Leaching and reusing analysis of calcium–zinc mixed oxides as heterogeneous catalysts in the biodiesel production from refined palm oil

  • J. F. Sierra-Cantor
  • J. J. Parra-Santiago
  • C. A. Guerrero-FajardoEmail author
Original Paper


The scarcity of fossil oils in medium and long term has led to propose different alternatives to replace it, and this is the reason why biodiesel has been proposed as a suitable replacement of conventional diesel oil. One of the most widely inquired heterogeneous catalysts in biodiesel production is calcium oxide (CaO) due to some advantages such as low price and high activity. Unfortunately, this compound is leached by methanol, and in this case, compounds such as CaO and ZnO have been suggested as an alternative to avoid this unwanted phenomenon. According to this, in the current work mixed oxides of calcium–zinc catalysts were synthesized using the co-precipitation method, and later, they were characterized and their behaviors were studied identifying transesterification yields and catalysts life cycle varying some of its operational conditions. Methanol/oil ratio over catalyst amount and Zn/Ca atomic ratio were identified as the main factors that affect the transesterification reaction yield. The maximum yield was 86.99%, obtained with 7.5 wt% catalyst, Zn/Ca atomic ratio of 3.0, methanol/oil molar ratio of 30:1 and a reaction time of 2 h at 56.9 °C. To test its reactivation capacity, a reactivated catalyst with the best behavior was used again obtaining a yield of 83.87% which indicates an insignificant decrease in its catalytic activity. However, the leaching process was detected which does not allow a decrease in purification costs due to residual calcium oxide.


Biodiesel Mixed oxides Ca–Zn Reusing analysis Transesterification reaction 



The authors thank the Energy Recovery of Natural Resources-APRENA research group from the Chemistry Department of the National University of Colombia, for their contribution to the development of this research.


