Energy & Fuels 2002, 16, 1121-1127

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Extraction and Characterization of Asphaltenes from Different Crude Oils and Solvents
J. Ancheyta,*,, G. Centeno, F. Trejo,, G. Marroqun, J. A. Garca, E. Tenorio, and A. Torres
Instituto Mexicano del Petroleo, Eje Central Lazaro Cardenas 152, Mexico 07730 D.F., Mexico, Instituto Politecnico Nacional, ESIQIE, Mexico 07738 D. F., Mexico, and Facultad de Qumica, UNAM, Ciudad Universitaria, Mexico 04510 D.F., Mexico Received December 21, 2001

Three crude oils were employed for precipitation of asphaltenes using two solvents, n-pentane and n-heptane. Crude oils were analyzed by API gravity, elemental composition and metals content. Asphaltenes were characterized by VPO molecular weight, liquid State 1H and 13C NMR, elemental composition, and metals content. Spectra were divided in three and two different regions for 1H and 13C NMR, respectively, to determine the most important structural parameters of asphaltenes. To avoid errors when determining asphaltene content and characterization, a solventto-oil (S/O) ratio of 60:1 was used. This optimal ratio was defined after conducting various experiments with different values of S/O in the range of 5:1 to 100:1. It was found that solvent type has a very important influence in composition of asphaltenes, which were also very different for the three crude oils studied. Aromaticity of asphaltenes was higher when n-heptane was employed.

Introduction Asphaltenes are the heaviest and most complex fraction of crude oil. It consists of condensed polynuclear aromatics and contains small amounts of heteroatoms (S, N, and O), and traces of nickel and vanadium. Speight1 has defined asphaltenes as the brown and black powdery material produced by treatment of petroleum, petroleum residua, or bituminous materials with a low-boiling liquid hydrocarbon, e.g., pentane or heptane; being soluble in benzene (and other aromatics solvents), carbon disulfide, and chloroform (or other chlorinated hydrocarbon solvents). Asphaltenes are the main cause of problems associated with catalytic processing of petroleum residua, since they adversely affect the overall rate of hydrodesulfurization, act as coke precursors, contribute to catalyst deactivation, etc.2 Studies of petroleum asphaltenes have rapidly increased during the past years because of the increasing production of heavier crude oils. This can be clearly seen in Figure 1, which illustrates the number of papers published in scientific journals from year 1950 until November 2001. Due to this growing volume of heavy crude oils refiners face drastic changes in petroleum feed properties, which will affect all refinery conversion processes. For this reason, our research group has been extensively studying how to improve the quality of
* Author to whom correspondence should be addressed. FAX (+52-5) 333-8429. E-mail: jancheyt@imp.mx. Instituto Mexicano del Petroleo. Instituto Politecnico Nacional. Ciudad Universitaria. (1) Speight, J. G. Handbook of Petroleum Analysis; John Wiley & Sons: New York, 2001. (2) Calemma, V.; Rausa, R.; DAntona, P.; Montanari, R. Energy Fuels 2001, 12, 422-428.

Figure 1. Number of publications about asphaltenes in the period 1950-2001.

heavy oils by catalytic hydrotreating in one3,4 and two reaction stages.5 As it is well-known asphaltenes are the primary cause of catalysts deactivation during hydrotreating of heavy oils, in which oil and resin fractions are converted very fast to smaller fragments compared to asphaltenes fraction. These complex molecules are precipitated on the catalyst surface and block the pore mouth.6 Hydrotreating catalysts used for heavy oils are different than those employed for lighter fractions, since the formers are operated comparatively at higher reac(3) Ancheyta, J.; Betancourt, G.; Marroqun, G.; Perez, A.; Maity, S. K.; Cortes, M. T.; del Ro, R. Energy Fuels 2001, 15, 120-127. (4) Ancheyta, J.; Maity, S. K.; Betancourt, G.; Centeno, G.; Rayo, P.; Gomez, M. T. Appl. Catal., A 2001, 216, 195-208. (5) Ancheyta, J.; Betancourt, G.; Marroqun, G.; Centeno, G.; Cas taneda, L. C.; Alonso, F.; Munoz, J. A. D.; Gomez, M. T.; Rayo, P. Appl. Catal., A 2002, 233, 159-170. (6) Trimm, D. L. Deactivation, Regeneration and Disposal of Hydroprocessing Catalysts. In Catalysts in Petroleum Refining 1989; Trimm, D. L., Ed.; Elsevier: Amsterdam; Vol. 41.

