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On the Nature and Origin of Acidic Species in Petroleum. 1. Detailed Acid Type Distribution in a California Crude Oil
N. A. Tomczyk and R. E. Winans*
Chemistry Division, Argonne National Laboratory, Argonne, Illinois 60439

J. H. Shinn and R. C. Robinson

Chevron Research and Technology Company, Richmond, California 94802-0627 Received April 30, 2001. Revised Manuscript Received August 13, 2001

Acidity in crude oils has long been a problem for refining. Knowledge of the detailed chemical composition of the acids responsible for corrosion can facilitate identification of problem crude oils and potentially lead to improved processing options for corrosive oils. A highly aerobically biodegraded crude from the San Joaquin Valley, which has a long history of causing corrosion problems during refining, was the subject of this study. The oil was first extracted with base, then acidified and extracted with petroleum ether. A portion of the resulting acid fraction was methylated. The unmethylated extract was analyzed by FTIR, NMR, and the methylated sample was analyzed by high-resolution mass spectrometry (HRMS). Over 96% of the ions observed in HRMS have been assigned reliable formulas. Considerably greater functionality is seen in this sample than would be presumed from the naphthenic acid title typically assigned to these species. Although over 60% of the compounds contained two or more oxygens, compounds containing only oxygen heteroatoms accounted for less than 10% of the acidic compounds identified. Approximately one-half of the species contained nitrogen and about one-fourth contained sulfur. It is believed that microbial degradation is a major source of these acidic components. It was also observed that acid species with higher degrees of heteroatom substitution generally also had a higher degree of saturation than those species having less heteroatoms, possibly due to impeded migration of highly substituted, less-saturated species.

Introduction A well-known and significant problem in crude oil processing is corrosion associated with acidic constituents. To better understand the source of this corrosive behavior it would be valuable to know the full range of species that may be responsible. While several researchers have identified certain classes of acid species in crude oils, little work has been reported that identifies the full range of molecular species present in a known corrosive oil. In Seiferts work,1,2 acids containing only oxygen are discussed. The main focus of Hsu et al.3 is the abundance of naphthenic acids in crude oils. A recent paper describes the extraction of acids from crude oil using nonaqueous ion exchange.4 Some of the aliphatic acids were determined by GCMS, but in the analysis of a biodegraded oil, a large unresolved hump in the chromatogram was observed. Under this unre* Corresponding author. Fax: (630) 252-9288. E-mail: rewinans@ anl.gov. (1) Seifert, W. K.; Howells, W. G. Anal. Chem. 1968, 41, 1 (4), 554562. (2) Seifert, W. K.; Moldown, J. M. Geochim. Cosmochim. Acta 1981, 45, 783-794. (3) Hsu, C. S.; Dechert, G. J.; Robbins, W. K.; Fukuda, E. Energy Fuels 2000, 14, 217-223. (4) Jones, D. M.; Watson, J. S.; Meredith, W.; Chen, M.; Bennett, B. Anal. Chem. 2001, 73, 703-707.

solved peak are the compounds that can be observed by direct desorption HRMS. Much has also been written about amino acid content in geological deposits in regard to their origin, possible reactions with relation to time, and which acids are stable enough to survive unchanged to present day.5,6 Others, such as Filby and Olsen,7 and Miller et al.,8 looked at trace elements in petroleum and asphaltenes, but did not discuss the role these elements play in the corrosion of distillation equipment. Ramljak et al.9 further discuss the possibility of other heteroatom acids being present in asphaltenes, but concentrated on the various carboxylic acids. Based on these references, it is a long-standing belief that the cause of corrosion in oil refining equipment is due to naphthenic acids. This paper tests this conclusion by examining the distribution of all acid forms present in a known corrosive crude oil from Californias San Joaquin Valley. Data from analysis by high-resolution mass spectrom(5) Abelson, P. H. Org. Geochem. 1963, 10, 431-455. (6) Schopf, J. W.; Kvenvolden, K. A.; Barghoorn, E. S. PNAS 1968, 59, 639-646. (7) Filby, R. H.; Olsen, S. D. J. Radioanal. Nucl. Chem. 1994, 180 (2), 285-294. (8) Miller, J. T.; Fisher, R. B.; Thiyagarajan, P.; Winans, R. E.; Hunt, J. E. Energy Fuels 1998, 12, 1290-1298. (9) Ramljak, Z.; Solc, A.; Arpino, P.; Schmitter, J.; Guiochon, G. Anal. Chem. 1977, 49 (8), 1222-1225.