  1. Abbaszaadeh A, Ghobadian B, Omidkhah MR, Najafi G (2012) Current biodiesel production technologies: a comparative review. Energy Convers Manag 63:138–148CrossRefGoogle Scholar
  2. Albuquerque M et al (2008) CaO supported on meso-porous silicas as basic catalysts for transesterification reactions. Appl Catal A Gen 334:35–43CrossRefGoogle Scholar
  3. Aransiola EF, Ojumu TV, Oyekola OO, Madzimbamuto TF (2014) A review of current technology for biodiesel production: state of the art. Biomass Bioenergy 61:276–297CrossRefGoogle Scholar
  4. Atadashi IM, Aroua MK, Abdul Aziz R, Sulaiman NMN (2012) The effects of water on biodiesel production and refining technologies: a review. Renew Sust Energy Rev 16(5):3456–3470CrossRefGoogle Scholar
  5. Atadashi IM, Aroua MK, Abdul Aziz R, Sulaiman NMN (2013) The effects of catalysts in biodiesel production: a review. J Ind Eng Chem 19(1):14–26CrossRefGoogle Scholar
  6. Basumatary S (2013) Review article transesterification with heterogeneous catalyst in production of biodiesel: a review. J Chem Pharm Res 5(1):1–7Google Scholar
  7. Bet-Moushoul E, Farhadi K, Mansourpanah Y, Nikbakht AM, Molaei R, Forough M (2016) Application of CaO-based/Au nanoparticles as heterogeneous nanocatalysts in biodiesel production. Fuel 164:119–124CrossRefGoogle Scholar
  8. Boey P, Maniam G, Hamid S (2011) Performance of calcium oxide as a heterogeneous catalyst in biodiesel production: a review. Chem Eng J 168:15–22CrossRefGoogle Scholar
  9. Borges ME, Díaz L (2012) Recent developments on heterogeneous catalysts for biodiesel production by oil esterification and transesterification reactions: a review. Renew Sust Energy Rev 16:2839–2849CrossRefGoogle Scholar
  10. British Petroleum (2015) BP statistical review of world energy 2015. British Petroleum, LondonGoogle Scholar
  11. Chang F et al (2014) Solid mixed-metal-oxide catalysts for biodiesel production: a review. Energy Technol 2(11):865–873CrossRefGoogle Scholar
  12. Chantara-arpornchai S, Luengnaruemitchai A, Jai-in S (2012) Biodiesel production from palm oil using heterogeneous base catalyst. Int J Innov Res Sci Eng Technol 6(4):477–482Google Scholar
  13. Chen G, Shan R, Li S, Shi J (2015) A biomimetic silicification approach to synthesize CaO–SiO2 catalyst for the transesterification of palm oil into biodiesel. Fuel 153:48–55CrossRefGoogle Scholar
  14. Cho YB, Seo G, Chang DR (2009) Transesterification of tributyrin with methanol over calcium oxide catalysts prepared from various precursors. Fuel Process Technol 90:1252–1258CrossRefGoogle Scholar
  15. Contreras I, Sierra FE, Guerrero-Fajardo CA (2013) Biodiesel production from waste cooking oil by enzymatic catalysis process. J Chem Chem Eng 7:993–1000Google Scholar
  16. Contreras I, Parra J, Sebastian J, Guerrero-Fajardo CA (2014) Transesterification reaction of waste cooking oil and chicken fat by homogeneous catalysis. J Chem Chem Eng 8:736–743Google Scholar
  17. ExxonMobil (2015) The outlook for energy: a view to 2040. ExxonMobil, IrvingGoogle Scholar
  18. Fujimori Y et al (2016) Interaction of water with the CaO(001) surface. J Phys Chem C 120(10):5565–5576CrossRefGoogle Scholar
  19. Hajjari et al (2017) A review on the prospects of sustainable biodiesel production: a global scenario with an emphasis on waste-oil biodiesel utilization. Renew Sust Energy Rev 72:445–464CrossRefGoogle Scholar
  20. Hoekman SK, Broch A, Robbins C, Ceniceros E, Natarajan E (2012) Review of biodiesel composition, properties, and specifications. Renew Sust Energy Rev 16:143–169CrossRefGoogle Scholar
  21. Issariyakul T, Dalai AK (2014) Biodiesel from vegetable oils. Renew Sust Energy Rev 31:446–471CrossRefGoogle Scholar
  22. Istadi I, Prasetyo SA, Nugroho TS (2015) Characterization of K2O/CaO–ZnO catalyst for transesterification of soybean oil to biodiesel. Procedia Environ Sci 23:394–399CrossRefGoogle Scholar
  23. Kaur N, Ali A (2014) Kinetics and reusability of Zr/CaO as heterogeneous catalyst for the ethanolysis and methanolysis of Jatropha crucas oil. Fuel Process Technol 119:173–184CrossRefGoogle Scholar
  24. Kesic Z et al (2012) Mechanochemical preparation and characterization of CaO·ZnO used as catalyst for biodiesel synthesis. Appl Catal A Gen 427–428:58–65CrossRefGoogle Scholar
