Abstract
Many crude oils have high levels of acidity due to the presence of naphthenic acids, which under certain conditions form insoluble salts in water and/or oil. Chemical additives are a good alternative to avoid formation of these deposits, or at least to cause the formation of a weak film. In this work, four commercial molecules based on ethoxylated nonylphenol were investigated, with varying hydrophilic-lipophilic balances (HLB) (12.3, 13.3, 14.1 and 17.1), to evaluate their action on calcium naphthenate formation. Moreover, the influence of the addition of monoacids (C4, C10 and C18) on the additives’ performance was also evaluated. Tetraprotic acid (ARN) was extracted from an industrial deposit and was characterized for use in the tests. The additives were investigated at 100, 500, 1000 and 2000 mg. L−1. The performance was evaluated by the biphasic mixture test and oscillatory interfacial rheology (using a Du Noüy ring), being characterized by the reduction of precipitate amount and the time for the formation of the film, respectively. The performance increased with rising additive HLB and concentration within the range tested. Concerning the monoacid, the best result was obtained using butyric acid. By using the additive with HLB of 17.1 and butyric acid together, a synergistic effect was observed, with better performances at lower additive concentrations. Moreover, the surfactant:monoacid ratio played an important role in the formulations’ performance, with the best result achieved at 75:25 wt/wt.
Similar content being viewed by others
Data availability
Not applicable
Code availability
Not applicable
References
Barros EV, Filgueiras PR, Lacerda V Jr, Rodgers RP, Romão W (2022) Characterization of naphthenic acids in crude oil samples – A literature review. Fuel 319:123775. https://doi.org/10.1016/j.fuel.2022.123775
Bertelli J, Dip R, Pires R, Albuquerque F, Lucas E (2014) Shear Rheology Using De Noüy Ring to Evaluate Formation and Inhibition of Calcium Naphthenate at the Water/Oil Interface. Energy Fuels 28(3):1726–1735. https://doi.org/10.1021/ef402025a
Bertheussen A, Simon S, Sjöblom J (2017) Equilibrium partitioning of naphthenic acids and bases and their consequences on interfacial properties. Colloids Surf. A 529:45–56. https://doi.org/10.1016/j.colsurfa.2017.05.068
Borhan N, Ramli A, Salleh IK (2018) Synthesis and Evaluation of Novel Naphthenate Inhibitor Demulsifier from Fatty Hydrazide Derivatives. Int J Eng Technol 7:191–195
Debord J, Srivastava P (2009) Development and field application of a novel non-acid calcium naphthenate inhibitor. In SPE Annual Technical Conference and Exhibition SPE-123660-MS. https://doi.org/10.2118/123660-MS
Dip R, Costa M, Lucas E (2017) Interfacial Films of Calcium Naphthenate: Influence of Polycardanol Structures. Energy Fuels 31(9):9275–9282. https://doi.org/10.1021/acs.energyfuels.7b01675
Dorian J, Franssen H, Simbeck D (2006) Global challenges in energy. Energy Policy 34(15):1984–1991. https://doi.org/10.1016/j.enpol.2005.03.010
Eke W, Victor-Oji C, Akaranta O (2020) Oilfield metal naphthenate formation and mitigation measures: a review. J Petrol Explor Prod Technol 10(2):805–819. https://doi.org/10.1007/s13202-019-00797-0
Facanali R, Porto NA, Crucello J, Carvalho RM, Vaz BG, Hantao LW (2021) Naphthenic Acids: Formation, Role in Emulsion Stability, and Recent Advances in Mass Spectrometry-Based Analytical Methods. J Anal Method Chem. https://doi.org/10.1155/2021/6078084
Fernandes HA, Freitas RR, Ribeiro DC, Vicente MA, Santos MFP (2019) Acidez total em petróleos: uma análise Bibliométrica. Res Soc Dev 8(1):1–25. https://doi.org/10.33448/rsd-v8i1.505
Hanneseth AM, Brandal O, Sjoblom J (2006) Formation, growth, and inhibition of calcium naphthenate particles in oil/water systems as monitored by means of near infrared spectroscopy. J Dispers Sci Technol 27:185–192. https://doi.org/10.1080/01932690500265896
Juyal P, Mapolelo M, Yen A, Rodgers R, Allenson S (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
Kashif K, 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. https://doi.org/10.1016/j.fuproc.2017.05.015
Kelland MA (2009) Production Chemicals for the Oil and Gas Industry. CRC Press, Boca Raton
Knudsen A, Nordgård E, Diou O, Sjöblom J (2012) Methods to Study Naphthenate Formation in w/o Emulsions by the Use of a Tetraacid Model Compound. J Disp Sci Technol 33(10):1514–1524. https://doi.org/10.1080/01932690903543329
Lawal O, Adekola SA, Akinlua A (2021) Occurrence of naphthenate deposition in crude oil production field offshore Niger Delta. J Pet Explor Prod 11:531–537. https://doi.org/10.1007/s13202-020-01029-6
Ma S, Cai Z, Zhou Y, Li S, Liang S (2016) Synthesis of acrylic acid-allylpolyethoxy amino carboxylate copolymer and its application for removing calcium from crude oil. RSC Adv 6(63):58426–58433. https://doi.org/10.1039/C6RA01743F
Mohammed MA, Sorbie KS (2010) Thermodynamic modelling of calcium naphthenate formation: Model predictions and experimental results. Colloids Surf. A Physicochem. Eng. Asp 369:1–10. https://doi.org/10.1016/j.colsurfa.2010.08.034
Neervannan S, Southard M, Stella V (2012) Dissolution of Weak Acids Under Laminar Flow and Rotating Disk Hydrodynamic Conditions: Application of a Comprehensive Convection–Diffusion–Migration–Reaction Transport Model. J Pharm Sci 101(9):3180–3189. https://doi.org/10.1002/jps.23209
Nichols DA, Rosário FF, Bezerra MCM, Gorringe SE, Williams HL, Graham GM (2014) Calcium naphthenates in complex production systems-Evaluation and chemical inhibition challenges. In SPE International Oilfield Scale Conference and Exhibition. SPE-169756-MS. https://doi.org/10.2118/SPE-169756-MS
Nordgård E, Hanneseth A, Sjöblom J (2010) Inhibition of Calcium Naphthenate Experimental Methods to Study the Effect of Commercially Available Naphthenate Inhibitors. J Disp Sci Technol 31(5):668–67. https://doi.org/10.1080/01932690903212891
Nordgård E, Simon S, Sjöblom J (2012) Interfacial Shear Rheology of Calcium Naphthenate at the Oil/Water Interface and the Influence of pH, Calcium, and in Presence of a Model Monoacid. J Disp Sci Technol 33(7):1083–1092. https://doi.org/10.1080/01932691.2011.579834
Oxiteno available in: <https://oxiteno.com/br/pt-br/portfolio/derivados-fenol-etoxilados/>, accessed in February 15th, 2022.
