Modified Malleus malleus Shells for Biodiesel Production from Waste Cooking Oil: An Optimization Study Using Box–Behnken Design

  • S. NijuEmail author
  • R. Rabia
  • K. Sumithra Devi
  • M. Naveen Kumar
  • M. Balajii
Original Paper


Biodiesel has been attracting the whole world in overcoming energy crisis due to stupendous advantages over petrochemical fuels. The high production cost hampered the applicability of biodiesel in replacing non-renewable fuels. The present study aims to reduce the cost by employing waste cooking oil as feedstock for biodiesel production using heterogeneous catalyst derived from waste Malleus malleus shells (MMS) via transesterification reaction. Catalytic activity of the MMS was enhanced by the calcination–hydration–dehydration method to increase the rate of biodiesel conversion. The developed catalyst was characterized by X-ray powder diffraction, Brunauer–Emmett–Teller, scanning electron microscope and Fourier-transform infrared spectroscopy techniques. Response surface methodology based on Box–Behnken design was applied to investigate the optimum transesterification process conditions. The effect of process variables such as catalyst concentration (4–8% w/w), methanol to oil molar ratio (6:1–12:1), and reaction time (30–120 min) was varied to obtain the maximum biodiesel conversion. A quadratic model was predicted and the obtained regression equation was expressed as three-dimensional response surfaces to study the interaction between independent variables on the response biodiesel conversion. The experimental results revealed that a maximum biodiesel conversion of 93.81% was obtained at optimal operating conditions of 7.5 wt% catalyst concentration, 11.85:1 methanol to oil molar ratio, and 86.25 min reaction time.

Graphical Abstract


Waste cooking oil Malleus malleus shells Response surface methodology Biodiesel 



SN is grateful to SERB-DST, New Delhi, India for Early Career Research Award (ECR/2015/000036) and MB is thankful to SERB-DST for the award of Junior Research Fellowship (JRF).


