BioEnergy Research

, Volume 11, Issue 4, pp 772–783 | Cite as

Performance Evaluation of Carbon-based Heterogeneous Acid Catalyst Derived From Hura crepitans Seed Pod for Esterification of High FFA Vegetable Oil

  • Ikechukwu Martin OgbuEmail author
  • Vincent Ishmael Egbulefu Ajiwe
  • Chukwunonso Peter Okoli


Efficient and recyclable heterogeneous catalysts from low-cost material is a research target in biodiesel industry to reduce production cost and minimize waste generation. The performance of carbon-based heterogeneous acid catalysts prepared from Hura crepitans seed pod via partial carbonization and sulfonation was evaluated in this study. Different catalysts, 0HuSO3H, 30HuSO3H, 60HuSO3H, 90HuSO3H, and 120HuSO3H, obtained by varying preparation conditions were characterized using emission scanning electron microscope, Fourier transform infrared spectroscopy, X-ray powder diffraction, and thermogravimetric and titrimetric analyses. The activity of the catalysts towards esterification of high free fatty acid-containing H. crepitans seed oil was assessed. Effects of process parameters, temperature, catalyst load, methanol/oil ratio, reaction time, and their various optimum levels on the esterification reaction, were investigated using Taguchi L9 orthogonal array method of optimization. The results showed that the H. crepitans seed pod-derived solid acid catalysts exhibited superior catalytic properties primarily due to high acid density (2.0 mmol/g). The resident time of carbonization before sulfonation showed a strong influence on the acid site density, pore sizes, hydrophobicity, and acid site retention capacity. The optimum process conditions as predicted by the optimization model gave 94.81% ester conversion. The catalyst was effective up to four cycles with only 1.44% decrease in activity.


Hura crepitans Seed pod Solid catalysts Esterification Taguchi design Optimization 



The authors are grateful to the Department of Chemistry/Biochemistry, Alex-Ekweme Federal University Ndufu-Alike Ikwo for their laboratory facilities.

Supplementary material

12155_2018_9938_MOESM1_ESM.docx (379 kb)
ESM 1 (DOCX 379 kb)