Rodrigues A, Ubbels S (2007) Understanding naphthenate salt issues in oil production. World oil 228(8):143-145. http://pascal-francis.inist.fr/vibad/index.php?action=getRecordDetail&idt=19009979.
Simon S, Nordgård E, Bruheim P, Sjöblom J (2008) Determination of C80 tetra-acid content in calcium naphthenate deposits. J Chrom 1200(2):136–143. https://doi.org/10.1016/j.chroma.2008.05
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
Skoog DA, West DM, Holler FJ, Crouch SR (2013) Fundamentals of Analytical Chemistry, 7th edn. Belmont, Thomson
Soares IF, Oliveira MCK, Naccache MF, Nele M (2021) Effects of monovalent and divalent cations on the rheology of organic acid laden interfaces. J Dispers Sci Technol. https://doi.org/10.1080/01932691.2021.2017296
Souza AVA, Rosário F, Cajaiba J (2019) Evaluation of Calcium Carbonate Inhibitors Using Sintered Metal Filter in a Pressurized Dynamic System. Materials 12(11):1849. https://doi.org/10.3390/ma12111849
Sulaimon AA, Masri AN, Sabri UAAJ, Adeyemi BJ (2022) Predicting naphthenate precipitation and evaluating the effect of ionic liquids on its deposition. J Pet Sci Eng 209:109865. https://doi.org/10.1016/j.petrol.2021.109865
Turner MS, Smith PC (2005) Controls on Soap Scale Formation, Including Naphthenate Soaps-Drivers and Mitigation. In SPE International Oilfield Scale Conference and Exhibition. SPE 94339. https://doi.org/10.2118/94339-MS
Vargas J (2022) Mechanistic Study of Non Acid Chemistries in the Inhibition of Calcium Naphthenates. In Offshore Technology Conference. OTC-31768-MS. https://doi.org/10.4043/31768-MS
Zan S, Wang J, Wang F, Han Y, Du M, Fan J (2019) Variation and distribution of naphthenic acids in Dalian Bay sediment. Marine poll bull 140:597–602. https://doi.org/10.1016/j.marpolbul.2019.01.061
Funding
This study was funded by ANP (Agência Nacional do Petróleo, Gás Natural e Biocombustíveis)–Programa de Recursos Humanos (PRH16.1), suportado com recursos provenientes do investimento de empresas petrolíferas qualificadas na Cláusula de P,D&I da Resolução ANP nº 50/2015, FINEP (Financiadora de Estudos e Projetos), FAPERJ (Fundação Carlos Chagas Filho de Amparo à Pesquisa do Estado do Rio de Janeiro–E-26/200.974/2021), CNPq (Conselho Nacional de Desenvolvimento Científico e Tecnológico–303583/2019-3), and Petrobras.
Author information
Authors and Affiliations
Contributions
Elizabete Fernandes Lucas contributed to the study conception and design. Material preparation, data collection and analysis were performed by Bianca Bassetti e Silva and Carla Michele Frota da Silva. The first draft of the manuscript was written by Bianca Bassetti e Silva and all authors commented on previous versions of the manuscript. All authors read and approved the final manuscript. *This is an invited and extended version of the manuscript presented at the 1st Flow Assurance Technology Congress and published in the FATC22 Anais.
Corresponding author
Ethics declarations
Conflicts of interest
The authors declare that they have no conflict of interest.
Additional information
Publisher's Note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
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
Silva, B.B., Silva, C.M.F. & Lucas, E.F. Synergistic effect between surfactant and monoacid in inhibiting the formation of naphthenates. Braz. J. Chem. Eng. (2024). https://doi.org/10.1007/s43153-024-00443-1
Received:
Revised:
Accepted:
Published:
DOI: https://doi.org/10.1007/s43153-024-00443-1