Optimizing heavy crude oil conversion: Catalytic thermolysis with TiO₂@α-Fe₂O₃ nanocomposite and surfactant dynamics

Abstract

Currently, as the production of light crude oil is reaching its peak, the focus of the petroleum industry is shifting towards significant amount of heavy oil to meet the increasing need for energy and fuels. Heavy oil is typically categorized by its high density, great viscosity with small API gravity, high hetero-atom content and limited low boiling point fuel fraction yield compared to light oil. One approach for enhancing the flow characteristics of heavy oil before the recovery process is introducing catalysts into the reservoir. This scientific research focuses on the preparation and characterization of (10%, 20%, 30%) TiO₂@α-Fe₂O₃ nanocomposite catalysts for potential catalytic applications. The study outlines the synthesis method used to create different ratios of as-prepared nanocomposites. It provides detailed characterization through various analytical techniques. The results highlight the successful formation of X% TiO₂@α-Fe₂O₃ nanocomposites with well-defined structures and optimized properties for catalytic reactions. The study investigates the impact of this nanocomposite on the rheological characterizations of heavy crude oil, focusing on the capability of decreasing viscosity and advance flow characteristics. The experimental results demonstrate notable improvements in viscosity reduction and enhancing heavy crude oil production processes as the best results obtained by (0.5 wt%) 20% TiO₂@α-Fe₂O₃ (62.6% after 2 h at 200°C). The asphaltene and resin ratio decreased by 54.5% and 68.1% respectively. The saturated and aromatic content shows 67.56% and 15.91% respectively at the same conditions. The presence of different surfactants (non-ionic and anionic) gives a synergetic effect which reveals active participation of contact angle changing and Interfacial tension (IFT) reduction. This research contributes to the advancement of methods for upgrading heavy crude oil, offering a promising avenue for increasing efficiency and productivity in the oil industry.

Keywords

TiO₂ / Water-assisted thermal cracking / Nanocomposites / Surfactants / Rheology

CRediT authorship contribution statement

Asmaa S. Morshedy: Writing-review & editing, Writing-original draft, Visualization, Validation, Resources, Methodology, Investigation, Formal analysis, Data curation, Conceptualization. Tahany Mahmoud: Writing-review & editing, Writing-original draft, Visualization, Validation, Resources, Methodology, Investigation, Formal analysis, Data curation, Conceptualization.

Availability of data and materials

The data that support the findings of this study are available from the authors upon reasonable request. Email: [e-mail], [e-mail].

Declaration of competing interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

Acknowledgements

The authors would like to thank [Egyptian Petroleum Research Institute] for their invaluable support and assistance in conducting this research. The Institute's resources and collaborative environment played a vital role in enabling the completion of this work.

References

[1] X. Chapter,The oxidation of carbon monoxide, in: G. I. Golodets (Ed.), Studies in Surface Science and Catalysis, Elsevier, 1983, pp. 280-311.

[2] A. Tajik, et al., Optimization of heavy crude oil recovery using oil-soluble catalyst precursor under electromagnetic heating, Fuel 379 (2025) 133043.

[3] M.A. Betiha, et al., Catalytic aquathermolysis for altering the rheology of asphaltic crude oil using ionic liquid modified magnetic MWCNT, Energy Fuel. 34 (9) (2020) 11353-11364.

[4] M.S. Rana, et al., A review of recent advances on process technologies for upgrading of heavy oils and residua, Fuel 86 (9) (2007) 1216-1231.

[5] R. Sahu, et al., A review of recent advances in catalytic hydrocracking of heavy residues, J. Ind. Eng. Chem. 27 (2015) 12-24.

[6] S. Zhang, et al., A review of slurry-phase hydrocracking heavy oil technology, Energy Fuel. 21 (6) (2007) 3057-3062.

[7] M.J. Angeles, et al., A review of experimental procedures for heavy oil hydrocracking with dispersed catalyst, Catal. Today 220-222 (2014) 274-294.

[8] O. Muraza, A. Galadima, Aquathermolysis of heavy oil: a review and perspective on catalyst development, Fuel 157 (2015) 219-231.

[9] Y.M. Mikhailov, et al., Fischer-Tropsch synthesis in presence of composite materials containing iron and cobalt nanoparticles, Chem. Technol. Fuels Oils 48 (4) (2012) 253-261.

