A kinetic study of esterification of naphthenic acids from a Colombian Heavy Crude Oil
Abstract
This article presents the kinetic study of the esterification reaction of naphthenic acids from a Colombian heavy crude oil, with a Total Acid Number (TAN) of 7,33 mgKOH/g, in a batch type reactor. Temperature was changed between 150 - 250°C while the ratio moles of methanol per mole of carboxylic groups, remained constant in 20:1. The reaction time was varied from 0 - 600 minutes. Reduction in the concentration of naphthenic acids in the reactor is determined by the measurement of Number Total Acid (TAN), ASTM D 664. Naphthenic acids were extracted from the crude and structurally characterized by Fourier Transform Infrared Spectroscopy (FTIR), Nuclear Magnetic Resonance (NMR) and Gel Permeation Chromatography (GPC).
The esterified oil was analyzed by FTIR, to identify the variation of the main functional groups. After determining the activation energy, frequency factor and, reaction order, a kinetic law was proposed for the esterification of naphthenic acids in Colombian heavy oil. Finally, it was evaluated the effect of esterification of naphthenic acids on the corrosion of steel ASTM A106 Gr.B. The corrosion of steel was reduced from 34,16 to 3,08 mils per year, (mpy), after esterification of naphthenic acids.
References
A kinetic study of esterification of naphthenic acids from a Colombian Heavy Crude Oil
Alvisi, P. & Lins, V. (2011). An overview of naphthenic acid corrosion in a vacuum distillation plant. Engin.
Failure Anal., 18 (5), 1403-1406.
ASTM A106 / A106M - 11 Standard Specification for Seamless Carbon Steel Pipe for High-Temperature Service.
ASTM International, West Conshohocken, PA, 2006.
ASTM Standard D 287. Test Method for API Gravity of Crude Petroleum and Petroleum Products (Hydrometer Method).
ASTM International, West Conshohocken, PA, 2006.
ASTM Standard D 664. Test Method for Acid Number of Petroleum Products by Potentiometric Titration.
ASTM International, West Conshohocken, PA, 2001.
ASTM Standard G 1. Practice for Preparing, Cleaning, and Evaluating Corrosion Test Specimens.
ASTM International, West Conshhocken, PA, 1990.
ASTM Standard D 1552. Test Method for Sulfur in Petroleum Products (High-Temperature Method). ASTM International. West Conshohocken, PA, 2008.
ASTM Standard D 5002. Test Method for Density and Relative Density of Crude Oils by Digital Density Analyzer.
ASTM International. West Conshohocken, PA, 2010.
Biryukova, V., Fedorak, P. & Quideau, S. (2007). Biodegradation of naphthenic acids by rhizosphere microorganisms. Chemosphere, 67 (10), 2058–2064.
Borges, B. & Acevedo, S. (2007). Caracterización estructural de distintas fracciones aisladas del crudo extrapesado Carabobo. Revista Latinoamericana de Metalurgia y Materiales, 27 (2), 83-94.
Dettman, H., Li, N. & Luo, J. (2009). Refinery corrosion, organic acid structure and athabasca bitumen. NACE
International, Paper 09336.
Dettman, H., Li, N., Luo, J. & Wickramasinghe, D. (2010). The influence of naphthenic acid and sulphur compound structure on global crude corrosivity under vacuum distillation conditions. NACE. Northem Area Western Conference.
Ding, L., Rahimi, P., Hawkins, R., Bhatt, S. & Shi, Y. (2009). Naphthenic acid removal from heavy oils on alkaline earth-metal oxides and ZnO catalysts. Applied Catalysis A: General, 371 (1-2), 121–130.
Dos Santos, R., Mohamed, R., Bannwart, A. & Loh, W. (2006). Contact angle measurements and wetting behavior of inner surfaces of pipelines exposed to heavy crude oil and water. J. of Petrol. Science and Engin., 51 (1), 9-16.
