Catalytic Upgrading of Bio-oil from Ulva lactuca using Amberlyst-15 Catalyst: Experimental and Kinetic Model

Document Type : Original Article


1 Department of Mechanical Engineering, Lambung Mangkurat University, Banjarmasin, South Kalimantan, Indonesia

2 Department of Mechanical and Biosystem Engineering, Faculty of Agricultural Engineering and Technology, IPB University (Bogor Agricultural University), IPB Darmaga Campus, Bogor, Indonesia

3 Research Center for Biomass and Bioproducts, National Research and Innovation Agency (BRIN), Jl, Raya Bogor KM. 46 Cibinong, Indonesia


Catalytic pyrolysis of Ulva lactuca macroalgae was studied over Amberlyst-15 catalyst at temperature 400, 500, and 600 oC. The comparison between catalytic and non-catalytic pyrolysis in the conversion of Ulva lactuca was determined. Intriguingly, it was found that Amberlyst-15 catalyst improved bio-oil production efficiency. The highest bio-oil yield of 29.54 wt% was achieved at 600 oC with the presence of an Amberlyst-15 catalyst. Furthermore, Amberlyst-15 catalyst could enhance gas production by over 73.88%. It could be attributed due to the catalytic pyrolysis could promote more small molecules that are more volatile through a cracking process. Elemental and functional groups in pyrolytic bio-oils were identified via GC-MS analysis. The acidity and structure of Amberlyst-15 catalyst significantly affected the distribution of product components, especially the formation of aromatic hydrocarbons, with a 27.78% relative yield. The first-order kinetic model showed that the production of aromatic hydrocarbons follows Arrhenius law.                  


