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Energy & Fuels 2003, 17, 378-386
Density Estimation of Asphaltenes Using Molecular Dynamics Simulations
E. Rogel* and L. Carbognani
PDVSA-INTEVEP, P.O. Box 76343, Caracas 1070A, Venezuela Received September 4, 2002
Molecular dynamics simulations are carried out to estimate the density of average structures representative of various asphaltenes in an effort to evaluate the predictive capacities of this kind of structural models. Comparison between calculated and experimental values reveals that calculated densities are lower than experimental ones, but nevertheless calculated values show the correct tendency. This indicates that the chemical information provided by the average structures of asphaltenes is essentially correct and can be used to qualitatively estimate densities. On the basis of these results, the effect of different structural factors on calculated densities of asphaltenes was systematically studied. Large condensed aromatic rings and low hydrogen-tocarbon ratio are the main characteristics of the molecules which yield the highest densities. Also, it was found that a group-contribution method recently developed yields better density values than molecular dynamics simulations, although still lower than experimental values.
Introduction The addition of n-heptane or other alkanes to crude oils originates the selective precipitation of the highmolecular-weight, high-aromaticity, and high-polarity components.1 The precipitated material which is further soluble in aromatic solvents is known as asphaltenes and is a complex mixture of substances with similar solubility properties.2 Asphaltenes can also separate from crude oils as insoluble solid phases when pressure and temperature conditions vary.3,4 Asphaltenes are a well-known problem for the oil industry. Their tendency to form deposits on wells, tubing, piping, and also during refining processes causes heavy losses to the oil industry every year.5 Although the chemical composition of asphaltenes varies little for diverse crude oils (hydrogen/carbon ratio ≈ 1.15, aromaticity ≈ 0.50), these small variations induce important changes for asphaltene stability within crude oil.4-6 For instance, asphaltenes from unstable crude oils (crude oils with asphaltene precipitation problems during production operations) and from deposits show slightly higher aromaticities and lower hydrogen-to-carbon ratios than asphaltenes from stable crude oils.6-8 Therefore, it is clear that small changes
* Present address: 15315 SW 78 Court, Miami, FL 33157. (1) Mullins, O. C. Anal. Chem. 1990, 62, 508. (2) Bestougeff, M. A.; Byramjee, R. J. In Asphaltenes and Asphalts. 1. Developments in Petroleum Science; Yen, T. F., Chilingarian, G. V., Eds.; Elsevier: Amsterdam, 1994. (3) Peramanu, S.; Clarke, P. F.; Pruden, B. B. J. Pet. Sci. Eng. 1999, 23, 13. (4) Rassamdana, H.; Farhani, M.; Dabir, B.; Mozaffarian, M.; Sahimi, M. Energy Fuels 1999, 13, 176. (5) Thawer, R.; Nicols, D.; Dick, G. SPE Prod. Eng. 1990, November, 475. (6) Carbognani, L.; Orea, M.; Fonseca, M. Energy Fuels 1999, 13, 351. (7) Carbognani, L.; Espidel, J.; Izquierdo, A. In Asphaltenes & Asphalts. 2. Developments in Petroleum Science; Yen, T. F., Chilingarian, G. V., Eds.; Elsevier: Amsterdam, 2000.
in composition and chemical characteristics induce significant differences in stability behavior. For this reason, the study of asphaltene molecular structures is of great practical interest. However, the asphaltene fraction contains at least 105 different molecules9 which makes the isolation and even the identification of individual components impossible.10 As a consequence of their extraordinary complexity, the chemical characterization of asphaltenes and other heavy fractions is based on the identification of molecular types and structural groups. It has been found that asphaltenes are composed of polyaromatic condensed rings, aliphatic chains, and heteroatoms such as nitrogen, oxygen, sulfur, and various metals.11 The chemical information of asphaltenes obtained from diverse techniques is usually summarized in a condensed way using average molecular parameters. The values of these parameters indicate the structural types contained in the asphaltenes.10 Even more, using these parameters it is possible to build a molecular average structure that represents the main chemical characteristics of the studied asphaltene sample. Although the use of average structures to represent asphaltenes is a very common technique, very few attempts have been made to determine whether this type of models can predict the physical and chemical behavior of the fractions that they represent.11 In fact, many limitations have been attributed to the use of average structures.10,12,13 The value of a unique or even several structures to describe the wide variety of dif(8) Rogel, E.; Leon, O.; Espidel, J.; Gonzalez, J. SPE Prod. Facil. 2001, SPE72050. (9) Wiehe, I. A.; Liang, K. S. Fluid Phase Equilib. 1996, 117, 201. (10) Speight, J. G. Appl. Spectrosc. Rev. 1994, 29, 269. (11) Speight J. G. In Asphaltenes and Asphalts. 1. Developments in Petroleum Science; Yen, T. F., Chilingarian, G. V., Eds.; Elsevier: Amsterdam, 1994. (12) Boduszynski, M. M. Liquid Fuels Technol. 1984, 2, 211. (13) Shenkin, P. S. Liquid Fuels Technol. 1984, 2, 233.
