite trend. The adsorption and dehydrogenation of propane on Li/MgO surface are controlled by both thermodynamic and kinetic factors, whilst the dispersion of the active Li⁺O^- sites is related to the loading of Li. Over the highly-dispersed active Li⁺O^- sites, the dehydrogenation is thermodynamically controlled, which favors the formation of propene, whereas over the poorly-dispersed Li⁺O^- sites, the reaction is dominated by the kinetic factor, leading to a high selectivity to ethene and other by-products.
- propane,
- oxidative dehydrogenation,
- Li/MgO,
- olefins,
- Li loading,
- dispersion
1. [1]
  LI Fu-chao, ZHANG Jiu-shun, YUAN Qi-min. Advances in catalytic processing of paraffin for propylene production[J]. Pet Process Petrochem, 2013,44(10):1-7.
2. [2]
  HU Yuan-jue. How to choose the raw material routes at low oil price period[J]. Chin Pet Chem Ind, 2015(6):35-38.
3. [3]
  China Petroleum and Chemical Industry Federation International Exchanges and Foreign Committee . China's petrochemical industry development direction and focus in the next decade[J]. Chin Pet Chem Ind Econ Anal, 2015(7):18-22.
4. [4]
  SATTLER J J H B, RUIZ-MARTINEZ J, SANTILLAN-JIMENEZ E, WECKHUYSEN B M. Catalytic dehydrogenation of light alkanes on metals and metal oxides[J]. Chem Rev, 2014,114(20):10613-10653. doi: 10.1021/cr5002436
5. [5]
  ZHANG Ling-feng, LIU Ya-lu, HU Zhong-pan, YANG Yu-wang, YU Hai-bin, YUAN Zhong-yong. Advance in catalysts for propane dehydrogenation to propylene[J]. Acta Pet Sin:Pet Process Sect, 2015,31(2):400-417.
6. [6]
  WANG Hai-nan, WANG Hong. Progress in studying of catalysts for propane oxidative dehydrogenation to propylene[J]. Nat Gas Chem Ind, 2003,28(6):25-31.
7. [7]
  WANG Yu, XIE Song-hai, YUE Bin, FENG Su-jiao, HE He-yong. Oxidative dehydrogenation of propane to propene over mesoporous alumina-supported vanadium oxide catalyst[J]. Chin J Catal, 2010,31(8):1054-1060.
8. [8]
  ABELLO M C, GOMEZ M F, FERRETTI O. Mo/g-Al₂O₃ catalysts for the oxidative dehydrogenation of propane[J]. Wien Med Wochenschr, 2001,121(19):398-399.
9. [9]
  ITO T, WANG J, LIN C H, LUNSFORD J H. Oxidative dimerization of methane over a lithium-promoted magnesium oxide catalyst[J]. J Am Chem Soc, 1985,107(18):5062-5068. doi: 10.1021/ja00304a008
10. [10]
  FEI Jin-hua, ZHAO Lei-hong, ZHU Bo, CAI Bing-xin, ZHENG Xiao-ming. Effect of addition of Li⁺ on properties of MgO catalyst[J]. Chem J Chin Univ, 1993,14(2):248-251.
11. [11]
  SINEV M. Y. Elementary steps of radical-surface interactions in oxidative coupling of methane[J]. Catal Today, 1992,13(4):561-564. doi: 10.1016/0920-5861(92)80081-W
12. [12]
  GAAB S, MACHLI M, FIND J, GRASSELLI R K, LERCHER J A. Oxidative dehydrogenation of ethane over novel Li/Dy/Mg mixed oxides:Structure-activity study[J]. Top Catal, 2003,23(1):151-158.
13. [13]
  TRIONFETTI C, BABICH I V, SESHAN K, LEFFERTS L. Presence of lithium ions in MgO lattice:Surface characterization by infrared spectroscopy and reactivity towards oxidative conversion of propane[J]. Langmuir, 2008,24(15):8220-8228. doi: 10.1021/la8006316
14. [14]
  LANDAU M V, KALIYA M L, OOSTERKAMP P F V D, BOCQUE P S G, HERSKOWITZ M. Produce light olefins from paraffins by catalytic oxidation[J]. Chemtech, 1996,26(2).
15. [15]
  TRIONFETTI C, BABICH I V, SESHAN K, LEFFERTS L. Formation of high surface area Li/MgO-Efficient catalyst for the oxidative dehydrogenation/cracking of propane[J]. Appl Catal A:Gen, 2006,310(8):105-113.
16. [16]
  LANDAU M V, KALIYA M L, GUTMAN A, KOGAN L O, HERSKOWITZ M, OOSTERKAMP P F V D. Oxidative conversion of LPG to olefins with mixed oxide catalysts:Surface chemistry and reactions network[J]. Stud Surf Sci Catal, 1997,110(97):315-326.
17. [17]
  TRIONFETTI C, BABICH I V, SESHAN K, LEFFERTS L. Efficient catalysts for olefins from alkanes:Sol-gel synthesis of high surface area nano scale mixed oxide clusters[J]. Top Catal, 2006,39(3/4):191-198.
