Citation: HUANG Chun-jie, CHEN Shao-yun, FEI Xiao-yao, LIU Dai, CHEN Jian, ZHANG Yong-chun. Preparation of nanometer CuO-ZnO-ZrO₂ catalysts through citrate-gel process and their catalytic properties for methanol synthesis from CO₂[J]. Journal of Fuel Chemistry and Technology, ;2016, 44(3): 375-384. shu

Preparation of nanometer CuO-ZnO-ZrO₂ catalysts through citrate-gel process and their catalytic properties for methanol synthesis from CO₂

State Key Laboratory of Fine Chemistry, Dalian University of Technology, Dalian 116023, China

Corresponding author: ZHANG Yong-chun, zalidy5518@vip.sina.com
Received Date: 20 October 2015
Revised Date: 30 December 2015

Figures(8)

CuO-ZnO-ZrO₂(CZZ) nanocatalysts were successfully prepared by citrate-gel method. The catalysts and their precursors were characterized by X-ray photoelectron spectroscopy (XPS), N₂ adsorption specific surface area measurement (BET), X-ray diffraction (XRD), H₂-temperature-programmed reduction (H₂-TPR), H₂ and CO₂-temperature-programmed desorption (H₂ and CO₂-TPD) and thermogravimetric analysis (TG-DTA). Drying time of the wet gel and the dosage of citric acid were systematicly studied, while combustion method was also conducted with the comparison of those obtained catalysts. Results show that, prolonged drying process can effectively prevent particle spattering during calcination, benefit the dispersion of different components in the catalyst, and improve the adsorption ability of catalyst for H₂ and CO₂. Sample CZZ-48h, which was dried at 112℃, 48h, maintained a much higher BET specific surface area than that prepared by combustion method. The CuO-ZnO-ZrO₂ catalyst, in which 100% of stoichiometric amount of citric acid was added, exhibited an optimum catalytic behavior with a space-time-yield of methanol 109.4g·h^-1·kg^-1 under the condition of 240℃, 2.6 MPa, 3600h^-1, H₂/CO₂=3. The detriment of the catalytic performance excessive amounts of citric acid is ascribed to decline dispersion of the catalyst component, and decomposition residual covering on the surface active species of the catalyst.
- citrate-gel process,
- CuO-ZnO-ZrO₂,
- CO₂ catalytic hydrogenation,
- methanol
1. [1]
  OLAH G A, PRAKASH G K S, GOEPPERT A. Anthropogenic chemical carbon cycle for a sustainable future[J]. J Am Chem Soc, 2011,133(33):12881-12898. doi: 10.1021/ja202642y
2. [2]
  OLAH G A. Towards oil independence through renewable methanol chemistry[J]. AngewChemInt Ed, 2013,52(1):104-107.
3. [3]
  MEITZNER G, IGLESIA E. New insights into methanol synthesis catalysts from X-ray absorption spectroscopy[J]. Catal Today, 1999,53(3):433-441. doi: 10.1016/S0920-5861(99)00135-2
4. [4]
  CONG Yu, BAO Xin-he, ZHANG Tao, SUN Xiao-ying, LIANG Dong-bai, TIAN Jin-zhong, HUANG Ning-biao. TPSR and TPD studies of ultrafine Cu-ZnO-ZrO₂ catalysts for methanol synthesis[J]. J Fuel Chem Technol, 2000,28(3):238-243.
5. [5]
  SUN Q, LIU C W, PAN W, ZHU Q M, DENG J F. In situ IR studies on the mechanism of methanol synthesis over an ultrafine Cu/ZnO/Al₂O₃ catalyst[J]. ApplCatal A: Gen, 1998,171:301-308.
