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Naphthenic acids, total acid number and sulfur content prole characterization in Isthmus and Maya crude oils
lvarez, Jose pez, Regina E. A L. Cano Georgina C. Laredo*, Carla R. Lo
leo, Programa de Tratamiento de Crudo Maya, Eje Central La zaro Ca rdenas 152, Col. San Bartolo Atepehuacan, Instituto Mexicano del Petro xico, Me xico DF 07730 Me Received 10 March 2003; revised 19 January 2004; accepted 4 February 2004; available online 3 March 2004

Abstract In order to understand the origin of the corrosive behavior presented in the Atmospheric/Vacuum Distillation Unit in the Salina Cruz Renery, Mexico, where a 90/10 Isthmus/Maya crude blend is processed, distributions of sulfur content and total acid number along the distillation curves of the Maya and Isthmus crude oils were performed. Naphthenic acids characterizations for both crude oils are also presented. According to our results, the Isthmus crude oil may be more corrosive than the Mayan crude oil, apparently due to the presence of low molecular weight naphthenic acids and very low sulfur contents observed in the fractions distilled at temperatures below 200 8C. The occurrence of this type of acids and the lack of a protective sulfur lm might be the reason for this behavior. Nevertheless, other factors like salt content or equipment metallurgy should be considered before giving a nal conclusion. q 2004 Elsevier Ltd. All rights reserved.
Keywords: Naphthenic acids; Sulfur content; Total acid number; Isthmus crude oil; Maya crude oil; Corrosion

1. Introduction A well known problem in crude oil processing is corrosion associated with acidic constituents. In order to understand the source of this corrosive behavior, it is very important to know the full range of species that may be responsible. Naphthenic acids present in crude oils found in many countries are currently considered as being part of the problem [1 7]. Table 1 is illustrative of this type of organic acids [8]. At the operating temperatures relevant to crude oil rening, these acids can be corrosive and the form of attack is called naphthenic acid corrosion. However, crude oils are complex mixtures and sulfur species and chlorides may be present, which in different ways can inuence the nature and extent of the corrosion [7]. Naphthenic acid corrosion was observed for the rst time during the distillation process of some kind of crude oils since 1920 [1 7]. Recent reports about naphthenic acid corrosion have been found in China, India, Venezuela,
* Corresponding author. Tel.: 52-55-91756615; fax: 52-5591758429. E-mail address: glaredo@imp.mx (G.C. Laredo). 0016-2361/$ - see front matter q 2004 Elsevier Ltd. All rights reserved. doi:10.1016/j.fuel.2004.02.004

Eastern Europe, Russia and the USA [7]. In the past, there were certain difculties to differentiate if the observed corrosion at high temperatures was due to naphthenic acids or sulfur. Nowadays it is known that naphthenic acid corrosion is associated to the total acid number (TAN), sulfur content, temperature and uid rate [1 7]. This type of corrosion generally is higher when the crude oil processed has a TAN higher to 0.5, however, commercial experience reveals that while such test may be sufcient for providing an indication of whether a given crude may be corrosive, is a poor quantitative indicator of the severity of the expected corrosion. It has been observed that crude oils with fairly low TAN values were comparable in corrosive behavior as others with high TAN values, while others with high TAN values have been observed to be less corrosive than their TAN values might indicate. A light Indonesian crude with a TAN value well below 0.5 mg KOH g21 [7] and a Nigerian crude having a neutralization number slightly higher than 0.3 and 0.24% sulfur content [4] have proved to present naphthenic acid corrosion problems. A suspected explanation for this observation is that corrosion is not caused by the total acids, but rather by a select group of acids. Slavcheva et al. [7,8] reported that signicant variations

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Table 1 Major naphthenic acids types

in corrosivity can be obtained at the same TAN values depending on the chemical structure of the naphthenic acids. Sulfur content in a crude oil is an important factor in naphthenic acid corrosion, mainly due to a competition between the two kinds of processes, naphthenic attack and hydrogen sulde attack according to the following equations [6,7]: Fe 2RCOOH ! FeRCOO2 H2 Fe H2 S ! FeS H2 FeRCOO2 H2 S ! FeS 2RCOOH 1 2 3