Main Subjects

  1. Lu, Q., Zhou, M. xing, Li, W. tao, Wang, X., Cui, M. shu, and Yang, Y. ping. “Catalytic fast pyrolysis of biomass with noble metal-like catalysts to produce high-grade bio-oil: Analytical Py-GC/MS study.” Catalysis Today, Vol. 302, (2018), 169-179.
  2. Leong, W. H., Lim, J. W., Lam, M. K., Uemura, Y., and Ho, Y. C. “Third generation biofuels: A nutritional perspective in enhancing microbial lipid production.” Renewable and Sustainable Energy Reviews, Vol. 91, (2018), 950–961.
  3. Biswas, B., Singh, R., Krishna, B. B., Kumar, J., and Bhaskar, T. “Pyrolysis of azolla, sargassum tenerrimum and water hyacinth for production of bio-oil.” Bioresource Technology, Vol. 242, , (2017), 139-145.
  4. Mironova, N., Mateyuk, O., Biletska, H., Shevchenko, S., Kazimirova, L., Artamonov, B., Kravchuk, V., and Bloshchynskyi, I. “Parametric Assessment of Macrophytes Ecological Niches in Solving Problems of Sand Quarry Lakes Phytomelioration,” Journal of Human, Earth, and Future, 3, No. 4, (2022), 423-429.
  5. Amrullah, A., Farobie, O., Septarini, S., and Satrio, J. A. “Synergetic biofuel production from co-pyrolysis of food and plastic waste: reaction kinetics and product behavior.” Heliyon, Vol. 8, No. 8, (2022), e10278.
  6. Farobie, O., Syaftika, N., Masfuri, I., Rini, T. P., Lanank Es, D. P. A., Bayu, A., Amrullah, A., Hartulistiyoso, E., Moheimani, N. R., Karnjanakom, S., and Matsumura, Y. “Green algae to green fuels: Syngas and hydrochar production from Ulva lactuca via sub-critical water gasification.” Algal Research, Vol. 67, No. 1, (2022), 102834.
  7. Yi, B., Chen, M., Gao, Y., Cao, C., Wei, Q., Zhang, Z., and Li, L. “Investigation on the co-combustion characteristics of multiple biomass and coal under O2/CO2 condition and the interaction between different biomass.” Journal of Environmental Management, Vol. 325, (2023), 116498.
  8. Amrullah, A., Farobie, O., Bayu, A., Syaftika, N., Hartulistiyoso, E., Moheimani, N. R., Karnjanakom, S., and Matsumura, Y. “Slow Pyrolysis of Ulva lactuca (Chlorophyta) for Sustainable Production of Bio-oil and Biochar.” Sustainability (Switzerland), Vol. 14, No. 6, (2022), 1-14.
  9. Yang, G., Hu, Q., Hu, J., Yang, H., Yan, S., Chen, Y., Wang, X., and Chen, H. “Hydrogen-rich syngas production from biomass gasification using biochar-based nanocatalysts.” Bioresource Technology, Vol. 379, (2023), 129005.
  10. Batubara, F., Turmuzi, M., Irvan, I., and Yanqoritha, N. “Variations of Organic Loading Rate on Tofu Wastewater Degradation using Upflow Anaerobic Sludge Blanket Reactor by Modified Stover-Kincannon Model.” International Journal of Engineering Transactions C: Aspects, Vol. 36, No. 3, (2023), 490-496.
  11. Chen, X., Chen, Y., Yang, H., Wang, X., Che, Q., Chen, W., and Chen, H. “Catalytic fast pyrolysis of biomass: Selective deoxygenation to balance the quality and yield of bio-oil.” Bioresource Technology, Vol. 273, (2019), 153-158.
  12. Chow, M. C., Jackson, W. R., Chaffee, A. L., and Marshall, M. “Thermal treatment of algae for production of biofuel.” Energy and Fuels, Vol. 27, No. 4, (2013), 1926-1950.
  13. French, R., and Czernik, S. “Catalytic pyrolysis of biomass for biofuels production.” Fuel Processing Technology, Vol. 91, No. 1, (2010), 25-32.
  14. Biswas, B., Pandey, N., Bisht, Y., Singh, R., Kumar, J., and Bhaskar, T. “Pyrolysis of agricultural biomass residues: Comparative study of corn cob, wheat straw, rice straw and rice husk.” Bioresource Technology, Vol. 237, (2017), 57-63.
  15. Amrullah, A., Farobie, O., and Widyanto, R. “Pyrolysis of purun tikus (Eleocharis dulcis): Product distributions and reaction kinetics.” Bioresource Technology Reports, Vol. 13, (2021), 100642.