Gaikar, V. & Maiti, D. (1996). Adsorptive recovery of naphthenic acids using ion-exchange resins. Reactive and Functional Polymers, 31 (2), 155-164.
Hoeiland, S., Barth, T., Blokhus, A. M. & Skauge, A. (2001). The effect of crude oil acid fractions on wettability as studied by interfacial tension and contact angles. J. Pet. Sci. Eng., 30 (2), 91 – 103.
Kane, R & Cayard, M. (2002). A comprehensive study on naphthenic acid corrosion. Corrosion. Paper 02555.
Messer, B., Beaton, M., Tarleton, B. & Phillpis, T. (2004). New theory for naphthenic acid corrosivity of athabascaoilsands crudes. NACE. Paper 04634.
Qu, D. & Zheng, Y. (2006). High temperature naphthenic acid corrosion and sulphidic corrosion of Q235 and 5Cr1/2Mo steels in synthetic refining media. Corrosion Science, 48 (8), 1960-1985.
Rikka, P. (2007). Spectrometric identification of naphthenic acids isolated from crude oil. Thesis postgrademaster in science. Department of chemistry & biochemistry, Texas State University, San Marcos, Texas, U.S.A., 67 pp.
Sartori, G. (2001). U.S. Patent No. 6,252,305. Annandale, NJ (US). Patent and Trademark Office.
Simon, S., Nordgård, E., Bruheim, P. & Sjöblom, J. (2008). Determination of C80 tetra-acid content in calcium
naphthenate deposits. J. of Chromatography A, 1200 (2), 136-143.
Wang, Y., Chu, Z., Qiu, B., Liu, C. & Zhang, Y. (2006). Removal of naphthenic acids from vacuum fraction oil with an ammonia solution of ethylene glycol. Fuel, 85 (17-18), 2489–2493.
Wang, Y., Liu, Y. & Liu, C. (2008). Kinetics of the esterification of low-concentration naphthenic acids and methanol in oils with or without SnO as a catalyst. Energy & Fuels, 22 (4), 2203-2206.
Wang, Y., Sun, X., Liu. Y. & Liu. C. (2007). Removal of naphthenic acids from a diesel fuel by esterification. Energy & Fuels, 21 (2), 941-943.
Yépez, O. (2007). On the chemical reaction between carboxylic acids and iron, including the special case of naphthenic acid. Fuel, 86 (7-8), 1162–1168.
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. Applied Catalysis A: General, 303 (1), 103-109.
Alvisi, P. & Lins, V. (2011). An overview of naphthenic acid corrosion in a vacuum distillation plant. Engin.
Failure Anal., 18 (5), 1403-1406.
ASTM A106 / A106M - 11 Standard Specification for Seamless Carbon Steel Pipe for High-Temperature Service.
ASTM International, West Conshohocken, PA, 2006.
ASTM Standard D 287. Test Method for API Gravity of Crude Petroleum and Petroleum Products (Hydrometer Method).
ASTM International, West Conshohocken, PA, 2006.
ASTM Standard D 664. Test Method for Acid Number of Petroleum Products by Potentiometric Titration.
ASTM International, West Conshohocken, PA, 2001.
ASTM Standard G 1. Practice for Preparing, Cleaning, and Evaluating Corrosion Test Specimens.
ASTM International, West Conshhocken, PA, 1990.
ASTM Standard D 1552. Test Method for Sulfur in Petroleum Products (High-Temperature Method). ASTM International. West Conshohocken, PA, 2008.
ASTM Standard D 5002. Test Method for Density and Relative Density of Crude Oils by Digital Density Analyzer.
ASTM International. West Conshohocken, PA, 2010.
Biryukova, V., Fedorak, P. & Quideau, S. (2007). Biodegradation of naphthenic acids by rhizosphere microorganisms. Chemosphere, 67 (10), 2058–2064.
Borges, B. & Acevedo, S. (2007). Caracterización estructural de distintas fracciones aisladas del crudo extrapesado Carabobo. Revista Latinoamericana de Metalurgia y Materiales, 27 (2), 83-94.