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Table 1. Elemental Analysis of SJV Acid Extract element carbon hydrogen sulfur nitrogen oxygen percent in extract 73.6 9.0 2.4 1.3 14.0 percent in whole crude 83.5 11.0 1.2 0.75 0.66

etry, Fourier transform infrared spectrometry, ultraviolet spectrometry, and elemental analysis are discussed. The San Joaquin Valley (SJV) oil is believed to be biodegraded, a process which occurs in deposits that remain below 75 C, and causes the oils to gradually increase in density. Over geologic time, the microorganisms remove alkanes, branched alkanes, and cycloalkanes,10,11 and may also attack aromatics in the order of ring number (smaller rings degraded first). The resulting decrease in lighter components is evident in the SJV crude from the total mass spectra that indicates a mean molecular weight of 580 m/z. Teschner and Wehner12 found that the organisms do not appear to affect the traditional biomarkers, such as triterpanes and steranes, which seems to ignore the fact that bacteria can be a source of these compounds. Hunt,13 in his review of biodegradation, indicates that there is an increase in nitrogen-containing compounds and a decrease in paraffinic compounds with increased biodegradation. The increase in nitrogen is believed to be related to the organisms themselves, and not simply the reduction in specific compound types. The crude in this study shows clear evidence of such nitrogen enrichment. Many of Hunts references also indicate that the deposit must come in contact with surface water for significant biodegradation to occur. Another possible source of these nitrogen-rich acids could be amino acids from the cell walls of the microorganisms. As the bacteria complete their life cycle, they leave behind their amino acid-rich cell walls. Although amino acids could be the source of these nitrogencontaining compounds, there is some disagreement as to whether they could even survive diagenesis. Jones and Vallentyne17 tested a Miocene lignite and found no positive results for amino acid nitrogen. Abelson5 tested peats and coals and found mono- and di-amino acids. Podkletnov18 found several stable amino acids in the Sakhalin oil, but stated that the nonthermally stable acids that were present were due to chelation with either an organic or inorganic phase. Regardless of the source, the acids present in the oil cause much corrosion in the refinery equipment. The most common current measure of the corrosive potential of a crude oil is the Neutralization Number (Neut Number) or Total Acid Number (TAN). These are total acidity measurements determined by base titration. Commercial experience reveals that while such tests may be sufficient for providing an indication of whether a given crude may be corrosive, the tests are poor quantitative indicators of the severity of corrosion
(10) Cassani, F.; Elington, G. Chem. Geol. 1991, 91, 315-333. (11) Armanios, C.; Alexander, R.; Kagi, R. I. Org. Geochem. 1992, 18, 641-645. (12) Teschner, M.; Wehner, H. Chromatographia 1985, 20, 407416. (13) Hunt, J. M. In Petroleum Geochemistry and Geology; W. H. Freeman & Co.: San Francisco, 1979. (14) Jones, J. D.; Vallentyne, J. R. Geochim. Cosmochim. Acta 1960, 21, 1-34. (15) Podkletov, N. Y. Geokhimiya 1976, 12, 1893-1895. (16) Winans, R. E. In Advances in Spectroscopy; Meuzelaar, H. L. C., Ed.; Plenum Press: New York, 1992; pp 255-274. (17) Larter, S. R.; Bowler, B. F. J.; Li, M.; Chen, M.; Brincat, D.; Bennett, B.; Noke, K.; Donohoe, P.; Simmons, D. Nature 1996, 383, 593-597. (18) Tissot, B. P.; Welte, D. H. In Petroleum Formation and Occurrence; Springer-Verlag: Berlin, 1984.