10.1021/ef010300h CCC: $22.00 2002 American Chemical Society Published on Web 08/14/2002

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Table 1. Summary of Recent Works about Characterization of Asphaltenesa author technique ESR ST, EC, VPO, 13C NMR OST al.10 XRD HRTEM FD, FES, 13C NMR, IR VPO VPO, TLC VPO, IT GC/MS, EC, FTIR FD TGC SEC, PDMS, VPO, LDMS, MALDI FD SEC, IR, 13C NMR Py/GC/MS, GPC, 1H/13C NMR, MALDI TOF VPO, GPC, EC, 13C NMR VPO, 1H NMR VPO, SEC, EC, SANS, 13C NMR, LDMS, HRMS FTIR, 13C NMR FTIR, EC, HPLC-SEC 1H/13C NMR, FS, HPLC-SEC, VPO, EC VPO, 13C NMR VPO, 13C NMR objective of the research

Ancheyta et al.

Wong and

Yen7

Leon et al.8 Joshi et al.9 Shirokoff et

Sharma et al.11 Buenrostro et al.12 Alboudwarej et al.13 Gutierrez et al.14 Yarranton et al.15 Guiliano et al.16 Groenzin and Mullins17 Fuhr et al.18 Domin et al.19 Groenzin and Mullins20 Carbognani et al.21 Artok et al.22 Peramanu et al.23 Tojima et al.24 Miller et al.25 McLean and Kilpatrick26 Andersen27 Andersen28-29 Fuhr et al.30 Adarme et al.31

To examine the ability of microwave power to dissociate petroleum asphaltenes macrostructures To study aspects related to the asphaltene deposition and composition of crude oils To study the characteristics of the asphaltene precipitate To report the structural characterization of Saudi Arabia asphaltenes To test the stacking and stacking disruption To explore the aspects of asphaltene chemical structure To examine the effect of different degrees of washing on the asphaltene properties To isolate asphaltene fractions and study the solubility in toluene To study the molar mass and solvent-water interfacial tensions of asphaltenes To investigate the potential of supercritical fluid extraction for crude oil asphaltenes To survey the molecular size of a broad range of asphaltenes To examine the analytical separation of asphaltenes, wax, and soluble oil fractions To examine and compare the molecular-weight distributions To analyze FD rates of very dilute solutions of asphaltenes To study the precipitation of asphaltenes during oil production and storage To elucidate the distribution of the aliphatic carbons To analyze the molecular weight of asphaltenes and their composition To apply a new asphaltene fractionation method using a binary solvent system To separate and characterize Mayan asphaltene in two fractions To determine and compare the composition of asphaltenes of four different crude types To investigate whether asphaltenes could be extracted directly from the crude oil by a polar solvent mixture To investigate effects of the temperature on precipitation of asphaltenes To study some properties of asphaltenes precipitated as a function of the solvent and temperature To study how metals are removed from asphaltenes and study thermal and catalytic effects

a OST: Optical scattering technique. FD: Fluorescence depolarization. FES: Fluorescence emission spectroscopy. 13C NMR: 13-Carbon Nuclear magnetic resonance. IR: Infrared. ST: Surface tension. EC: Elemental composition. VPO: Vapor pressure osmometry. GPC: Gel permeation chromatography. IT: Interfacial tension. ESR: Electron spin resonance. GC/MS: Gas chromatography/mass spectrometry. FTIR: Fourier transformed infrared. SEC: Size-exclusion chromatography. HTGC: High-temperature gas chromatography. XRD: X-ray diffraction. py/GC/MS: Pyrolysis gas chromatography/mass spectrometry. MALDI TOF: Matrix-assisted laser desorption/ionization timeof-flight. PDMS: Plasma desorption mass spectrometry. LDMS: Laser desorption mass spectrometry. HRTEM: High-resolution transmission electron microscopy. SANS: Small-angle neutron scattering. HRMS: High-resolution mass spectrometry. TLC: Thin-layer chromatography. FS: Fluorescence spectroscopy. HPLC: High-performance liquid chromatography.

