Synthesis and performance evaluation of silica-supported copper chromite catalyst for glycerol dehydration to acetol

  • S Basu
  • A K SenEmail author
  • M Mukherjee
Regular Article


Sol-gel technique was used to prepare silica-supported copper chromite catalyst from acid hydrolysis of sodium silicate. The catalyst was characterized by BET surface area, FESEM, XRD, H2-TPR and pyridine adsorption by FTIR. The catalyst was activated in a hydrogen atmosphere based on H2-TPR result. The surface acidity of the catalyst was evaluated by NH3-TPD and pyridine adsorption. XRD result of reduced catalyst showed the presence of Cu0, Cu1+ and Cr2O3 in the catalyst. Glycerol dehydration was carried out at different temperature (180 °C to 240 °C) from aqueous glycerol solution with the reduced catalyst in a batch reactor. The glycerol conversion was reached 100% with maximum acetol selectivity of 70% for highest Copper chromite loaded (40 wt%) on silica at 220 °C in atmospheric pressure. The distilled liquid product was analyzed by high-performance liquid chromatography. Oxidized catalyst and spent catalyst showed lower glycerol conversion with low acetol selectivity than the reduced form of the catalyst. This is due to the cuprous ion in the reduced form of the catalyst, which acts as Lewis acid sites in glycerol dehydration.

Graphic abstract

Glycerol dehydration to acetol with reduced form of silica-supported copper chromite catalyst is reported. The reduced form of copper chromite (cuprous oxide) on silica surface acts as a lewis acid in glycerol dehydration. Cuprous oxide coordinates with terminal hydroxyl group of glycerol and forms low energy six-membered transition state in the dehydration reactions.


Glycerol copper chromite acetol pyridine-FTIR H2-TPR XRD 



The authors gratefully acknowledge the state of the art testing facility at Central Instrumentation Facility of Birla Institute of Technology Mesra.