  16. Idris, R., Chong, W. W. F., Ali, A., Idris, S., Hasan, M. F., Ani, F. N., and Chong, C. T. “Phenol-rich bio-oil derivation via microwave-induced fast pyrolysis of oil palm empty fruit bunch with activated carbon.” Environmental Technology and Innovation, Vol. 21, (2021), 101291.
  17. Cheng, S., Shu, J., Xia, H., Wang, S., Zhang, L., Peng, J., Li, C., Jiang, X., and Zhang, Q. “Pyrolysis of Crofton weed for the production of aldehyde rich bio-oil and combustible matter rich bio-gas.” Applied Thermal Engineering, Vol. 148, (2019), 1164-1170.
  18. Xie, Q., Addy, M., Liu, S., Zhang, B., Cheng, Y., Wan, Y., Li, Y., Liu, Y., Lin, X., Chen, P., and Ruan, R. “Fast microwave-assisted catalytic co-pyrolysis of microalgae and scum for bio-oil production.” Fuel, Vol. 160, (2015), 577-582.
  19. Yu, J., Maliutina, K., and Tahmasebi, A. “A review on the production of nitrogen-containing compounds from microalgal biomass via pyrolysis.” Bioresource Technology, Vol. 270, (2018), 689-701.
  20. Thangalazhy-Gopakumar, S., Adhikari, S., Chattanathan, S. A., and Gupta, R. B. “Catalytic pyrolysis of green algae for hydrocarbon production using H +ZSM-5 catalyst.” Bioresource Technology, Vol. 118, (2012), 150-157.
  21. Hematkhah, R., Majidian, N., Hallajisani, A., and Samipoorgiri, M. “Investigation of catalytic pyrolysis of spirulina for bio-oil production.” Arabian Journal of Chemistry, Vol. 16, No. 5, (2023), 104691.
  22. Hita, I., Cordero-Lanzac, T., Bonura, G., Cannilla, C., Arandes, J. M., Frusteri, F., and Bilbao, J. “Hydrodeoxygenation of raw bio-oil towards platform chemicals over FeMoP/zeolite catalysts.” Journal of Industrial and Engineering Chemistry, Vol. 80, (2019), 392-400.
  23. Anand, V., Gautam, R., and Vinu, R. “Non-catalytic and catalytic fast pyrolysis of Schizochytrium limacinum microalga.” Fuel, Vol. 205, (2017), 1-10.
  24. Wang, S., Cao, B., Liu, X., Xu, L., Hu, Y., Afonaa-Mensah, S., Abomohra, A. E. F., He, Z., Wang, Q., and Xu, S. “A comparative study on the quality of bio-oil derived from green macroalga Enteromorpha clathrata over metal modified ZSM-5 catalysts.” Bioresource Technology, Vol. 256, (2018), 446–455.
  25. Zainan, N. H., Srivatsa, S. C., Li, F., and Bhattacharya, S. “Quality of bio-oil from catalytic pyrolysis of microalgae Chlorella vulgaris.” Fuel, Vol. 223, (2018), 12-19.
  26. Uslamin, E. A., Luna-Murillo, B., Kosinov, N., Bruijnincx, P. C. A., Pidko, E. A., Weckhuysen, B. M., and Hensen, E. J. M. “Gallium-promoted HZSM-5 zeolites as efficient catalysts for the aromatization of biomass-derived furans.” Chemical Engineering Science, Vol. 198, (2019), 305-316.
  27. Limlamthong, M., and Yip, A. C. K. “Recent advances in zeolite-encapsulated metal catalysts: A suitable catalyst design for catalytic biomass conversion.” Bioresource Technology, Vol. 297, (2020), 122488.
  28. Chen, L., Yu, Z., Fang, S., Dai, M., and Ma, X. “Co-pyrolysis kinetics and behaviors of kitchen waste and chlorella vulgaris using thermogravimetric analyzer and fixed bed reactor.” Energy Conversion and Management, Vol. 165, (2018), 45-52.
  29. Dewangan, A., Pradhan, D., and Singh, R. K. “Co-pyrolysis of sugarcane bagasse and low-density polyethylene: Influence of plastic on pyrolysis product yield.” Fuel, Vol. 185, (2016), 508-516.
  30. Chen, C., Fan, D., Zhao, J., Qi, Q., Huang, X., Zeng, T., and Bi, Y. “Study on microwave-assisted co-pyrolysis and bio-oil of Chlorella vulgaris with high-density polyethylene under activated carbon.” Energy, Vol. 247, (2022), 123508.
  31. White, J. E., Catallo, W. J., and Legendre, B. L. “Biomass pyrolysis kinetics: A comparative critical review with relevant agricultural residue case studies.” Journal of Analytical and Applied Pyrolysis, Vol. 91, No. 1, (2011), 1-33.
  32. D’Almeida, A. L. F. S., Barreto, D. W., Calado, V., and D’Almeida, J. R. M. “Thermal analysis of less common lignocellulose fibers.” Journal of Thermal Analysis and Calorimetry, Vol. 91, No. 2, (2008), 405-408.