to be expected. Certain oils with fairly low TANs are observed to be comparable in corrosive behavior as others with far higher TANs, while others with high TANs have been observed to be less corrosive than their TANs might indicate. A suspected explanation for this observation is that corrosion is not caused by the total acids, but rather by a select group of acids. The TAN test may be insufficiently specific to measure the concentration of such corrosive species. Experimental Section
Sample. The oil was sourced from Californias San Joaquin Valley and was desalted in the commercial refinery operation. The elemental analysis is given in Table 1. Nitrogen and oxygen contents are particularly high relative to oils of similar origins, a classic first indication of a biodegraded oil. The TAN for the crude prior to extraction was 5.18. Extraction. The extraction procedure used is a modified version of the one developed by Seifert and Howells.2 Approximately 45 g of sample was dissolved in 67 g of isopentane. The mixture was then extracted 10 times with a base solution of 1% NaOH in a 70% ethanol and H2O mixture, followed by two times with a 70% ethanol solution. The solution was centrifuged after each extraction to separate the layers. Centrifuging often resulted in three layers, an organic and an aqueous separated by solids, which contain asphaltenes. These solid layers were set off to the side until the extraction of the oil was complete. The solids were dissolved in xylene and extracted with base. The two base extracts were combined prior to cleanup and acidification at 0 C. Once acidified, the solution was extracted with ethyl ether. The ether fraction was washed to neutrality with distilled water and dried with MgSO4. The solution was filtered and evaporated to dryness. Extraction yield was 4.9%. The extract was methylated by adding 100 mg of sample, 1.0 mL of BF3 in MeOH, and 20 mL of MeOH to a 100 mL round-bottom flask and refluxed for 48 h. When cool, 25 mL of saturated NaHCO3 was added while the solution was stirred. The mixture was poured into a 125 mL separatory funnel and shaken for 30 s. It was then centrifuged for 15 min and the organic layer was placed in a 100 mL round-bottom flask. This was repeated until the organic layer was colorless. The solution was dried with MgSO4, filtered into a 250 mL round-bottom flask, and evaporated to dryness. The solid was transferred into a vial using DCM, blown down with N2, and a final weight was taken. Analysis. Prior to methylation, the samples were analyzed for C, H, N, and S, and by FTIR and NMR. The elemental analysis results are in Table 1. The FTIR spectra were taken on a Nicolet 510P. A portion of the sample was dissolved in ethyl ether and placed on a NaCl plate. The data were acquired over 200 s, followed by a background subtraction. All NMR experiments were performed on a Bruker model DMX 500 NMR spectrometer (11.7 T). With the use of the nitrogen pre-cooler, heater coil, and the variable temperature controller, the temperature was stable at 294.3 ( 0.1 K. The 13C NMR spectra were recorded with a two-channel 10 mm broadband, direct detection, variable temperature probe with proton decoupling and 2H lock at 76.773 MHz. Inverse gated proton decoupling was accomplished via the WALTZ 16 sequence. 13C spectra (125.76 MHz) were recorded with 11 000

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Figure 3. C13 NMR spectrum of SJV acid extract, carboxylic acid region.

Figure 1. FTIR spectrum of the acid extract of San Joaquin Valley Crude.

Figure 4. Mass distribution of acid extract from SJV Crude.

Figure 2. FTIR of acid-extracted raffinate from SJV Crude. acquisitions, 20 s recycle delay, 9 ms pulse width (70), and 33 kHz sweep width. Data were acquired with 64k points for an acquisition time of 931 ms. After methylation, the samples were analyzed on a Kratos 3-sector MS-50 high-resolution mass spectrometer (HRMS). The instrument was run in electron impact mode. The analysis was performed using low electronvoltage (17 eV) ionization at 40 000 resolution. The samples were heated from 200 to 400 C on a probe in the source. Mass measurements were a result of averaging the data from all the scans taken throughout the temperature range. Molecular formulas were assigned on the basis of the exact mass measurements and a set of possible heteroatoms and combination of heteroatoms. The carbon distributions reported are calculated from extract yields and can only be semiquantitative since the ionization efficiencies for all the different molecules have not been measured and are assumed to be the same.

Figure 5. Distribution of heteroatom species types in acid extract from SJV Crude.

Results The extract was analyzed by FTIR as an initial screening of acid content. A comparison of the peak at 1706 in Figure 1, which is assigned to CdO stretch of aliphatic carboxylic acids, to shoulder at 1612, which is attributed to aromatic carboxylic acid CdO stretch, suggests that aliphatic acids are much more abundant. A broad CAr-O stretch is observed, which is likely due to phenolic compounds. The extracted oil was also analyzed to ensure that the extraction of acids was complete and that peaks assigned to acidic compounds were absent in the extracted oil raffinate (Figure 2). 13C NMR analysis was also performed to examine the state of carbon in the acid species (Figure 3). The aromatic acid carbonyls are known to have a chemical