  1. 1.
    Reyes-Trejo, B., Guerra-Ramírez, D., Zuleta-Prada, H., Cuevas-Sánchez, J.A., Reyes, L., Reyes-Chumacero, A., Rodríguez-Salazar, J.A.: Annona diversifolia seed oil as a promising non-edible feedstock for biodiesel production. Ind. Crops Prod. 52, 400–404 (2014). CrossRefGoogle Scholar
  2. 2.
    Ong, L.K., Effendi, C., Kurniawan, A., Lin, C.X., Zhao, X.S., Ismadji, S.: Optimization of catalyst-free production of biodiesel from Ceiba pentandra (kapok) oil with high free fatty acid contents. Energy 57, 615–623 (2013). CrossRefGoogle Scholar
  3. 3.
    Demirbas, A.: Progress and recent trends in biodiesel fuels. Energy Convers. Manag. 50, 14–34 (2009). CrossRefGoogle Scholar
  4. 4.
    Tan, P., Hu, Z., Lou, D., Li, Z.: Exhaust emissions from a light-duty diesel engine with Jatropha biodiesel fuel. Energy 39, 356–362 (2012). CrossRefGoogle Scholar
  5. 5.
    Shahabuddin, M., Kalam, M.A., Masjuki, H.H., Bhuiya, M.M.K., Mofijur, M.: An experimental investigation into biodiesel stability by means of oxidation and property determination. Energy 44, 616–622 (2012). CrossRefGoogle Scholar
  6. 6.
    Ushakov, S., Valland, H., Æsøy, V.: Combustion and emissions characteristics of fish oil fuel in a heavy-duty diesel engine. Energy Convers. Manag. 65, 228–238 (2013). CrossRefGoogle Scholar
  7. 7.
    Khan, T.M.Y., Atabani, A.E., Badruddin, I.A., Badarudin, A., Khayoon, M.S., Triwahyono, S.: Recent scenario and technologies to utilize non-edible oils for biodiesel production. Renew. Sustain. Energy Rev. 37, 840–851 (2014). CrossRefGoogle Scholar
  8. 8.
    Atabani, A.E., Mahlia, T.M.I., Masjuki, H.H., Badruddin, I.A., Yussof, H.W., Chong, W.T., Lee, K.T.: A comparative evaluation of physical and chemical properties of biodiesel synthesized from edible and non-edible oils and study on the effect of biodiesel blending. Energy 58, 296–304 (2013). CrossRefGoogle Scholar
  9. 9.
    Chen, X., Khanna, M.: Food vs. fuel: the effect of biofuel policies. Am. J. Agric. Econ. 95, 289–295 (2013). CrossRefGoogle Scholar
  10. 10.
    Elsheikh, Y.A.: Preparation of Citrullus colocynthis biodiesel via dual-step catalyzed process using functionalized imidazolium and pyrazolium ionic liquids for esterification step. Ind. Crops Prod. 49, 822–829 (2013). CrossRefGoogle Scholar
  11. 11.
    Kalam, M.A., Saifullah, M.G., Masjuki, H.H., Husnawan, M., Mahlia, T.M.I.: PAH and other emissions from coconut oil blended fuels. J. Sci. Ind. Res. 67, 1031–1035 (2008)Google Scholar
  12. 12.
    Silitonga, A.S., Masjuki, H.H., Mahlia, T.M.I., Ong, H.C., Chong, W.T.: Experimental study on performance and exhaust emissions of a diesel engine fuelled with Ceiba pentandra biodiesel blends. Energy Convers. Manag. 76, 828–836 (2013). CrossRefGoogle Scholar
  13. 13.
    Ong, Y.K., Bhatia, S.: The current status and perspectives of biofuel production via catalytic cracking of edible and non-edible oils. Energy 35, 111–119 (2010). CrossRefGoogle Scholar
  14. 14.
    Ramadhas, A.S., Jayaraj, S., Muraleedharan, C.: Use of vegetable oils as I.C. engine fuels—a review. Renew. Energy 29, 727–742 (2004). CrossRefGoogle Scholar
  15. 15.
    Tariq, M., Ali, S., Khalid, N.: Activity of homogeneous and heterogeneous catalysts, spectroscopic and chromatographic characterization of biodiesel: a review. Renew. Sustain. Energy Rev. 16, 6303–6316 (2012). CrossRefGoogle Scholar
  16. 16.
    Kouzu, M., Kasuno, T., Tajika, M., Sugimoto, Y., Yamanaka, S., Hidaka, J.: Calcium oxide as a solid base catalyst for transesterification of soybean oil and its application to biodiesel production. Fuel 87, 2798–2806 (2008). CrossRefGoogle Scholar
  17. 17.
    Sani, Y.M., Daud, W.M.A.W., Abdul Aziz, A.R.: Solid acid-catalyzed biodiesel production from microalgal oil—the dual advantage. J. Environ. Chem. Eng. 1, 113–121 (2013). CrossRefGoogle Scholar
  18. 18.
    Takagaki, A., Toda, M., Okamura, M., Kondo, J.N., Hayashi, S., Domen, K., Hara, M.: Esterification of higher fatty acids by a novel strong solid acid. Catal. Today 116, 157–161 (2006). CrossRefGoogle Scholar
  19. 19.
    Sani, Y.M., Daud, W.M.A.W., Abdul Aziz, A.R.: Activity of solid acid catalysts for biodiesel production: a critical review. Appl. Catal. A 470, 140–161 (2014). CrossRefGoogle Scholar
  20. 20.
    Niju, S., Begum, M.M.M.S., Anantharaman, N.: Modification of egg shell and its application in biodiesel production. J. Saudi Chem. Soc. 18, 702–706 (2014). CrossRefGoogle Scholar
  21. 21.
    Viriya-empikul, N., Krasae, P., Puttasawat, B., Yoosuk, B., Chollacoop, N., Faungnawakij, K.: Waste shells of mollusk and egg as biodiesel production catalysts. Bioresour. Technol. 101, 3765–3767 (2010). CrossRefGoogle Scholar
  22. 22.
    Niju, S., Sheriffa Begum, K.M., Anantharaman, N.: Enhancement of biodiesel synthesis over highly active CaO derived from natural white bivalve clam shell. Arab. J. Chem. 9, 633–639 (2016). CrossRefGoogle Scholar
  23. 23.
    Eswararao, Y., Niju, S., Meera Sheriffa Begum, K.M., Anantharaman, N., Malik Raj, S.: Transesterification of jatropha oil using a mixture of natural shells as solid catalyst. Biofuels 7, 345–351 (2016). CrossRefGoogle Scholar
  24. 24.