Eq. (1) represents the direct attack of naphthenic acid on iron (carbon steel), while Eq. (2) represents the corrosion

by hydrogen sulde. A highly signicant difference is that, the corrosion product, iron naphthenate, is very soluble in oil, while iron sulde tends to form a protective lm on the metal. Eq. (3) represents the case where hydrogen sulde reacts with the soluble iron naphthenate to produce iron sulde, precipitated in the oil. Note that naphthenic acid is regenerated by this reaction. In order to form the protective layer, crude oils need to have 2 3% sulfur content, if this lm is not removed [4]. Therefore, a crude oil with a relative high naphthenic acid number and low sulfur content seems to be more corrosive at high temperature than a crude oil with the same naphthenic acid content and high sulfur content [4]. Naphthenic acid corrosion occurs in distillation units where the oil temperature is in the range of 220 400 8C

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[1 7] and the corrosion is more severe at the condensation point where the vapor stream draws liquid over the metal [2,3]. It seems probable that the temperature associated to naphthenic acid corrosion is related to the condensation temperature for specic naphthenic acids [7]. In order to obtain a better understanding of corrosion problems associated when processing different types of crude oils, a fair amount of work has been done dealing with naphthenic acid characterization [9 17]. A serious trouble faced recently by Mexican Reneries is the unexpected severe corrosive behavior observed in the Atmospheric/ Vacuum Distillation Unit in the Salina Cruz Renery in Oaxaca, when processing a 90/10 Isthmus/Maya crude oils blend and not detected when processing blends with relative higher Maya crude oil contents. The objective of this work was to obtain the TAN and the total sulfur content along the distillation curve and by means of a conventional procedure already described elsewhere [9], the detailed naphthenic acid characterization of two Mexican Crude Oils (Isthmus and Maya), in an attempt to relate this properties with the observed corrosive behavior of both crude oils.

Fig. 1. Sample preparation scheme for separating naphthenic acids from crude oil using preparative ion-exchange column chromatography [8].

2. Experimental The separation in 50 8C fractions of Isthmus and Maya crude oils samples was carried out in an Older Shaw distillation equipment following the ASTM D-2892 Standard Test Method for Distillation of Crude Petroleum (15Theoretical Plate Column). TAN values were obtained according to the ASTM Methods D 664 Standard Test Method for Acid Number of Petroleum Products by Potentiometric Titration and D 974 Standard Test Method for Acid and Base Number by Color Indicator Titration. Total Sulfur Content values were obtained according to the ASTM D 4294 Sulfur in Petroleum and Petroleum Products by Energy-Dispersive X-Ray Fluorescence Spectrometry. The commercial sample of naphthenic acids for Mass Spectroscopy evaluation was purchased from Fluka. Naphthenic acids were isolated from Isthmus and Maya crude oil samples with TAN values of 0.14 and 0.20 mg KOH g21, respectively, by the ion-exchange separation method developed by Jewell and described by Fan [9]. The resin fraction, containing the naphthenic acids, was rst isolated from the crude oil, followed by anion-exchange column separation as shown in Fig. 1. The components were eluted in four fractions based on acidity by using four solvents of increasing polarity. Naphthenic acids were found only in the acid fraction eluted with acidic methanol. The average recovery from the column was 95 wt%. Identication was accomplished using a JEOL-JMS-AX505 WA mass spectrometer. The instrument was operated in negative ion mode at 3 kV acceleration voltages. A Xe atom beam at 20 mA ion current and 3 kV kinetic energy was

used for ionization. The neat acid extract was rst dissolved in toluene, approximately 1:5. One microliter of the solution was then mixed with triethanolamine (TEA) and loaded on the FAB probe. The scanning rate was 30 s per decade from 100 to 1200 amu at a resolution of M =DM 2000: Normally 10 20 scans were acquired and a representative spectrum was obtained by averaging 5 10 scans.

3. Results TAN values in the complete samples of Isthmus and Maya crude oils were 0.14 and 0.20 mg KOH g21, respectively. In both cases, the TAN values are lower than 0.5, therefore, naphthenic acid corrosion by this parameter could be discarded [1 7]. In the same samples, sulfur contents were 1.34 and 3.42 wt %. According to the literature, crude oils having sulfur content between 2 and 3% form a protective layer against naphthenic acid corrosion [4]. 3.1. Distributions of total acid number and total sulfur content in the Isthmus and Maya crude oils The Isthmus and Maya crude oil TAN distributions (Fig. 2) follow a pattern in which the acidity seems to be concentrated at boiling points below 350 8C. TAN values in both crude oils show a tri-modal behavior with three peaks at 75, 175 and 325 8C. In the whole range of fractions studied, Isthmus crude oil had lower TAN values than Maya crude oil. The sulfur content in each fraction of the Isthmus and Maya crude oils is shown in Fig. 2. The sulfur content increases as the boiling point increases in both crude oils, following a pattern already described elsewhere [18]. In the Isthmus crude oil, the sulfur concentration is lower than in