shift of 172-175 ppm, while the aliphatic acids are found in the 178-184 ppm region. There is an almost complete absence of aromatic carbons in this carboxylic acid region, showing that the acid groups in this oil are predominantly attached to aliphatic carbons (in agreement with the FTIR observations). HRMS provides a wealth of data on the heteroatom distribution, mass, and ring systems present in the acid species. The raw data produced by the HRMS16 was analyzed using a program developed within Argonne designed to extract these key structural features. The program produces formulas based on the information described above, but does not produce structural data. In the figures detailing DBE information, possible structures are included. These structures are based on known structures given in the literature. The total averaged mass spectra for the entire crude shows the dominance of high mass species (mean mass at 580 amu), indicative of a heavy crude oil (Figure 4). The high-resolution capability of this analysis provides elemental composition information of the molecular ions. Figure 5 shows the heteroatom substitution as number of moles of molecular ions of this type per 10 000 mol of carbon in the whole crude. (This type of normalization facilitates comparisons among several oils

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Figure 6. DBE distribution of components containing two oxygens.

Figure 7. Mass data of compounds containing two oxygens.

of differing total acid levels). The notation of substitution used here, such as N2O3, only indicates that a compound contains two nitrogens and three oxygen and does not indicate that all five atoms are in one functional group. For ease of discussion, the quantities will be referred to as carbons. It is commonly assumed that acidity in crude oils is related to carboxylic acid species, i.e., components containing a -COOH functional group. Numerous acids of this type have been previously reported, particularly those involving ring species with long aliphatic chains. Our data reveals far greater diversity in acid types than previously reported. While it is clear that carboxylic acid functionality is an important feature (60% of the ions have two or more oxygen atoms), a major portion (40%) of the acid types are not carboxylic acids. Even the carboxylic acids are more diverse than expected s85% contain more heteroatoms than the two oxygens needed to account for the carboxylic acid groups. Examining the distribution of component types in the acid fraction, we see a broad distribution of species. Eight different component types are present in quantities ranging from 20 to 35 mol per 10 000 whole crude carbons, including O2, O4, S, N2, NO, NO2, N2O, and N2O2. The presumption of O2-only species as suggested by the term naphthenic acids is clearly not valid for this oil. Judging from the presence of these species in the acid extract, we assume that the most likely compound types in these categories would be carboxylic acids for species with two or more oxygen atoms, pyroles/carbonzoles/indoles for N-species, phenols for single oxygen species, and thiols for the sulfur species. The HRMS data also provides information on hydrogen deficiency and mass distributions in each heteroatom class. For example, for ions containing two oxygens, there is a concentration of species at 12 and 13 double bond equivalents (DBE). Representative molecules for these species are C34 and C36 for DBE 12 and C33, C38, and C40 for DBE 13. For these and the majority of the data, a series is present. That is, there are homologous series of formulas that differ only by number of CH2s. It is believed that these compounds are tricyclic and pentacyclic in nature. Both groups are possibly terpenoid derivatives. In Figure 6, a possible structure is shown, which is a partially aromatized terpenoid. The arrangement of functionality is based on what is known about these molecules and are only representative. The mass distribution appears to be tightly grouped between 300 and 600 mass units (Figure 7). While these

Figure 8. DBE distribution of components containing one oxygen.

types do fit the classical description of naphthenic acids (multiple saturated ring systems with an attached partially oxidized aliphatic side chain), there is also considerable diversity in number of rings, aromaticity, and side chain distribution. Nonetheless, the NMR and FTIR data strongly indicate that the acid function for these is most likely attached to the aliphatic portion. It is difficult to conceive of a sufficiently broad range of acidities of such species to explain the discrepancies between observed corrosivity and total acid number. For compounds containing one oxygen, the representative molecules are phenols for DBE 4 through 6, with 0 to 2 additional naphthenic rings. For DBE 8 and 9, the molecules are naphthols with one and two extra naphthenic rings. At DBE 14, the representative molecules are C20 and C40, and it is believed that these are also biomarkers. A possible structure for these compounds is shown in Figure 8. The structure is based on data reported by Seifert.1 For compounds with four oxygens, the representatives are not as specific as the O and O2 compounds. As shown in Figure 9, compounds for the DBE 7 range from C20 to C36, while DBE 8 and 9 compounds range from C27 to C41. These compounds are possibly terpenoid dicarboxylic acids. The largest concentration of compounds in this class appear between 6 and 9 DBE, unlike O2, which has its highest abundance peak between 9 and 14 DBE. At this trend of higher substitution, lower DBE is seen throughout the groupings with the exception of the N compounds. The distribution of compounds with six oxygens, shown in Figure 10, is shifted even lower in aromaticity. The compounds are almost entirely below 10 DBE, with the majority between 2 and 6 DBE. With the exception

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Figure 9. DBE distribution of components containing four oxygens. Figure 12. DBE distribution of components containing one oxygen and one sulfur.

