Size Distributions of Sulfur, Vanadium and Nickel Compounds in

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Size Distributions of Sulfur, Vanadium and Nickel Compounds in Crude Oils, Residues and Their SARA Fractions Determined by Gel Permeation Chromatography Inductively Coupled Plasma High-Resolution Mass Spectrometry German Gascon, Vicmary Vargas, Llinaber Feo, Olga Luisa Castellano, Jimmy Castillo, Pierre Giusti, Socrates Alejandro Acevedo, Charles-Philippe Lienemann, and Brice Bouyssiere Energy Fuels, Just Accepted Manuscript • DOI: 10.1021/acs.energyfuels.7b00527 • Publication Date (Web): 21 Jun 2017 Downloaded from http://pubs.acs.org on July 3, 2017

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Size Distributions of Sulfur, Vanadium and Nickel Compounds in Crude Oils, Residues and Their SARA Fractions Determined by Gel Permeation Chromatography Inductively Coupled Plasma HighResolution Mass Spectrometry German Gascona,b,c, Vicmary Vargasb,c,d, Llinaber Feoa, Olga Castellanoa, Jimy Castillod, Pierre Giustie, Socrates Acavedod, Charles-Philippe Lienemann f, Brice Bouyssiere*b,c a

PDVSA Intevep, Apartado 76343, Caracas 1070-A, Venezuela

b

CNRS/ UNIV PAU & PAYS ADOUR, INSTITUT DES SCIENCES ANALYTIQUES ET DE

PHYSICO-CHIMIE POUR L'ENVIRONNEMENT ET LES MATERIAUX, UMR5254, 64000, Pau, France c

Joint Laboratory C2MC: Complex Matrices Molecular Characterization, Total Research &

Technology, Gonfreville, BP 27, F-76700 Harfleur, France d

UCV, Facultad de Ciencias, Escuela de Química, Caracas, 1053, Venezuela

e

TOTAL Raffinage Chimie, TRTG, BP 27, 76700 Harfleur, France

ACS Paragon Plus Environment

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IFP Energies Nouvelles-Lyon, Rond-point de l'échangeur de Solaize, BP 3, 69360 Solaize,

France

ABSTRACT: The size distributions of sulfur (S), vanadium (V) and nickel (Ni) compounds in four crude oils, two residues and their SARA fractions were determined using gel permeation chromatography (GPC) coupled to inductively coupled plasma high-resolution mass spectrometry (ICP HR MS). The results show trimodal distributions of V, Ni and S compounds in the crude oils and residues. V and Ni compounds are present in both resins and asphaltenes. Trimodal distributions are clearly apparent in the resins but not apparent in the asphaltenes. In the latter, the predominant compounds have a high molecular weight (HMW) even when the solution of asphaltenes is diluted by 40,000-fold. In the resins, compounds with a medium molecular weight (MMW) were expected; however, HMW compounds were observed, indicating that nanoaggregates or large molecules exist in both the asphaltenes and the resins. Low molecular weight (LMW) compounds are predominantly present in the resins and do not represent more than 22% of the V and Ni present in crude oil. These compounds appear to have molecular weights similar to simple metalloporphyrins.

KEYWORDS: Vanadium, Nickel, Sulfur, Crude oil, Distribution INTRODUCTION Crude oil is a very complex mixture primarily composed of carbon, hydrogen, sulfur, nitrogen and trace metals (Ni and V).1 The oil quality is defined by the types of hydrocarbons and potential contaminant species that are present. Among the metals naturally present in crude oil, V and Ni are the most abundant.1 Because of their high boiling point, minimal V and Ni are contained in the distillates (< 375°C); the majority are present in the vacuum residue.2


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Additionally, the low solubility of several V and Ni compounds in most (if not all) solvents, specifically metalloporphyrins (MPs),3-5 facilitates a partitioning between the asphaltenes and maltenes. The specific relationship between these two fractions depends on the solvent used to precipitate the asphaltenes.6,7 The metallocompounds (MCs) soluble in maltenes are principally found in the resins.8,9 Regarding the nature of V and Ni compounds present in crude oil, several MPs have been identified10-13 although the amount of known species represents a minor part of the total V and Ni present in crude oil. Because not all the V and Ni present in the asphaltenes (and crude oil) can be accounted for by the MPs (less than 50%, as estimated by elemental analysis), the existence of non-porphyrinic compounds has been proposed.14-17 These compounds include other ring systems, such as chlorophylls, chlorins, corrins (reduced porphyrins), highly substituted aromatic porphyrins and porphyrins with UV-vis properties (unlike porphyrins that exhibit the Soret band).14 However, much controversy exists regarding non-porphyrinic compounds,18,19 and several hypotheses suggesting that all of the V and Ni present in crude oil are MPs20 and that some may be trapped in either asphaltene aggregates in solution,21-25 in a supramolecular assembly of molecules26 or in large molecules.27,28 Large compounds containing V and Ni have been investigated using size exclusion chromatography (SEC) or GPC coupled with optical emission spectroscopy (ICP OES)17,29 or inductively coupled plasma (ICP MS)2, and a bimodal distribution of V has been found with maxima at approximate molecular weights (MWs) of 800 and 9000 (polystyrene (PS) equivalent).17 By contrast, trimodal distributions, divided into high-, medium-, and low-molecular weight (HMW, MMW and LMW) components, have been reported for V and Ni in various crude oils and residues.2 Regarding the size distributions of V and Ni in SARA fractions, Park et al.30 recently measured these distributions in asphaltenes and resins to different atmospheric residues (ARs) using SEC - ICP MS (the size


