Catalytic Conversion of Pyrolysis Oil into Liquid Hydrocarbon Fuel via Deoxygenation Using Solid Pyrolysis Products of Buton Rock Asphalt
DOI:
https://doi.org/10.48048/tis.2026.12983Keywords:
Asphalt pyrolysis oil, Liquid fuel upgrading, Buton rock asphalt, Catalytic deoxygenation, Metal impregnation, Asphalt pyrolysis oil, Liquid fuel upgrading, Buton rock asphalt, Catalytic deoxygenation, Metal impregnationAbstract
Asphalt Pyrolysis Oil (APO) obtained from Buton rock asphalt pyrolysis contains high oxygenate compounds, which cause the oil to be acidic and unstable; thus, it requires upgrading to improve its quality. Oxygenate compounds can be reduced by catalytic deoxygenation. This study utilized Buton rock asphalt solid residue (CRA), which is rich in CaCO₃, impregnated with Fe, Ni, and Zn metals as a deoxygenation catalyst (Fe/CRA, Ni/CRA, and Zn/CRA). GC-MS analysis revealed that the initial APO was predominantly composed of oxygenates and heavy fractions (C₁₈ and above) (45.91%). After deoxygenation using Ni/CRA, the C₁₁-C₁₈ fraction increased to 77.40% and the fraction greater than C₁₈ decreased to 16.32%. The Ni/CRA catalyst also showed the best performance with the highest liquid yield (69.11%) and the lowest coke (1.42%). These results indicate that Fe/CRA, Ni/CRA, and Zn/CRA have the potential to improve the quality of APO liquid fuel.
HIGHLIGHTS
- Char residue asphalt (CRA) impregnated with Ni, Fe, and Zn deoxygenation catalysts for asphalt pyrolysis oil (APO).
- Ni/CRA capable of increasing the C11–C18 fraction up to 77% and the fraction greater than C₁₈ decreased to 16.32% after deoxygenation reaction.
- The Ni/CRA catalyst showed the highest liquid yield (69.11%) with the lowest coke (1.42%).
- The Ni-CRA catalyst promoted the hydrogenation and hydrogenolysis of oxygenate compounds (acids, ketones, esters), so it was effective in reducing oxygenate content.
- Fe/CRA and Zn/CRA also showed an upgrading effect, although with lower activity than Ni/CRA.
GRAPHICAL ABSTRACT
Downloads
References
J Hao, P Zong, Y Tian, J Zhang and Y Qiao. Distribution and chemical structure characteristic of the fast thermal-cracking products of Buton oil sand bitumen by Py-GC/TOF-MS and a fluidized bed reactor. Energy Conversion and Management 2019; 183, 485-499.
JL Sihombing, H Herlinawati, N Pulungan, L Simatupang, R Rahayu and AA Wibowo. Effective hydrodeoxygenation bio-oil via natural zeolite supported transition metal oxide catalyst. Arabian Journal of Chemistry 2023; 16(50), 104707.
K Primerano, J Mirwald and B Hofko. Asphaltenes and maltenes in crude oil and bitumen: A comprehensive review of properties, separation methods, and insights into structure, reactivity and aging. Fuel 2024; 368, 131616.
Y Liu, Q Yao, M Sun and X Ma. Catalytic fast pyrolysis of coal tar asphaltene over zeolite catalysts to produce high-grade coal tar: An analytical Py-GC/MS study. Journal of Analytical and Applied Pyrolysis 2021; 156, 105127.
T He, Z Zhong and B Zhang. Bio-oil upgrading via ether extraction, looped-oxide catalytic deoxygenation, and mild electrocatalytic hydrogenation techniques. 2020; 34(8), 9725-9733.
Z Guo, K Li, L Jiang, Y Ran, EK Sarkodie, J Yang, J Shi, S Liu, M Li, J Li, H Liu, Y Liang, H Yin and X Liu. Removal mechanisms of phosphate from water by calcium silicate hydrate supported on hydrochar derived from microwave-assisted hydrothermal treatment. Environmental Technology & Innovation 2022; 28, 102942.