  1. 1.
    Kong P S, Kheireddine M, Mohd W and Wan A 2016 Conversion of crude and pure glycerol into derivatives: A feasibility evaluation Renew. Sustain. Energy Rev. 63 533CrossRefGoogle Scholar
  2. 2.
    Meher L C, Dharmagadda V S S and Naik S N 2006 Optimization of alkali-catalyzed transesterification of Pongamia pinnata oil for production of biodiesel Bioresour. Technol. 97 1392CrossRefGoogle Scholar
  3. 3.
    Xiao Z, Li C, Xiu J, Wang X, Williams C T and Liang C 2012 Chemical Insights into the reaction pathways of glycerol hydrogenolysis over Cu – Cr catalysts J. Mol. Catal. A Chem. 365 24CrossRefGoogle Scholar
  4. 4.
    Yue C J, Gan M M, Gu L P and Zhuang Y F 2014 In situ synthesized nano-copper over ZSM-5 for the catalytic dehydration of glycerol under mild conditions J. Taiwan Inst. Chem. Eng. 45 1443CrossRefGoogle Scholar
  5. 5.
    Magar S, Kamble S, Mohanraj G T, Jana S K and Rode C 2017 Solid-acid-catalyzed etherification of glycerol to potential fuel additives Energy Fuels 31 1227CrossRefGoogle Scholar
  6. 6.
    Behr A 2008 The future of glycerol. New usages for a versatile raw material. By Mario Pagliaro and Michele Rossi ChemSusChem 1 653CrossRefGoogle Scholar
  7. 7.
    Pagliaro M, Ciriminna R, Kimura H, Rossi M and Della Pina C 2007 From glycerol to value-added products Angew. Chem. Int. Ed. 46 4434CrossRefGoogle Scholar
  8. 8.
    Suthagar K, Shanthi K and Selvam P 2018 Hydrogenolysis of glycerol over silica-supported copper-nanocatalyst: Effect of precipitating-agent and copper metal-loading Mol. Catal. 458 307CrossRefGoogle Scholar
  9. 9.
    Dasari M A, Kiatsimkul P P, Sutterlin W R and Suppes G J 2005 Low-pressure hydrogenolysis of glycerol to propylene glycol Appl. Catal. A Gen. 281 225CrossRefGoogle Scholar
  10. 10.
    Liang C, Ma Z and Ding L 2009 template preparation of highly active and selective Cu–Cr catalysts with high surface area for glycerol hydrogenolysis Catal. Lett. 130 169CrossRefGoogle Scholar
  11. 11.
    Huang Z, Cui F, Kang H, Chen J, Zhang X and Xia C 2008 Highly dispersed silica-supported copper nanoparticles prepared by precipitation–Gel Method: A Simple but Efficient and Stable Catalyst for Glycerol Hydrogenolysis Chem. Mater. 20 5090CrossRefGoogle Scholar
  12. 12.
    Kim N D, Oh S, Joo JB, Jung K S and Yi J 2010 The promotion effect of Cr on copper catalyst in hydrogenolysis of glycerol to propylene glycol Top. Catal. 53 517CrossRefGoogle Scholar
  13. 13.
    Rode C V, Ghalwadkar A A, Mane R B, Hengne A M, Jadkar S T and Biradar N S 2010 Selective hydrogenolysis of glycerol to 1,2-propanediol: Comparison of batch and continuous process operations Org. Process Res. Dev. 14 1385CrossRefGoogle Scholar
  14. 14.
    Pantaleo G, Liotta L F, Venezia A M, Deganello G, Ezzo E M, El Kherbawi M A and Atia H 2009 Support effect on the structure and CO oxidation activity of Cu-Cr mixed oxides over Al2O3 and SiO2 Mater. Chem. Phys. 114 604CrossRefGoogle Scholar
  15. 15.
    Sato S, Akiyama M, Takahashi R, Hara T, Inui K and Yokota M 2008 Vapor-phase reaction of polyols over copper catalysts Appl. Catal. A Gen. 347 186CrossRefGoogle Scholar
  16. 16.
    Chiu C-W, Dasari M A, Suppes G J and Sutterlin W R 2005 Dehydration of glycerol to acetol via catalytic reactive distillation AIChE J. 52 3543CrossRefGoogle Scholar
  17. 17.
    Braga T P, Pinheiro A N, Teixeira C V and Valentini A 2009 Dehydrogenation of ethylbenzene in the presence of CO2 using a catalyst synthesized by polymeric precursor method Appl. Catal. A Gen. 366 193CrossRefGoogle Scholar
  18. 18.
    Vasiliadou E S and Lemonidou A A 2011 Investigating the performance and deactivation behaviour of silica-supported copper catalysts in glycerol hydrogenolysis Appl. Catal. A Gen. 396 177CrossRefGoogle Scholar
  19. 19.
    Miyazawa T, Kusunoki Y, Kunimori K and Tomishige K 2006 Glycerol conversion in the aqueous solution under hydrogen over Ru/C+ an ion-exchange resin and its reaction mechanism J. Catal. 240 213CrossRefGoogle Scholar
  20. 20.
