Rare Metals

, Volume 38, Issue 1, pp 1–13 | Cite as

Recovery and regeneration of Al2O3 with a high specific surface area from spent hydrodesulfurization catalyst CoMo/Al2O3

  • Qi Liu
  • Wen-Qiang Wang
  • Yue Yang
  • Xue-Gang Liu
  • Sheng-Ming Xu


Aluminum recovery is a key issue for the overall recycling of valuable metals from spent catalysts. This paper focuses on the recovery and regeneration of alumina with high additional value from the spent hydrodesulfurization catalyst CoMo/Al2O3. The results indicate that 98.13% alumina is successfully leached from the treated spent catalysts by an alkaline leaching process under the conditions of 5 mol·L−1 sodium hydroxide, a liquid/solid ratio of 20 ml·g−1, a temperature of 160 °C and a reaction time of 4 h. In the leaching residue, no difficult leaching compound is found and cobalt and nickel are enriched, both of which are conducive to the subsequent metal recovery step. The reaction order of aluminum leaching is 0.99. This reaction fits well with the interfacial chemical reaction model, and its apparent activation energy is calculated as 45.50 kJ·mol−1. Subsequently, γ-Al2O3 with a high specific surface area of 278.3 m2·g−1, a mean size of 2.2 μm and an average pore size of 3.10 nm is then regenerated from the lixivium, indicating its suitability for use as a catalyst carrier. The recovery and regeneration of alumina from spent catalysts can not only significantly contribute to the total recycling of such hazardous spent catalysts but also provide a new approach for the preparation of γ-Al2O3 with a high specific surface area using spent catalysts as the aluminum sources.


Spent catalysts CoMo/Al2O3 Aluminum leaching Regeneration γ-Al2O3 



This study was financially supported by the National Natural Science Commission-Yunnan Joint Fund Project (No. U1402274).