Figure 10. DBE distribution of components containing six oxygens.

Figure 13. DBE distribution of components containing two oxygens and one sulfur.

Figure 11. DBE distribution of components containing one sulfur.

Figure 14. DBE distribution of components containing two oxygens and one sulfur.

of compounds with 2 DBE, the compounds most likely contain three carboxyl groups. Representative molecules for DBE 2 and 3 are likely to be paraffinic fatty acids containing 12 to 19 carbons. Molecules with a DBE of 4 to 6 probably range in structure from one to three naphthenic rings and 18 to 25 carbons. The most abundant S species are at 10 and 11 DBE. Representative molecules of those compounds at 11 DBE range from C28 to C46. These are possibly aromatic thiols. As with the oxygen compounds, this grouping shows a homologous series differing by the number of CH2 groups. The first structure in Figure 11 is based on data from Figure 4.1.14 in Tissot and Welte,18 but is not acidic and it is not clear that such a structure could be extracted under the conditions used in this study. The second structure would be extracted in the basic solution, but is very susceptible to oxidation to a disulfide.

As is found with the oxygen-only compounds, the aromaticity decreases with increased number of oxygens in the compounds containing both sulfur and oxygen. The SO and SO2 groups are based on similar compounds as can be seen in Figures 12 and 13. For the SO, there is a family of compounds grouped at DBE 9. This is possibly a dibenzothiophene base with a hydroxyl group and alkyl chains of varying lengths somewhere on the molecule. The prominent SO2 compounds are most likely benzothiophenes with a carboxylic acid and an alkyl chain elsewhere on the molecule. Molecules with SO3 functionality have low DBE and therefore cannot be benzothiophenes with carboxylic acid and an additional one oxygen functionality. They are possibly benzene sulfonic acids with various side chains ranging from C9H18 to C36H69, and containing zero, one, or two double bonds. See Figure 14. Although sulfonic acids are prepared from petroleum syntheti-

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Figure 15. DBE distribution of components containing one oxygen and one nitrogen.

Figure 17. DBE distribution of components containing one oxygen and two nitrogens.

Figure 16. DBE distribution of components containing two oxygens and one nitrogen.

Figure 18. DBE distribution of components containing two oxygens and two nitrogens.

cally, no references could be found indicating that they were identified in untreated crudes. Compounds containing one nitrogen and one oxygen are almost entirely dominated by the compounds with 13 DBE (Figure 15). It is most likely that compounds containing this substitution are of one molecular type with varying side-chain lengths. Some of the representative molecules range from C29 to C44. These compounds must be pyrollic or phenolic (or both) to be acidic. The second structure shown in Figure 15 is actually amphoteric. The acidic hydrogen on the phenol would draw this compound into the acidic fraction, but the nitrogen is basic. It is believed that the first compound is most likely the representative structure for this group. The results for the compounds with one nitrogen and two oxygen are shown in Figure 16 and most likely contain a combination of a carboxylic group and a nitrogen elsewhere on the molecule. For 2 DBE, the core of the molecule is a nonaromatic ring. For DBE 5, a possible compound is the amino acid phenylalanine (formula C9H11NO2). A representative molecule for DBE 12 contains 30 carbons and most likely contains a carbazole core with a combination of aliphatic rings and side chains. As with the NO grouping, the carbazolebased structure is most likely the representative structure due to the fact that the structure on the left is amphoteric. DBE 13 species dominates the components containing two nitrogens and a single oxygen, as is also seen in the NO group. Representative molecules for this group range from C30 to C39. Compounds with the formula C35H48N2O (mass 512.3794) represent one of the most