Dettman, H., Li, N. & Luo, J. (2009). Refinery corrosion, organic acid structure and athabasca bitumen. NACE
International, Paper 09336.
Dettman, H., Li, N., Luo, J. & Wickramasinghe, D. (2010). The influence of naphthenic acid and sulphur compound structure on global crude corrosivity under vacuum distillation conditions. NACE. Northem Area Western Conference.
Ding, L., Rahimi, P., Hawkins, R., Bhatt, S. & Shi, Y. (2009). Naphthenic acid removal from heavy oils on alkaline earth-metal oxides and ZnO catalysts. Applied Catalysis A: General, 371 (1-2), 121–130.
Dos Santos, R., Mohamed, R., Bannwart, A. & Loh, W. (2006). Contact angle measurements and wetting behavior of inner surfaces of pipelines exposed to heavy crude oil and water. J. of Petrol. Science and Engin., 51 (1), 9-16.
Gaikar, V. & Maiti, D. (1996). Adsorptive recovery of naphthenic acids using ion-exchange resins. Reactive and Functional Polymers, 31 (2), 155-164.
Hoeiland, S., Barth, T., Blokhus, A. M. & Skauge, A. (2001). The effect of crude oil acid fractions on wettability as studied by interfacial tension and contact angles. J. Pet. Sci. Eng., 30 (2), 91 – 103.
Kane, R & Cayard, M. (2002). A comprehensive study on naphthenic acid corrosion. Corrosion. Paper 02555.
Messer, B., Beaton, M., Tarleton, B. & Phillpis, T. (2004). New theory for naphthenic acid corrosivity of athabascaoilsands crudes. NACE. Paper 04634.
Qu, D. & Zheng, Y. (2006). High temperature naphthenic acid corrosion and sulphidic corrosion of Q235 and 5Cr1/2Mo steels in synthetic refining media. Corrosion Science, 48 (8), 1960-1985.
Rikka, P. (2007). Spectrometric identification of naphthenic acids isolated from crude oil. Thesis postgrademaster in science. Department of chemistry & biochemistry, Texas State University, San Marcos, Texas, U.S.A., 67 pp.
Sartori, G. (2001). U.S. Patent No. 6,252,305. Annandale, NJ (US). Patent and Trademark Office.
Simon, S., Nordgård, E., Bruheim, P. & Sjöblom, J. (2008). Determination of C80 tetra-acid content in calcium
naphthenate deposits. J. of Chromatography A, 1200 (2), 136-143.
Wang, Y., Chu, Z., Qiu, B., Liu, C. & Zhang, Y. (2006). Removal of naphthenic acids from vacuum fraction oil with an ammonia solution of ethylene glycol. Fuel, 85 (17-18), 2489–2493.
Wang, Y., Liu, Y. & Liu, C. (2008). Kinetics of the esterification of low-concentration naphthenic acids and methanol in oils with or without SnO as a catalyst. Energy & Fuels, 22 (4), 2203-2206.
Wang, Y., Sun, X., Liu. Y. & Liu. C. (2007). Removal of naphthenic acids from a diesel fuel by esterification. Energy & Fuels, 21 (2), 941-943.
Yépez, O. (2007). On the chemical reaction between carboxylic acids and iron, including the special case of naphthenic acid. Fuel, 86 (7-8), 1162–1168.
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. Applied Catalysis A: General, 303 (1), 103-109.
How to Cite
Quiroga Becerra, H., Mejía Miranda, C., Laverde Cataño, D., Hernández López, M., & Gómez Sánchez, M. (2012). A kinetic study of esterification of naphthenic acids from a Colombian Heavy Crude Oil. CT&F - Ciencia, Tecnología Y Futuro, 4(5), 21–31. https://doi.org/10.29047/01225383.219
Downloads
Download data is not yet available.
Published
2012-05-31
Issue
Section
Scientific and Technological Research Articles
