Citation: ZHANG Fan, FENG Bo, DUAN Xue-lei, LI Jing, CHEN Jing-yun, ZHANG Yu-long, SUN Qi. Effect of aluminum proportion on the Cu/ZnO/Al₂O₃ methanol-synthesis catalyst[J]. Journal of Fuel Chemistry and Technology, ;2019, 47(3): 323-328. shu

Effect of aluminum proportion on the Cu/ZnO/Al₂O₃ methanol-synthesis catalyst

National Institute of Clean-and-Low-Carbon Energy, Beijing 102211, China

Corresponding author: ZHANG Yu-long, zhangyulong@nicenergy.com
Received Date: 21 November 2018
Revised Date: 17 January 2019

Fund Project: The project was supported by the Methanol-synthesis Catalyst Research Project supported by CHN ENERGY group (CF9300162131)The project was supported by the Methanol-synthesis Catalyst Research Project supported by CHN ENERGY group CF9300162131

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The objective of this work is to investigate the effect of Al contents on the performance of methanol-synthesis catalysts. A series of catalyst samples with various Al contents were prepared with fractional precipitation method, and characterized with methods including XRD, TG-MS, XRF, N₂ physisorption and H₂-TPR. Results show that Al addition affected the subcarbonate structure in precursors, which promoted the formation of high temperature carbonates, and thus has an effect on the catalyst performance. With Al addition, the BET surface area of the calcined catalysts, catalyst activity and thermostability increased to different degrees. When the molar ratio of Al³⁺ in catalyst increased to 30%, the CO conversions before and after heat treatment were 76% and 67%, respectively, at the conditions of 230 ℃, 4 MPa and syngas composition of 13%CO, 1.2%CO₂, 80%H₂ and 5.8%Ar. The catalyst sample with 0.3 of Al³⁺/(Cu²⁺+Zn²⁺+Al³⁺) molar ratio remains good catalyst performance.
- Al contents,
- high temperature carbonates,
- thermostability,
- malachite decomposition
1. [1]
  XU X, LIU Y, ZHANG F, DI W, ZHANG Y L. Clean coal technologies in China based on methanol platform[J]. Catal Today, 2017,298:61-68. doi: 10.1016/j.cattod.2017.05.070
2. [2]
  ZHANG F, FAN M, HUANG X, ARGYLE M, ZHANG B, TOWLER B, ZHANG Y L. Catalytic gasification of a Powder River Basin coal with CO₂ and H₂O mixtures[J]. Fuel Process Technol, 2017,161:145-154. doi: 10.1016/j.fuproc.2017.03.010
3. [3]
  XIA Wang-xiong, TANG Hao-dong, LIN Sheng-da, CEN Ya-qing, LIU Hua-zhang. Phase transformation of Cu/ZnO catalyst precursors for methanol synthesis[J]. Chin J Catal, 2009,30(9):879-884. doi: 10.3321/j.issn:0253-9837.2009.09.006
4. [4]
  LIU Yan-xia, WANG Li-li, WANG Qi, CHEN Ai-ping, HOU Gong-huai, YANG Yi-quan. The promoting effect of γ-Al₂O₃ on copper-based catalysts for methanol synthesis[J]. J Xiamen Univ, Nat Sci, 2007,46(5):661-664. doi: 10.3321/j.issn:0438-0479.2007.05.016
5. [5]
  BEHRENS M. Meso-and nano-structuring of industrial Cu/ZnO/(Al₂O₃) catalysts[J]. J Catal, 2009,267(1):24-29. doi: 10.1016/j.jcat.2009.07.009
6. [6]
  BEHRENS M. Coprecipitation:An excellent tool for the synthesis of supported metal catalysts-From the understanding of the well known recipes to new materials[J]. Catal Today, 2015,246:46-54. doi: 10.1016/j.cattod.2014.07.050
7. [7]
  LIN Sheng-da, TANG Hao-dong, LV Zhao-bo, LIU Cai-lai, CEN Ya-qing, LIU Hua-zhang. Influence of precipitation methods on precursors and properties of Cu-based catalyst for methanol synthesis[J]. Chin J Catal, 2010,31(10):1257-1262.
8. [8]
  BALTES C, VUKOJEVI ĆS, SCHÜTH F. Correlations between synthesis, precursor, and catalyst structure and activity of a large set of CuO/ZnO/Al₂O₃ catalysts for methanol synthesis[J]. J Catal, 2008,258(2):334-344. doi: 10.1016/j.jcat.2008.07.004