10.1021/ef020200r CCC: $25.00 © 2003 American Chemical Society Published on Web 02/22/2003
Elsevier: Amsterdam. The effect of different structural and compositional aspects such as connectivity. . (19) Favre. Phys. 104. 66. heteroatom content. Fluid Phase Equilib. O.. (30) Nakamura. A. 68. (33) Diallo. 79.. E. N. 469... J. K. BO7. The average structures selected for this study are shown in Figure 1. D. S. 14..13 Additionally. 1077. and even a value of 90 rings per aromatic nucleus has been reported... Tavitian. 7. In particular.12. Lown. J. Nakamura.20-23 Rather recently. One of the solids came from production tubing of a well located in western Venezuela (DTJ).10. J.. Chem.. (28) Neubauer. Energy Fuels 1996. S. L. These structures correspond to asphaltenes isolated from Venezuelan crude oils of different origin using the standard method IP-143.38 The force field cvff (consistent valence force field) was used in the calculations. M...19 The average molecular weight of asphaltenes also varies widely depending on the technique used to determine them.. Pet. E. Artok. 1990. Fuel 1992. Energy Fuels 2001. (37) Satou.21-23 The charges in the atoms are assigned according to the database cvff and remain constant during the calculations. (24) Rogel.. Energy Fuels 1999. T. A. A. O.24. 29. 1355. even though the functionality and polyaromatic ring systems experimentally determined are real. E. Fuel 2000. 1985. Energy Fuels 2001. H. C. Vol. Murata..8 Six of the structures (CN.. Inc. 11237.. M.. Nakamura. E. T. W. Wernick. (17) Groenzin. Miura. S. 1057. O... BC6. L. M.. CO2) to asphaltenes from unstable crude oils and finally two correspond to asphaltenes isolated from solid deposits removed from field facilities. T. 16. Y. MO21. BC5) correspond to asphaltenes from stable crude oils. Delhommelle.10 Despite the significant progress in asphaltene characterization during the last years. B. Energy Fuels 1993. 13. Fuchs. M. H. 347. C. J. E. 1265. Y. Y. Strausz.14-18 The number of rings per aromatic nucleus reported10 using different techniques varies from 6 to 20. temperature. D. 2000. Mullins.. S.34. 116. Tavitian. T. (31) Murata.25 These theoretical studies have provided useful information about the nature of the interaction in these complex systems. L. R. FU1. 485.. Murata. 161. Pet. The other solid is a bottom tank sediment formed in about 4 years in a tank located in eastern Venezuela (34) Laux. Fuel 1987. (21) Murgich. 15... 167. Based on this diverse experimental information. H. No. O. H. M. 45. Leon. Ed. They were obtained based on elemental analysis and 1H NMR data according to a procedure previously described. J. This study also includes the comparison of the calculated densities using molecular simulations with experimental values and with calculated densities using a group-contribution model. Discover 2. including the comparison of different structural models such as those containing large and small polyaromatic rings. San Diego. Aray. S. Masakatsu. (26) van Gunsteren. (27) Cuia. 14. Contreras.. molecular dynamics and molecular mechanics simulations have been successfully used to describe the aggregation and solubility behavior of molecules that represent asphaltenes and resins. 40. Savage.. Rev. Kumagai. H. The main objective of the present work is to evaluate the predictive capacities of the average structural models of asphaltenes using the density as a reference property and also to determine the effect of different structural factors on asphaltene density. Fr.. 992.Density Estimation of Asphaltenes Using MD Simulations Energy & Fuels. that the densities of different solid products of crude oil correlate very well with the hydrogen-to-carbon ratio and also with solubility. (15) Strausz. (18) Groenzin. this approach has been extended to the study of the activity of amphiphiles as asphaltene stabilizers. (20) Rogel. Rev. Methods Simulation Details. 