P Zhang, M He, S Huo, F Li and K Li. Recent progress in metal-based composites toward adsorptive removal of phosphate: Mechanisms, behaviors, and prospects. Chemical Engineering Journal 2022; 446(2), 137081.
R Tamim, D Prasetyoko, S Jovita, YL Ni’mah, RE Nugraha, H Holilah, H Bahruji, R Yusop, N Asikin-Mijan, AA Jalil, H Hartati and DD Anggoro. Low temperature pyrolysis of waste cooking oil using marble waste for bio-jet fuel production. Renewable Energy 2024; 232, 121135.
SF Basumatary, S Brahma, M Hoque, BK Das, M Selvaraj, S Brahma and S Basumatary. Advances in CaO-based catalysts for sustainable biodiesel synthesis. Green Energy and Resources 2023; 1(3), 100032.
P Maneechakr and S Karnjanakom. Improving the Bio-oil quality via effective pyrolysis/deoxygenation of palm kernel cake over a metal (Cu, Ni, or Fe)-doped carbon catalyst. ACS Omega 2021; 6(30), 20006-20014.
M Ambarita, D Ardiansyah, WW Schmahl, YM Pusparizkita, R Ismail, J Jamari and AP Bayuseno. Indirect mineral carbonation of natural asphalt extraction solid waste residue via pH and temperature control. Case Studies in Chemical and Environmental Engineering 2024; 9, 100715.
C Jia, H Yu, H Liu, H Qin and Q Wang. Pyrolysis characteristics of Indonesian oil sand in a fixed bed. ACS Omega 2022; 7(27), 23315-23321.
N Widiarti, Wijianto, N Wijayati, Harjito, SBW Kusuma, D Prasetyoko and Suprapto. Catalytic activity of calcium oxide from fishbone waste in waste cooking oil transesterification process. Jurnal Bahan Alam Terbarukan 2017; 6(2), 97-106.
R Tamim, D Prasetyoko, S Jovita, R Subagyo, YL Ni’Mah, H Holilah, H Bahruji, N Asikin-Mijan, AA Jalil, H Hartati and DD Anggoro. Ni-activated marble waste nanoparticles for catalyzed pyrolysis of waste cooking oil into hydrocarbon. Renewable Energy 2025; 248, 123128.
H Vicente, C Liu, AG Gayubo, P Cast and EA Pidko. Improving the dehydrogenation function and stability of Zn-modified ZSM-5 catalyst in methanol-to-aromatics reaction by Ca addition. Applied Catalysis A: General 2024; 683, 119854.
RSRM Hafriz, IN Sha, NA Ari, A Salmiaton, R Yunus, YH Tau and AH Shamsuddin. Effect of Ni/Malaysian dolomite catalyst synthesis technique on deoxygenation reaction activity of waste cooking oil. Renewable Energy 2021; 178, 128-143.
S Lv, J Yuan, X Peng, MB Cabrera, S Guo, X Luo and J Gao. Performance and optimization of bio-oil/Buton rock asphalt composite modified asphalt. Construction and Building Materials 2020; 264, 120235.
S Oh, HS Choi, IG Choi and JW Choi. Evaluation of hydrodeoxygenation reactivity of pyrolysis bio-oil with various Ni-based catalysts for improvement of fuel properties. RSC Advances 2017; 7(25), 15116-15126.
X Yu and CT Williams. Recent applications of nickel and nickel-based bimetallic catalysts for hydrodeoxygenation of biomass-derived oxygenates to fuels. Catalysis Science & Technology 2023; 13(3), 802-825.
A Gil and SA Korili. Progress and perspectives in the catalytic hydrotreatment of Bio-oils: Effect of the nature of the metal catalyst. Industrial & Engineering Chemistry Research 2024; 63(27), 11759-11775.
