Citation: FU Jin-song, LIANG Wu-yang, LEI Qian, SUN Bing, CHEN Hong-lin, ZHANG Xiao-ming. Enhancement of the activity and stability of Au/TS-1 catalyst in the gas-phase epoxidation of propene through alkali carbonate modification[J]. Journal of Fuel Chemistry and Technology, ;2020, 48(10): 1256-1262. shu

Enhancement of the activity and stability of Au/TS-1 catalyst in the gas-phase epoxidation of propene through alkali carbonate modification

FU Jin-song ^1,2,3 ,
LIANG Wu-yang ^1,2 ,
LEI Qian ¹ ,
SUN Bing ⁴ ,
CHEN Hong-lin ¹ ,
ZHANG Xiao-ming ^1,,

1.
Chengdu Institute of Organic Chemistry, Chinese Academy of Sciences, Chengdu 610041, China
2.
University of Chinese Academy of Sciences, Beijing 100049, China
3.
College of Chemistry and Materials Science, Sichuan Normal University, Chengdu 610068, China
4.
Sinopec Research Institute of Safety Engineering, Qingdao 266000, China

Corresponding author: ZHANG Xiao-ming, xm.zhang@cioc.ac.cn
Received Date: 8 June 2020
Revised Date: 8 July 2020

Fund Project: The National Natural Science Foundation of China 21606258The project was supported by the National Natural Science Foundation of China (21606258)

Figures(5)

