Characterization and antioxidant properties of ethyl acetate fractions from pyroligneous acid obtained by slow pyrolysis of palm kernel shell


  • Zainab Rabiu Universiti Teknologi Malaysia
  • Khoirun Nisa Mahmud Universiti Teknologi Malaysia
  • Rosnani Hasham Universiti Teknologi Malaysia
  • Zainul Akmar Zakaria Universiti Teknologi Malaysia



Palm kernel shell, Slow Pyrolysis, Pyroligneous acid, Antioxidants, Fractionation and GCMS


Sustainable and renewable utilization of Palm kernel shell biomass, can be achieved by thermochemical conversion method of slow pyrolysis which is simple, cost effective and eco-friendly.  Palm kernel shell biomass has unlimited potential, as an alternative form of fossil fuels and source of value added chemicals. The refined bio-oil termed Pyroligneous Acid (PA) has been found to contain phenolic and antioxidant activity. These compounds have various applications. However, the low concentration of the antioxidant phenols makes producing chemicals and medicines from palm kernel shell less viable. A higher yield percentage can be obtained from fractionation which also simplifies identification of compounds. The total phenolic contents and antioxidant activities are determined by the Folin ciocalteau and (DPPH and FRAP) assay, column chromatography is used to separate the Pyroligneous acid sample into different fractions, characterization of chemical constituents of the fractions with phenolic activities is carried out by GC-MS. Optimum pyrolysis condition achieved at 429°C residence time 39 o Min-1 with a 40.44 % wt. yield. The obtained results show the presence of phenolic activity in different fractions, the fraction with the highest phenolic activity Fraction 9 (181.75 µg/ml ± 17.0), Fraction 21-25(174.95 µg/ml ± 0.39) and 26-30 (181.76 µg/ml ± 15.54) simultaneously exhibiting high antioxidant activity DPPH Fraction 9 (23.97%), Fraction 21-25(31.39%) and Fraction 26-30 (52.58%). Sixteen different types of phenolic chemical compounds and their derivatives were also identified with up to 60% higher concentrations when compared to previous studies without fractionation. This allows for more economical utilization of viable, pure natural alternatives for producing chemicals and medicines, while simultaneously reducing agricultural waste. 


Keywords: Palm kernel shell, Slow Pyrolysis, Pyroligneous acid, Antioxidants, Fractionation and GCMS

Author Biographies

Zainab Rabiu, Universiti Teknologi Malaysia

Institute of Bioproduct and Development


Khoirun Nisa Mahmud, Universiti Teknologi Malaysia

Institute of Bio-product and Development, Faculty of Chemical and Energy Engineering

Rosnani Hasham, Universiti Teknologi Malaysia

 Institute of Bio-product and Development, Faculty of Chemical and Energy Engineering

Zainul Akmar Zakaria, Universiti Teknologi Malaysia

 Institute of Bio-product and Development, Faculty of Chemical and Energy Engineering


Abnisa, F., Arami-Niya, A., Daud, W. W., Sahu, J., Noor, I. M. 2013. "Utilization of oil palm tree residues to produce bio-oil and bio-char via pyrolysis." Energy Conversion and Management 76, 1073-1082.

Ahmad, R., Hamidin, N., Md Ali, U., Abidin, C. Z. A. 2014. "Characterization of bio-oil from palm kernel shell pyrolysis." Journal of Mechanical Engineering and Sciences 7, 1134-1140.

Asadullah, M., Rasid, N. S. A., Kadir, S. A. S. A., Azdarpour, A. 2013. "Production and detailed characterization of bio-oil from fast pyrolysis of palm kernel shell." Biomass and Bioenergy 59, 316-324.

Ateş, F., Pütün, E., Pütün, A. 2004. "Fast pyrolysis of sesame stalk: yields and structural analysis of bio-oil." Journal of Analytical and Applied Pyrolysis 71, 779-790.

Bardalai, M. 2015. "A review of physical properties of biomass pyrolysis oil." International Journal of Renewable Energy Research 5, 277-286.

Brebu, M. and Vasile, C. 2010. Thermal degradation of lignin – A Review. Cellulose Chemistry & Technology 44, 353-363.

Collard, F.-X., J. Blin 2014. "A review on pyrolysis of biomass constituents: Mechanisms and composition of the products obtained from the conversion of cellulose, hemicelluloses and lignin." Renewable and Sustainable Energy Reviews 38, 594-608.

Coskun, O. 2016. "Separation techniques: Chromatography." Northern Clinics of Istanbul 3, 156-160.

Eom, I.-Y., Yu, J.-H., Jung, C.-D., Hong, K.-S. 2015. "Efficient ethanol production from dried oil palm trunk treated by hydrothermolysis and subsequent enzymatic hydrolysis." Biotechnology for Biofuels 8, 1-11.

French, R., Czernik, S. 2010. "Catalytic pyrolysis of biomass for biofuels production." Fuel Processing Technology 91, 25-32.

Gan, J., Yuan, W. 2013. "Operating condition optimization of corncob hydrothermal conversion for bio-oil production." Applied Energy 103, 350-357.

Goh, C. S., Tan, K. T., Lee, K. T., Bhatia, S. 2010. "Bio-ethanol from lignocellulose: Status, perspectives and challenges in Malaysia." Bioresource Technology 101, 4834 - 4841.

Greenhalf, C., Nowakowski, D., Harms, A., Titiloye, J., Bridgwater, A. 2013. "A comparative study of straw, perennial grasses and hardwoods in terms of fast pyrolysis products." Fuel 108, 216-230.