  1. [1]
    Ramírez S, Schacht P, Quintana-Solórzano R, Aguilar J. Leaching of heavy metals under ambient resembling conditions from hydrotreating spent catalysts. Fuel. 2013;110(10):286.Google Scholar
  2. [2]
    Song CS. An overview of new approaches to deep desulfurization for ultra-clean gasoline, diesel fuel and jet fuel. Catal Today. 2003;86(1–4):211.Google Scholar
  3. [3]
    Villarreal A, Ramírez J, Caero LC, Villalón PC, Gutiérrez-Alejandre A. Importance of the sulfidation step in the preparation of highly active NiMo/SiO2/Al2O3 hydrodesulfurization catalysts. Catal Today. 2015;250:60.Google Scholar
  4. [4]
    Dai XP, Du KL, Li ZZ, Liu MZ, Ma YD, Sun H, Zhang X, Yang Y. Co-doped MoS2 nanosheets with the dominant CoMoS phase coated on carbon as an excellent electrocatalyst for hydrogen evolution. ACS Appl Mater Interfaces. 2015;7(49):27242.Google Scholar
  5. [5]
    Layan Savithra GH, Bowker RH, Carrillo BA, Bussell ME, Brock SL. Mesoporous matrix encapsulation for the synthesis of monodisperse Pd5P2 nanoparticle hydrodesulfurization catalysts. ACS Appl Mater Interfaces. 2013;5(12):5403.Google Scholar
  6. [6]
    van Haandel L, Bremmer M, Kooyman PJ, van Veen JAR, Weber T, Hensen EJM. Structure-activity correlations in hydrodesulfurization reactions over Ni-promoted MoxW(1– x)S2/Al2O3 catalysts. ACS Catal. 2015;5(12):7276.Google Scholar
  7. [7]
    Furimsky E, Massoth FE. Deactivation of hydroprocessing catalysts. Catal Today. 1999;52(4):381.Google Scholar
  8. [8]
    Ruiz V, Meux E, Schneider M, Georgeaud V. Hydrometallurgical treatment for valuable metals recovery from spent CoMo/Al2O3 catalyst. 2. Oxidative leaching of an unroasted catalyst using H2O2. Ind Eng Chem Res. 2011;50(9):5307.Google Scholar
  9. [9]
    Akcil A, Vegliò F, Ferella F, Okudan MD, Tuncuk A. A review of metal recovery from spent petroleum catalysts and ash. Waste Manag. 2015;45:420.Google Scholar
  10. [10]
    Asghari I, Mousavi S, Amiri F, Tavassoli S. Bioleaching of spent refinery catalysts: a review. J Ind Eng Chem. 2013;19(4):1069.Google Scholar
  11. [11]
    Barik S, Park K-H, Parhi P, Park J. Direct leaching of molybdenum and cobalt from spent hydrodesulphurization catalyst with sulphuric acid. Hydrometallurgy. 2012;111(1):46.Google Scholar
  12. [12]
    Zeng L, Cheng CY. A literature review of the recovery of molybdenum and vanadium from spent hydrodesulphurisation catalysts: Part I: metallurgical processes. Hydrometallurgy. 2009;98(1):1.Google Scholar
  13. [13]
    Huang XW, Long ZQ, Wang LS, Feng ZY. Technology development for rare earth cleaner hydrometallurgy in China. Rare Met. 2015;34(4):215.Google Scholar
  14. [14]
    Tian L, Liu Y, Zhang TA, Lv GZ, Zhou S, Zhang GQ. Kinetics of indium dissolution from marmatite with high indium content in pressure acid leaching. Rare Met. 2017;36(1):69.Google Scholar
  15. [15]
    Chauhan G, Pant KK, Nigam KD. Metal recovery from hydroprocessing spent catalyst: a green chemical engineering approach. Ind Eng Chem Res. 2013;52(47):16724.Google Scholar
  16. [16]
    Zeng L, Cheng CY. A literature review of the recovery of molybdenum and vanadium from spent hydrodesulphurisation catalysts: Part II: separation and purification. Hydrometallurgy. 2009;98(1):10.Google Scholar
  17. [17]
    Cortés-Torres R, Nolasco-Terrón EY, Olea-Mejia O, Varela-Guerrero V, Barrera-Díaz CE, Cuevas-Yañez E. Solvent mediated impurity removal process for a spent hydroprocessing catalyst and its use in alcohol oxidations. Catal Today. 2018;305:126.Google Scholar
  18. [18]
    Khalid M, Athraa B. Experimental study on factors affecting the recovery of nickel from spent catalyst. J Powder Metall Min. 2017;6(1):1.Google Scholar
  19. [19]
    Zhang Y, Lin H, Dong YB, Xu XF, Wang X, Gao YJ. Comprehensive recovery of iron, niobium rare earth and fluorite in Bayan Obo tailings. Chin J Rare Met. 2017;41(7):799.Google Scholar
