Reaction Kinetics, Mechanisms and Catalysis

, Volume 125, Issue 1, pp 111–126 | Cite as

Effect of citric acid on CoO–MoO3/Al2O3 catalysts for sulfur-resistant methanation

  • Baowei Wang
  • Wenxia Yu
  • Dajun Meng
  • Zhenhua Li
  • Yan Xu
  • Xinbin Ma


CoO–MoO3/Al2O3 catalysts with different contents of citric acid were prepared by the simultaneous impregnation method and were tested for sulfur-resistant methanation. The catalysts were characterized with N2-physisorption, XRD, scanning electron microscopy (SEM), H2-TPR, Raman spectroscopy, ultraviolet–visible spectroscopy, and XPS. The N2-physisorption and SEM results indicated that the addition of citric acid could increase the BET surface area and the amount of smaller particles in catalysts, improving the monolayer loading capacity. It would result in the better dispersion of metal active components (Co, Mo species). The combined results of various characterization suggested that the addition of citric acid could avoid the formation of crystalline CoMoO4 while the Mo–CA complex was found in the Raman spectrum. As the mole ratio of n(CA)/n(Mo) increased up to 2.0, the catalysts showed the highest activity in sulfur-resistant methanation as there were the most MoS2 on the surface of Al2O3 supports according to the results of XPS.


Citric acid Sulfur-resistant Methanation Co–Mo catalysts Synthetic nature gas 



Financial supports from the National High Technology Research and Development Program of China (863 Project) (2015AA050504) is gratefully acknowledged.