    Chaminand J, Djakovitch LA, Gallezot P, Marion P, Pinel C and Rosier C 2004 Glycerol hydrogenolysis on heterogeneous catalysts Green Chem. 6 359CrossRefGoogle Scholar
  21. 21.
    Li K T, Li J Y and Li H H 2017 Conversion of glycerol to lactic acid over Cu–Zn–Al and Cu–Cr catalysts in alkaline solution J. Taiwan Inst. Chem. Eng. 79 74CrossRefGoogle Scholar
  22. 22.
    Suprun W, Lutecki M, Haber T and Papp H 2009 Acidic catalysts for the dehydration of glycerol: Activity and deactivation J. Mol. Catal. A Chem. 309 71CrossRefGoogle Scholar
  23. 23.
    Shree V and Sen A K 2018 Study of thermal and flame behavior of phosphorus-based silica for epoxy composites J. Sol-Gel. Sci. Technol. 85 269CrossRefGoogle Scholar
  24. 24.
    Mane R B and Rode C V 2012 Continuous dehydration and hydrogenolysis of glycerol over non-chromium copper catalyst: Laboratory-scale process studies Org. Process. Res. Dev. 16 1043CrossRefGoogle Scholar
  25. 25.
    Raksaphort S, Pengpanich S and Hunsom M 2014 Products Distribution of glycerol hydrogenolysis over supported co catalysts in a liquid phase Kinet. Catal. 55 456CrossRefGoogle Scholar
  26. 26.
    Hao S, Peng W, Zhao N and Xiao F 2010 Hydrogenolysis of glycerol to 1,2-propanediol catalyzed by Cu-H4SiW12O40/Al2O3 in liquid J. Chem. Tech. Biotech. 85 1499Google Scholar
  27. 27.
    Vankudoth K, Gutta N, Velisoju V K, Mutyala S, Aytam H P and Akula V 2017 CuCr2O4 derived by the sol-gel method as a highly active and selective catalyst for the conversion of glycerol to 2,6-dimethylpyrazine: A benign and eco-friendly process Catal. Sci. Technol. 7 3399CrossRefGoogle Scholar
  28. 28.
    Kinage A K, Upare P P, Kasinathan P, Hwang Y K and Chang J S 2010 Selective conversion of glycerol to acetol over sodium-doped metal oxide catalysts Catal. Commun. 11 620CrossRefGoogle Scholar
  29. 29.
    Zhang B, Hui S, Zhang S, Ji Y, Li W and Fang D 2012 Effect of copper loading on texture, structure and catalytic performance of Cu/SiO2 catalyst for hydrogenation of dimethyl oxalate to ethylene glycol J. Nat. Gas Chem. 21 563CrossRefGoogle Scholar
  30. 30.
    Mobini S, Meshkani F and Rezaei M 2017 Surfactant-assisted hydrothermal synthesis of CuCr2O4 spinel catalyst and its application in CO oxidation process J. Environ. Chem. Eng. 5 4906CrossRefGoogle Scholar
  31. 31.
    Santacesaria E, Carotenuto G, Tesser R and Di Serio M 2012 Ethanol dehydrogenation to ethyl acetate by using copper and copper chromite catalysts Chem. Eng. J. 179 209CrossRefGoogle Scholar
  32. 32.
    Hosseini S G, Abazari R and Gavi A 2014 Pure CuCr2O4 nanoparticles: Synthesis, characterization and their morphological and size effects on the catalytic thermal decomposition of ammonium perchlorate Solid State Sci. 37 72CrossRefGoogle Scholar
  33. 33.
    Khasin A A, Yur’eva T M, Plyasova L M, Kustova G N, Jobic H, Ivanov A, Chesalov Y A, Zaikovskii V I, Khasin A V, Davydova L P and Parmon V N 2008 Mechanistic features of reduction of copper chromite and state of absorbed hydrogen in the structure of reduced copper chromite Russ. J. Gen. Chem. 78 2203CrossRefGoogle Scholar
  34. 34.
    Kawamoto A M, Pardini L C and Rezende L C 2004 Synthesis of copper chromite catalyst Aerosp. Sci. Technol. 8 591CrossRefGoogle Scholar
  35. 35.
    Luo M-F, Zhong Y-J, Yuan X-X and Zheng X-M 1997 TPR and TPD studies of CuOCeO2 catalysts for low temperature CO oxidation Appl. Catal. A Gen. 162 121CrossRefGoogle Scholar
  36. 36.
    Xiao Z, Wang X, Xiu J, Wang Y, Williams C T and Liang C 2014 Synergetic effect between Cu0 and Cu + in the Cu-Cr catalysts for hydrogenolysis of glycerol Catal. Today 234 200CrossRefGoogle Scholar
  37. 37.
    Braga T P, Essayem N and Valentini A 2017 Correlation between the basicity of Cu-MxOy-Al2O3(M = Ba, Mg, K or La) oxide and the catalytic performance in the glycerol conversion from adsorption microcalorimetry characterization J. Therm. Anal. Calorim. 129 65CrossRefGoogle Scholar
  38. 38.