  20. [20]
    Sahu K, Agrawal A, Mishra D. Hazardous waste to materials: Recovery of molybdenum and vanadium from acidic leach liquor of spent hydroprocessing catalyst using alamine 308. J Environ Manage. 2013;125(1):68.Google Scholar
  21. [21]
    Pinto IS, Soares HM. Recovery of molybdates from an alkaline leachate of spent hydrodesulphurisation catalyst–proposal of a nearly-closed process. J Clean Prod. 2013;52:481.Google Scholar
  22. [22]
    Erust C, Akcil A, Bedelova Z, Anarbekov K, Baikonurova A, Tuncuk A. Recovery of vanadium from spent catalysts of sulfuric acid plant by using inorganic and organic acids: laboratory and semi-pilot tests. Waste Manag. 2016;49:455.Google Scholar
  23. [23]
    Zhan C, Zhang YM, Bao SX, Huang J, Yang X. Separation and enrichment of vanadium from stone coal acidic leach solution using tertiary amine N235. Chin J Rare Met. 2017;41(4):422.Google Scholar
  24. [24]
    Li Z, Chen M, Zhang QW, Liu XZ, Saito F. Mechanochemical processing of molybdenum and vanadium sulfides for metal recovery from spent catalysts wastes. Waste Manag. 2017;60:734.Google Scholar
  25. [25]
    Nguyen TH, Lee MS. Development of a hydrometallurgical process for the recovery of calcium molybdate and cobalt oxalate powders from spent hydrodesulphurization (HDS) catalyst. J Clean Prod. 2015;90(10):388.Google Scholar
  26. [26]
    Cibati A, Cheng KY, Morris C, Ginige MP, Sahinkaya E, Pagnanelli F, Kaksonen AH. Selective precipitation of metals from synthetic spent refinery catalyst leach liquor with biogenic H2S produced in a lactate-fed anaerobic baffled reactor. Hydrometallurgy. 2013;139(3):154.Google Scholar
  27. [27]
    Feng ZY, Huang XW, Wang M, Zhang GC. Progress and trend of green chemistry in extraction and separation of typical rare earth resources. Chin J Rare Met. 2017;41(5):604.Google Scholar
  28. [28]
    Wang B, Meng Y, Duan CS. New process for complete recycling of metals from spent Co, Mo, and-Al2O3 catalyst. Mod Chem Ind. 2005;25(S1):204.Google Scholar
  29. [29]
    Busnardo RG, Busnardo NG, Salvato GN, Afonso JC. Processing of spent NiMo and CoMo/Al2O3 catalysts via fusion with KHSO4. J Hazard Mater. 2007;139(2):391.Google Scholar
  30. [30]
    Huang SB, Zhao ZW, Chen XY, Li F. Alkali extraction of valuable metals from spent Mo–Ni/Al2O3 catalyst. Int J Refract Metal Hard Mater. 2014;46(9):109.Google Scholar
  31. [31]
    Tabesh S, Davar F, Loghman-Estarki MR. Preparation of γ-Al2O3 nanoparticles using modified sol-gel method and its use for the adsorption of lead and cadmium ions. J Alloy Compd. 2018;730:441.Google Scholar
  32. [32]
    Svetlichnyi VA, Stadnichenko AI, Lapin IN. Preparation of γ-Al(OH)3 and γ-Al2O3 nanoparticles by the method of pulsed laser ablation of metal aluminum in water. Russ Phys J. 2017;60(2):377.Google Scholar
  33. [33]
    Yang Y, Xu SM, Li Z, Wang JL, Zhao ZW, Xu ZH. Oil removal of spent hydrotreating catalyst CoMo/Al2O3 via a facile method with enhanced metal recovery. J Hazard Mater. 2016;318:723.Google Scholar
  34. [34]
    Jin HX, Wu FZ, Mao XH, Wang ML, Xie HY. Leaching isomorphism rare earths from phosphorite ore by sulfuric acid and phosphoric acid. Rare Met. 2017;36(10):840.Google Scholar
  35. [35]
    Wang JY, Xu Y, Wang LS, Zhao LS, Wang Q, Cui DL, Long ZQ, Huang XW. Recovery of rare earths and aluminum from FCC catalysts manufacturing slag by stepwise leaching and selective precipitation. J Environ Chem Eng. 2017;5(4):3711.Google Scholar
  36. [36]
    Whittington BI, Fletcher BL, Talbot C. The effect of reaction conditions on the composition of desilication product (DSP) formed under simulated Bayer conditions. Hydrometallurgy. 1998;49(1–2):1.Google Scholar
  37. [37]
