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Assaying of lube oil and petroleum distillation cuts for associated naphthenic acids and other selected properties

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Abstract

The occurrence of naphthenic acids (NAs) in crude oil and its fractional distillation cuts have been widely recognized to be a natural phenomenon. Despite this, they continue to generate wide interest due to the ecological and industrial concerns emanating from their toxicity and corrosion effects. In this study, refined petroleum products were assayed for their physical and chemical properties as well as associated NAs. The NAs were removed using the solvent extraction method and characterized using the gas chromatography–mass spectrometry technique. The total acid number and densities of the gasoline, kerosene, diesel, and lubricating oil samples were 9.37, 5.44, 12.45, and 5.72 mg KOH/g, and 0.63, 0.66, 0.72, and 0.75 g/cm3, respectively. In consonance with other estimated properties, it was observed that lubricating oil was the heaviest of the studied oil samples while gasoline was the lightest. This was attributed to the presence of more aromatic compounds in the lubricating oil sample. Although there were slight variations in the profiles of NAs from sample to sample, they generally contained degree of unsaturation (z), z = 0 to z = − 16 compounds with a high predominance of aliphatic naphthenic acid types. The carbon numbers of the NAs detected in the oil samples ranged from 8 to 15. The estimated carbon preference index (CPI) indicated that the lubricating oil sample may have emanated from biogenic contribution (CPI >  > 1) while the other samples likely emanated from petrogenic sources (CPI < 1). The even–odd carbon ratio (E/O) indicated that there is no carbon preference among the studied oil samples.

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References

  • Acevedo S, Cordero T, Josmelith M, Herve C, Bouyssiere B, Lobinski R (2009) Trapping of paraffin and other compounds by asphaltenes detected by laser desorption ionization− time of flight mass spectrometry (LDI− TOF MS): role of A1 and A2 asphaltene fractions in this trapping. Energy fuels 23(2):842–848

    Article  CAS  Google Scholar 

  • Adbul-Munaim AM, Reuter M, Koch M, Watson DG (2015) Distinguishing gasoline engine oils of different viscosities using terahertz time-domain spectroscopy. J Infrared Milli Terahertz Waves 36(7):687–696

    Article  CAS  Google Scholar 

  • Adebiyi FM, Ore OT (2021) EDXRF analysis and risks assessment of potentially toxic elements in sand fraction (tailing) of Nigerian oil sands. Energy, Ecol Environ 6(3):258–270

    Article  Google Scholar 

  • Adebiyi FM, Oyedele JT (2022) Liquid–liquid-mediated extraction of metals from crude oils using tetramethylammonium hydroxide pentahydrate ionic liquid. Pet Sci Technol 40(7):787–802

    Article  CAS  Google Scholar 

  • Adeola AO, Akingboye AS, Ore OT, Oluwajana OA, Adewole AH, Olawade DB, Ogunyele AC (2022) Crude oil exploration in Africa: socio-economic implications, environmental impacts, and mitigation strategies. Environ Syst Decis 42:26–50

    Article  PubMed  Google Scholar 

  • Ahad JM, Pakdel H, Savard MM, Calderhead AI, Gammon PR, Rivera A, Headley JV (2013) Characterization and quantification of mining-related “naphthenic acids” in groundwater near a major oil sands tailings pond. Environ Sci Technol 47(10):5023–5030

    Article  CAS  PubMed  Google Scholar 

  • Ali I, Basit MA (1993) Significance of hydrogen content in fuel combustion. Int J Hydrog Energy 18(12):1009–1011

    Article  CAS  Google Scholar 

  • Barros EV, Dias HP, Pinto FE, Gomes AO, Moura RR, Neto AC et al (2018) Characterization of naphthenic acids in thermally degraded petroleum by ESI (−)-FT-ICR MS and 1H NMR after solid-phase extraction and liquid/liquid extraction. Energy Fuels 32(3):2878–2888

    Article  CAS  Google Scholar 

  • Barrow MP, Headley JV, Peru KM, Derrick PJ (2009) Data visualization for the characterization of naphthenic acids within petroleum samples. Energy Fuels 23(5):2592–2599

    Article  CAS  Google Scholar 

  • Barrow MP, Peru KM, Headley JV (2014) An added dimension: GC atmospheric pressure chemical ionization FTICR MS and the Athabasca oil sands. Anal Chem 86(16):8281–8288