LI Al-ali, O Elmutasim, KA Ali, N Singh and K Polychronopoulou. Transition Metal Phosphides (TMP) as a versatile class of catalysts for the hydrodeoxygenation reaction (HDO) of oil-derived compounds. Nanomaterials 2022; 12(9), 1435.
Y Yee, S Thangalazhy-gopakumar, H Kiat, L Yee and S Gan. Effect of oxide catalysts on the properties of bio-oil from in-situ catalytic pyrolysis of palm empty fruit bunch fiber. Journal of Environmental Management 2019; 247, 38-45.
A Peter, B Chabot and E Loranger. Pre ‑ and post ‑ pyrolysis effects on iron impregnation of ultrasound pre ‑ treated softwood biochar for potential catalysis applications. SN Applied Sciences 2021; 3, 643.
Y Wang, L Li, Z Liu and Z Ren. Frontier research and prospect of phosphate adsorption in wastewater by red mud: A review. Desalination and Water Treatment 2023; 310, 86-108.
RE Nugraha, H Purnomo, A Aziz, H Holilah, H Bahruji, N Asikin-Mijan, S Suprapto, YH Taufiq-Yap, AA Jalil, H Hartati and D Prasetyoko. The mechanism of oleic acid deoxygenation to green diesel hydrocarbon using porous aluminosilicate catalysts. South African Journal of Chemical Engineering 2024; 49, 122-135.
X Liu, F Shen and X Qi. Adsorption recovery of phosphate from aqueous solution by CaO-biochar composites prepared from eggshell and rice straw. Science of The Total Environment 2019; 666, 694-702.
NA Zul, S Ganesan, TS Hamidon, WD Oh and MH Hussin. A review on the utilization of calcium oxide as a base catalyst in biodiesel production. Journal of Environmental Chemical Engineering 2021; 9(4), 105741.
M Kouser, B Chowhan, N Sharma and M Gupta. Transformation of waste toner powder into valuable Fe2O3 nanoparticles for the preparation of recyclable Co(II)-NH2‑SiO2@Fe2O3 and its applications in the synthesis of polyhydroquinoline and quinazoline derivatives. ACS Omega 2022; 7(51), 47619-47633.
L Liu, S Fu, X Lv, L Yue, L Fan, H Yu, X Gao, W Zhu, W Zhang, X Li and W Zhu. A gas sensor with Fe2O3 nanospheres based on trimethylamine detection for the rapid assessment of spoilage degree in fish. Frontiers in Bioengineering and Biotechnology 2020; 8, 567584.
Z Mohammadpour and HR Zare. A comparative study on the effect of MWCNT as reinforcement on the corrosion parameters of different Ni–W/MWCNTs nanocomposite coatings in various corrosive media. Metals and Materials International 2018; 24, 761-772.
OS Vereshchagin, IA Chernyshova, MA Kuz and OV Frank-Kamenetskaya. Calcium carbonate precipitation behavior in the system Ca-Me2+-CO3-H2O (Me2+ = Co, Ni, Cu, Fe): Ion incorporation, effect of temperature and aging. Minerals 2023; 13(12), 1497.
E Hadjittofis, SM Vargas, JD Litster and KLS Campbell. Exploring the role of crystal habit in the Ostwald rule of stages. Proceedings Mathematical, Physical, and Engineering Sciences 2022; 478(2258), 20210601.
K Haiouani, S Hegazy, H Alsaeedi, M Bechelany and A Barhoum. Green synthesis of hexagonal-like ZnO nanoparticles modified with phytochemicals of clove (Syzygium aromaticum) and Thymus capitatus extracts: Enhanced antibacterial, antifungal, and antioxidant activities. Materials 2024; 17(17), 4340.
S Dampang, E Purwanti, F Destyorini, SBKB Kurniawan, SRS Abdullah and MF Imron. Analysis of optimum temperature and calcination time in the production of CaO using seashells waste as CaCO3 source. Journal of Ecological Engineering 2021; 22(5), 221-228.