    Niju, S., Indhumathi, J., Begum, K.M.M.S., Anantharaman, N.: Tellina tenuis: a highly active environmentally benign catalyst for the transesterification process. Biofuels 8, 565–570 (2016). CrossRefGoogle Scholar
  25. 25.
    Boro, J., Thakur, A.J., Deka, D.: Solid oxide derived from waste shells of Turbonilla striatula as a renewable catalyst for biodiesel production. Fuel Process. Technol. 92, 2061–2067 (2011). CrossRefGoogle Scholar
  26. 26.
    Boey, P., Pragas, G., Abd, S.: Biodiesel production via transesterification of palm olein using waste mud crab (Scylla serrata) shell as a heterogeneous catalyst. Bioresour. Technol. 100, 6362–6368 (2009). CrossRefGoogle Scholar
  27. 27.
    Boey, P.-L., Maniam, G.P., Hamid, S.A., Ali, D.M.H.: Crab and cockle shells as catalysts for the preparation of methyl esters from low free fatty acid chicken fat. J. Am. Oil Chem. Soc. 88, 283–288 (2011). CrossRefGoogle Scholar
  28. 28.
    Margaretha, Y.Y., Prastyo, H.S., Ayucitra, A., Ismadji, S.: Calcium oxide from Pomacea sp. shell as a catalyst for biodiesel production. Int. J. Energy Environ. Eng. 3, 33 (2012)CrossRefGoogle Scholar
  29. 29.
    Jairam, S., Kolar, P., Sharma-Shivappa Ratna, R., Osborne, J.A., Davis, J.P., Sharma-shivappa, R., Osborne, J.A., Davis, J.P.: KI-impregnated oyster shell as a solid catalyst for soybean oil transesterification. Bioresour. Technol. 104, 329–335 (2012). CrossRefGoogle Scholar
  30. 30.
    Lee, S.L., Wong, Y.C., Tan, Y.P., Yew, S.Y.: Transesterification of palm oil to biodiesel by using waste obtuse horn shell-derived CaO catalyst. Energy Convers. Manag. 93, 282–288 (2015). CrossRefGoogle Scholar
  31. 31.
    Kaur, M., Ali, A.: Lithium ion impregnated calcium oxide as nano catalyst for the biodiesel production from karanja and jatropha oils. Renew. Energy 36, 2866–2871 (2011). CrossRefGoogle Scholar
  32. 32.
    Modiba, E., Enweremadu, C., Rutto, H.: Production of biodiesel from waste vegetable oil using impregnated diatomite as heterogeneous catalyst. Chin. J. Chem. Eng. 23, 281–289 (2015). CrossRefGoogle Scholar
  33. 33.
    Kaur, N., Ali, A.: Biodiesel production via ethanolysis of jatropha oil using molybdenum impregnated calcium oxide as solid catalyst. RSC Adv. 5, 13285–13295 (2015). CrossRefGoogle Scholar
  34. 34.
    Sadhukhan, S., Sarkar, U.: Production of biodiesel from Crotalaria juncea (Sunn-Hemp) oil using catalytic trans-esterification: process optimisation using a factorial and Box–Behnken design. Waste Biomass Valorization 7, 343–355 (2016). CrossRefGoogle Scholar
  35. 35.
    Syazwani, O.N., Rashid, U., Yap, Y.H.T.: Low-cost solid catalyst derived from waste Cyrtopleura costata (Angel Wing Shell) for biodiesel production using microalgae oil. Energy Convers. Manag. 101, 749–756 (2015). CrossRefGoogle Scholar
  36. 36.
    Buasri, A., Chaiyut, N., Loryuenyong, V., Worawanitchaphong, P., Trongyong, S.: Calcium oxide derived from waste shells of mussel, cockle, and scallop as the heterogeneous catalyst for biodiesel production. Sci. World J. (2013). CrossRefGoogle Scholar
  37. 37.
    Pandit, P.R., Fulekar, M.H.: Egg shell waste as heterogeneous nanocatalyst for biodiesel production: optimized by response surface methodology. J. Environ. Manag. 198, 319–329 (2017). CrossRefGoogle Scholar
  38. 38.
    Mehmood, T., Shaheen, Z., Malik, S.A., Tabassam, Q., Siddique, F., Jabeen, L.: Utilization of waste and under-utilized Pongamia pinnata seed oil for acquiring maximal process to get ameliorate yield of biodiesel through response surface methodology. Waste Biomass Valorization 7, 495–506 (2016). CrossRefGoogle Scholar
  39. 39.
    Tan, Y.H., Abdullah, M.O., Nolasco-Hipolito, C., Taufiq-Yap, Y.H.: Waste ostrich- and chicken-eggshells as heterogeneous base catalyst for biodiesel production from used cooking oil: catalyst characterization and biodiesel yield performance. Appl. Energy 160, 58–70 (2015). CrossRefGoogle Scholar
  40. 40.
    Makareviciene, V., Skorupskaite, V.: The optimization of biodiesel fuel production from microalgae oil using response surface methodology. Int. J. Green Energy. 37–41 (2013).
  41. 41.
    Tshizanga, N., Aransiola, E.F., Oyekola, O.: Optimisation of biodiesel production from waste vegetable oil and eggshell ash. S. Afr. J. Chem. Eng. 23, 145–156 (2017). CrossRefGoogle Scholar
  42. 42.
    Niju, S., Sheriffa Begum, K.M.M., Anantharaman, N.: Preparation of biodiesel from waste frying oil using a green and renewable solid catalyst derived from egg shell. Environ. Prog. Sustain. Energy 34, 248–254 (2015). CrossRefGoogle Scholar
  43. 43.
    Eevera, T., Rajendran, K., Saradha, S.: Biodiesel production process optimization and characterization to assess the suitability of the product for varied environmental conditions. Renew. Energy 34, 762–765 (2009). CrossRefGoogle Scholar
  44. 44.
    Atabani, A.E., Silitonga, A.S., Ong, H.C., Mahlia, T.M.I., Masjuki, H.H., Badruddin, I.A., Fayaz, H.: Non-edible vegetable oils: a critical evaluation of oil extraction, fatty acid compositions, biodiesel production, characteristics, engine performance and emissions production. Renew. Sustain. Energy Rev. (2013). CrossRefGoogle Scholar

Copyright information

© Springer Nature B.V. 2018

Authors and Affiliations

  1. 1.Department of BiotechnologyPSG College of TechnologyCoimbatoreIndia

Personalised recommendations