Abstract
Naphthenate deposits are a major obstacle in ensuring an economic and successful flow in the production and processing of crude oil. The formation of these deposits depends mainly on a specific group of high molecular weight tetrameric acids, sometimes called ARN. Among the challenges of identifying and characterizing the ARN of this complex matrix, we propose the use of a new analysis methodology for identifying these species in oil samples and naphthenate deposits with minimal sample preparation. Such methodology is based on an unconventional approach to the negative-mode electrospray ionization technique, combined with high resolution and precision mass spectrometry. The methodology proved to be promising and advantageous, since it requires a simpler sample preparation and a reduced consumption of reagents and analysis time. With good feasibility of application to identify the nature of deposits and to estimate, in an initial phase, the potential for inorganic scale and the need for oil treatment in production units.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
Albuquerque FC, Brito RSN, Lopes MA (2016) System for extracting precursor acids from calcium naphthenate deposits and method. U S Patent 20160153956A1. https://patents.google.com/patent/US20160153956A1/en
ASTM D664-17 (2017) Standard test method for acid number of petroleum products by potentiometric titration. American Society for Testing and Materials, West Conshohocken
ASTM E 203-01 (2001) Standard test method for water using volumetric Karl Fischer titration. American Society for Testing and Materials, West Conshohocken
Barros EV, Filgueiras PR, Lacerda V Jr, Rodgers RP, Romão W (2022) Characterization of naphthenic acids in crude oil samples—a literature review. Fuel 319:123775https://doi.org/10.1016/j.fuel.2022.123775
Barros EV, Souza LM, Madeira NC, Chinelatto LS Jr, Bertelli JN, Carvalho RM, Vaz BG, Simas RC, Neto AC, Lacerda V Jr, Romão W (2022) Isolation of tetrameric acids from naphthenates deposits and characterization by high-resolution analytical techniques. Fuel 308:122065. https://doi.org/10.1016/j.fuel.2021.122065
Bretherton N, Smith R, Keilty G, Ubbels S (2005) Napthenate control: Is acetic acid injection the answer? In SPE international symposium on oilfield corrosion. OnePetro. https://doi.org/10.2118/95115-MS
ISO 12185 (1996) Crude petroleum and petroleum products—determination of density-oscillating U-tube method, International Organization for Standardization. Conshohocken, PA, USA
Juyal P, Mapolelo MM, Yen A, Rodgers RP, Allenson SJ (2015) Identification of calcium naphthenate deposition in South American oil fields. Energy Fuels 29(4):2342–2350. https://doi.org/10.1021/acs.energyfuels.5b00414
Kelly MA, Vestling MM, Fenselau CC, Smith PB (1992) Electrospray analysis of proteins: a comparison of positiveion and negative-ion mass spectra at high and low pH. Org Mass Spectrom 27:1143–1147. https://doi.org/10.1002/oms.1210271028
Li H, Li S, Wu J, Huo D, Zhang Y, Shi Q (2022) Molecular characterization of naphthenic acids and naphthenates in the oil sludge: a Case Study in Bohai Basin, China. Energy Fuels 36(24):14907–14912. https://doi.org/10.1021/acs.energyfuels.2c03329
Lutnaes BF, Brandal Ø, Sjöblom J, Krane J (2006) Archaeal C80 isoprenoid tetraacids responsible for naphthenate deposition in crude oil processing. Org Biomol Chem 4(4):616–620. https://doi.org/10.1039/B516907K
Mapolelo MM, Stanford LA, Rodgers RP, Yen AT, Debord JD, Asomaning S, Marshall AG (2009) Chemical speciation of calcium and sodium naphthenate deposits by electrospray ionization FT-ICR mass spectrometry. Energy Fuels 23(1):349–355. https://doi.org/10.1021/ef800642b
Mapolelo MM, Rodgers RP, Blakney GT, Yen AT, Asomaning S, Marshall AG (2011) Characterization of naphthenic acids in crude oils and naphthenates by electrospray ionization FT-ICR mass spectrometry. Int J Mass Spectrom 300:149–157. https://doi.org/10.1016/j.ijms.2010.06.005
Marshall AG, Juyal P, Mapolelo MM, Rodgers RP (2011) Method for identifying naphthenates in a hydrocarbon containing liquid. U S Patent 8084264B2. https://patents.google.com/patent/US8084264B2/en
Mediaas H, Grande KV, Hustad BM, Rasch A, Rueslatten HG, Vindstad JE (2003) The Acid-IER Method-A method for selective isolation of carboxylic acids from crude oils and other organic solvents. In SPE International Symposium on Oilfield Scale. OnePetro. https://doi.org/10.2118/80404-MS
Mediaas H, Wolf NO, Baugh TD, Grande KV, Vinstad JE (2005) The Discovery of High Molecular Weight Naphthenic Acids (ARN Acid) responsible for calcium naphthenate deposits. In spe international symposium on oilfield scale. OnePetro. https://doi.org/10.2118/93011-MS
Mediaas H, Grande K, Kummernes H, Vindstad J (2014) Method for isolation and quantification of naphthenate forming acids (ARN-acids). U S Patent 8674161B2. https://patents.google.com/patent/US8674161B2/en
Nordgård EL, Ahmad J, Simon S, Sjöblom J (2012) Oil-water partitioning of a synthetic tetracarboxylic acid as a PH function. J Dispers Sci Technol 33:871–880. https://doi.org/10.1080/01932691.2011.579836