    Célerier S, Morisset S, Batonneau-gener I, Belin T, Younes K and Batiot-dupeyrat C 2018 Glycerol dehydration to hydroxyacetone in gas phase over copper supported on magnesium oxide(hydroxide)fluoride catalysts Appl. Catal. A Gen. 557 135CrossRefGoogle Scholar
  39. 39.
    Tendam J and Hanefeld U 2011 Renewable chemicals: Dehydroxylation of glycerol and polyols ChemSusChem 4 1017CrossRefGoogle Scholar
  40. 40.
    Rodríguez-González L, Hermes F, Bertmer M, Rodríguez-Castellón E, Jiménez-López A and Simon U 2007 The acid properties of H-ZSM-5 as studied by NH3-TPD and 27Al-MAS-NMR spectroscopy Appl. Catal. A Gen. 328 174CrossRefGoogle Scholar
  41. 41.
    Krishna V, Naresh G, Kumar V V, Sarkari R, Padmasri A H and Venugopal A 2016 Synthesis of 2,6-dimethylpyrazine by dehydrocyclization of aqueous glycerol and 1,2-propanediamine over CuCrO catalyst: Rationalization of active sites by pyridine and formic acid adsorbed IR studies Appl. Catal. B Environ. 193 58CrossRefGoogle Scholar
  42. 42.
    Stošić D, Bennici S, Sirotin S, Stelmachowski P, Couturier J L, Dubois J L, Travert A and Auroux A 2014 Examination of acid-base properties of solid catalysts for gas phase dehydration of glycerol: FTIR and adsorption microcalorimetry studies Catal. Today 226 167CrossRefGoogle Scholar
  43. 43.
    Alhanash A, Kozhevnikova E F and Kozhevnikov I V 2010 Gas-phase dehydration of glycerol to acrolein catalysed by caesium heteropoly salt Appl. Catal. A Gen. 378 11CrossRefGoogle Scholar
  44. 44.
    Nimlos M R, Blanksby S J, Qian X, Himmel M E and Johnson D K 2006 Mechanisms of glycerol dehydration J. Phys. Chem. A 110 6145CrossRefGoogle Scholar
  45. 45.
    Martin A and Richter M 2011 Oligomerization of glycerol - a critical review Eur. J. Lipid Sci. Technol. 113 100CrossRefGoogle Scholar
  46. 46.
    de Sousa F F, Campos A, Filho E C da S, Millet E R C, Pinheiro L G, Carvalho D C, Fonseca M G, Filho J M, Oliveira A C and Saraiva G D 2013 Characterization and catalytic performances of copper and cobalt-exchanged hydroxyapatite in glycerol conversion for 1-hydroxyacetone production Appl. Catal. A Gen. 471 39Google Scholar
  47. 47.
    Goula M A, Charisiou N D, Pandis P K and Stathopoulos V N 2016 A Ni/apatite-type lanthanum silicate supported catalyst in glycerol steam reforming reaction RSC Adv. 6 78954CrossRefGoogle Scholar
  48. 48.
    Iriondo A, Barrio V L, Cambra J F, Arias P L, Guemez M B, Sanchez-Sanchez M C, Navarro R M and Fierro J L G 2010 Glycerol steam reforming over Ni catalysts supported on ceria and ceria-promoted alumina Int. J. Hydrogen Energy 35 11622CrossRefGoogle Scholar
  49. 49.
    Sad M E, Duarte H A, Vignatti C, Padró C L and Apesteguía C R 2015 Steam reforming of glycerol: Hydrogen production optimization Int. J. Hydrogen Energy 40 6097CrossRefGoogle Scholar
  50. 50.
    Mane R B, Yamaguchi A, Malawadkar A, Shirai M and Rode C V 2013 Active sites in modified copper catalysts for selective liquid phase dehydration of aqueous glycerol to acetol RSC Adv. 3 16499CrossRefGoogle Scholar
  51. 51.
    Davda R R, Shabaker J W, Huber G W, Cortright R D and Dumesic J A 2005 A review of catalytic issues and process conditions for renewable hydrogen and alkanes by aqueous-phase reforming of oxygenated hydrocarbons over supported metal catalysts Appl. Catal. B Environ. 56 171CrossRefGoogle Scholar
  52. 52.
    Braga T P, Essayem N, Prakash S and Valentini A 2016 Gas-Phase conversion of glycerol to acetol: Influence of support acidity on the catalytic stability and copper surface properties on the activity J. Braz. Chem. Soc. 27 2361Google Scholar
  53. 53.
    Torresi P A, Díez V K, Luggren P J and Di Cosimo J I 2013 Conversion of diols by dehydrogenation and dehydration reactions on silica-supported copper catalysts Appl. Catal. A Gen. 458 119CrossRefGoogle Scholar

Copyright information

© Indian Academy of Sciences 2019

Authors and Affiliations

  1. 1.Department of Chemical EngineeringBirla Institute of Technology MesraRanchiIndia

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