1459. Murata. Nomura. Engl. Chem. Ungerer. Sci.. A 1999. 45. W.37 Therefore. F. S. Leon. K. Energy Fuels 1998. 2. Mullins. M. The molecular mechanics and molecular dynamics methods used are those included in the commercial programs InsightII. Angew. L. F.. Chilingarian. T.. Energy Fuels 1993..26 Volumetric calculations have been carried out for pure hydrocarbons27. 141. Nomura. ´ (22) Murgich. In the present work. 85. (16) Su. ¨ (35) Carbognani. MO29. A 1995. Fr. 51. Yen.. Nomura. (38) Molecular Simulations. In Asphaltenes & Asphalts. A. W. 677. O. and concentration.. B. R. Besides information about the atomistic behavior of a system. W. Chiba. P. Nakamura. Boutin. 155. Energy Fuels 2000. H. and hydrogen-to-carbon ratio on the calculated densities is explored.. E. 566.. P. B. 278. K. J. Cummings.. 1997.33 It has been found (14) Speight. 2... there are still some doubts about the structural characteristics of this fraction. H. 39.29 There are also volumetric studies for coals using average structures and molecular simulations30-32 and. Overfield. 1123. the connectivity or the combination of these parameters can be misleading. A.14 This is because asphaltenes tend to self-assemble and such behavior depends on many factors such as solvent. V. Berendsen. T. 2003 379 ferent compounds that compose the asphaltenes is considered doubtful. B. Fluid Phase Equilib... 12. (32) Dong... M.28 and for natural gas. Energy Fuels 2000. M. G. 10. I. density values for average structures of asphaltenes from Arab Berri crude oil have been calculated using molecular dynamics simulations. Energy Fuels 1993. B.. Sanada.. K. J. (25) Rogel. the size of the aromatic nuclei and the asphaltene molecular weight are still open to question. T. 1999. Technol. the density is a physical property strongly related to the molecular topological characteristics and also to the molecular size of the molecules. Erdol Erdgas Kohle 2000. III. 17.. 7. Fluid Phase Equilib. D. Hattori. in press.. 1013. J. Developments in Petroleum Science. J.9. O.. E. Cagin. Molecular mechanics and molecular dynamics simulations were carried out to determine the density of average structures representative of various asphaltenes. (36) Zander. Rodrıguez. this property can be a useful tool for evaluating the predictive capacities of the average structure approach. 7. Abanero. T. Even more. (29) Neubauer. 1999.. 71. 15.36. asphaltenes are represented by aromatic structures of widely different size.. M. the molecular simulations can also be used to determine thermodynamic properties such as density or solvation free energy.35 Density can be easily determined in the lab and it is often used to calculate other thermophysical properties. This force field has been successfully used to describe the aggregation behavior of asphaltenes and resins as well as the activity of amphiphiles as asphaltene stabilizers in previous works. Boutin. molecular mechanics and molecular dynamics simulations were carried out to determine the density of average structures representative of various asphaltenes. MG27.. four of them (VG3. Cochrana. G. Rahimian. C. 1984.. Inst.. Rao.. Mojeslsky. 103. and Amorphous Cell of Molecular Simulations Inc. Int. (23) Rogel. Colloids Surf. V.. Pet. Boulet. Eds. A. rather recently. Gould. L. P. H.. During the past few years. Goddard. Inst. 1994. Faulon.