    Liu CL, Xia JP, Zhang YB. Optimization and kinetics on extraction of alumina from coal gangue by acid leaching. Chin J Process Eng. 2015;15(04):579.Google Scholar
  38. [38]
    Chen Y, Feng QM, Shao YH, Zhang GF, Ou LM, Lu YP. Research on the recycling of valuable metals in spent Al2O3-based catalyst. Miner Eng. 2006;19(1):94.Google Scholar
  39. [39]
    Wang B, Hao YL, Chu WQ, Rong S, Sun HL. Kinetics of leaching of 20CaO13Al2O33MgO3SiO2. Miner Process Extr Metall IMM Trans C. 2016;126(4):1.Google Scholar
  40. [40]
    Nayl AEAA, Aly HF. Extraction equilibria and kinetics of Ti(IV) from leached chloride liquors of ilmenite. Rare Met. 2017;36(8):676.Google Scholar
  41. [41]
    Amini M, Mirzaee M. Effect of solution chemistry on preparation of boehmite by hydrothermal assisted sol-gel processing of aluminum alkoxides. J Sol-Gel Sci Technol. 2005;36(1):19.Google Scholar
  42. [42]
    Okada K, Nagashima T, Kameshima Y, Yasumori A, Tsukada T. Relationship between formation conditions, properties, and crystallite size of boehmite. J Colloid Interface Sci. 2002;253(2):308.Google Scholar
  43. [43]
    Santos PdS, Coelho ACV, Santos HdS, Kiyohara PK. Hydrothermal synthesis of well-crystallised boehmite crystals of various shapes. Mater Res. 2009;12(4):437.Google Scholar
  44. [44]
    Wang JQ, Liu JL, Liu XY, Qiao MH, Pei Y, Fan KN. Hydrothermal transformation of bayerite to boehmite. Sci Adv Mater. 2009;1(1):77.Google Scholar
  45. [45]
    Mishra D, Anand S, Panda R, Das R. Hydrothermal preparation and characterization of boehmites. Mater Lett. 2000;42(1):38.Google Scholar
  46. [46]
    Mishra D, Anand S, Panda R, Das R. Effect of anions during hydrothermal preparation of boehmites. Mater Lett. 2002;53(3):133.Google Scholar
  47. [47]
    Wang WW, Zhou JB, Zhang Z, Yu JG, Cai WQ. Different surfactants-assisted hydrothermal synthesis of hierarchical γ-Al2O3 and its adsorption performances for parachlorophenol. Chem Eng J. 2013;233(2):168.Google Scholar
  48. [48]
    Wang Q, Cheng XH, Zheng L, Shen LY, Li JJ, Zhang DL, Qian R, Yu YH. Interface engineering of an AlNO/AlGaN/GaN MIS diode induced by PEALD alternate insertion of AlN in Al2O3. RSC Adv. 2017;7(19):11745.Google Scholar
  49. [49]
    Cai WQ, Yu JG, Jaroniec M. Template-free synthesis of hierarchical spindle-like γ-Al2O3 materials and their adsorption affinity towards organic and inorganic pollutants in water. J Mater Chem. 2010;20(22):4587.Google Scholar
  50. [50]
    Inoue M, Kominami H, Inui T. Synthesis of large pore-size and large pore-volume aluminas by glycothermal treatment of aluminium alkoxide and subsequent calcination. J Mater Sci. 1994;29(9):2459.Google Scholar
  51. [51]
    Cao JM, Hou HT, Ma XJ, Ji GB, Zheng MB, Lu HX. Solvothermal synthesis of nanoporous gamma aluminum oxide. Chin J Inorg Chem. 2005;9(21):1379.Google Scholar
  52. [52]
    Meng XH, Duan LH, Xie XH, Wang Q, Wang HY. Synthesis of macro-mesostructured γ-Al2O3 with large pore volume and high surface area by a facile secondary reforming method. China Pet Process Petrochem Technol. 2014;16(2):20.Google Scholar
  53. [53]
    Potdar HS, Jun K, Bae JW, Kim S, Lee Y. Synthesis of nano-sized porous γ-alumina powder via a precipitation/digestion route. Appl Catal A-Gen. 2007;321(2):109.Google Scholar
  54. [54]
    Li GM, Guo FX, Fan GQ. Standard of activated inorganic chemical products in China. Inorg Chem Ind. 2009;41(1):60.Google Scholar

Copyright information

© The Nonferrous Metals Society of China and Springer-Verlag GmbH Germany, part of Springer Nature 2018

Authors and Affiliations

  1. 1.Institute of Nuclear and New Energy Technology, Tsinghua UniversityBeijingChina
  2. 2.Beijing Key Laboratory of Fine CeramicsTsinghua UniversityBeijingChina
  3. 3.School of Minerals Processing and BioengineeringCentral South UniversityChangshaChina

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