tion severity. In the case of heavy crude oils, the design of hydrotreating catalyst is a challenging problem because of the presence of asphaltenes which deactivate the catalyst at a faster rate. Therefore, to develop suitable catalysts for heavy crude oil hydrotreating, studies of characterizing asphaltenes are very important. Much emphasis has been put on characterization in terms of chemical structure and elemental analysis. The techniques frequently used to characterize asphaltenes are IR, NMR, ESR, mass spectroscopy, X-ray, electron microscopy, VPO, GPC, among others. The use of a specific technique depends mainly on the objective of the research. For instance, Wong and Yen7 used ESR to examine the ability of microwave power to

dissociate petroleum asphaltene macrostructure. Leon et al.8 employed elemental analysis, VPO, and NMR to explore the possible relations among the structural parameters of the asphaltenes, their self-aggregation, and the instability behavior of crude oils. Joshi et al.9 studied the characteristics of the asphaltene precipitate utilizing optical scattering techniques. Shirokoff et al.10 reported the structural characterization of four Saudi Arabian crude-oil-derived asphaltenes by X-ray diffrac(7) Wong, G. K.; Yen, T. F. J. Pet. Sci. Eng. 2000, 28, 55-64. (8) Leon, O.; Rogel, E.; Espidel, J.; Torres, G. Energy Fuels 2000, 14, 6-10. (9) Joshi, N. B.; Mullins, O. C.; Jamaluddin, A.; Creek, J.; McFadden, J. Energy Fuels 2001, 15, 976-986. (10) Shirokoff, J. W.; Siddiqui, M. N.; Ali, M. F. Energy Fuels 1997, 11, 561-565.

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Energy & Fuels, Vol. 16, No. 5, 2002 1123

Table 2. Properties of Crude Oils Maya API gravity elemental analysis (wt %) carbon hydrogen oxygen nitrogen sulfur H/C atomic ratio metals (wppm) nickel vanadium asphaltenes (wt %) in nC5 in nC7 21.3 83.96 11.80 0.35 0.32 3.57 1.687 53.4 298.1 14.10 11.32 Isthmus 33.1 85.40 12.68 0.33 0.14 1.45 1.782 10.2 52.7 3.63 3.34 Olmeca 38.7 85.91 12.80 0.23 0.07 0.99 1.788 1.6 8.0 1.05 0.75