two structures obtained using experimental data from ruthenium ion catalyzed oxidation were used in the calculations. L. when compared with the structures presented in Figure 1. 2. Espidel. Energy Fuels 1999.. Vol. Y.. (DTQ). 17. Average structures for the studied asphaltene samples. the potential energy of each one was minimized again in order to lower the . Some of these structures have been previously reported. 14. J. (39) Leon. (40) Artok... M. Murata. followed by the calculation of a constant temperature (NVT) molecular dynamics of 100 ps. M. G. Y. 2003 Rogel and Carbognani Figure 1. Energy Fuels 2000.. Hosokawa. 6. The first is the reported structure for Athabasca asphaltene. 287. Su. The five conformations of lowest energy from the molecular dynamics calculation were selected. O. 13.. E. different molecules that do not represent specifically any asphaltene fraction were employed to evaluate the methodology used and also the effect of different structural parameters on the calculated density values. Torres. Additionally to the structures mentioned.15 while the second corresponds to the proposed structure of Arab crude oil asphaltene.40 These structures are characterized by a lower number of rings per aromatic nuclei.380 Energy & Fuels.. The optimized average structures for each asphaltene were obtained using the following procedure: the potential energy of the constructed model was minimized..39 Besides. Rogel. S. Hirose. and then. Nomura. No.
Density Estimation of Asphaltenes Using MD Simulations Energy & Fuels. Each NPT molecular dynamics run started with an equilibration phase of 50 ps (that is. The data (densities) was collected during the last 100 ps.9666 (1) The original experimental data used to obtain this correlation comprised crude oil related materials including asphaltenes from virgin and processed crude oils.34 This correlation is the following: F ) 1. At the end of each annealing cycle. 2003 381 Figure 2. 2. isothermal-isobaric (NPT) molecular dynamics for 300 ps were run at 298 K. . No. Vol. A scheme of the calculation procedure is shown in Figure 2. These five molecules were used to generate five amorphous structures. The initial density for these structures was estimated from a correlation between the density (F) and the hydrogen-to-carbon ratio (H/C) based on experimental data. Simplified scheme of the calculation of densities by molecular simulation. 50 000 molecular dynamics steps with time step ) 1 fs).34 The five amorphous structures obtained in the previous procedure were relaxed to minimize energy and the relaxed structures were subject to simulated annealing (five repeated cycles of 5000 ps from 200 to 500 K and back) using NVT molecular dynamics. the structure was again minimized.5396 r2 ) 0. This procedure was used to prevent metastable local high-energy minima.3447 H/C-0. 17. For the fully relaxed amorphous structures. energy even more.
2. Table 1 shows the experimental densities determined for the selected asphaltenes including a sample of Venezuelan coal used as reference.614 MHz. 2003 Rogel and Carbognani Table 1.96 0. Figure 4. Samples were dissolved in CD2Cl2. Experimental Density and Other Properties of the Studied Asphaltene Samples asphaltene BC5 BC6 MG27 MO21 MO29 CN CO2 BO7 VG3 FU1 DTJ DTQ Coal A origin stable crude oil stable crude oil stable crude oil stable crude oil stable crude oil stable crude oil unstable crude oil unstable crude oil unstable crude oil unstable crude oil deposit deposit coal H/C 1. show the experimental densities as a function of the H/C ratio and asphaltene aromaticity. Fuel 2000.61 0. Spectra were determined with a Brucker ACP-400 spectrometer at a frequency of 100. and weighed.47 0.18 1.05 1. Results and Discussion Experimental Densities. In these figures. The stopper is pressed firmly in place. and deposits.16 1. density of polyaromatics is closely related to the molecular topology. Aromaticity Determination.00 0.02 g/cm3. and (b) aromaticity (fa). Experimental Methods Density Measurements.41 This comparison indicates that the obtained densities are similar to values previously reported using more sophisticated techniques.50 to 0.55 fa 0. No.7 Since the (41) Strugala. adding 0. Carbon aromaticity was determined by 13C nuclear magnetic resonance.99 1. unstable crude oils. the pycnometer is removed. 79. asphaltenes from unstable crude oils and deposits exhibit higher densities. Then 9 to 9.17 1. Comparison between experimental densities obtained in this work and results previously reported for similar samples.19 1.15 1. the experimental values obtained in this work are compared to similar results obtained by different techniques for crude oil related materials34 and coals.58 0.53 0.02 1.6-8 .59 0.23 1. An inverse gated decoupled technique was adopted for suppression of the Overhauser effect. lower hydrogen-to-carbon ratios. Carbon and hydrogen contents were determined by a combustion method using a Leco instrument. Chemical shifts were referenced to tetramethylsilane. Asphaltene density is calculated as the ratio of the used mass and determined volume. and higher aromaticities than asphaltenes from stable crude oils. and trapped air bubbles are eliminated by ultrasonication. The determinations were found to be accurate to the second decimal figure. This kind of tendency has been previously reported for different samples.17 1.28 1. In Figure 3. The procedure was as follows: 0.22 1.52 0. Elemental Analysis.59 density (g/cm3) 1.52 Figure 3.11 1.20 1.55 g of the sample are placed in the pycnometer. As previously mentioned.5 cm3 of n-heptane are added.19 1. The pycnometer has a capacity of 10 cm3.11 1. n-Heptane was used as displacing fluid. The pycnometer is filled with n-heptane and thermostated by inmersion in a water bath maintained at 25 °C. respectively. A.23 1. Experimental densities as a function of (a) H/C ratio. The density of the asphaltenes shown in Figure 1 was measured using a standard glass pycnometer. the selected asphaltene samples included asphaltenes extracted from stable crude oils. asphaltenes from stable crude oils are clearly separated from asphaltenes from unstable crudes and solid deposits. model CHSN-932.382 Energy & Fuels. parts a and b. 17. Absolute deviations were (0.25 1. Vol.49 0.26 1. 