abundant sets of compounds in the extract. Examining the data more closely, a homologous series from C35H48 to C31H40 differing by CH2s, and a final difference of CH3 to C30H37, is found. A difference of C4H8 from C39H56N2O is also present. It is believed that the base molecule may look similar to the one in Figure 17. The specific location of the alkyl groups cannot be determined from this analysis. A similar series of components is seen in compounds containing a single nitrogen and oxygen. When comparing several of the formulas for the N2O and NO at DBE 13, there is a difference of CH3N. It is possible that these two groups of compounds are somehow related, but if the base molecule seen in Figure 17 is indeed correct, that does not seem directly possible. There is no obvious way to remove the nitrogen in the aromatic ring and keep the rest of the molecule intact. A different base configuration could be the cause or there may be no relationship between the two species. For compounds containing two nitrogens and two oxygens, shown in Figure 18, the dominant species has a DBE of 11. The most abundant molecules are C31, C33, and C39, and these are possibly terpenoid in nature. A potential analogue, the amino acid tryptophan, has a formula of C11H12N2O2, and a DBE of 7. Conclusions The crude oil from the San Joaquin Valley comes from a shallow source and is highly aerobically bacterially biodegraded. The elemental analysis (rich in oxygen and nitrogen) and mass distribution of the whole oil (majority of species over 400 amu) support this conclusion.

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There is a broad richness of component types found in the oil. While classical naphthenic acids are certainly present, many other acidic species containing varying amounts of nitrogen, oxygen, and sulfur are also present. The larger compounds are less substituted with heteroatoms than the smaller compounds, and, as heteroatom substitution increases, the aromaticity decreases. Also, on a per carbon basis, the acidic compounds contain more nitrogen and nitrogen/oxygen compounds combined than oxygen-only compounds. It appears likely that the presence of a series of oxygen-only types such as two, four, and six oxygencontaining species is indicative of varying degrees of successive oxidation of the parent oil species. The observation that those species containing higher oxygen contents also typically have higher degrees of saturation (lower degrees of aromatization) may be best explained by the increase in polarity of species as oxidation proceeds. As additional acid groups are added via oxidation, only those species having very low polarity due to other functionality (lower aromaticity, higher saturation) are capable of further migration. Components that are both highly substituted and highly aromatic would be expected to have impeded migration due to a chromatographic effect of the accompanying rock materials. Larter et al.17 have examined this effect looking at the migration of aromatic nitrogen-containing compounds. An alternative explanation for the trend of functionality versus aromaticity is in the degradation pathway. There is conflicting information as to whether aerobic organisms preferentially attack unsubstituted alkanes18 or aromatics.19 It is possible that both kinds of organisms can exist at the same time. The data shown above suggest that the aromatic functionalities are the most degraded portions of this oil. It is possible that the organisms cleaved off these unsubstituted fractions, leaving behind compounds with higher heteroatom-tocarbon ratios. It is also possible that these remnants could reconfigure, creating the highly substituted, lowaromaticity compounds that are so evident in the data. Species containing more than carboxylic acid functionality are abundant in this oil. This is particularly
(19) Blanc, Ph.; Connan, J. In Applied Petroleum Geochemistry; M. L. Bordenave; Paris, 1993; pp 160-161.

true of species containing both nitrogen and oxygen. Possible reasons behind this trend are based on the interaction with microorganisms. The first, most obvious source of some of these acids are the bacteria themselves. As their life cycles complete themselves, they leave behind their amino acid-rich cell walls. These amino acids contain complex arrangements of nitrogenand oxygen-substituted alkanes. Arginine, for example, has a formula of C6H15N4O2. These may be stabilized by initial aromatization of the nitrogen ring system. Such species would be themselves subject to further oxidation in a manner similar to the oxygen-only species. Yet another prospect for the presence of such species could be the oxidative degradation of porphyrinring structures. Single oxygen and single sulfur species are also observed among the acidic components. These are probably phenols and thiols, respectively. At this time, the majority of the structures present in this crude are not known. Ultimately, whether the amino acids are from the original organic matter that created the crude, or whether they are from the cell walls of the microorganisms, is unimportant for this study. The fact that they are present and adding to the acidity of the crude is the main issue. The diversity of species provides a more satisfying prospect for a broad range of corrosive behaviors than might be expected from naphthenic acids alone, and could explain the inadequacy of TAN for corrosion prediction. The focus of continuing work is the extension of these techniques to acidic oils of differing geologic origins, and the identification of the compounds that specifically contribute to corrosive behavior. Acknowledgment. This work was supported by a CRADA agreement between Chevron Research and Technology Company and Argonne National Laboratory under the U.S. Department of Energy, Office of Fossil Energy, contract number W-31-109-ENG-38. We are grateful for the financial and technical support of the Chevron Pascagoula Refinery and Mr. Arnold Vanderschoot, to Ms. Anne Shafizadeh of Chevron Research and Technology for the acquisition of oil samples, to Mr. Larry Kineer for his technical support, and to Ms. Karin Moszur for sample preparation and analysis.
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