tion, NMR, and HP-GPC. Table 1 summarizes some of the recent reports about asphaltenes characterization where techniques and objectives of the research are highlighted.7-31 During our studies of hydrotreating process to improve the quality of heavy crude oils, such as Maya (21.3API), our main goal is to transform this crude into light crude oils, such as Isthmus (33.1API) or, even better, into an Olmeca crude oil (38.7API). To do this requires an appropriate catalytic system. The main concept for developing a suitable catalyst for this purpose depends on the particle size, pore size, and its distribution in order to achieve optimum heteroatoms removal as well as high metal tolerance. Here is where asphaltenes characterization becomes very important since these complex molecules are precipitated on the catalyst surface during hydrotreating and block the pore mouth. They are also coke precursors and deactivate the HDT catalysts. As was mentioned previously, Maya heavy crude oil is being used in our HDT experiments, and we want the hydrotreated crude oils to have properties similar to those lights crude oils (Isthmus or Olmeca). Therefore, it is mandatory to know details about asphaltene structure and composition of these crudes in order to have more information for catalyst design purposes. For this reason, we extract and characterize the asphaltenes fraction of Maya, Isthmus, and Olmeca crude oils, which have very different properties and asphaltene contents. Experimental Section
Feedstocks. Maya, Isthmus, and Olmeca crude oils were employed for asphaltenes extraction. Main properties of these three crudes are shown in Table 2. It can be seen that Maya
(11) Sharma, A.; Groenzin, H.; Tomita, A.; Mullins, O. C. Energy Fuels 2002, 16, 490-496. (12) Buenrostro, E.; Groenzin, H.; Lira-Galeana, C.; Mullins, O. C. Energy Fuels 2001, 15, 972-978. (13) Alboudwarej, H.; Beck, J.; Svrcek, W. Y.; Yarranton, H. W.; Akbarzadeh, K. Energy Fuels 2002, 16, 462-469. (14) Gutierrez, L. B.; Ranaudo, M. A.; Mendez, B.; Acevedo. S. Energy Fuels 2001, 15, 624-628 (15) Yarranton, H. W.; Alboudwarej, H.; Jakher, R. Ind. Eng. Chem. Res. 2000, 39, 2916-2924. (16) Guiliano, M.; Boukir, A.; Doumenq, P.; Mille, G.; Crampon, C.; Badens, E.; Charbit, G. Energy Fuels 2000, 14, 89-94. (17) Groenzin, H.; Mullins, O. C. Energy Fuels 2000, 14, 677-384. (18) Fuhr, B. J.; Holloway, L. R.; Hammami. A. Energy Fuels 1999, 13, 336-339. (19) Domin, M.; Herod, A.; Kandiyoti, R.; Larsen, J. W.; Lazaro, M-J.; Li, S.; Rahimi, P. Energy Fuels 1999, 13, 552-557. (20) Groenzin, H.; Mullins, O. C. J. Phys. Chem. A 1999, 103, 11237-11245. (21) Carbognani, L.; Orea, M.; Fonseca, M. Energy Fuels 1999, 13, 3, pp 351-358. (22) Artok, L.; Su, Y.; Hirose, Y.; Hosokawa, M.; Murata, S.; Nombra, M. Energy Fuels 1999, 13, 287-296. (23) Peramanu, S.; Pruden, B.; Rahimi, P. Ind. Eng. Chem. Res. 1999, 38, 3121-3130. (24) Tojima, M.; Suhara, S.; Imamura, M.; Furuta, A. Catal. Today 1998, 43, 347-351. (25) Miller, J. T.; Fisher, R. B.; Thiyagarajan, P.; Winans, R. E.; Hunt, J. E. Energy Fuels 1998, 12, 1290-1298. (26) McLean, J. D.; Kilpatrick, P. L. Energy Fuels 1997, 11, 570585. (27) Andersen, S. I. Pet. Sci. Technol. 1997, 15, 185-198. (28) Andersen, S. I. Fuel Sci. Technol. Int. 1995, 13, 579-604. (29) Andersen, S. I. Fuel Sci. Technol. Int. 1994, 12, 51-74. (30) Fuhr, B. J.; Cathrea, C.; Jcoates, L.; Kalra, H.; Majeed, A. I. Fuel 1991, 70, 1293-1297. (31) Adarme, R.; Sughrve, F. I.; Jonson, M. M.; Kidd, D. R.; Phillips, M. D.; Shaw, J. E. Symposium on Resid Upgrading; American Chemical Society: Washington, DC, 1990, 614-618.