[10] A.V. Galukhin, et al., Catalytic aquathermolysis of heavy oil with iron tris(acetylacetonate): changes of heavy oil composition and in situ formation of magnetic nanoparticles, Energy Fuel. 29 (8) (2015) 4768-4773.

[11] E. Mar Juárez, F.J. Ortega García, P. Schacht Hernández, Hydrocracking of vacuum residue by homogeneous catalysis, Fuel 135 (2014) 51-54.

[12] K.M. Kadiev, et al., Hydroconversion of radiation-activated vacuum tower bottoms in the presence of ultrafine molybdenum disulfide, Petrol. Chem. 55 (3) (2015) 209-216.

[13] H. Martinez-Grimaldo, et al., Hydrocracking of Maya crude oil in a slurry-phase reactor. I. Effect of reaction temperature, Catal. Today 220-222 (2014) 295-300.

[14] M. Hosseinpour, S.J. Ahmadi, S. Fatemi, Successive co-operation of supercritical water and silica-supported iron oxide nanoparticles in upgrading of heavy petroleum residue: suppression of coke deposition over catalyst, J. Supercrit. Fluids 100 (2015) 70-78.

[15] D.R. Isakov, et al., Physico-chemical and technological aspects of the use of catalysts during in-situ combustion for the production of high-viscosity crude oils and natural bitumens, Chem. Technol. Fuels Oils 50 (6) (2015) 541-546.

[16] S.M. Shuwa, et al., Novel deep eutectic solvent-dissolved molybdenum oxide catalyst for the upgrading of heavy crude oil, Ind. Eng. Chem. Res. 54 (14) (2015) 3589-3601.

[17] J. Li, et al., Influences on the aquathermolysis of heavy oil catalyzed by two different catalytic ions: Cu²⁺ and Fe³⁺, Energy Fuel. 27 (5) (2013) 2555-2562.

[18] I.V. Kozhevnikov, A.L. Nuzhdin, O.N. Martyanov, J. Supercrit. Transformation of petroleum asphaltenes in supercritical water, Fluids 55 (1) (2010) 217-222.

[19] Y. Chen, et al., Laboratory experiments and field tests of an amphiphilic metallic chelate for catalytic aquathermolysis of heavy oil, Energy Fuel. 22 (3) (2008) 1502-1508.

[20] A. Laachachi, et al., Influence of TiO₂ and Fe₂O₃ fillers on the thermal properties of poly(methyl methacrylate) ( PMMA), Mater. Lett. 59 (1) (2005) 36-39.

[21] S.J. Armaković, M.M. Savanović, S. Armaković, Titanium dioxide as the most used photocatalyst for water purification: an overview, Catalysts 13 (1) (2023) 26.

[22] Y. Chen, C. Yang, Y. Wang, Gemini catalyst for catalytic aquathermolysis of heavy oil, J. Anal. Appl. Pyrolysis 89 (2) (2010) 159-165.

[23] A.M. Alsabagh, et al., Improvement of heavy oil recovery by nonionic surfactant/alcohol flooding in light of the alkane carbon number and interfacial tension properties, ACS Omega 6 (29) (2021) 18668-18683.

[24] T. Mahmoud, et al., Modification wettability and interfacial tension of heavy crude oil by green bio-surfactant based on Bacillus licheniformis and Rhodococcus erythropolis strains under reservoir conditions: microbial enhanced oil recovery, Energy Fuel. 35 (2) (2021) 1648-1663.

[25] N.A. Samak, et al., Enhanced biosurfactant production using developed fed-batch fermentation for effective heavy crude oil recovery, Energy Fuel. 34 (11) (2020) 14560-14572.

[26] M.M. Mostafa, M. El saied, A.S. Morshedy, Novel Calcium Carbonate-titania nanocomposites for enhanced sun light photo catalytic desulfurization process, J. Environ. Manag. 250 (2019) 109462.

[27] M.A. Betiha, et al., Experimental evaluation of cationic-Schiff base surfactants based on 5-chloromethyl salicylaldehyde for improving crude oil recovery and bactericide, J. Mol. Liq. 316 (2020) 113862.