J Qiao, Y Gao, K Zheng, C Shen, A Jia and Q Zhang. One-pot synthesis of magnetic core-shell Fe3O4@C nanospheres with Pt nanoparticle immobilization for catalytic hydrogenation of nitroarenes. Applied Sciences 2025; 15(10), 5773.
Y Lv, H Wang, H Wu, Q Luo, L Wang and F Xiao. Silica modulation of raney nickel catalysts for selective hydrogenation. Precision Chemistry 2023; 1(5), 309-315.
AN Hadi, MH Meteab and MK Mohammed. Influence of inclusion Sb2O3/NiO nanostructures on the morphological, microstructural, and optical characteristics of PVA polymeric for gamma-ray shielding applications. Revue des Composites et des Matériaux Avancés 2025; 35(3), 581-591.
A Hamid, A Fadhel and S Azara. Studying the effect of irradiation time in preparing zinc oxide nanoparticles prepared by microwave method. Digest Journal of Nanomaterials and Biostructures 2022; 17(4), 1417-1422.
Y Zhang, W Lu, D Han, H Guo, X Peng, W Zhu, N Xie, X Zuo, H Zhang, Q Pan and M Xie. Laboratory investigation of modified asphalt containing buton rock asphalt or ash from buton rock asphalt. Case Studies in Construction Materials 2023; 18, 02124.
N Nazarudin, YY Hans, O Alfernando, U Ulyarti and IB Adilina. Catalytic cracking of methyl ester derived from used cooking oil over Ni-impregnated activated charcoal catalyst. Reaktor 2022; 22(1), 21-27.
C Mata, V Rojas-reinoso and JA Soriano. Experimental determination and modelling of fuel rate of injection: A review. Fuel 2023; 343, 127895.
S Collins, N Serge, K Regonne, Z Bilo and N Martin. Optimized biofuel production from Triplochiton scleroxylon sawdust via microwave-assisted pyrolysis and hydrocracking: Process analysis and production revenue forecasting with Aspen Plus. Sustainable Chemistry for the Environment 2025; 12, 100294.
MA Nawaz, R Blay-roger, M Saif, F Meng, LF Bobadilla. TR Reina and JA Odriozola. Redefining the symphony of light aromatic synthesis beyond fossil fuels: A journey navigating through a Fe-Based/HZSM‑5 tandem route for syngas conversion. ACS Catalysis 2024; 14(20), 15150-15196.
RE Nugraha, D Prasetyoko, H Bahruji, S Suprapto, N Asikin-Mijan, TP Oetami, AA Jalil, DVN Vo and YH Taufiq-Yap. Lewis acid Ni/Al-MCM-41 catalysts for H2-free deoxygenation of Reutealis trispermaoil to biofuels. RSC Advances 2021; 11(36), 21885-21896.
LGG Pereira, Q Yuan, HJ Heeres, SB Lima and CAM Pires. Catalytic hydrotreatment of fast pyrolysis oils using Ni-Cu / Al-MCM-41 catalysts. Journal of Analytical and Applied Pyrolysis 2024; 181, 106593.
D Prangklang, D Tumnantong, B Yoosuk, C Ngamcharussrivichai and P Prasassarakich. Selective deoxygenation of waste cooking oil to diesel-like hydrocarbons using supported and unsupported NiMoS2 catalysts. ACS Omega 2023; 8(43), 40921-40933.
C Muangsuwan, W Kriprasertkul, S Ratchahat, C Liu, P Posoknistakul, N Laosiripojana and C Sakdaronnarong. Upgrading of light bio-oil from solvothermolysis liquefaction of an oil palm empty fruit bunch in glycerol by catalytic hydrodeoxygenation using NiMo/Al2O3 or CoMo/Al2O3 catalysts. ACS Omega 2021; 6(4), 2999-3016.
Downloads
Published
How to Cite
Issue
Section
License
Copyright (c) 2026 Walailak University
This work is licensed under a Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International License.