Figure 2. Effect of solvent-to-oil ratio on asphaltenes extraction. (O) Refinery solvent and (b) n-C5. (/) Repetitions with refinery solvent. crude is the heaviest with more content of contaminants and Olmeca is the lightest. Extraction of Asphaltenes. The asphaltenes fraction was isolated by addition of an excess of solvent to each of the three crude oils used in this study. Various tests with different solvent-to-oil (S/O) ratios were performed in order to determine the appropriate ratio for asphaltene precipitation. Figure 2 illustrates the results obtained for precipitation of asphaltenes in Maya crude oil. Two solvents were used for these tests: (1) a high-pentane content refinery stream (composition in mol %: 40.9% n-C5, 30.5% i-C5, 3.4% C3-C4, and 25.9% C6-C7) and (2) n-pentane. For these tests we used a refinery stream because we were trying to substitute n-pentane solvent by another cheaper solvent. However, asphaltene content was quite different with both solvents, and we finally decided to use the common solvents. Anyhow, all these experimental information was useful for deciding the optimal S/O ratio. Results showed in Figure 2 clearly indicate that asphaltenes content remains constant after an S/O ratio of 40:1 for both solvents. Extraction with refinery solvent exhibited higher asphaltenes content than n-pentane, which is mainly due to the content of isopentane in the former.32 To avoid errors in the determination of the amount of asphaltene fraction and in its characterization, we decided to use a solvent-to-oil ratio of 60:1. Figure 2 also shows results of repetition of some values of asphaltene content with refinery solvent. The maximum absolute difference observed was 0.1 wt %. This indicates that repeatability of extraction method is very good. Once the S/O ratio was defined, asphaltenes were extracted for other crude oils and solvent following the procedure described in ASTM D-3279 method. Briefly, a sample of crude oil (7.5 g) was mixed with 450 mL of solvent in a 500 mL round-bottom flask in order to have
(32) Mitchell, D. L.; Speight, J. G. Fuel 1973, 52, 149-152.

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Table 3. Assignments of 1H and chemical shift range (ppm from TMS)
1H 1H 13C 13C

Ancheyta et al.
Chemical Shifts in NMR assignment + hydrogen-to-aromatic ring (H+) R hydrogen-to-aromatic ring (HR) aromatic hydrogen (Har) aliphatic carbon (Cal) aromatic carbon (Car)

aliphatic NMR aromatic NMR NMR

0.5-2 2-4 6-9 10-60 110-160

an S/O ratio of 60 g/mL. The resulting solution was stirred gently for 20 min, heated to reflux (92 C), and then allowed to settle for 1 h at room temperature. Afterward, the suspension was filtered on a 1.5 m pore size microfiber filter (Whatman GF/A). The precipitate was washed with three portions of n-heptane of about 10 mL each until the solvent wash was colorless. Asphaltenes from Maya crude oil required up to 50 mL of n-heptane during washing. This washing was used to drain out the precipitate coating the flask wall and to thoroughly rinse the solid collected on the filter. Finally, the filtered sample was dried at 107 C during 20 min and weighted for determining asphaltenes content. Taking into account that precipitated asphaltenes can absorb certain amount of maltenes and/or resin, before analytical characterization we have checked it these components are still present. To do this some of extracted asphaltenes were dissolved in toluene at about 100 C, and after allowing the mixture to stand for 4 h, a total dissolution was observed. Additionally, asphaltenes were reprecipitated with n-heptane following the above-described procedure and high percentages of this material were found (about 98%). During the washing step, n-heptane was also very light in color. All this indicates that the original asphaltene sample had very little contamination of other materials. Various extractions were needed to have enough amount of sample for characterization, especially with Isthmus and Olmeca crude oils due to their small content of asphaltenes. Analysis of Asphaltenes. The following methods were employed to analyze both crude oils and asphaltenes properties: (1) C, H, and N contents were obtained by combustion at 950 C on an ELEMENTAR VARIO EL model analyzer. (2) Sulfur content was determined by combustion at 1350 C using a LECO SC-444 model analyzer. (3) The measurements for oxygen contents were obtained by difference then they are less accurate than the others. (4) Nickel and vanadium contents were obtained by atomic absorption. Solid samples were first heated at high temperature (550 C) to eliminate possible organic material. They were then digested in a mixture of HCl/HNO3 with heating until total dissolution. Finally, samples were filtered and analyzed in a Perkin-Elmer 5000 model spectrophotometer. Additionally the following methods were used for characterizing the asphaltene fraction: (1) Molecular weight was evaluated by vapor pressure osmometry (VPO) in a Corona Wescan 232A Model equipment in toluene at 25 C. (2) Liquid State 1H and 13C NMR were carried out in a JEOL Eclipse 300 model spectrometer operating at 1H resonance frequency of 300 MHz and 13C resonance frequency of 75 MHz. 1 H NMR spectra were obtained using a deuterated chloroform (CDCl3) solution with a flip angle of 45, tube diameter of 5 mm, and spectral width of 12 ppm while 13C NMR spectra were evaluated by applying an inverse-gated decoupling technique to suppress NOE effect with a flip angle of 75 and spectral width of 220 ppm. Chromium acetylacetonate (Cr(acac)3 0.1 M in the final solution) was added to ensure complete nuclear magnetic moment relaxation between pulses. In addition, tetramethylsilane (TMS) was employed as an internal reference. These conditions are necessary to have quantitative 13C NMR signals.