743.2 M of CrIII acetylacetonate. dried. The n-heptane volume is determined by knowing its mass and its density previously determined at the operating temperature.22 1.36 it is worth evaluating the relationship between density and structural characteristics of asphaltenes.98 0. Their isolation either from crude oils or from solid deposits has been previously reported. Asphaltenes are defined as nC7-insoluble/toluene-soluble materials. According to these results. The asphaltene volume is calculated as the difference of the pycnometer volume and the n-heptane volume contained within it.53 0. Figure 4.46 0. although slightly lower than them.13 0.60 0.60 0.
However. All the densities reported in the present work were determined as an average of the set of five amorphous structures. 2. It is also interesting to observe that the density values obtained for the amphoteric molecule A are always lower than the densities calculated for the asphaltene model B. the calculated values corresponding to each set of results (assigned and not assigned heteroatoms) show the correct trend. the density was calculated according to the procedure previously detailed. Two different models were used in this section: a structure representative of an amphoteric fraction reported earlier11 and a hypothetical asphaltene structure with similar hydrogen-to-carbon ratio (H/C) and molecular weight. Effect of different structural modifications on calculated density by molecular simulations. Absolute deviations were around (0. On the basis of this preliminary work. In other words. H/C ratio. and chain positions. This reflects differences that are related to the topological characteristics of the molecules such as ring size. calculated densities are plotted as a function of the experimental densities for the studied samples with (a) assigned heteroatoms. Volumetric studies for coal have shown that the simulation techniques can be used to optimize the average models for coals. and (b) no assigned heteroatoms. The main difference between the molecules shown in Figure 7 is the size of their polyaromatic nuclei. Comparison between calculated densities by molecular simulation and experimental densities. a preliminary study based on structural changes of the ovalene molecule (Figure 6) was carried out. In view of these findings. . In this work. Then.02 g/cm3). 17. The two molecules studied were changed in order to decrease their H/C. The solid line indicates where the points would lay if experiments and calculations yield the same results. On the basis of these previous findings. The introduction of heteroatomic functionalities seems to improve the matching between determined and calculated values. In this figure. the effect of different structural factors on calculated densities of asphaltenes was systematically studied. despite the dispersion of results probably derived from the experimental uncertainty ((0. Both structures are shown in Figure 7. they increase as the experimental values increase. as can be seen in Figure 1. methylene and methyl groups were gradually eliminated from the structures and after each step. (1) The increase of the length of the alkyl appendages produces a decrease in the calculated densities (molecules A to E) with the exception of molecule C. different structural modifications were made on ovalene molecules to determine their effect on the calculated density. In fact. In Figure 5.e. (2) Different isomers such as molecules F and G or E and H can yield significant different densities. Calculated Densities. it is possible to suppose that the differences in density can be at least partially attributed to differences in the polyaromatic ring sizes. As expected. Vol. The comparison between calculated and experimental densities indicates that calculated values are considerably lower than experimental values. i. only a few of the average molecules studied included heteroatoms. molecular weight.Density Estimation of Asphaltenes Using MD Simulations Energy & Fuels. In Figure 8. The amphoteric model contains polyaromatic rings considerable smaller than the asphaltene model used. Effect of the Size of the Polyaromatic Nuclei. This aspect will be discussed in detail in an ensuing section.30-32 In fact. in these works it was found that slight structural variations can induce significant changes in the calculated densities. the density increases as the H/C ratio decreases.. To this end. connectivity.02 g/cm3 for all the cases studied. and heteroatom content are similar in both models. Figure 6. the structures qualitatively predict the tendency of the density. two tendencies can be identified. the density of the structures generated in each case is plotted as a function of the H/C ratio. Figure 6 shows the different molecules studied and the calculated density obtained for them using the procedure already described. The five independent amorphous configurations generated for each average structure shown in Figure 1 were used to estimate the densities according to the procedure previously described. these characteristics were also explored using molecular simulations. 2003 383 Figure 5. Effect of Hydrogen Deficiency. No. Unfortunately.