18. [18]
  TRIONFETTI C, CRAPANZANO S, BABICH I V, SESHAN K, LEFFERTS L. Lithium ions incorporation in MgO for oxidative dehydrogenation/cracking of propane:Active site characterization and mechanism of regeneration[J]. Catal Today, 2009,145(1/2):19-26.
19. [19]
  LEVELES L, SESHAN K, LERCHER J A, LEFFERTS L. Oxidative conversion of propane over lithium-promoted magnesia catalyst:Ⅱ. Active site characterization and hydrocarbon activation[J]. J Catal, 2003,218(2):307-314. doi: 10.1016/S0021-9517(03)00113-1
20. [20]
  CAI Bing-xin, ZHENG Xiao-ming. Studies on oxidative dehydrogenation of ethane to ethylene (Ⅱ)--The mechanism of catalytic action[J]. Chem J Chin Univ, 1995,16(6):929-932.
21. [21]
  CAI Bing-xin, MAO Jian-xin, ZHENG Xiao-ming. The effect of soaker on surface properties of magnesium oxide[J]. Chin J Catal, 1998,19(2):177-180.
22. [22]
  WANG J X, LUNSFORD J H. Characterization of (LiO/sup -/) centers in lithium-doped MgO catalysts[J]. J Phys Chem; (United States), 1986,90(22):5883-5887.
23. [23]
  LEVELES L, SESHAN K, LERCHER J A, LEFFERTS L. Oxidative conversion of propane over lithium-promoted magnesia catalyst:Ⅰ. Kinetics and mechanism[J]. J Catal, 2003,28(2):296-306.
24. [24]
  TRIONFETTI C, AĞIRAL A, LEFFERTS L, SESHAN K. Oxidative conversion of propane in a microreactor in the presence of plasma over MgO-based catalysts:An experimental study[J]. J Phys Chem C, 2008,112(11):4267-4274. doi: 10.1021/jp710642c
25. [25]
  ZHU Hong-juan. The investigation on the oxidative dehydrogenation of propane to propylene[D]. Dalian:Dalian Institute of Chemical Physics, Chinese Academy of Science, 2002.
26. [26]
  GUCZI L. Mechanism of reactions on multimetallic catalysts[J]. J Mol Catal, 1984,25(1/3):13-29.
1. [1]
  Danqing Wu , Jiajun Liu , Tianyu Li , Dazhen Xu , Zhiwei Miao . Research Progress on the Simultaneous Construction of C—O and C—X Bonds via 1,2-Difunctionalization of Olefins through Radical Pathways. University Chemistry, 2024, 39(11): 146-157. doi: 10.12461/PKU.DXHX202403087
2. [2]
  Weihan Zhang , Menglu Wang , Ankang Jia , Wei Deng , Shuxing Bai . 表面硫物种对钯-硫纳米片加氢性能的影响. Acta Physico-Chimica Sinica, 2024, 40(11): 2309043-. doi: 10.3866/PKU.WHXB202309043
3. [3]
  Pei Li , Yuenan Zheng , Zhankai Liu , An-Hui Lu . Boron-Containing MFI Zeolite: Microstructure Control and Its Performance of Propane Oxidative Dehydrogenation. Acta Physico-Chimica Sinica, 2025, 41(4): 100034-. doi: 10.3866/PKU.WHXB202406012
4. [4]
  Xuejie Gao , Xinyang Chen , Ming Jiang , Hanyan Wu , Wenfeng Ren , Xiaofei Yang , Runcang Sun . Long-lifespan thin Li anode achieved by dead Li rejuvenation and Li dendrite suppression for all-solid-state lithium batteries. Chinese Chemical Letters, 2024, 35(10): 109448-. doi: 10.1016/j.cclet.2023.109448
5. [5]
  Yongjian Li , Xinyu Zhu , Chenxi Wei , Youyou Fang , Xinyu Wang , Yizhi Zhai , Wenlong Kang , Lai Chen , Duanyun Cao , Meng Wang , Yun Lu , Qing Huang , Yuefeng Su , Hong Yuan , Ning Li , Feng Wu . Unraveling the chemical and structural evolution of novel Li-rich layered/rocksalt intergrown cathode for Li-ion batteries. Chinese Chemical Letters, 2024, 35(12): 109536-. doi: 10.1016/j.cclet.2024.109536
6. [6]
  Tianyi Hou , Yunhui Huang , Henghui Xu . Interfacial engineering for advanced solid-state Li-metal batteries. Chinese Journal of Structural Chemistry, 2024, 43(7): 100313-100313. doi: 10.1016/j.cjsc.2024.100313
7. [7]
  Zihao Wang , Jing Xue , Zhicui Song , Jianxiong Xing , Aijun Zhou , Jianmin Ma , Jingze Li . Li-Zn alloy patch for defect-free polymer interface film enables excellent protection effect towards stable Li metal anode. Chinese Chemical Letters, 2024, 35(10): 109489-. doi: 10.1016/j.cclet.2024.109489
8. [8]
  Kunyao Peng , Xianbin Wang , Xingbin Yan . Converting LiNO₃ additive to single nitrogenous component Li₂N₂O₂ SEI layer on Li metal anode in carbonate-based electrolyte. Chinese Chemical Letters, 2024, 35(9): 109274-. doi: 10.1016/j.cclet.2023.109274