  1. 1.
    Chen M, Zhou JZ, Zhang J et al (2017) Ferrite catalysts derived from electroplating sludge for high-calorie synthetic natural gas production. Appl Catal A 534:94–100CrossRefGoogle Scholar
  2. 2.
    Cai MD, Wen J, Chu W et al (2011) Methanation of carbon dioxide on Ni/ZrO2-Al2O3 catalysts: effects of ZrO2 promoter and preparation method of novel ZrO2-Al2O3 carrier. J Nat Gas Chem 20:318–324CrossRefGoogle Scholar
  3. 3.
    Miao B, Ma SSK, Wang X et al (2016) Catalysis mechanisms of CO2 and CO methanation. Catal Sci Technol 6:4048–4058CrossRefGoogle Scholar
  4. 4.
    Li J, Zhou L, Zhu Q et al (2015) CO methanation over a macro–mesoporous Al2O3 supported Ni catalyst in a fluidized bed reactor. RSC Adv 5:64486–64494CrossRefGoogle Scholar
  5. 5.
    Gao J, Liu Q, Gu F et al (2015) Recent advances in methanation catalysts for the production of synthetic natural gas. RSC Adv 5:22759–22776CrossRefGoogle Scholar
  6. 6.
    Liu J, Wang ED, Lv J et al (2013) Investigation of sulfur-resistant, highly active unsupported MoS2 catalysts for synthetic natural gas production from CO methanation. Fuel Process Technol 110:249–257CrossRefGoogle Scholar
  7. 7.
    Jiang MH, Wang BW, Yao YQ et al (2013) A comparative study of CeO2-Al2O3 support prepared with different methods and its application on MoO3/CeO2-Al2O3 catalyst for sulfur-resistant methanation. Appl Surf Sci 285:267–277CrossRefGoogle Scholar
  8. 8.
    Wang HY, Lin C, Li ZH et al (2015) Influence of water on the methanation performance of Mo-based sulfur- resistant catalysts with and without cobalt additive. Bull Korean Chem Soc 36:74–82CrossRefGoogle Scholar
  9. 9.
    Meng DJ, Wang BW, Yu WX et al (2017) Effect of citric acid on MoO3/Al2O3 catalysts for sulfur-resistant methanation. Catalysts 7:151–162CrossRefGoogle Scholar
  10. 10.
    Jiang MH, Wang BW, Yao YQ et al (2013) Effect of sulfidation temperature on CoO-MoO3/gamma-Al2O3 catalyst for sulfur-resistant methanation. Catal Sci Technol 3:2793–2800CrossRefGoogle Scholar
  11. 11.
    Wang BW, Ding GZ, Shang YG et al (2012) Effects of MoO3 loading and calcination temperature on the activity of the sulphur-resistant methanation catalyst MoO3/γ-Al2O3. Appl Catal A 431–432:144–150CrossRefGoogle Scholar
  12. 12.
    Valencia D, Klimova T (2013) Citric acid loading for MoS2-based catalysts supported on SBA-15 New catalytic materials with high hydrogenolysis ability in hydrodesulfurization. Appl Catal B 129:137–145CrossRefGoogle Scholar
  13. 13.
    Calderón-Magdaleno MÁ, Mendoza-Nieto JA, Klimova TE (2014) Effect of the amount of citric acid used in the preparation of NiMo/SBA-15 catalysts on their performance in HDS of dibenzothiophene-type compounds. Catal Today 220–222:78–88CrossRefGoogle Scholar
  14. 14.
    Pena L, Valencia D, Klimova T (2014) CoMo/SBA-15 catalysts prepared with EDTA and citric acid and their performance in hydrodesulfurization of dibenzothiophene. Appl Catal B 147:879–887CrossRefGoogle Scholar
  15. 15.
    Klimov OV, Pashigreva AV, Bukhtiyarova GA et al (2010) Bimetallic Co–Mo complexes: a starting material for high active hydrodesulfurization catalysts. Catal Today 150:196–206CrossRefGoogle Scholar
  16. 16.
    Klimov OV, Pashigreva AV, Fedotov MA et al (2010) Co–Mo catalysts for ultra-deep HDS of diesel fuels prepared via synthesis of bimetallic surface compounds. J Mol Catal A: Chem 322:80–89CrossRefGoogle Scholar
  17. 17.
    Tao M, Xin Z, Meng X et al (2017) Highly dispersed nickel within mesochannels of SBA-15 for CO methanation with enhanced activity and excellent thermostability. Fuel 188:267–276CrossRefGoogle Scholar
  18. 18.
    Rinaldi N, Kubota T, Okamoto Y (2009) Effect of citric acid addition on Co − Mo/B2O3/Al2O3 catalysts prepared by a post-treatment method. Ind Eng Chem Res 48:10414–10424CrossRefGoogle Scholar
  19. 19.
    Rinaldi N, Kubota T, Okamoto Y (2010) Effect of citric acid addition on the hydrodesulfurization activity of MoO3/Al2O3 catalysts. Appl Catal A 374:228–236CrossRefGoogle Scholar
  20. 20.
    Fujikawa T, Kimura H, Kiriyama K et al (2006) Development of ultra-deep HDS catalyst for production of clean diesel fuels. Catal Today 111:188–193CrossRefGoogle Scholar
  21. 21.
    Wang BW, Yao YQ, Jiang MH et al (2014) Effect of cobalt and its adding sequence on the catalytic performance of MoO3/Al2O3 toward sulfur-resistant methanation. J Energy Chem 23:35–42CrossRefGoogle Scholar
  22. 22.
    Wang BW, Meng DJ, Wang WH et al (2016) Effect of citric acid addition on the MoO3/CeO2-Al2O3 catalyst for sulfur-resistant methanation. J Fuel Chem Technol 44:1479–1484CrossRefGoogle Scholar
  23. 23.
    Wang BW, Liu SH, Hu ZY et al (2014) Active phase of highly active Co3O4 catalyst for synthetic natural gas production. RSC Adv 4:57185–57191CrossRefGoogle Scholar
  24. 24.
    Shirai H, Morioka Y, Nakagawa I (1982) Infrared and Raman spectra and lattice vibrations of some oxide spinels. J Phys Soc Jpn 51:592–597CrossRefGoogle Scholar
  25. 25.
    Díaz-García L, Santes V, Viveros-García T et al (2017) Electronic binding of sulfur sites into Al2O3-ZrO2 supports for NiMoS configuration and their application for hydrodesulfurization. Catal Today 282:230–239CrossRefGoogle Scholar
  26. 26.
    Qiu L, Xu G (2010) Peak overlaps and corresponding solutions in the X-ray photoelectron spectroscopic study of hydrodesulfurization catalysts. Appl Surf Sci 256:3413–3417CrossRefGoogle Scholar
  27. 27.
    Ge H, Li XK, Wang JG et al (2008) Activation and hydrodesulfurization activity of MoO3/Al2O3 catalyst presulfided by ammonium thiosulfate. Chin J Catal 29:921–927CrossRefGoogle Scholar
  28. 28.
    Bian ZC, Xin Z, Meng X et al (2017) Effect of citric acid on the synthesis of CO methanation catalysts with high activity and excellent stability. Ind Eng Chem Res 56:2383–2392CrossRefGoogle Scholar
  29. 29.
    Li H, Li M, Chu Y et al (2011) Essential role of citric acid in preparation of efficient NiW/Al2O3 HDS catalysts. Appl Catal A 403:75–82CrossRefGoogle Scholar
  30. 30.
    Vandewater L, Bezemer G, Bergwerff J et al (2006) Spatially resolved UV-vis microspectroscopy on the preparation of alumina-supported Co Fischer-Tropsch catalysts: linking activity to Co distribution and speciation. J Catal 242:287–298CrossRefGoogle Scholar
  31. 31.
    Windisch CF, Exarhos GJ, Owings RR (2004) Vibrational spectroscopic study of the site occupancy distribution of cations in nickel cobalt oxides. J Appl Phys 95:5435–5442CrossRefGoogle Scholar

Copyright information

© Akadémiai Kiadó, Budapest, Hungary 2018

Authors and Affiliations

  • Baowei Wang
    • 1
  • Wenxia Yu
    • 1
  • Dajun Meng
    • 1
  • Zhenhua Li
    • 1
  • Yan Xu
    • 1
  • Xinbin Ma
    • 1
  1. 1.Key Laboratory for Green Chemical Technology of the Ministry of Education, School of Chemical Engineering and TechnologyTianjin UniversityTianjinChina

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