the densities for both sets of molecules were calculated. according to the authors.00 g/cm3 for Athabasca and Arabian Mixture asphaltene. Vol. 17. Two other structures with relatively small polyaromatic rings were studied. Figure 8. The first structure corresponds to the Athabasca asphaltene15 and the second to an asphaltene isolated from a mixture of Arabian crude oils. No. AICHE J. 41.42 On (42) Yarranton. It has been shown to be clearly superior to other similar methods in its estimations.. As expected. These results contribute another point of view into the open debate on the size and condensation of asphaltenes. a comparison between both sets of values is shown. J. Masliyah. 2003 Rogel and Carbognani Figure 9.37 it can be used to estimate the density . the other hand. Average structures representative of (A) amphoteric fraction. this comparison reveals that the introduction of heteroatoms in the molecular structure induces a slight increase in the calculated density. Effect of the hydrogen deficiency on calculated density for molecules shown in Figure 7. H. Rather recently.17 g/cm3. The average molecular structures of the Athabasca asphaltene15 and the asphaltene from Arabian mixture40 were used as samples. at least in these cases. Effect of the heteroatoms on calculated density. H. 2.06 to 1.00 g/cm3 for both set of molecules. this new group contribution method is applicable in the case of polyaromatic hydrocarbons with aromatic rings of a number up to seven. Of course.03 g/cm3 and 1. respectively. Even though. and (B) asphaltene. experimental density for Athabasca asphaltenes is around 1. 1996.384 Energy & Fuels. This new calculation yields 1. These structures are composed of larger polyaromatic rings than structures for Athabasca and Arabian Mixture asphaltenes. there are not significant density differences considering the whole molecules (1. density values for average structures with assigned heteroatoms from Table 1 vary from 1. this last aspect is directly related to the type of functionality and its position inside the molecule. 3533. For some of the molecules studied. As a reference.00-1. In Figure 9.40 Both structures were obtained from ruthenium ion-catalyzed oxidation.37 This method has been successfully used to describe the molar volumes of heavy hydrocarbons which behave as sticky liquids or crystalline solids at 298 K. Then. Comparison of Molecular Dynamics with a Group Contribution Method Used To Estimate Density of Polyaromatics.03 g/cm3) or the set of their fragments in the calculations (1. Effect of Heteroatoms. This effect can be attributed to the introduction of heavier atoms in the molecule and also to the increase in the molecular interactions because of the presence of heteroatomic functionalities. W. Figure 7. respectively. These results indicated that.00 g/cm3). the density calculations were carried out using molecules with assigned heteroatoms and without assigned heteroatoms. Both molecules were split in 10 and four smaller molecules.16 g/cm3. The comparison between both sets of values indicates that the presence of larger polyaromatic nuclei increases the density of the structures. The density values calculated using these structures were: 1. a new method for estimation of the molar volume of hydrocarbons including condensed polyaromatic hydrocarbons was developed. Effect of the Connectivity.