  25. Kesić Ž, Lukić I, Zdujić M, Mojović L, Skala D (2016) Calcium oxide based catalysts for biodiesel production: a review. Chem Ind Chem Eng Q 22(4):1–10CrossRefGoogle Scholar
  26. Kiss AA (2014) Process intensification technologies for biodiesel production. Reactive separation processes. Springer, BerlinCrossRefGoogle Scholar
  27. Klinklom P, Luengnaruemitchai A, Jai-in S (2013) Effect of catalyst preparation on the performance of CaO–ZnO catalysts for transesterification. World Acad Sci Eng Technol 76:568–573Google Scholar
  28. Koh MY, Mohd TI, Ghazi A (2011) A review of biodiesel production from Jatropha curcas L. oil. Renew Sust Energy Rev 15(5):2240–2251CrossRefGoogle Scholar
  29. Konwar LJ, Boro J, Deka D (2014) Review on latest developments in biodiesel production using carbon-based catalyst. Renew Sust Energy Rev 29:546–564CrossRefGoogle Scholar
  30. Kouzu M, Hidaka J (2012) Transesterification of vegetable oil into biodiesel catalyzed by CaO: a review. Fuel 93:1–12CrossRefGoogle Scholar
  31. Kurnia JC et al (2016) Advances in biofuel production from oil palm and palm oil processing wastes: a review. Biofuel Res J 3:332–346CrossRefGoogle Scholar
  32. Lee AF, Bennett JA, Manayil JC, Wilson K (2014a) Heterogeneous catalysis for sustainable biodiesel production via esterification and transesterification. Chem Soc Rev 43(22):7887–7916CrossRefGoogle Scholar
  33. Lee HV, Juan JC, Binti Abdullah NF, Nizah Mf R, Taufiq-Yap YH (2014b) Heterogeneous base catalysts for edible palm and non-edible Jatropha-based biodiesel production. Chem Cent J 8:1–9CrossRefGoogle Scholar
  34. Lee HV, Juan JC, Taufiq-Yap JH, Kong PS, Rahman NA (2015a) Advancement in heterogeneous base catalyzed technology: an efficient production of biodiesel fuels. J Renew Sust Energy 3:7–12Google Scholar
  35. Lee HV, Juan JC, Taufiq-Yap JH (2015b) Preparation and application of binary acid-base CaO–La2O3 catalyst for biodiesel production. Renew Energy 74:124–132CrossRefGoogle Scholar
  36. Limmanee S, Naree T, Bunyakiat K, Ngamcharussrivichai C (2013) Mixed oxides of Ca, Mg and Zn as heterogeneous base catalysts for the synthesis of palm kernel oil methyl esters. Chem Eng J 225:616–624CrossRefGoogle Scholar
  37. Liu L, Wen Z, Cui G (2015) Preparation of Ca/Zr mixed oxide catalysts through a birch-templating route for the synthesis of biodiesel via transesterification. Fuel 158:176–182CrossRefGoogle Scholar
  38. Liu Y, Zhang P, Fan M, Jiang P (2016) Biodiesel production from soybean oil catalyzed by magnetic nanoparticle MgFe2O4–CaO. Fuel 164:314–321CrossRefGoogle Scholar
  39. Lohan Kumar S, Ram T, Mukesh S, Ali M, Arya S (2013) Sustainability of biodiesel production as vehicular fuel in Indian perspective. Renew Sust Energy Rev 25:251–259CrossRefGoogle Scholar
  40. Lukic I, Kesic Z, Maksimovic S, Zdujic M, Liu H, Krstic J (2013) Kinetics of sunflower and used vegetable oil methanolysis catalyzed by CaO·ZnO. Fuel 113:367–378CrossRefGoogle Scholar
  41. Macias EE, Desman CA, Malinski JB, Carreon MA, Runaway P (2011) Catalytic transformations of methyl oleate and biodiesel over mesoporous gallium–niobium oxides. Catal Commun 12:644–650CrossRefGoogle Scholar
  42. Marchetti JM, Miguel VU, Eras F (2008) Techno-economic study of different alternatives for biodiesel production. Fuel Process Technol 89(8):740–748CrossRefGoogle Scholar
  43. Mardhiah HH, Ong HC, Masjuki HH, Lim S, Lee HV (2017) A review on latest developments and future prospects of heterogeneous catalyst in biodiesel production from non-edible oils. Renew Sust Energy Rev 67:1225–1236CrossRefGoogle Scholar
  44. Marinković DM et al (2016) Calcium oxide as a promising heterogeneous catalyst for biodiesel production: current state and perspectives. Renew Sust Energy Rev 56:1387–1408CrossRefGoogle Scholar
  45. Meng Y-L, Wang B-Y, Li S-F, Tian S-J, Zhang M-H (2013) Effect of calcination temperature on the activity of solid Ca/Al composite oxide-based alkaline catalyst for biodiesel production. Bioresour Technol 128:305–309CrossRefGoogle Scholar
  46. Molaei Dehkordi A, Ghasemi M (2012) Transesterification of waste cooking oil to biodiesel using Ca and Zr mixed oxides as heterogeneous base catalysts. Fuel Process Technol 97:45–51CrossRefGoogle Scholar