Guillén, M. D., Manzanos, M. J. 2002. "Study of the volatile composition of an aqueous oak smoke preparation." Food Chemistry 79, 283-292.

Hooi, K. K. 2012. "Laboratory-scale pyrolysis of oil palm shells." Paper presented to Persidangan Kebangsaan Pembangunan dan Pendidikan Lestari 2012, Institut Pendilan Guru Kampus Tunku Bainun, Bukit Mertajam, Pulau Pinang, 9-10 September 2012. ?url=

Junaidah, S. A. 2017. "Optimization of pyroligneous acid from palm kernel shell and its potential as antibacterial and anti-biofilm activities", MSc Disseration, Universiti Teknologi Malaysia, Skudai.

Kim, J.-S. 2015. "Production, separation and applications of phenolic-rich bio-oil – A review." Bioresource Technology 178, 90-98.

Kim, S.-J., S.-H. Jung., J.-S. Kim 2010. "Fast pyrolysis of palm kernel shells: Influence of operation parameters on the bio-oil yield and the yield of phenol and phenolic compounds." Bioresource Technology 101, 9294-9300.

Kumar, G., Panda, A. K., Singh, R. 2010. "Optimization of process for the production of bio-oil from eucalyptus wood." Journal of Fuel Chemistry and Technology 38, 162-167.

Li, L., Zhang, H., Zhuang, X. 2005. "Pyrolysis of waste paper: Characterization and composition of pyrolysis oil." Energy Sources 27, 867-873.

Loo, A. Y., Jain, K., Darah, I. 2007. "Antioxidant and radical scavenging activities of the pyroligneous acid from a mangrove plant, Rhizophora apiculata." Food chemistry 104, 300-307.

Lv, G. Wu, S. 2012. "Analytical pyrolysis studies of corn stalk and its three main components by TG-MS and Py-GC/MS." Journal of Analytical and Applied Pyrolysis 97, 11-18.

Ma, C., Li, W. Zu, Y. Yang, L., Li, J. 2014. "Antioxidant properties of pyroligneous acid obtained by thermochemical conversion of Schisandra chinensis Baill." Molecules 19, 20821-20838.

McKendry, P. 2002. "Energy production from biomass (part 2): Conversion technologies." Bioresource Technology 83, 47-54.

Neutelings, G. 2011. "Lignin variability in plant cell walls: Contribution of new models." Plant Science 181, 379-386.

Nie, H., Li, S., Zhou, Y., Chen, T., He, Z., Su, S., Zhang, H., Xue, Y., Zhu, L. 2008. "Purification of bromelain using immobilized metal affinity membranes." Journal of Biotechnology 136S, S420-S459.

Oh, S.-J., G.-G. Choi and J.-S. Kim 2016. "Characteristics of bio-oil from the pyrolysis of palm kernel shell in a newly developed two-stage pyrolyzer." Energy 11, 108-115.

Omer, A. M. 2012. "Biomass energy resources utilisation and waste management." Blue Biotechnology Journal 3, 124-145.

Paethanom, A. and K. Yoshikawa 2012. "Influence of pyrolysis temperature on rice husk char characteristics and its tar adsorption capability." Energies 5, 4941-4951.

Park, Y.-K., J.-K. Jeon, S. Kim and J.-S. Kim 2004. "Bio-oil from rice straw by pyrolysis using fluidized bed and char removal system." Prepr. Pap.-American Chemical Society Division of Fuel Chemistry 49, 800-801.

Rabiu, Z. Zainul, A. Z 2017. "Pyrolignous Acid Production from Palm Kernel Shell Bioma." Journal of Applied Environmental and Biological Sciences 7, 59-62.

Rungruang, P., Junyapoon, S. 2010. "Antioxidative activity of phenolic compounds in pyroligneous acid produced from Eucalyptus wood". The 8th International Symposium on Biocontrol and Biotechnology, Pattaya, Thailand, 4-6 October.

Soare, J. R., Dinis, T. C., Cunha, A. P., Almeida, L. 1997. "Antioxidant activities of some extracts of Thymus zygis." Free radical research 26, 469-478.

Souza, J. B. G., Ré-Poppi, N., Raposo Jr, J. L. 2012. "Characterization of pyroligneous acid used in agriculture by gas chromatography-mass spectrometry." Journal of the Brazilian Chemical Society 23, 610-617.

Srimachai, T., Thonglimp, V. O-Thong, S. 2014. "Ethanol and methane production from oil palm frond by two stage SSF." Energy Procedia 52, 352-361.

Stichnothe, H., Schuchardt, F. 2011. "Life cycle assessment of two palm oil production systems." Biomass and Bioenergy 35, 3976-3984.

Bradbury, B. A. G., Yoshio, S., Fred, S. 1979. "A kinetic model for pyrolysis of cellulose." Journal of Applied Polymer Science 23, 3271-3280.

Yang, H., Yan, R., Chen, H., Lee, D. H., Zheng, C. 2007. "Characteristics of hemicellulose, cellulose and lignin pyrolysis." Fuel 86, 1781-1788.

Vigouroux, R. Z., Ferro, D. T., Torres, A., Soler, P. B., Björnbom, E. 2004. "Biomass torrefaction." Second World Conference on Biomass for Energy, Industry and Climate Protection. 10-14 May. Rome Italy, 859-862.

Zhai, M., Shi, G., Wang, Y., Mao, G., Wang, D., Wang, Z. 2015. "Chemical compositions and biological activities of pyroligneous acids from walnut shell". Bioresource 10, 1715-1729.