it is important to point out that any group contribution yields only one value of a particular property in some standard pressure-temperature conditions. 2. Even more. It is expected that the introduction of more molecules in the calculation would improve the calculated densities. it is clear from the results obtained that average structures cannot be used to calculate accurate values of properties for asphaltenes by means of molecular simulations. and second. It is also clear that there should be an effort to (1) develop better structural representations of asphaltenes from the experimental point of view. This gives a natural advantage for a method such as the group contribution method. For instance. different isomers can lead to different calculated densities when the molecular dynamics method is used. However. therefore. which averages over a significant number of different molecules. in the present work only one average molecule was used for each calculation. Therefore. if an optimized procedure for the use of average structures using molecular simulations is developed.6Nnr + 2. In contrast. The solid line indicates where the points would lie if experiments and calculations yield the same results. in some way. of the asphaltenes. as shown in a previous section. the presence of molecules of different sizes can improve their packing in the same volume. The results obtained in this work are just a first step toward the development of a new methodology which will help to find a link between molecular structure and thermophysical properties of asphaltenes.8Nac + 8. Another interesting aspect about Figure 10 is the fact that both sets of calculated values correlate quite well with a correlation coefficient of 0.3Nt . although they are still lower than the experimental values. Then. It was also found that a group-contribution method gives better results than the molecular simulations that were performed. Further work exploring these hypotheses is now in progress.848. Vol. In contrast. This last effect could play an important role for correction of the low calculated densities obtained in the present work using molecular dynamics. As can be seen. density seems to be a good candidate to be fitted because it can be easily determined experimentally and it strongly depends on the structural characteristics of the molecule. No. using molecular dynamics and the group contribution method. In Figure 10. eq 2 cannot make any difference between molecules with the same aliphatic chains in different aromatic positions or between molecules with the same number of aliphatic carbons but different chain lengths. can be a useful tool to improve their condensed structural representation. In this sense. This could improve the calculated densities in two ways: first. The calculation of asphaltenes density using average structures by molecular dynamics simulations is subject to large errors but nevertheless gives values that are qualitatively correct and in the right range.39. it could be possible to determine a wide variety of thermophysical properties under different conditions. Nac is the number of aromatic conjunction atoms. Conclusions Asphaltenes from unstable crude oils and deposits exhibit higher densities. is shown. This indicates that both molecular parameters and their graphic representation (average structures) supply information that is qualitatively correct. 2003 385 Figure 10. . a comparison between the two sets of calculated densities. the results obtained using the group contribution method are superior. Nar is the number of aromatic rings.Density Estimation of Asphaltenes Using MD Simulations Energy & Fuels. and lower hydrogen-to-carbon ratios than asphaltenes from stable crude oils. this information could be used to estimate trends in density values as well as in other thermodynamic properties. the obtained results reflect an average over a certain number of isomers that the method cannot distinguish. higher aromaticities. For instance. is expressed by Vm ) 32.6Nai (2) where Nt is the total number of carbons. Comparison between calculated densities using molecular simulations and a group additive method. According to this method. At the present moment. The proposed method employs structural information to obtain the molar volume of the molecule as a sum of contributions from the individual structural groups that compose the molecule. and Nai is the number of aromatic inner carbons. Nnr is the number of naphthenic rings. Besides. an asphaltene sample can be represented by a mixture of different molecules. molecular dynamics simulations can be further developed as a tool to improve the average structure based in the testing of different isomers and the fitting of the calculated properties to the experimental ones.6Nar 19. The superiority of the group contribution method over the molecular dynamics method can be attributed to the fact that group contribution methods are developed on the basis of a wide range of different molecules. the molar volume of a given hydrocarbon. partially eliminating the effect of considering different isomers. The results obtained have shown that the chemical information provided by the molecular parameters and average structures of asphaltenes is essentially correct and can be used to qualitatively estimate densities. Vm. Even more. and (2) improve the procedures used to calculate the properties of the average structures via molecular simulations. this method can show the effect in the density of different structural modifications in the average structures of asphaltenes and. 17.8 + 16.
The large differences found between experimental and calculated densities using molecular dynamics can be mainly attributed to the use of a unique molecule to represent the asphaltene which can lead to poor packing and therefore. 17. 2003 Rogel and Carbognani The average structures of asphaltenes which yields the highest densities are characterized by large condensed polyaromatic rings and low hydrogen-to-carbon ratios. Vol. No. 2. to lower densities. EF020200R . A group contribution calculation was observed to improve the matching between the experimentally determined and calculated density values.386 Energy & Fuels.
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