[28] B. Wang, Q. Wei, S. Qu, Synthesis and characterization of uniform and crystalline magnetite nanoparticles via oxidation-precipitation and modified co-precipitation methods, Int. J. Electrochem. Sci. 8 (3) (2013) 3786-3793.

[29] J. Morales, J.L. Tirado, C. Valera, Preferential X-ray line broadening and thermal behavior of γ-Fe₂O₃, J. Am. Ceram. Soc. 72 (7) (1989) 1244-1246.

[30] W. Feitknecht, U. Mannweiler, Der Mechanismus der Umwandlung von γ- zu α-Eisensesquioxid, Helv. Chim. Acta 50 (2) (1967) 570-581.

[31] R. Huang, et al., Enhanced photocatalytic fuel denitrification over TiO₂/α-Fe₂O₃ nanocomposites under visible light irradiation, Sci. Rep. 7 (1) (2017) 7858.

[32] G. Neri, et al., CO and NO₂ sensing properties of doped-Fe₂O₃ thin films prepared by LPD, Sensor. Actuator. B Chem. 82 (1) (2002) 40-47.

[33] U. Balachandran, N.G. Eror, Raman spectra of titanium dioxide, J. Solid State Chem. 42 (3) (1982) 276-282.

[34] O. Frank, et al., Raman spectra of titanium dioxide (anatase, rutile) with identified oxygen isotopes (16, 17, 18), Phys. Chem. Chem. Phys. 14 (42) (2012) 14567-14572.

[35] H. Mansour, et al., Structural, optical, magnetic and electrical properties of hematite (α-Fe₂O₃) nanoparticles synthesized by two methods: polyol and precipitation, Appl. Phys. A 123 (12) (2017) 787.

[36] P.M. Kouotou, et al., Selective synthesis of α-Fe₂O₃ thin films and effect of the deposition temperature and lattice oxygen on the catalytic combustion of propene, J. Mater. Chem. A 1 (35) (2013) 10495-10504.

[37] D. Bersani, P.P. Lottici, A. Montenero, Micro-Raman investigation of iron oxide films and powders produced by sol-gel syntheses, J. Raman Spectrosc. 30 (5) (1999) 355-360.

[38] D.L.A. de Faria, F.N. Lopes, Heated goethite and natural hematite: can Raman spectroscopy be used to differentiate them? Vib. Spectrosc. 45 (2) (2007) 117-121.

[39] C.P. León, et al., In situ laser-induced formation of α-Fe₂O₃ from Fe³⁺ ions in a cylindrical core-shell polymer brush, J. Raman Spectrosc. 35 (2) (2004) 165-169.

[40] R. Abazari, A.R. Mahjoub, S. Sanati, A facile and efficient preparation of anatase titania nanoparticles in micelle nanoreactors: morphology, structure, and their high photocatalytic activity under UV light illumination, RSC Adv. 4 (99) (2014) 56406-56414.

[41] B. Erdem, et al., XPS and FTIR surface characterization of TiO₂ particles used in polymer encapsulation, Langmuir 17 (9) (2001) 2664-2669.

[42] N.M. Mahmoodi, Equilibrium, kinetics, and thermodynamics of dye removal using alginate in binary systems, J. Chem. Eng. Data 56 (6) (2011) 2802-2811.

[43] G. Chizari Fard, et al., PAMAM grafted α-Fe₂O₃ nanofiber: preparation and dye removal abilityfrombinarysystem, J.TaiwanInst. Chem. Eng. 80(2017)156-167.

[44] M. Farahmandjou, F. Soflaee, Synthesis and characterization of α-Fe₂O₃ nanoparticles by simple Co-precipitation method, Phys. Chem. Res. 3 (3) (2015) 191-196.

[45] M.R.A. Kumar, et al., Enhanced photocatalytic and electrochemical performance of TiO₂-Fe₂O₃ nanocomposite: its applications in dye decolorization and as supercapacitors, Sci. Rep. 10 (1) (2020) 1249.

[46] J. Singh, et al., Synthesis of Fe₂O₃/TiO₂ monoliths for the enhanced degradation of industrial dye and pesticide via photo-Fenton catalysis, J. Photochem. Photobiol. Chem. 376 (2019) 32-42.