    Article  CAS  PubMed  Google Scholar 

  • Behar FH, Albrecht P (1984) Correlations between carboxylic acids and hydrocarbons in several crude oils alteration by biodegradation. Org Geochem 6:597–604

    Article  CAS  Google Scholar 

  • Bowman DT, Warren LA, McCarry BE, Slater GF (2019) Profiling of individual naphthenic acids at a composite tailings reclamation fen by comprehensive two-dimensional gas chromatography-mass spectrometry. Sci Total Environ 649:1522–1531

    Article  CAS  PubMed  Google Scholar 

  • Buckley JS, Wang J (2002) Crude oil and asphaltene characterization for prediction of wetting alteration. J Petrol Sci Eng 33(1–3):195–202

    Article  CAS  Google Scholar 

  • Chamkalani A (2012) Correlations between SARA fractions, density, and RI to investigate the stability of asphaltene. ISRN Anal Chem. https://doi.org/10.5402/2012/219276

    Article  Google Scholar 

  • Cho K, Rana BS, Cho DW, Beum HT, Kim CH, Kim JN (2020) Catalytic removal of naphthenic acids over Co-Mo/γ-Al2O3 catalyst to reduce total acid number (TAN) of highly acidic crude oil. Appl Catal A 606:117835

    Article  CAS  Google Scholar 

  • Colati KA, Dalmaschio GP, de Castro EV, Gomes AO, Vaz BG, Romão W (2013) Monitoring the liquid/liquid extraction of naphthenic acids in Brazilian crude oil using electrospray ionization FT-ICR mass spectrometry (ESI FT-ICR MS). Fuel 108:647–655

    Article  CAS  Google Scholar 

  • Curl Jr H, O'Donnell K (1977) Chemical and physical properties of refined petroleum products. Technical memo (No. PB-277100; NOAA-TM-ERL-MESA-17). National Oceanic and Atmospheric Administration, Boulder, CO (USA). Marine Ecosystems Analysis Program Office

  • Damasceno FC, Gruber LD, Geller AM, de Campos MCV, Gomes AO, Guimarães RC, Caramão EB (2014) Characterization of naphthenic acids using mass spectroscopy and chromatographic techniques: study of technical mixtures. Anal Methods 6(3):807–816

    Article  CAS  Google Scholar 

  • Demirbas A, Al-Ghamdi K (2015) Relationships between specific gravities and higher heating values of petroleum components. Pet Sci Technol 33(6):732–740

    Article  CAS  Google Scholar 

  • Dias HP, Pereira TM, Vanini G, Dixini PV, Celante VG, Castro EV et al (2014) Monitoring the degradation and the corrosion of naphthenic acids by electrospray ionization fourier transform ion cyclotron resonance mass spectrometry and atomic force microscopy. Fuel 126:85–95

    Article  CAS  Google Scholar 

  • Fan TP (1991) Characterization of naphthenic acids in petroleum by fast atom bombardment mass spectrometry. Energy Fuels 5(3):371–375

    Article  CAS  Google Scholar 

  • Fox MF, George ED, Totten E (2007) Sustainability and environmental aspects of lubricants. In: Handbook of Lubrication and Tribology

  • Freitas S, Malacarne MM, Romão W, Dalmaschio GP, Castro EVR, Celante VG, Freitas MBJG (2013) Analysis of the heavy oil distillation cuts corrosion by electrospray ionization FT-ICR mass spectrometry, electrochemical impedance spectroscopy, and scanning electron microscopy. Fuel 104:656–663

    Article  CAS  Google Scholar 

  • Gholami A, Ansari HR, Hosseini S (2017) Prediction of crude oil refractive index through optimized support vector regression: a competition between optimization techniques. J Pet Explor Prod Technol 7(1):195–204

    Article  CAS  Google Scholar 

  • Hughey CA, Rodgers RP, Marshall AG, Qian K, Robbins WK (2002) Identification of acidic NSO compounds in crude oils of different geochemical origins by negative ion electrospray Fourier transform ion cyclotron resonance mass spectrometry. Org Geochem 33(7):743–759

    Article  CAS  Google Scholar 

  • Isah A, Abdulkadir M, Onifade K, Musa U, Umar G, Bawa A, Sani Y (2013) Regeneration of used engine oil. Lecture Notes in Engineering and Computer Science, World Congress on Engineering, WCE 2013, London, 3 July 2013–5 July 2013