  1. 1.
    Azil I (2007) Biofuel demand: opportunities for rural development in Africa (Nigeria case-study). A paper presented at the 2nd European forum on sustainable development, Berlin, Germany. pp. 1–6Google Scholar
  2. 2.
    Lee AF, Bennet JA, Manayil JC, Wilson K (2014) Heterogeneous catalysis for sustainable biodiesel production via esterification and Transesterification. Review Article. Chem Soc Rev 43:7887–7916CrossRefGoogle Scholar
  3. 3.
    Ma FR, Hanna MA (1999) Biodiesel production: a review. Bioresour Technol 70:1–15CrossRefGoogle Scholar
  4. 4.
    Giakoumis EG (2013) A statistical investigation of biodiesel physical and chemical properties, and their correlation with the degree of unsaturation. Renew Energy 50:858–878CrossRefGoogle Scholar
  5. 5.
    Wang L, Dong X, Jiang H, Li G, Zhang M (2014) Preparation of a novel carbon-based solid acid from cassava stillage residue and its use for the esterification of free fatty acids in waste cooking oil. Bioresour Technol 158:392–395CrossRefGoogle Scholar
  6. 6.
    Agarwal AK (2007) Biofuels (alcohols and biodiesel) applications as fuels in internal combustion engines. Prog Energy Combust Sci 32:233–271CrossRefGoogle Scholar
  7. 7.
    Giakoumis EG, Rakopoulos CD, Dimaratos AM, Rakopoulos DC (2012) Exhaust emissions of diesel engines operating under transient conditions with biodiesel fuel blends. Prog Energy Combust Sci 38(5):691–715CrossRefGoogle Scholar
  8. 8.
    Marchetti JM, Miguel VU, Errazu A (2007) Heterogeneous esterification of oil with high amount of free fatty acids. Fuel 86:906–910CrossRefGoogle Scholar
  9. 9.
    ECN (2009) Biofuels training manual. Energy Commission of Nigeria, Abuja, pp 1–49Google Scholar
  10. 10.
    Yu H, Niu S, Lu C, Li J, Yang Y (2016) Preparation and esterification performance of Sulfonated coal-based heterogeneous acid catalyst for methyl Oleate production. Energy Convers Manag 126:488–496CrossRefGoogle Scholar
  11. 11.
    Ahmad J, Yusup S, Bokhari A, Kamil RNM (2014) Study of fuel properties of rubber seed oil based biodiesel. Energy Convers Manag 78:266–275CrossRefGoogle Scholar
  12. 12.
    Tiwari AK, Kumar A, Rahama H (2007) Biodiesel production from Jatropha carcus. L. as source of production of biofuel in Nicargia. Bioresour Technol 31:569–575Google Scholar
  13. 13.
    Ogbu IM, Ajiwe VIE (2016) Fuel properties and their correlations with fatty acids structures of methyl- and butyl-esters of Afzelia africana, Cucurbita pepo and Hura crepitans seed oils. Waste Biomass Valoriz 7:373–381CrossRefGoogle Scholar
  14. 14.
    Alamu OJ, Waheed MA, Jekayinfa SO (2007) Alkali-catalysed laboratory production and testing of biodiesel from Nigerian palm kernel oil. Agricultural engineering international: the CIGR ejournal manuscript number EE 07 009. Vol. IXGoogle Scholar
  15. 15.
    Nakajima K, Hara M, Hayashi S (2007) Environmentally benign production of chemicals and energy using a carbon-based strong solid acid. J Am Ceram Soc 90:3725–3734Google Scholar
  16. 16.
    Hara M, Yoshida T, Takagaki A (2004) A carbon material as a strong Protonic acid. Angew Chem Int Ed 43:2955–2958CrossRefGoogle Scholar
  17. 17.
    Chen G, Fang BS (2011) Preparation of solid acid catalyst from glucose–starch mixture for biodiesel production. Bioresour Technol 102:2635–2640CrossRefGoogle Scholar
  18. 18.
    Zong MH, Duan ZQ, Lou WY, Smith TJ, Wu H (2007) Preparation of a sugar catalyst and its use for highly efficient production of biodiesel. Green Chem 7:434–437CrossRefGoogle Scholar
  19. 19.
    Liu T, Li Z, Wei L, Shi C, Wang Y (2013) Preparation and characterization of biomass carbon-based solid acid catalyst for the esterification of oleic acid with methanol. Bioresour Technol 133:618–621CrossRefGoogle Scholar
  20. 20.
    Lou WY, Zong MH, Duan ZQ (2008) Efficient production of biodiesel from high free fatty acid-containing waste oils using various carbohydrate-derived solid acid catalysts. Bioresour Technol 99:8752–8758CrossRefGoogle Scholar
  21. 21.
    Emrani J, Shahbazi A (2012) A single bio-based catalyst for bio-fuel and bio-diesel. J Biotechnol Biomaterial 2(1):1–7CrossRefGoogle Scholar
  22. 22.
    Huang YB, Fu Y (2013) Hydrolysis of cellulose to glucose by solid acid catalysts. Green Chem 15:1095–1111CrossRefGoogle Scholar
  23. 23.
    Russo PA, Antunes MM, Neves P, Wiper PV, Fazio E, Neri F, Barreca F, Mafra L, Pillinger M, Pinna N, Valente AA (2014) Solid acids with SO3H groups and tunable surface properties. Versatile Catalysts for Biomass Conversion. J Mater Chem A 2:11813–11824CrossRefGoogle Scholar