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Fig. 2. Total acid number (TAN) and percent total sulfur in Isthmus (B, A) and Maya (V, S) crude oils.

the Maya crude oil in the whole range of the fractions studied. It is very important to observe in Fig. 2, that in the range between 25 and 275 8C, TAN values are high and the total sulfur contents are low in both crude oils. These results could give the impression that, even though the TAN is higher in the Maya crude, Isthmus crude would be less protected against naphthenic acid corrosion because

the sulfur content is nearly zero at distillation temperatures below 200 8C [4]. 3.2. Naphthenic acid characterization The scheme for the extraction of the naphthenic acids in the samples is shown in Fig. 1 [9]. The method is based on the use of an ion-exchange resin for the fractionation of

Fig. 3. Negative ion FAB of a naphthenic acid standard.

G.C. Laredo et al. / Fuel 83 (2004) 16891695 Table 2 Percent determination of naphthenic acids components by z and carbon numbers identied in the NA standard Carbon No. z Number 0 12 13 14 15 16 17 18 19 20 21 22 Percent by z number 2 2.12 3.45 5.16 6.81 7.55 6.67 5.20 3.45 2.07 1.01 0.46 43.96 4 1.66 3.04 4.60 5.75 6.26 5.20 3.87 2.49 1.24 0.74 0.23 35.08 6 8 3.77 7.27 12.36 15.80 17.47 15.37 12.00 8.34 4.60 2.22 0.78 100.00

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Percent by carbon number

1.15 1.38 1.72 1.75 1.47 1.44 0.92 0.47 0.09 10.39

0.55 1.01 1.38 1.47 1.29 1.01 0.69 0.37

0.23 0.44 0.47 0.47 0.46 0.44 0.28

7.78

2.79

the petroleum components. Once the resin fraction containing the naphthenic acids was separated, the other components were eluted into four fractions based on acidity by using four solvents of increasing polarity. Fig. 3 shows the negative ion FAB spectrum of a naphthenic acid standard mixture. The major series of carboxylic acid homologues are identied and labeled in the gure. Only (M 2 1)2 ions are observed in the spectrum. Ion m=z 148 corresponds to the deprotonated molecular ion of the TEA matrix. Table 2 indicates percentage composition of each compound found in the standard naphthenic acids sample determined by the relative abundance of each naphthenic acid ion. Only

the peaks at the characteristic naphthenic acids m=z ratios had been considered. It was assumed that all z homologues have equal ionization sensitivities. The observed compound distribution correlates well with the negative FAB spectrum of a Fluka Naphthenic Acid Standard already reported elsewhere [9,11,12]. FAB spectrums of the acidic fraction separated from Isthmus and Maya crude oils are shown in Figs. 4 and 5. Following the same procedure already described for the naphthenic acids standard, Tables 3 and 4 were prepared in order to show the percentage composition of naphthenic acid components by z and carbon number for Isthmus and Maya crude oils, respectively.

Fig. 4. FAB spectrum of the acid fraction separated from an Isthmus crude oil.

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Fig. 5. FAB spectrum of the acid fraction separated from a Maya crude oil.

According to Fig. 4 (Table 3) for the Isthmus crude oil sample, the most pronounced signals are those associated with the z 0 and 2 8 species (46 and 35%, respectively). The z 0 derivatives are present as an even distribution of acid compounds from C11 to C23, while the z 28 species show signals at C15 (m=z 233), C17 (m=z 261), C18 (m=z 275) and C20 (m=z 303) principally. Presence of z 26 (C15 m=z 235 and C18

m=z 277) and small amounts of C17 (m=z 267) and C19 (m=z 298) of z 22 compounds are also observed. The naphthenic acid distribution in the Maya crude oil is quite simple (Fig. 5, Table 4). The FAB spectrum is dominated (33%) by the C19 (m=z 297) aliphatic carboxylic acid (CnH2n20O2, z 0). An important signal at m=z 277 belonging to the C18H30O2 z 26 is also detected. Signals from C17 (m=z 261), C18 (m=z 275)

Table 3 Percent determination of naphthenic acids components by z and carbon numbers identied in the Isthmus crude oil Carbon No. z Number 0 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 Percent by z number 3.62 3.62 2.26 4.07 3.44 4.52 1.36 1.81 4.52 3.62 1.36 1.58 5.43 0.90 1.81 1.58 45.50 6.33 4.03 2 4 0.90 6 8 4.52 3.62 2.26 4.07 3.44 4.52 1.36 2.71 13.34 5.43 16.28 12.44 7.69 10.58 4.34 1.81 1.58 100.00 Percent by carbon number