Figure 3. Asphaltenes versus API Gravity of crude oils. (O) n-C7 and (b) n-C5. The measurements were performed for 30000 scans. For 1H NMR, the spectrum was divided into three regions (0.5-2, 2-4, and 6-9 ppm) and 13C NMR spectrum have been divided only into two different integration domains (10-60 and 110160 ppm). The assignments of chemical shift range for 1H and 13 C NMR spectra were made according to the data presented in Table 3. Structural parameters for asphaltenes were determined with the data of nuclear magnetic resonance, molecular weight, and elemental analyses.

Result and Discussion Crude Oil Properties. Asphaltenes contents against API gravity of crude oils are presented in Figure 3. Less asphaltenes precipitation was obtained with n-heptane compare to n-pentane. This behavior is well documented in the literature.33 Sulfur content and other heteroatoms content are very close related to asphaltene concentration in crude oil (Figure 4), which are lower in Olmeca crude and higher in Maya crude. The vanadium-to-nickel ratio is almost the same as that for the three crude oils (5.1-5.6). It is also observed in Table 2 that the hydrogen/carbon (H/C) atomic ratio is highest in Olmeca crude, which implies that it is more paraffinic than the others. Analytical Data of Asphaltenes. The elemental analysis (C, H, O, N, and S) and metals content (Ni and V) of asphaltenes obtained from Maya, Isthmus, and Olmeca crude oils with n-pentane and h-heptane are presented in Table 4. The asphaltene composition of these three crude oils shown in this table covers a wide range. Particularly, metals (Ni+V) vary between 580 and 1480 wppm while sulfur content is between 3.2 and 8.5 wt %. From left to right and for each solvent, carbon content increases while hydrogen, sulfur, and metals contents decrease as the crude oil becomes lighter. Nitrogen
(33) Speight, J. G. The Chemistry and Technology of Petroleum; Marcel Dekker, Inc.: New York, 1999.

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Energy & Fuels, Vol. 16, No. 5, 2002 1125

Table 4. Elemental Analysis and Metal Content of Asphaltenes Maya solvent: elemental analysis (wt %) carbon hydrogen oxygen nitrogen sulfur atomic ratios H/C O/C N/C S/C metals (wppm) nickel vanadium n-C5 81.23 8.11 0.97 1.32 8.25 1.198 0.009 0.014 0.038 268.7 1216.6 n-C7 81.62 7.26 1.02 1.46 8.46 1.067 0.009 0.015 0.039 320.2 1509.2 n-C5 83.90 8.00 0.71 1.33 6.06 1.144 0.006 0.013 0.027 155.4 710.3 Isthmus n-C7 83.99 7.30 0.79 1.35 6.48 1.043 0.007 0.014 0.029 180.4 746.6 n-C5 86.94 7.91 0.62 1.33 3.20 1.092 0.005 0.013 0.014 81.9 501.0 Olmeca n-C7 87.16 7.38 0.64 1.34 3.48 1.016 0.006 0.013 0.015 157.7 703.8

Table 5. Percentages of Asphaltenic Heteroatoms in Each Crude Oil with n-Pentane Solvent Maya sulfur nitrogen oxygen nickel vanadium ni+v 32.6 58.2 39.1 70.9 57.5 59.6 Isthmus 15.2 34.5 7.8 55.6 49.0 50.0 Olmeca 3.4 20.0 2.8 55.1 65.7 64.0

Figure 4. Asphaltenes in n-heptane versus heteroatoms contents of crude oils (O) metals (Ni + V) in wppm 102, (b) nitrogen in wt % 10-1, and (0) sulfur in wt %.