9. [9]
  BEHRENS M, ZANDER S, KURR P, JACOBSEN N, SENKER J, KOCH G, RESSLER T, FISCHER R, SCHLOGL R. Performance improvement of nanocatalysts by promoter-induced defects in the support material:Methanol synthesis over Cu/ZnO:Al[J]. J Am Chem Soc, 2013,135(16):6061-6068. doi: 10.1021/ja310456f
10. [10]
  LI Zhong, GUO Qi-hai, ZHANG Xiao-bing, ZHENG Hua-yan, FAN Hui, XIE Ke-chang. Influence of the precursor phase transition on the catalyst activity in slurry methanol synthesis[J]. Chem J Chin Univ, 2009,30:2215-2221. doi: 10.3321/j.issn:0251-0790.2009.11.023
11. [11]
  BEHRENS M, KASATKIN I, KÜHL S. Phase-pure Cu, Zn, Al hydrotalcite-like materials as precursors for copper rich Cu/ZnO/Al₂O₃ catalysts[J]. Chem Mater, 2010,22(2):386-397. doi: 10.1021/cm9029165
12. [12]
  BAHMANI M, VASHEGHANI FARAHANI B, SAHEBDELFAR S. Preparation of high performance nano-sized Cu/ZnO/Al₂O₃ methanol synthesis catalyst via aluminum hydrous oxide sol[J]. Appl Catal A:Gen, 2016,520:178-187. doi: 10.1016/j.apcata.2016.04.018
13. [13]
  CHU Z, CHEN H, YU Y, WANG Q, FANG D Y. Surfactant-assisted preparation of Cu/ZnO/Al₂O₃ catalyst for methanol synthesis from syngas[J]. J Mol Catal A:Chem, 2013,366:48-53. doi: 10.1016/j.molcata.2012.09.007
14. [14]
  LI Zhong, ZHANG Xiao-bing, GUO Qi-hai, LIU Yan, ZHENG Hua-yan. Influence of precipitation and aging temperature on the performance of CuO/ZnO/Al₂O₃ catalyst for methanol synthesis in slurry reactor[J]. J Fuel Chem Technol, 2012,40(5):569-575. doi: 10.3969/j.issn.0253-2409.2012.05.010
15. [15]
  SCHUMANN J, TARASOV A, THOMAS N, SCHLOGL R, BEHRENS M. Cu, Zn-based catalysts for methanol synthesis:On the effect of calcination conditions and the part of residual carbonates[J]. Appl Catal A:Gen, 2016,516:117-126. doi: 10.1016/j.apcata.2016.01.037
16. [16]
  ZHANG F, ZHANG Y L, LIU Y, GASEM K, CHEN J Y, CHIANG F G, WANG Y G, FAN M. Synthesis of Cu/Zn/Al/Mg catalysts on methanol production by different precipitation methods[J]. Mol Catal, 2017,441:190-198. doi: 10.1016/j.mcat.2017.08.015
17. [17]
  MILLAR G J, HOLM I H, UWINS P J R, DRENNAN J. Characterization of precursors to methanol synthesis catalysts Cu/ZnO system[J]. J Chem Soc Faraday Trans, 1998,94(4):593-600. doi: 10.1039/a703954i
18. [18]
  BEMS B, SCHUR M, DASSENOY A, JUNKES H, HEREIN D, SCHLOGL R. Relations between synthesis and microstructural properties of copper/zinc hydroxycarbonates[J]. Chem-Eur J, 2003,9(9):2039-2052. doi: 10.1002/chem.200204122
19. [19]
  GAO P, LI F, ZHAN H, ZHAO N, XIAO F, WEI W, ZHONG L, WANG H, SUN Y H. Influence of Zr on the performance of Cu/Zn/Al/Zr catalysts via hydrotalcite-like precursors for CO₂ hydrogenation to methanol[J]. J Catal, 2013,298:51-60. doi: 10.1016/j.jcat.2012.10.030
20. [20]
  KÜHL S, TARASOV A, ZANDER S, KASATKIN I, BEHRENS M. Cu-based catalyst resulting from a Cu, Zn, Al hydrotalcite-like compound:A microstructural, thermoanalytical, and in-situ XAS study[J]. Chem-Eur J, 2014,20(13):3782-3792. doi: 10.1002/chem.v20.13
21. [21]
  BEHRENS M. Promoting the synthesis of methanol:Understanding the requirements for an industrial catalyst for the conversion of CO₂[J]. Angew Chem Int Ed, 2016,55(48):14906-14908. doi: 10.1002/anie.201607600
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Effect of aluminum proportion on the Cu/ZnO/Al2O3 methanol-synthesis catalyst

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Effect of aluminum proportion on the Cu/ZnO/Al₂O₃ methanol-synthesis catalyst