[47] Z. Liu, et al., Low-temperature reverse microemulsion synthesis, characterization, and photocatalytic performance of nanocrystalline titanium dioxide, Int. J. Photoenergy 2012 (1) (2012) 702503.

[48] A. Muthuvel, et al., Biosynthesis of gold nanoparticles using Solanum nigrum leaf extract and screening their free radical scavenging and antibacterial properties, Biomed. Prev. Nutr. 4 (2) (2014) 325-332.

[49] N. Senthilkumar, et al., Synthesis of ZnO nanoparticles using leaf extract of Tectona grandis (L.) and their anti-bacterial, anti-arthritic, anti-oxidant and in vitro cytotoxicity activities, New J. Chem. 41 (18) (2017) 10347-10356.

[50] H. Sultan, et al., Green synthesis and investigation of surface effects of α-Fe₂O₃@TiO₂ nanocomposites by impedance spectroscopy, Materials 15 (2022) 5768.

[51] H.N. Dharma, et al., A review of titanium dioxide (TiO₂)-based photocatalyst for oilfield-produced water treatment, Membranes 12 (3) (2022) 345.

[52] S.S. Al-Taweel, et al., The influence of titanium dioxide nanofiller ratio on morphology and surface properties of TiO₂/chitosan nanocomposite, Results Phys. 13 (2019) 102296.

[53] M. Asif, et al., Effect of urea addition on anatase phase enrichment and nitrogen doping of TiO₂ for photocatalytic abatement of methylene blue, Appl. Sci. 11 (17) (2021) 8264.

[54] D. Subramanian, K. Wu, A. Firoozabadi, Ionic liquids as viscosity modifiers for heavy and extra-heavy crude oils, Fuel 143 (2015) 519-526.

[55] A. Datta, et al., Synthesis and characterization of a magnetically separable novel Fe₃O₄@L-DOPA@CuII nanocatalyst (L-DOPA = L-3,4-dihydroxyphenyylalanine): asymmetric aza-Michael addition reaction, Inorg. Chim. Acta. 444 (2016) 209-216.

[56] M. Rezaei, M. Schaffie, M. Ranjbar, Thermocatalytic in situ combustion: influence of nanoparticles on crude oil pyrolysis and oxidation, Fuel 113 (2013) 516-521.

[57] M. Khalil, Expediting the Chemistry of Hematite Nanocatalyst for Catalytic Aquathermolysis of Heavy Crude Oil, New Mexico Institute of Mining and Technology: United States-New Mexico, 2015, p. 93.

[58] J.H. Greff, T. Babadagli,Catalytic effects of nano-size metal ions in breaking asphaltene molecules during thermal recovery of heavy-oil, in: SPE Annual Technical Conference and Exhibition, 2011.

[59] X. Xing, et al., Fe⁰/Graphene nanocomposite as a catalyst for the viscosity reduction of heavy crude oil, Petrol. Sci. Technol. 33 (20) (2015) 1742-1748.

[60] Y. Hamedi Shokrlu, T. Babadagli, In-Situ upgrading of heavy oil/bitumen during steam injection by use of metal nanoparticles: a study on in-situ catalysis and catalyst transportation, SPE Reservoir Eval. Eng. 16 (3) (2013) 333-344.

[61] P. Noorlaily, et al., Ethylene glycol route synthesis of nickel oxide nanoparticles as a catalyst in aquathermolysis, Mater. Sci. Forum 737 (2013) 93-97.

[62] M.I. Nugraha, et al., Synthesis of Ni_xFe_3-xO₄ nanoparticles by microwave-assisted coprecipitation and their application in viscosity reduction of heavy oil, Mater. Sci. Forum 737 (2013) 204-208.

[63] R. Hashemi, N.N. Nassar, P. Pereira Almao, Enhanced heavy oil recovery by in situ prepared ultradispersed multimetallic nanoparticles: a study of hot fluid flooding for athabasca bitumen recovery, Energy Fuel. 27 (4) (2013) 2194-2201.

[64] C. Li, et al., Enhanced heavy oil recovery in mild conditions by/TiO₂-ZrO₂ solid superacid prepared by different methods, J. Nanomater. 2016 (1) (2016) 7436057.