  • Kannel PR, Gan TY (2012) Naphthenic acids degradation and toxicity mitigation in tailings wastewater systems and aquatic environments: a review. J Environ Sci Health A 47(1):1–21

    Article  CAS  Google Scholar 

  • Khan MR (1988) Correlations between physical and chemical properties of pyrolysis liquids derived from coal, oil shale, and tar sand. Energy Fuels 2(6):834–842

    Article  CAS  Google Scholar 

  • Khan MK, Riaz A, Yi M, Kim J (2017) Removal of naphthenic acids from high acid crude via esterification with methanol. Fuel Process Technol 165:123–130

    Article  CAS  Google Scholar 

  • Laredo GC, López CR, Alvarez RE, Cano JL (2004) Naphthenic acids, total acid number and sulfur content profile characterization in Isthmus and Maya crude oils. Fuel 83(11–12):1689–1695

    Article  CAS  Google Scholar 

  • Leyva C, Ancheyta J, Berrueco C, Millán M (2013) Chemical characterization of asphaltenes from various crude oils. Fuel Process Technol 106:734–738

    Article  CAS  Google Scholar 

  • Marcano F, Flores R, Chirinos J, Ranaudo MA (2011) Distribution of Ni and V in A1 and A2 asphaltene fractions in stable and unstable Venezuelan crude oils. Energy Fuels 25(5):2137–2141

    Article  CAS  Google Scholar 

  • Marshall AG, Rodgers RP (2004) Petroleomics: the next grand challenge for chemical analysis. Acc Chem Res 37(1):53–59

    Article  CAS  PubMed  Google Scholar 

  • Martínez-Palou R, Luque R (2014) Applications of ionic liquids in the removal of contaminants from refinery feedstocks: an industrial perspective. Energy Environ Sci 7(8):2414–2447

    Article  Google Scholar 

  • Miller JT, Fisher RB, Thiyagarajan P, Winans RE, Hunt JE (1998) Subfractionation and characterization of Mayan asphaltene. Energy Fuels 12(6):1290–1298

    Article  CAS  Google Scholar 

  • Neste (2022) Basic Concepts of Lubricants. https://www.neste.com/products/all-products/fossil-products) lubricants/basic-concepts-of-lubricants. Accessed 07–02–2022

  • Noestheden MR, Headley JV, Peru KM, Barrow MP, Burton LL, Sakuma T, Campbell JL (2014) Rapid characterization of naphthenic acids using differential mobility spectrometry and mass spectrometry. Environ Sci Technol 48(17):10264–10272

    Article  CAS  PubMed  Google Scholar 

  • Ore OT, Adebiyi FM (2021) A review on current trends and prospects in the pyrolysis of heavy oils. J Pet Explor Prod 11(3):1521–1530

    CAS  Google Scholar 

  • Ortiz X, Jobst KJ, Reiner EJ, Backus SM, Peru KM, McMartin DW, Headley JV (2014) Characterization of naphthenic acids by gas chromatography-fourier transform ion cyclotron resonance mass spectrometry. Anal Chem 86(15):7666–7673

    Article  CAS  PubMed  Google Scholar 

  • Parisotto G, Ferrao MF, Müller AL, Müller EI, Santos MF, Guimaraes RC et al (2010) Total acid number determination in residues of crude oil distillation using ATR-FTIR and variable selection by chemometric methods. Energy Fuels 24(10):5474–5478

    Article  CAS  Google Scholar 

  • Pereira TM, Vanini G, Tose LV, Cardoso FM, Fleming FP, Rosa PT et al (2014) FT-ICR MS analysis of asphaltenes: asphaltenes go in, fullerenes come out. Fuel 131:49–58

    Article  CAS  Google Scholar 

  • Ramasamy KK, Ali TJCT (2007) Hydrogen production from used lubricating oils. Catal Today 129(3–4):365–371

    Article  CAS  Google Scholar 

  • Ramirez-Corredores, MM (2017) Acidity in crude oils: naphthenic acids and naphthenates. The science and technology of unconventional oils, 295-385

  • Rana BS, Cho DW, Cho K, Kim JN (2018) Total Acid Number (TAN) reduction of high acidic crude oil by catalytic esterification of naphthenic acids in fixed-bed continuous flow reactor. Fuel 231:271–280