Orrego-Ruiz JA, Gomez-Escudero A, Rojas-Ruiz FA (2016) Combination of negative electrospray ionization and positive atmospheric pressure photoionization Fourier transform ion cyclotron resonance mass spectrometry as a quantitative approach of acid species in crude oils. Energy Fuels 30(10):8209–8215. https://doi.org/10.1021/acs.energyfuels.6b01524
Paek C, Mennito AS (2017) Selective isolation of ARN from crude oils. U.S. Patent 2017/0269042 A1. https://patents.google.com/patent/US20170269042A1/en
Palacio Lozano DC, Thomas MJ, Jones HE, Barrow MP (2020) Petroleomics: tools, challenges, and developments. Ann Rev Anal Chem 13:405–430. https://doi.org/10.1146/annurev-anchem-091619-091824
Putman JC, Marshall AG (2016) Screening petroleum crude oils for ARN tetraprotic acids with molecularly imprinted polymers. Energy Fuels 30(7):5651–5655. https://doi.org/10.1021/acs.energyfuels.6b01090
Simon S, Subramanian S, Gao B, Sjöblom J (2015) Interfacial shear rheology of gels formed at the oil/water interface by tetrameric acid and calcium ion: influence of tetrameric acid structure and oil composition. Ind Eng Chem Res 54(35):8713–8722. https://doi.org/10.1021/acs.iecr.5b02165
Simon S, Blanco E, Gao B, Sjöblom J, Passade-Boupat N, Palermo T, Rondon-Gonzalez M (2019) Rheological properties of gels formed at the oil–water interface by the reaction between tetrameric acid and calcium ion under flow conditions and at the batch scale. Ind Eng Chem Res 58(34):15516–15525. https://doi.org/10.1021/acs.iecr.9b02751
Simon S, Gao B, Tofte S, Sjöblom J, Passade-Boupat N, Palermo T, Rondon-Gonzalez M (2020) Influence of asphaltenes on gelation of tetrameric acid with calcium ion at the oil/water interface under flow-model condition. Energy Fuels 34(5):5846–5855. https://doi.org/10.1021/acs.energyfuels.0c00829
Simon S, Ruwoldt J, Sjöblom J (2020) A critical update of experimental techniques of bulk and interfacial components for fluid characterization with relevance to well fluid processing and transport. Adv Colloid Interface Sci 277:102120. https://doi.org/10.1016/j.cis.2020.102120
Sjöblom J, Simon S, Xu Z (2014) The chemistry of tetrameric acids in petroleum. Adv Colloid Interface Sci 205:319–338. https://doi.org/10.1016/j.cis.2013.12.007
Subramanian S, Simon S, Sjöblom J (2017) Interfacial dilational rheology properties of films formed at the oil/water interface by reaction between tetrameric acid and calcium ion. J Dispers Sci Technol 38(8):1110–1116. https://doi.org/10.1080/01932691.2016.1224718
Wang G, Cole RB (1994) Disparity between solution-phase equilibria and charge state distributions in positive-ion electrospray mass spectrometry. Org Mass Spectrom 29:419–427. https://doi.org/10.1002/oms.1210290805
Wang G, Cole RB (1997) Solution, gas-phase, and instrumental parameter influences on charge-state distributions in electrospray ionization mass spectrometry. In: Cole RB (ed) Electrospray ionization mass spectrometry. Wiley, New York, pp 137–174
Wu Z, Gao W, Phelps MA, Wu D, Miller DD, Dalton JT (2004) Favorable effects of weak acids on negative-ion electrospray ionization mass spectrometry. Anal Chem 76(3):839–847. https://doi.org/10.1021/ac0351670
Zook DR, Forsmo-Bruce H, Briem S (2000) ESI-MS response characteristics of a synthetic peptide. Chromatographia 52:S60–S64
Acknowledgements
The authors would like to thank CENPES/PETROBRAS (Rio de Janeiro, Brazil) for funding the research (process no 2018/00110-4). The authors would also like to thank the Federal Institute of Espírito Santo (IFES, Espírito Santo, Brazil) for the financial support, the Center for Competence in Petroleum Chemistry, and the Graduate Program in Chemistry of the Federal University of Espírito Santo (UFES, Espírito Santo, Brazil).
Author information
Authors and Affiliations
Contributions
EVB: Research; Methodology; Writing—proofreading and editing. TMCP: Research; Methodology; Writing—proofreading and editing. LMS: Research; Methodology; Writing—proofreading and editing. LSCJ: Research, Supervision, Writing—proofreading and editing. VLJ: Research, Supervision, Writing—proofreading and editing. WR: Research, Supervision, Writing—proofreading and editing.
Corresponding authors
Ethics declarations
Conflict of interest
The authors declare competing financial interest.
Additional information
Publisher’s Note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Electronic supplementary material
Below is the link to the electronic supplementary material.
Rights and permissions
Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.
About this article
Cite this article
de Barros, E.V., Pereira, T.M.C., Souza, L.M. et al. ESI-FT-ICR MS in the identification and characterization of tetrameric acids (ARN) in petroleum and naphthenates with minimal sample preparation. Braz. J. Chem. Eng. (2023). https://doi.org/10.1007/s43153-023-00416-w
Received:
Revised:
Accepted:
Published:
DOI: https://doi.org/10.1007/s43153-023-00416-w