1.76 1.36 2.71 2.26 1.36

3.44

3.62 0.81 1.72

0.90 3.62 0.45 10.85 7.24 9.77 1.72

9.59

34.55

G.C. Laredo et al. / Fuel 83 (2004) 16891695 Table 4 Percent determination of naphthenic acids components by z and carbon numbers identied in the Maya crude oil Carbon No. z Number 0 12 13 14 15 16 17 18 19 20 21 22 Percent by z number 2.71 0.00 0.36 6.15 4.34 0.02 2.53 33.27 2 4 6 8 2.71 0.00 0.36 6.15 5.42 6.89 23.87 40.14 10.85 0.36 3.25 100.00 Percent by carbon number

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4. Conclusion Although the TAN value of the Isthmus crude oil is lower than the TAN value of the Maya crude oil, this more mature crude oil has a higher proportion of low molecular weight naphthenic acids. Consequently, according to the data obtained in this work, the corrosivity observed in the Atmospheric/Vacuum Distillation Unit of the Salina Cruz Renery, when distilling blends with higher relations of the Isthmus crude oil, may occur at boiling point temperatures below 200 8C when the distilled fractions are rich in naphthenic acids of low molecular weight and the sulfur content is nearly zero, and therefore, the protective lm is not formed. Nevertheless, other factors like salt content or equipment metallurgy should be considered before giving a nal conclusion.

1.08 15.91 6.87 10.85 0.36 6.87 5.42

3.25 52.63 6.87 17.00 23.50

Acknowledgements leo for its The authors thank Instituto Mexicano del Petro nancial support.

References
[1] [2] [3] [4] [5] [6] Cooper CM. Hydrocarbon Process 1972;51:75. Gutzeit J. Oil Gas J 1976;74:156. Gutzeit J. Mater Perform 1977;16:24. Jayaraman A, Singh H, Lefebvre Y. Rev Inst Fr Pet 1986;41:265. Babaian-Kibala E, Craig HL, Rusk GL, Blanchard KV, Rose TJ, Uehlein BL, Quinter RC, Summers MA. Mater Perform 1993;32:50. Babaian-Kibala E, Craig HL, Rusk GL, Blanchard KV, Rose TJ, Uehlein R, Quinter RC, Summers MA, Proceedings of the Conference on Corrosion, New Orleans, LA, USA, vol. 93.; 1993. Paper 631. Slavcheva E, Shone B, Turnbull A. Br Corr J 1999;34:125. Slavcheva E, Shone B, Turnbull A. Corrosion 1994;54:922. Fan T. Energy Fuels 1991;5:371. Koike L, Reboucas LMC, Reis FAM, Marsaioli AJ, Richnow JJ, Michaelis W. Org Geochem 1992;18:851. St John WP, Rughani J, Green SA, McGinnis GD. J Chromatogr A 1998;807:241. Hsu CS, Dechert GJ, Robbins WK, Fukuda EK. Energy Fuels 2000; 14:217. Qian K, Robbins WK, Hughey CA, Cooper HJ, Rodgers RP, Marshall AG. Energy Fuels 2001;15:1505. Rudzinski WE, Oehlers L, Zhang Y, Najera B. Energy Fuels 2002;16: 1178. Clemente JS, Prasad NGN, MacKinnon MD, Fedorak PM. Chemosphere 2003;50:1265. Gabryelsky W, Froese KL. Anal Chem 2003;75:4612. Barrow MP, McDonnell LA, Feng X, Walker J, Derrick PJ. Anal Chem 2003;75:860. Speight JM. The chemistry and technology of petroleum. New York: Marcel Dekker; 1991. p. 269.

Fig. 6. Estimated mole percent against carbon number in Isthmus (A) and Maya (V) crude oils.

[7] [8] [9] [10] [11] [12] [13] [14] [15] [16] [17] [18]

and C20 (m=z 303) from z 28 are present. High molecular weight components are not observed. According to Fig. 6, the carbon number distribution in Isthmus and Maya crude oils present an interesting behavior. Forty percent of the naphthenics acids found in the Isthmus crude oil have low molecular weights (C7 C15), while 97% of the naphthenic acids observed in the Maya crude oil have high molecular weights (C15 C22). The particular high corrosive behavior observed for the Isthmus crude oil may relay on these low molecular weight naphthenic acids which are expected to distill at lower temperatures.