6. [6]
  CONG Yu, TIAN Jin-zhong, HUANG Ning-biao, XU Zhang-hai, ZHANG Tao, SUN Xiao-ying, GUAN Wen, LIANG Dong-bai. Preparation of ultrafine Cu-ZnO-ZrO₂catalysts and CO₂ hydrogenation performance[J]. Chin J Catal, 2000,21(3):247-250.
7. [7]
  ARENA F, BARBERA K, ITALIANO G, BONURAG , SPADARO L, FRUSTERI F. Synthesis, characterization and activity pattern of Cu-ZnO/ZrO₂ catalystsin the hydrogenation of carbon dioxide to methanol[J]. J Catal, 2007,249(2):185-194. doi: 10.1016/j.jcat.2007.04.003
8. [8]
  LI C M, YUAN X D, FUJIMOTO K. Development of highly stable catalyst for methanol synthesis from carbon dioxide[J]. Appl Catal A: Gen, 2014,469:306-311. doi: 10.1016/j.apcata.2013.10.010
9. [9]
  GAO P, LI F, XIAO F K, ZHAO N, WEI W, ZHONG L S, SUN Y H. Effect of hydrotalcite-containing precursors on the performance of Cu/Zn/Al/Zr catalysts for CO₂ hydrogenation: Introduction of Cu²⁺ at different formation stages of precursors[J]. Catal Today, 2012,194(1):9-15. doi: 10.1016/j.cattod.2012.06.012
10. [10]
  YANG R Q, YU X C, ZHANG Y, LI W Z, TSUBAKI N. A new method of low-temperature methanol synthesis on Cu/ZnO/Al₂O₃ catalysts from CO/CO₂/H₂[J]. Fuel, 2008,87(4/5):443-450.
11. [11]
  GUO X M, MAO D S, WANG S, WU G S, LU G Z. Combustion synthesis of CuO-ZnO-ZrO₂ catalysts for the hydrogenation of carbon dioxide to methanol[J]. Catal Commun, 2009,10(13):1661-1664. doi: 10.1016/j.catcom.2009.05.004
12. [12]
  GUO Xiao-ming, MAO Dong-sen, LU Guan-zhong, WANG Song. Preparation of CuO-ZnO-ZrO₂ by citric acid combustion method and its catalytic property for methanol synthesis from CO₂ hydrogenation[J]. Acta Phys-Chem Sin, 2012,28(1):170-176.
13. [13]
  SHI L, YANG R Q, TAO K, YONEYAMA Y, TAN Y S, TSUBAKI N. Surface impregnation combustion method to prepare nanostructured metallic catalysts without further reduction: As-burnt Cu-ZnO/SiO₂ catalyst for low-temperature methanol synthesis[J]. Catal Today, 2012,185(1):54-60. doi: 10.1016/j.cattod.2011.10.015
14. [14]
  ZHU Yi-qing, WEN Yi, LAI Li-fang, ZONG Feng-qi, WANG Jian. Characterization and catalytic activity evaluation of ultrafine CuO/ZnO/TiO₂-SiO₂ catalysts for CO₂ hydrogenation to methanol[J]. J Fuel Chem Technol, 2004,32(4):486-491.
15. [15]
  JUN K W, SHEN W J, RAO KS R, LEE K W. Residual sodium effect on the catalytic activity of Cu/ZnO/Al₂O₃ in methanol synthesis from CO₂ hydrogenation[J]. Appl Catal A: Gen, 1998,174:231-238. doi: 10.1016/S0926-860X(98)00195-1
16. [16]
  KONG Xiu-qin, TANG Xing-jiang, XU Shan, WANG Xiao-lai. Preparation of CuO-ZnO/Al₂O₃ by sol-gel auto-combustion method and its catalytic property for methanol synthesis from CO₂ hydrogenation[J]. J Mol Catal, 2013,27(2):159-165.
17. [17]
  LIN Jian-xin, WANG Zi-qing, ZHANG Liu-ming, NI Jun, WANG Rong, WEI Ke-mei. Ammonia synthesis over ruthenium catalysts using barium-doped zirconia as supports prepared by citric acid method[J]. Chin J Catal, 2012,33(7):1075-1079.