    Article  CAS  Google Scholar 

  • Riazi MR, Roomi YA (2001) Use of the refractive index in the estimation of thermophysical properties of hydrocarbons and petroleum mixtures. Ind Eng Chem Res 40(8):1975–1984

    Article  CAS  Google Scholar 

  • Rita AI, Monteiro AL, Albuquerque RM, Santos M, Ribeiro JC, Madeira LM, Sanches S (2022) Unravelling the relation between processed crude oils and the composition of spent caustic effluents as well as the respective economic impact. J Hazard Mater 421:126629

    Article  CAS  PubMed  Google Scholar 

  • Salifu AS (2015) Determination of hydrogen content of petroleum products from tema oil refinery using neutron backscatter technique Doctoral dissertation, University of Ghana

  • Shakirullah M, Ahmad W, Ahmad I, Ishaq M (2010) Oxidative desulphurization study of gasoline and kerosene: role of some organic and inorganic oxidants. Fuel Process Technol 91(11):1736–1741

    Article  CAS  Google Scholar 

  • Shohaimi NAM, Bakar WAWA, Jaafar J (2014) Catalytic neutralization of acidic crude oil utilizing ammonia in ethylene glycol basic solution. J Ind Eng Chem 20(4):2086–2094

    Article  CAS  Google Scholar 

  • Silva JP, Costa AL, Chiaro SS, Delgado BE, de Figueiredo MA, Senna LF (2013) Carboxylic acid removal from model petroleum fractions by a commercial clay adsorbent. Fuel Process Technol 112:57–63

    Article  CAS  Google Scholar 

  • Suri SK, Prasad K, Ahluwalia JC, Rogers DW (1981) Application of phase-titrations for estimation of adulteration of gasoline and high-speed diesel with kerosene. Talanta 28(5):281–286

    Article  CAS  PubMed  Google Scholar 

  • Valencia-Dávila JA, Witt M, Blanco-Tirado C, Combariza MY (2018) Molecular characterization of naphthenic acids from heavy crude oils using MALDI FT-ICR mass spectrometry. Fuel 231:126–133

    Article  Google Scholar 

  • Wang YZ, Sun XY, Liu YP, Liu CG (2007) Removal of naphthenic acids from a diesel fuel by esterification. Energy Fuels 21(2):941–943

    Article  CAS  Google Scholar 

  • Woudneh MB, Hamilton MC, Benskin JP, Wang G, McEachern P, Cosgrove JR (2013) A novel derivatization-based liquid chromatography tandem mass spectrometry method for quantitative characterization of naphthenic acid isomer profiles in environmental waters. J Chromatogr A 1293:36–43

    Article  CAS  PubMed  Google Scholar 

  • Wu B, Zhu J (2009) Identification of petroleum acids in Liaohe super-heavy oil. Pet Sci 6(4):433–437

    Article  CAS  Google Scholar 

  • Wu Z, Rodgers RP, Marshall AG (2004) Compositional determination of acidic species in Illinois no 6 coal extracts by electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry. Energy fuels 18(5):1424–1428

    Article  CAS  Google Scholar 

  • Yang C, Brown CE, Hollebone B, Yang Z, Lambert P, Fieldhouse B, Landriault M, Wang Z (2017) Chemical fingerprints of crude oil and petroleum products. In: Fingas M (ed) Oil spill science and technology, 2nd edn. Gulf Professional Publishing (Elsevier), Cambridge, MA, pp 209–304

    Chapter  Google Scholar 

  • Yang C, Zhang G, Serhan M, Koivu G, Yang Z, Hollebone B et al (2019) Characterization of naphthenic acids in crude oils and refined petroleum products. Fuel 255:115849

    Article  CAS  Google Scholar 

  • Zhang A, Ma Q, Wang K, Liu X, Shuler P, Tang Y (2006) Naphthenic acid removal from crude oil through catalytic decarboxylation on magnesium oxide. Appl Catal A 303(1):103–109

    Article  CAS  Google Scholar 

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Adebiyi, F.M., Ore, O.T. & Afe, F.A. Assaying of lube oil and petroleum distillation cuts for associated naphthenic acids and other selected properties. Chem. Pap. 77, 921–934 (2023). https://doi.org/10.1007/s11696-022-02531-3

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