  24. 24.
    Zhou Y, Niu S (2016) Li J (2016) activity of the carbon-based heterogeneous acid catalyst derived from bamboo in esterification of oleic acid with ethanol. Energy Convers Manag 114:188–196CrossRefGoogle Scholar
  25. 25.
    Lee D (2013) Preparation of a Sulfonated carbonaceous material from Lignosulfonate and its usefulness as an esterification catalyst. Molecules 18:8168–8180CrossRefGoogle Scholar
  26. 26.
    Bennett JA, Wilson K, Lee AF (2016) Catalytic application of waste derived materials. J Mater Chem A 4:3617–3637CrossRefGoogle Scholar
  27. 27.
    Arora R, Kapoor V, Toor AP (2014) Esterification of free fatty acids in waste oil using a carbon-based solid acid catalyst. 2nd international conference on emerging trends in engineering and technology (ICETET'2014), may 30-31, 2014 London (UK). Pp. 1–10Google Scholar
  28. 28.
    Abdulkadir MN, Amoo IA, Adesina AO (2013) Chemical composition of Hura Crepitans seeds and antimicrobial activities of its oil. Int J Sci Res 2(3):2319–7064Google Scholar
  29. 29.
    Oyeleke GO, Olayiwola OA, Latona DF (2012) Chemical examination of sandbox (Hura Crepitans) seed proximate. J Appl Chem (IOSRJAC) 1(2):10–13Google Scholar
  30. 30.
    Nsi EW, Akpakpan AE, Ukpong EJ, Akpabio UD (2016) Preparation and characterization of activated carbon from Hura Crepitans Linn seed shells. Int J Eng Sci (IJES) 5(9):38–41Google Scholar
  31. 31.
    Dhawane H, Bora AP, Kumar T (2017) Halder G (2017) parametric optimization of biodiesel synthesis from rubber seed oil using Iron doped carbon catalyst by Taguchi approach. Renew Energy 105:616–624CrossRefGoogle Scholar
  32. 32.
    Mohammad IJ, Mohammad GR, Ashfaque AC, Nanjappa A (2012) Biofuels production through biomass pyrolysis —a technological review. Energies 5:4952–5001CrossRefGoogle Scholar
  33. 33.
    Shah KA, Maheria KC, Parikh JK, Maheria KC (2013) Use of sulfonic acid-functionalized silica as catalyst for esterification of free fatty acids (FFA) in acid oil for biodiesel production and optimization study. Res Chem Intermed 41:1035CrossRefGoogle Scholar
  34. 34.
    Khan MA, Yusup S, Ahmad MM (2010) Acid esterification of a high free fatty acid crude palm oil and crude rubber seed oil blend: optimization and parametric analysis. Biomass and bioenergy 3 4: 1 7 5 1-1 7 5 6Google Scholar
  35. 35.
    Morrison RT, Boyd RN (2011) Organic chemistry. Dorling Kindersley (India) Pvt. ltd, 7th Ed. P 812Google Scholar
  36. 36.
    Dunn JG (2002) Characterization of materials: Thermogravimetric analysis. Second Ed., John Wiley & Sons, Inc. p. 1–145Google Scholar
  37. 37.
    Liu X-Y, Huang M, Ma H-L, Zhang Z-Q, Gao J-M, Zhu Y-L, Han X-J, Guo X-Y (2010) Preparation of a carbon-based solid acid catalyst by Sulfonating activated carbon in a chemical reduction process. Molecules 15:7188–7196CrossRefGoogle Scholar
  38. 38.
    Kumar N, Mohapatra SK, Ragit SS, Kundu K, Karmakar R (2017) Optimization of safflower oil transesterification using the Taguchi approach. Pet Sci 14:798–805CrossRefGoogle Scholar
  39. 39.
    Nandhini M, Suchithra B, Saravanathamizhan R, Prakash DG (2014) Optimization of parameters for dye removal by electro-oxidation using Taguchi design. J Electrochem Sci Eng 4(4):227–234CrossRefGoogle Scholar
  40. 40.
    Kumar S, Chary GHVC, Dastidar MG (2015) Optimization studies on Coale oil agglomeration using Taguchi (L16) experimental design. Fuel 141:9–16CrossRefGoogle Scholar
  41. 41.
    Hidayat A, Rochmadi WK, Nurdiawati A, Kurniawan W, Hinode H, Yoshikawa K, Budiman A (2015) Esterification of palm fatty acid distillate with high amount of free fatty acids using coconut Shell char based catalyst. Energy Procedia 75:969–974CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media, LLC, part of Springer Nature 2018

Authors and Affiliations

  • Ikechukwu Martin Ogbu
    • 1
    • 2
    Email author
  • Vincent Ishmael Egbulefu Ajiwe
    • 2
  • Chukwunonso Peter Okoli
    • 1
    • 3
  1. 1.Department of Chemistry/Biochemistry/Molecular BiologyAlex Ekwueme Federal University Ndufu-AlikeIkwoNigeria
  2. 2.Department of Pure and Industrial ChemistryNnamdi Azikiwe UniversityAwkaNigeria
  3. 3.Department of ChemistryVaal University of Science and TechnologyVanderbijlparkSouth Africa

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