  33. Chen, C., Zeng, T., Qi, Q., Qiu, H., Zhao, J., and Fan, D. “Microwave catalytic pyrolysis production and characterization of Chlorella vulgaris under different compound additives.” Journal of the Energy Institute, Vol. 100, (2022), 160–169.
  34. Kumar, A., Biswas, B., and Bhaskar, T. “Effect of cobalt on titania, ceria and zirconia oxide supported catalysts on the oxidative depolymerization of prot and alkali lignin.” Bioresource Technology, Vol. 299, (2020), 122589.
  35. Ye, Y., Zhang, Y., Fan, J., and Chang, J. “Novel method for production of phenolics by combining lignin extraction with lignin depolymerization in aqueous ethanol.” Industrial and Engineering Chemistry Research, Vol. 51, No. 1, (2012), 103–110.
  36. Yorgun, S., and Yildiz, D. “Slow pyrolysis of paulownia wood: Effects of pyrolysis parameters on product yields and bio-oil characterization.” Journal of Analytical and Applied Pyrolysis, Vol. 114, (2015), 68-78.
  37. Mo, L., Dai, H., Feng, L., Liu, B., Li, X., Chen, Y., and Khan, S. “In-situ catalytic pyrolysis upgradation of microalgae into hydrocarbon rich bio-oil: Effects of nitrogen and carbon dioxide environment.” Bioresource Technology, Vol. 314, (2020), 123758.
  38. Yaman, E., Yargic, A. S., Ozbay, N., Uzun, B. B., Kalogiannis, K. G., Stefanidis, S. D., Pachatouridou, E. P., Iliopoulou, E. F., and Lappas, A. A. “Catalytic upgrading of pyrolysis vapours: Effect of catalyst support and metal type on phenolic content of bio-oil.” Journal of Cleaner Production, Vol. 185, (2018), 52-61.
  39. Tan, H., Yang, M., Chen, Y., Chen, X., Fantozzi, F., Bartocci, P., Tschentscher, R., Barontini, F., Yang, H., and Chen, H. “Preparation of aromatic hydrocarbons from catalytic pyrolysis of digestate.” Chinese Journal of Chemical Engineering, Vol. 57, (2022), 1-9.
  40. Pütün, E. “Catalytic pyrolysis of biomass: Effects of pyrolysis temperature, sweeping gas flow rate and MgO catalyst.” Energy, Vol. 35, No. 7, (2010), 2761-2766.
  41. Pato, U., Ayu, D. F., Riftyan, E., Restuhadi, F., Pawenang, W. T., Firdaus, R., Rahma, A., and Jaswir, I. “Cellulose Microfiber Encapsulated Probiotic: Viability, Acid and Bile Tolerance during Storage at Different Temperature.” Emerging Science Journal, Vol. 6, No. 1, (2022), 106-117.
  42. Asadpour, R., Sapari, N. B., Hasnain Isa, M., and Kakooei, S. “Further study of adsorption of crude oils onto acetylated corn silk and its kinetics and equilibrium isotherm.” International Journal of Engineering, Transactions B: Applications, Vol. 32, No. 2, (2019), 284-291.
  43. Biswas, B., Fernandes, A. C., Kumar, J., Muraleedharan, U. D., and Bhaskar, T. “Valorization of Sargassum tenerrimum: Value addition using hydrothermal liquefaction.” Fuel, Vol. 222, (2018), 394-401.
  44. Xia, S., Yang, H., Lei, shuaishuai, Lu, W., Cai, N., Xiao, H., Chen, Y., and Chen, H. “Iron salt catalytic pyrolysis of biomass: Influence of iron salt type.” Energy, Vol. 262, (2023), 125415.
  45. LI, B., FENG, B., WU, K., and YANG, T. “Hydrodeoxygenation of lignin derived bio-oil into aromatic hydrocarbons over Ni-Cu-Ru/HZSM-5 catalyst.” Journal of Fuel Chemistry and Technology, Vol. 51, No. 3, (2023), 358-365.
  46. Zhang, S., Liang, Y., Qian, X., Hui, D., and Sheng, K. “Pyrolysis kinetics and mechanical properties of poly(lactic acid)/bamboo particle biocomposites: Effect of particle size distribution.” Nanotechnology Reviews, Vol. 9, No. 1, (2020), 524-533.
  47. Shahdan, N. A., Balasundram, V., Ibrahim, N., Isha, R., and Manan, Z. A. “Catalytic Co-pyrolysis of empty fruit bunch and high-density polyethylene mixtures over rice husk ash: Thermogravimetric, kinetic and thermodynamic analyses.” Cleaner Engineering and Technology, Vol. 9, (2022), 100538.