content did not change when n-pentane was used, but it decreased when n-heptane was employed as solvent. Oxygen as calculated by difference, although not a very accurate measure is also lower in asphaltenes from light crude oil. The H/C atomic ratio and other elements-tocarbon ratio varied in the same way as the corresponding element was changed. n-Heptane solvent yields a product that is different from the n-pentane solvent. For example, the H/C atomic ratio of asphaltenes obtained with n-C7 solvent is lower than that of the n-C5 precipitating medium. This indicates a higher degree of aromaticity in the n-heptane precipitate. N/C, O/C, and S/C atomic ratios were higher in the n-C7 precipitate, indicating higher proportions of these heteroatoms in this material.33 Differences in some heteroatom content between n-pentane and n-heptane solvents are smaller in Olmeca crude compared to that among other crude oils, which is mainly due to Olmeca crudes smaller asphaltene and heteroatom contents. With asphaltene and sulfur contents in each crude oil and sulfur content in the corresponding asphaltene fraction, a mass balance procedure has been performed to determine how much sulfur in each crude oil is present in asphaltenes fraction (asphaltenic sulfur). We also performed this mass balance procedure for other elements, and the final results are summarized in Table 5. Only the results for n-pentane are presented in this table because asphaltene extraction is more complete with this solvent, and hence, calculations gave higher

Figure 5. NMR spectra of asphaltenes using n-pentane solvent. (A) Olmeca, (B) Isthmus, and (C) Maya.

percentages of asphaltenic elements than those obtained when n-heptane was used. It is observed that the three crude oils exhibited very different percentages of asphaltenic heteroatoms. Asphaltenic sulfur, nitrogen, and oxygen are higher in Maya crude and lower in Olmeca crude, which corresponds to the behavior observed with these elements in the whole crude oils. Asphaltenic nickel follows the same trend with very similar percentages in Isthmus and Olmeca crudes. However, percentage of asphaltenic vanadium was higher in Olmeca crude compared to the others. This may be attributed to its very low asphaltenes content (1 wt %), in which vanadium surely concentrates. Structural Properties of Asphaltenes. 13C NMR spectra of asphaltenes obtained with n-pentane as precipitating medium are presented in Figure 5. The differences in aliphatic (Cal: 10-60 ppm) and aromatic (Car: 110-160 ppm) carbons for asphaltenes of the three crude oils are clearly distinguished. Similar differences

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Ancheyta et al.
Table 7. Properties of Hydrotreated Crude Oil and of Its Asphaltenes hydrotreated crude H/C molar ratio Ni, wppm V, wppm sulfur, wt % asphaltenes content, wt % MW fa n Ra As 1.230 144 36.9 2.0 6.5 asphaltenes in n-C7 1.097 378 1893 6.47 1513 0.58 5.05 17.3 35.6

Table 6. Structural Parameters for Average Molecule of Asphaltenes Maya solvent: MW fa n Ra As n-C5 n-C7 Isthmus n-C5 n-C7 Olmeca n-C5 n-C7

3680 5190 2603 3375 1707 2663 0.47 0.52 0.59 0.57 0.61 0.62 7.4 6.8 4.8 5.0 4.1 5.5 35 62 34 45 24 40 35.6 38.9 37.9 41.0 39.1 32.9

are observed with the other solvent and 1H NMR spectra. The main molecular parameters from NMR spectra are the aromatic carbon fraction or better known as aromaticity factor (fa), average number of carbons per alkyl side chain (n), percent of substitution of aromatic rings (As), and the aromatic ring number (Ra), which are evaluated as follow:34,35

fa )

Car Car + Cal Cal Csub

(1)

n)

(2)

As ) 100

percent substituted aromatic carbon percent nonbridge aromatic carbon Ra ) Car - Cp -1 2