A serious of robust Au/TS-1 catalysts were prepared by modifying with various alkali carbonates including Na₂CO₃, K₂CO₃, Rb₂CO₃ and Cs₂CO₃ via the ultrasonic impregnation. The alkali carbonate-modified Au/TS-1 catalysts were characterized by XRD, ICP, XPS, UV-vis, FT-IR, NH₃-TPD and HAADF-STEM and their catalytic activity and stability in the gas-phase epoxidation of propene were investigated in a fixed-bed reactor in the presence of H₂ and O₂. The results indicate that the modification with alkali carbonates can decrease the surface acidity and inhibit the aggregation of Au particles; moreover, Rb₂CO₃ and Cs₂CO₃ can even reduce the content of extra-framework Ti in Rb-Au/TS-1 and Ce-Au/TS-1. The catalytic activity and stability of Au/TS-1 in the gas-phase epoxidation of propene are significantly improved after the modification with alkali carbonates. In particular, Cs₂CO₃-modified Cs-Au/TS-1 catalyst exhibits the best performance, with a propene conversion of 6.2%, selectivity of 86.2% to propene oxide (PO) and H₂ utilization efficiency of 26.2%. The results suggest that alkali carbonate modification could be a novel strategy to enhance the catalytic activity and stability of Au/TS-1 in propene epoxidation.
- alkali carbonate,
- Au/TS-1,
- propene epoxidation,
- ultrasonic impregnation,
- activity and stability
1. [1]
  HONG Y, KE L, LI Z, HUANG J, ZHAN G, ZHOU Y, SUN D, ZHANG J, LI Q. Seed-induced zeolitic TS-1 immobilized with bioinspired-Au nanoparticles for propylene epoxidation with O₂ and H₂[J]. Catal Lett, 2020,150(6):1798-1811. doi: 10.1007/s10562-019-03086-x
2. [2]
  YAN Feng. The production technique and research progress of propylene oxide production by chlorohydrination method[J]. Acetaldehyde Acetic Acid Chem Ind, 2016,9:11-13+23.
3. [3]
  LIU Yu. A preliminary study on the developing of propylene oxide production process[J]. Chem Eng Des Commun, 2018,44(7)156.
4. [4]
  SONG Zhao-ning, FENG Xiang, LIU Yi-bin, YANG Chao-he, ZHOU Xing-gui. Advance in manipulation of catalyst structure and relationship of structure performance for direct propene epoxidation with H₂ and O₂[J]. Prog Chem, 2016,28(12):1762-1773.
5. [5]
  PANG Yi-jun, CHEN Xiao-hui, XU Cheng-zhi, LEI Yang-jun, WEI Ke-mei. Metal catalysts and reaction mechanisms in propylene epoxidation in gas phase by molecular oxygen[J]. Prog Chem, 2014,26(8):1307-1316.
6. [6]
  LI Z, GAO L, MA W, ZHONG Q. Higher gold atom efficiency over Au-Pd/TS-1 alloy catalysts for the direct propylene epoxidation with H₂ and O₂[J]. Appl Surf Sci, 2019,497.
7. [7]
  LI N, CHEN Y, SHEN Q, YANG B, LIU M, WEI L, TIAN W, ZHOU J. TS-1 supported highly dispersed sub-5 nm gold nanoparticles toward direct propylene epoxidation using H₂ and O₂[J]. J Solid State Chem, 2018,261:92-102. doi: 10.1016/j.jssc.2018.02.016
8. [8]
  FENG X, SHENG N, LIU Y, CHEN X, CHEN D, YANG C, ZHOU X. Simultaneously enhanced stability and selectivity for propene epoxidation with H₂ and O₂ on Au catalysts supported on nano-crystalline mesoporous TS-1[J]. Acs Catal, 2017,7(4):2668-2675. doi: 10.1021/acscatal.6b03498
9. [9]
  YUAN T, ZHU Q, GAO L, GAO J, MA W. The nitriding of titanium silicate-1 and its effect on gas-phase epoxidation of propylene[J]. J Mater Sci, 2020,55(9):3803-3811. doi: 10.1007/s10853-019-04166-4
10. [10]
  LIU Y W, ZHANG X M, SUO J S. Gold supported on nitrogen-incorporated TS-1 for gas-phase epoxidation of propylene[J]. Chin J Catal, 2013,34(2):336-340. doi: 10.1016/S1872-2067(11)60474-9
11. [11]
  CHOWDHITRY B, BRAVO-SUAREZ J J, DATE M, TSUBOTA S, HARUTA M. Trimethylamine as a gas-phase promoter:Highly efficient epoxidation of propylene over supported gold catalysts[J]. Angew Chem Int Ed, 2006,45(3):412-415. doi: 10.1002/anie.200502382
12. [12]
  HUANG Jia-hui, REN Yue-gong. Preparation and application of catalyst which used in gas phase epoxidation of propene to propene oxide by a gas assistant: CN, 109926098 A[P]. 2018-01-30.
13. [13]
  SONG Wan-cang, XIONG Guang, ZANG Jia-zhong, YU Hai-bin, WANG Xiang-sheng. Effect of basic additive in feedstock on propylene epoxidation catalyzed by TS-1/H₂O₂[J]. Chem Ind Eng Prog, 2020,39(3):1021-1028.
14. [14]
  KHOMANE R B, KULKARNI B D, PARASKAR A, SAINKAR S R. Synthesis, characterization and catalytic performance of titanium silicalite-1 prepared in micellar media[J]. Mater Chem Phys, 2002,76(1):99-103.
15. [15]
  LEE W-S, AKATAY M C, STACH E A, RIBEIRO H, DELGASS N. Enhanced reaction rate for gas-phase epoxidation of propylene using H₂ and O₂ by Cs promotion of Au/TS-1[J]. J Catal, 2013,308:98-113. doi: 10.1016/j.jcat.2013.05.023