9. [9]
  Xi Tang , Chunlei Zhu , Yulu Yang , Shihan Qi , Mengqiu Cai , Abdullah N. Alodhayb , Jianmin Ma . Additive regulating Li⁺ solvation structure to construct dual LiF−rich electrode electrolyte interphases for sustaining 4.6 V Li||LiCoO₂ batteries. Chinese Chemical Letters, 2024, 35(12): 110014-. doi: 10.1016/j.cclet.2024.110014
10. [10]
  Yue Wang , Caixia Xu , Xingtao Tian , Siyu Wang , Yan Zhao . Challenges and Modification Strategies of High-Voltage Cathode Materials for Li-ion Batteries. Chinese Journal of Structural Chemistry, 2023, 42(10): 100167-100167. doi: 10.1016/j.cjsc.2023.100167
11. [11]
  Zizhuo Liang , Fuming Du , Ning Zhao , Xiangxin Guo . Revealing the reason for the unsuccessful fabrication of Li3Zr2Si2PO12 by solid state reaction. Chinese Journal of Structural Chemistry, 2023, 42(11): 100108-100108. doi: 10.1016/j.cjsc.2023.100108
12. [12]
  Qingyan JIANG , Yanyong SHA , Chen CHEN , Xiaojuan CHEN , Wenlong LIU , Hao HUANG , Hongjiang LIU , Qi LIU . Constructing a one-dimensional Cu-coordination polymer-based cathode material for Li-ion batteries. Chinese Journal of Inorganic Chemistry, 2024, 40(4): 657-668. doi: 10.11862/CJIC.20240004
13. [13]
  Zhenqiang Guo , Huicong Yang , Qian Wei , Shengjun Xu , Guangjian Hu , Shuo Bai , Feng Li . Dual-additives enable stable electrode-electrolyte interfaces for long life Li-SPAN batteries. Chinese Chemical Letters, 2024, 35(5): 108622-. doi: 10.1016/j.cclet.2023.108622
14. [14]
  Peng Jia , Yunna Guo , Dongliang Chen , Xuedong Zhang , Jingming Yao , Jianguo Lu , Liqiang Zhang . In-situ imaging electrocatalysis in a solid-state Li-O₂ battery with CuSe nanosheets as air cathode. Chinese Chemical Letters, 2024, 35(5): 108624-. doi: 10.1016/j.cclet.2023.108624
15. [15]
  Yu ZHANG , Fangfang ZHAO , Cong PAN , Peng WANG , Liangming WEI . Application of double-side modified separator with hollow carbon material in high-performance Li-S battery. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1218-1232. doi: 10.11862/CJIC.20230412
16. [16]
  Long Li , Kang Yang , Chenpeng Xi , Mengchao Li , Borong Li , Gui Xu , Yuanbin Xiao , Xiancai Cui , Zhiliang Liu , Lingyun Li , Yan Yu , Chengkai Yang . Highly-chlorinated inert and robust interphase without mineralization of oxide enhancing high-rate Li metal batteries. Chinese Chemical Letters, 2024, 35(6): 108814-. doi: 10.1016/j.cclet.2023.108814
17. [17]
  Cuiwu MO , Gangmin ZHANG , Chao WU , Zhipeng HUANG , Chi ZHANG . A(NH₂SO₃) (A=Li, Na): Two ultraviolet transparent sulfamates exhibiting second harmonic generation response. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1387-1396. doi: 10.11862/CJIC.20240045
18. [18]
  Miaomiao Li , Mengwei Yuan , Xingzi Zheng , Kunyu Han , Genban Sun , Fujun Li , Huifeng Li . Highly polar CoP/Co₂P heterojunction composite as efficient cathode electrocatalyst for Li-air battery. Chinese Chemical Letters, 2024, 35(9): 109265-. doi: 10.1016/j.cclet.2023.109265
19. [19]
  Jianjun Fang , Kunchen Xie , Yongli Song , Kangyi Zhang , Fei Xu , Xiaoze Shi , Ming Ren , Minzhi Zhan , Hai Lin , Luyi Yang , Shunning Li , Feng Pan . Break the capacity limit of Li4Ti5O12 anodes through oxygen vacancy engineering. Chinese Journal of Structural Chemistry, 2025, 44(2): 100504-100504. doi: 10.1016/j.cjsc.2024.100504
20. [20]
  Shuang Ma , Guangying Wan , Zhuoying Yan , Xuecheng Liu , Tiezhu Chen , Xinmin Wang , Jinhang Dai , Juan Lin , Tiefeng Liu , Xingxing Gu . Eco-friendly aqueous binder derived from waste ramie for high-performance Li-S battery. Chinese Chemical Letters, 2025, 36(5): 109853-. doi: 10.1016/j.cclet.2024.109853

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(1577)
HTML views(53)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142