  47. Mooser BR (2009) Biodiesel production, properties, and feedstocks. In Vitro Cell Dev Biol Plant 45:229–266CrossRefGoogle Scholar
  48. Ngamcharussrivichai C, Prangsinan T, Kunchana B (2008) Ca and Zn mixed oxide as a heterogeneous base catalyst for transesterification of palm kernel oil. Appl Catal A Gen 341:77–85CrossRefGoogle Scholar
  49. Ramachandran K, Suganya T, Nagendra-Ghandi N, Renganathan S (2013) Recent developments for biodiesel production by ultrasonic assist transesterification using different heterogeneous catalyst: a review. Renew Sust Energy Rev 22:410–418CrossRefGoogle Scholar
  50. Renewable Energy Policy Network for the 21st Century (REN21) (2016) Renewables 2016 global status report. REN21 Secretariat, ParisGoogle Scholar
  51. Rubio-Caballero JM et al (2013) Calcium zincate derived heterogeneous catalyst for biodiesel production by ethanolysis. Fuel 105:518–522CrossRefGoogle Scholar
  52. Sahid Z, Khan F, Zhang Y (2016) Process simulation and life cycle analysis of biodiesel production. Renew Energy 85:945–952CrossRefGoogle Scholar
  53. Salvi BL, Panwar NL (2012) Biodiesel resources and production technologies—a review. Renew Sust Energy Rev 16(6):3680–3689CrossRefGoogle Scholar
  54. Shahid EM, Jamal Y (2011) Production of biodiesel: a technical review. Renew Sust Energy Rev 15(9):4732–4745CrossRefGoogle Scholar
  55. Shan R, Zhao C, Lv P, Yuan H, Yao J (2016) Catalytic applications of calcium rich waste materials for biodiesel: current state and perspectives. Energy Convers Manag 127:273–283CrossRefGoogle Scholar
  56. Sharma YC, Singh B, Upadhyay SN (2008) Advancements in development and characterization of biodiesel: a review. Fuel 87:2355–2373CrossRefGoogle Scholar
  57. Sierra-Cantor JF, Guerrero-Fajardo CA (2017) Methods for improving the cold flow properties of biodiesel with high saturated fatty acids content: a review. Renew Sust Energy Rev 72:774–790CrossRefGoogle Scholar
  58. Sowa H, Ahsbahs H (2006) High-pressure X-ray investigation of zincite ZnO single crystals using diamond anvils with an improved shape. J Appl Crystallogr 39(2):169–175CrossRefGoogle Scholar
  59. Tasic MB, Stamenkovic OS, Veljkovic VB (2014) Cost analysis of simulated base-catalyzed biodiesel production processes. Energy Convers Manag 84:405–413CrossRefGoogle Scholar
  60. Taufiq-Yap YH, Lee HV, Hussein MZ, Yunus R (2011) Calcium-based mixed oxide catalysts for methanolysis of Jatropha curcas oil to biodiesel. Biomass Bioenergy 35(2):827–834CrossRefGoogle Scholar
  61. Thitsartarn W, Maneerung T, Kawi S (2015) Highly active and durable Ca-doped Ce-SBA-15 catalyst for biodiesel production. Energy 89:946–956CrossRefGoogle Scholar
  62. Wan Z, Hameed BH (2011) Transesterification of palm oil to methyl ester on activated carbon supported calcium oxide catalyst. Bioresour Technol 102(3):2659–2664CrossRefGoogle Scholar
  63. Wilson K, Lee AF (2012) Rational design of heterogeneous catalyst for biodiesel synthesis. Catal Sci Technol 2:884–897CrossRefGoogle Scholar
  64. Wyckoff R (1963) Crystal structures, vol 1. Interscience Publishers, New York, pp 85–237Google Scholar
  65. Yaakob Z, Mohammad M, Alherbawi M, Alam Z, Sopian K (2013) Overview of the production of biodiesel from waste cooking oil. Renew Sust Energy Rev 18:184–193CrossRefGoogle Scholar
  66. Yan S, Kim M, Salley SO, Ng KYS (2009) Oil transesterification over calcium oxides modified with lanthanum. Appl Catal A Gen 360:163–170CrossRefGoogle Scholar
  67. Yan Y et al (2014) Biotechnological preparation of biodiesel and its high-valued derivatives: a review. Appl Energy 113:1614–1631CrossRefGoogle Scholar
  68. Yulianti CH et al (2014) Synthesis of CaOZnO nanoparticles catalyst and its application in transesterification of refined palm oil. Bull Chem React Eng Catal 9(2):100–110CrossRefGoogle Scholar

Copyright information

© Islamic Azad University (IAU) 2018

Authors and Affiliations

  • J. F. Sierra-Cantor
    • 1
  • J. J. Parra-Santiago
    • 1
  • C. A. Guerrero-Fajardo
    • 2
    Email author
  1. 1.Department of ChemistryUniversidad Nacional de ColombiaBogotáColombia
  2. 2.Department of ChemistryUniversidad Nacional de ColombiaBogotáColombia

Personalised recommendations