18. [18]
  JING Mao-xiang, SHEN Xiang-qian, SHEN Yu-jun. Preparation of nanometer nickel oxide by the citrate-gel process[J]. J Inorg Mater, 2004,19(2):289-294.
19. [19]
  BONURA G, CORDARO M, CANNILLA C, ARENA F, FRUSTERI F. The changing nature of the active site of Cu-Zn-Zr catalysts for the CO₂ hydrogenation reaction to methanol[J]. Appl Catal B: Environ, 2014,52-153:152-161.
20. [20]
  KARELOVIC A, BARGIBANT A, FERNÁNDEZ C, RUIZ P. Effect of the structural and morphological properties of Cu/ZnO catalysts prepared by citrate method on their activity toward methanol synthesis from CO₂ and H₂ under mild reaction conditions[J]. Catal Today, 2012,197(1):109-118. doi: 10.1016/j.cattod.2012.07.029
21. [21]
  ZHANG Lu-xiang, ZHANG Yong-chun, CHEN Shao-yun. Effect of promoter TiO₂ on the performance of CuO-ZnO-Al₂O₃ catalyst for CO₂ catalytic hydrogenation to methanol[J]. J Fuel Chem Technol, 2011,39(12):912-917. doi: 10.1016/S1872-5813(12)60002-4
22. [22]
  ZHANG Y P, FEI J H, YU Y M, ZHENG X M. Methanol synthesis from CO₂ hydrogenation over Cu based catalyst supported on zirconia modified Al₂O₃[J]. Energy Convers Manage, 2006,47(18/19):3360-3367.
23. [23]
  DONG X, ZHANG H B, LIN G D, YUAN Y Z, TSAI K R. Highly active CNT-promoted Cu-ZnO-Al₂O₃ catalyst for methanol synthesis from H₂/CO/CO₂[J]. Catal Lett, 2003,85(3):237-246.
24. [24]
  LI Ji-tao, ZHANG Wei-de, CHEN Ming-dan, QU Ze-tang. TPD and TPSR study of CO₂ adsorption on Cu-based catalysts[J]. J Nat Gas Chem, 1998,23(5):14-17.
25. [25]
  ARENA F, ITALIANO G, BARBERA K, BORDIGA S, BONURA G, SPADARO L, FRUSTERI F. Solid-state interactions, adsorption sites and functionality of Cu-ZnO/ZrO₂ catalysts in the CO₂ hydrogenation to CH₃OH[J]. Appl Catal A: Gen, 2008,350:16-23. doi: 10.1016/j.apcata.2008.07.028
26. [26]
  ZHUANG Hao-ren, LI Cheng-en, YIN Zhi-wen. Pyrolysis of PLZT citrate precursor[J]. J Inorg Mater, 1988,3(1):27-31.
27. [27]
  SHI L, ZENG C Y, JIN Y Z, WANG T J, TSUBAKI N. A sol-gel auto-combustion method to prepare Cu/ZnO catalysts for low-temperature methanol synthesis[J]. Catal Sci Technol, 2012,2:2569-2577. doi: 10.1039/c2cy20423a
28. [28]
  XU Zheng, MAO Li-qun, QIAN Zai-hu, SHENG Shi-shan, XIONG Guo-xing. Photoelectron spectroscopic study of CuO/ZnO/ZrO₂ catalyst in low pressure methanol synthesis from CO₂ and H₂[J]. J Fuel Chem Technol, 1992,20(3):272-277.
29. [29]
  BIESINGER M C, LAU L W M, GERSON A R, SMART R S C. Resolving surface chemical states in XPS analysis of first row transition metals, oxides and hydroxides: Sc, Ti, V, Cu and Zn[J]. Appl Surf Sci, 2010,257(3):887-898. doi: 10.1016/j.apsusc.2010.07.086
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Preparation of nanometer CuO-ZnO-ZrO2 catalysts through citrate-gel process and their catalytic properties for methanol synthesis from CO2

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Preparation of nanometer CuO-ZnO-ZrO₂ catalysts through citrate-gel process and their catalytic properties for methanol synthesis from CO₂