16. [16]
  LI Z, MA W, ZHONG Q. Effect of core-shell support on Au/S-1/TS-1 for direct propylene epoxidation and design of catalyst with higher activity[J]. Ind Eng Chem Res, 2019,58(10):4010-4016. doi: 10.1021/acs.iecr.8b04662
17. [17]
  LI Z, GAO L, ZHU X, MA W, FENG X, ZHONG Q. Synergistic Enhancement over Au-Pd/TS-1 bimetallic catalysts for propylene epoxidation with H₂ and O₂[J]. ChemCatChem, 2019,11(20):5116-5123. doi: 10.1002/cctc.201900845
18. [18]
  SONG Z, FENG X, SHENG N, LIN D, LI Y, LIU Y, CHEN X, CHEN D, ZHOU X, YANG C. Cost-efficient core-shell TS-1/silicalite-1 supported Au catalysts:Towards enhanced stability for propene epoxidation with H₂ and O₂[J]. Chem Eng J, 2019,377.
19. [19]
  SHAM T K, LAZARUS M S. X-ray photoelectron-spectroscopy (XPS) studies of clean and hydrated TiO₂(rutile) surfaces[J]. Chem Phys Lett, 1979,68(2/3):426-432.
20. [20]
  ARILLO M A, LOPEZ M L, PICO C, VEIGA M L, JIMENEZ-LOPEZ A, RODRIGUEZ-CASTELLON E. Surface characterisation of spinels with Ti(IV) distributed in tetrahedral and octahedral sites[J]. J Alloys Compd, 2001,317:160-163.
21. [21]
  FU J, ZHANG X, LIANG W, LEI Q, SUN B, HE W, DENG G. Direct gas-phase oxidation of propylene to acetone in the presence of H₂ and O₂ over Au/TS-1 catalyst[J]. Curr Org Synth, 2020. doi: 10.2174/1570179417666200615154837
22. [22]
  SHENG N, LIU Z, SONG Z, LIN D, FENG X, LIU Y, CHEN X, CHEN D, ZHOU X, YANG C. Enhanced stability for propene epoxidation with H₂ and O₂ over wormhole-like hierarchical TS-1 supported Au nanocatalyst[J]. Chem Eng J, 2019,377.
23. [23]
  REN Y, HUANG J, LV Q, XIE Y, LU A, HARUTA M. Dual-Component Sodium and Cesium Promoters for Au/TS-1:Enhancement of Propene Epoxidation with Hydrogen and Oxygen[J]. Ind Eng Chem Res, 2020,59(17):8155-8163. doi: 10.1021/acs.iecr.9b07011
24. [24]
  LEE W-S, AKATAY M C, STACH E A, RIBEIRO H, DELGASS W N. Gas-phase epoxidation of propylene in the presence of H₂ and O₂ over small gold ensembles in uncalcined TS-1[J]. J Catal, 2014,313:104-112. doi: 10.1016/j.jcat.2014.02.013
25. [25]
  FENG X, DUAN X, QIAN G, ZHOU X, CHEN D, YUAN W. Insights into size-dependent activity and active sites of Au nanoparticles supported on TS-1 for propene epoxidation with H₂ and O₂[J]. J Catal, 2014,317:99-104. doi: 10.1016/j.jcat.2014.05.006
26. [26]
  HONG Y, HUANG J, ZHAN G, LI Q. Biomass-Modified Au/TS-1 as Highly Efficient and Stable Nanocatalysts for Propene Epoxidation with O₂ and H₂[J]. Ind Eng Chem Res, 2019,58(48):21953-21960. doi: 10.1021/acs.iecr.9b04107
27. [27]
  MUL G, ZWIJNENBURG A, Van Der LINDEN B, MAKKEE M, MOULIJN J A. Stability and selectivity of Au/TiO₂ and Au/TiO₂/SiO₂ catalysts in propene epoxidation:An in situ FT-IR study[J]. J Catal, 2001,201(1):128-137. doi: 10.1006/jcat.2001.3239
28. [28]
  LU J, ZHANG X, BRAVO-SUAREZ J J, FUJITANI T, OYAMA S T. Effect of composition and promoters in Au/TS-1 catalysts for direct propylene epoxidation using H₂ and O₂[J]. Catal Today, 2009,147(3/4):186-195.
29. [29]
  LI Z, WANG Y, ZHANG J, WANG D, MA W. Better performance for gas-phase epoxidation of propylene using H₂ and O₂ at lower temperature over Au/TS-1 catalyst[J]. Catal Commun, 2017,90:87-90. doi: 10.1016/j.catcom.2016.12.002
30. [30]
  RUIZ A, VAN DER LINDEN B, MAKKEE M, MUL G. Acrylate and propoxy-groups:Contributors to deactivation of Au/TiO₂ in the epoxidation of propene[J]. J Catal, 2009,266(2):286-290. doi: 10.1016/j.jcat.2009.06.019
31. [31]
  QI C, HUANG J, BAO S, SU H, AKITA T, HARUTA M. Switching of reactions between hydrogenation and epoxidation of propene over Au/Ti-based oxides in the presence of H₂ and O₂[J]. J Catal, 2011,281(1):12-20.
32. [32]
  YAO S N, XU L H, WANG J, JING X L, ODOOM-WUBAH T, SUN D D, HUANG J L, LI Q B. Activity and stability of titanosilicate supported Au catalyst for propylene epoxidation with H₂ and O₂[J]. Mol Catal, 2018,448:144-152. doi: 10.1016/j.mcat.2018.01.039
33. [33]
  HUYBRECHTS D R C, VAESEN I, LI H X, JACOBS P A. Factors influencing the catalytic activity of titaniumsilicalites in selective oxidations[J]. Catal Lett, 1991,8(2/4):237-244.
34. [34]
  LIU C, HUANG J, SUN D, ZHOU Y, JING X, DU M, WANG H, LI Q. Anatase type extra-framework titanium in TS-1:A vital factor influencing the catalytic activity toward styrene epoxidation[J]. Appl Catal A:Gen, 2013,459:1-7. doi: 10.1016/j.apcata.2013.03.013
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