(3) (4)

where Car are the total aromatic carbons, Cal the total aliphatic carbons, Csub the alkyl-substituted aromatic carbons, and Cp the peripheral aromatic carbons (Cp ) Cus + Csub, Cus representing the unsubstituted aromatic carbons). The molecular parameters evaluated with eqs 1-4 and VPO molecular weights of the three different origin asphaltenes using n-pentane and n-heptane solvents are listed in Table 6. Asphaltenes precipitated with n-heptane showed higher MW than those obtained with n-pentane, which is mainly due to the solvent power: the ability of the solvent to dissolve asphaltenes. For instance, asphaltene content in n-heptane for Maya crude oil were lower than that in n-pentane (11.32 and 14.10 wt %, respectively): both asphaltenes are different in composition as was shown with elemental analyses. In the case of nheptane, the asphaltene fraction is heavier than that obtained with n-pentane implying that n-pentane precipitates fractions with lighter asphaltenes. As consequence of the higher MW exhibited by asphaltenes precipitated with n-heptane solvent, other molecular parameters are also different than those obtained with n-pentane. In general, fa, n, As, and Ra were also higher when n-heptane was employed. Some data do not followed this behavior may be due to experimental error. Number of aromatic rings of asphaltenes in n-C7 almost doubles those in n-C5, and they decreased as the crude oil is lighter. Aromaticity factors were also higher
(34) Seki, H.; Kumata, F. Energy Fuels 2000, 14, 980-985. (35) Calemma, V.; Iwanski, P.; Nali, M.; Scotti, R.; Montanari, L. O. Energy Fuels 1995, 9, 225-230.

with n-heptane. With these results it is also confirmed that n-heptane gives a more aromatic asphaltenic fraction than n-pentane. Aromaticity factor was higher in Olmeca crude and lower in Maya crude. In addition, light crude oil has higher percentage of asphaltenic vanadium as was shown by elemental analyses. This implies that the almost insignificant amount of asphaltenes in light crudes is more refractory than heavy ones. Application of Results of Asphaltenes Characterization. To understand the mechanisms of catalyst deactivation by coke during HDT of heavy crude oils it is important to study the changes of asphaltene structure and composition. First, it is necessary to know the asphaltene properties of the HDT feedstock, i.e., Maya crude oil, and second, characterizing the asphaltenes obtained from light crudes, i.e., Isthmus or Olmeca, is also necessary. Finally, asphaltenes from hydrotreated crude oils should be analyzed. All this information can be employed to make changes in the properties of the HDT catalyst, mainly in pore size distribution. In the case of the present study we have extracted asphaltenes from a hydrotreated crude oil with nheptane, which was obtained at the following operating conditions: 70 kg/cm2 pressure, 5000 ft3/bbl H2-to-oil ratio, 0.5 h-1 LHSV, and reaction temperature of 420 C. Properties of this sample together with those of the hydrotreated crude oil are presented in Table 7. It can be observed that hydrotreated product has almost the same sulfur content in asphaltenes and more than twice the asphaltene content than Isthmus crude oil. With respect to asphaltenes, it is seen that the H/C molar ratio of hydrotreated crude is higher than that of the Maya crude oil indicating, that asphaltenes are more aromatic in the former, which is also verified with NRM results. fa and n of asphaltenes from Isthmus and hydrotreated crudes are equal; however, Ra and MW are considerably lower in HDT crude oil asphaltenes, which indicates that the latter has a lesser number of aromatic rings. Metals content increased in asphaltenes of HDT crude oils which is due to the localization of these heteroatoms inside the asphaltene molecule, and because of this, they remain almost unchanged after HDT, and hence they are concentrated in asphaltenes. Conclusions Asphaltenes obtained from three crude oils have been precipitated with two solvents (n-pentane and n-heptane) and characterized using common techniques.

Asphaltenes from Crude Oils and Solvents

Energy & Fuels, Vol. 16, No. 5, 2002 1127

Solvent type has a very important influence in composition of asphaltenes. Molecular weight of asphaltenes precipitated with n-heptane showed higher values than those obtained with n-pentane, which was attributed to solvent power. Number of aromatic rings and aromaticity factors were higher with n-heptane compared to n-pentane,

which indicates a higher degree of aromaticity in asphaltenes obtained with the former solvent. Acknowledgment. The authors thank Instituto Mexicano del Petroleo for its financial support. F. Trejo also thanks CONACyT for financial support.
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