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distribution for S was not reported). The distributions are dramatically different than those reported by Reynolds and Wiggs29 and other works studying size distributions only in asphaltenes.21 We believe this difference results from the nature of the crude oil and residues studied. Using SEC for this type of characterization has been questioned,18 and several limitations should be noted. These include the dependence of MW on the solvent used, the interactions that form between PS particles and asphaltenes, the use of polystyrene (PS) to calibrate SEC columns,31 and individual parameters relayed to columns and flow.32 However, the technique continues to be important for discriminating the size distributions of compounds that occur naturally in crude oil,33 including V, Ni and S, which cannot be measured using other techniques such as matrix assisted laser desorption-ionization mass spectrometry (MALDI-MS)19 or Fourier transform-ion cyclotron-mass spectrometry (FT-ICR MS).10 The results obtained from SEC provide insight into the interactions of important components in V, Ni and S present in heavier fractions of crude oil such as resins and asphaltenes. The best solvent for ascertaining the size distributions of asphaltenes using SEC has been reported to be tetrahydrofuran (THF).34 On the basis of the preceding discussion, we proposed to determine the size distributions of different crude oils and their SARA fractions using SEC-ICP HR MS and complete the work presented by Desprez et al.2 because we strongly believe that improved demetallization strategies can be realized if the size distributions of V, Ni and S compounds are known in the heavier fractions of crude oils and residues. This knowledge would allow the oil industry to select and design better catalysts for the conversion of heavier fractions. For example, the use of more active, smallerpored catalysts to process deasphalted oil (DAO) has been recommended.35 The importance of removing V and Ni compounds has previously been mentioned.1,36,37


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MATERIALS AND METHODS Instrumentation. The detailed conditions for ICP MS detection have been previously reported2 and a summarized description is given below. A high-resolution (Element XR, Thermo Scientific) ICP MS instrument operated at a resolution of 4000 was used to access spectrally interfered isotopes of 60 Ni, 32 S, and 51 V. The mass spectrometer was equipped with a quartz injector (1.0 mm inner diameter), a Pt sampler cone (1.1 mm orifice diameter), a Pt skimmer cone (0.8 mm orifice diameter), an interface based on microflow total consumption, and a nebulizer (DS5, Teledyne-CETAC) mounted on a glass spray chamber without a drain kept at 60°C with a water-glycol mixture using a temperature-controlled bath circulator (Neslab RTE111, Thermo Fisher Scientific) to minimize signal suppression and increase the sensitivity by 3to 4-fold compared to existing setups, as described elsewhere.38 An oxygen flow of 0.08 mL/min was continuously added to the nebulizer Ar gas flow to avoid the deposition of carbon on the cones. A high-performance liquid chromatography (HPLC) (UltiMate 3000, Dionex) was used for the coupling. Reagents, Samples and Materials. n-Heptane was used to precipitate the asphaltenes, and toluene, methanol and THF (all HPLC-grade from Sharlau) were used for the fractionation of the maltenes. The chromatography column (l = 50 cm, i.d. = 2.5 cm) was filled with alumina CG-20 (Sigma-Aldrich). For the GPC experiments, THF was used for the sample dilutions and as the mobile phase. Samples of four Venezuelan crude oils, which were identified as CO1, CO2, CO3 and CO4 on the basis of their high V and Ni contents, two residues of different crude oils and their SARA fractions were analyzed. The samples were prepared at different concentrations in THF for the GPC analyses. Resins, crude oils and residues were diluted 100-fold, whereas saturates and aromatics were diluted 50-fold because of their reported low concentrations of V


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and Ni.8,9 The asphaltenes were diluted 200-fold. The separations were carried out using three styrene-divinylbenzene gel permeation columns connected in series (i.d. = 7.8 mm, l = 300 mm) in the following order: HR4, HR2, HR0.5 (all Styragel). A guard column (i.d. = 4.6 mm, l = 30 mm) was used to protect the columns and increase their lifetime. To evaluate the reproducibility of the system, the vanadium reference standards 2,3,7,8,12,13,17,18-octaethyl-21H,23Hporphine vanadium(IV) oxide (V600) and vanadyl 2,9,16,23-tetraphenoxy-29H,31Hphthalocyanine (V948) were evaluated. Oil Fractionation. The fractionation of crude oil included two separation steps: (1) precipitation of the asphaltenes with n-heptane and (2) fractionation of the maltenes by chromatography. To avoid variations in the mass balance caused by evaporation losses of light hydrocarbons, all oil samples (2 g) were heated overnight at 80°C before further use. The samples (after evaporation) were mixed with 80 mL of n-heptane and maintained at 70°C for 1 h. The precipitated asphaltenes were separated by filtration with 2.5 µm Whatman filter paper. The precipitate was washed with hot heptane until the heptane wash was colorless. The washed precipitate was combined with the maltenes. The asphaltenes were dried at 70°C. The maltene fraction was rota-evaporated, dissolved (1.5 g) in heptane and placed on top of the column filled with calcined CG-20 alumina for separation into the SARA fractions by pumping an eluotropic series of elution solvents at a flow rate of 3.0 mL/min. The saturates were eluted with 300 mL of heptane and then toluene until a fluorescent-orange band reached the bottom of the column. The aromatics were eluted with a 1:1 toluene:methanol mixture until a dark band reached the bottom of the column. The resins were eluted with THF. The eluted fractions were recovered by removing the solvent prior to the final weighing.


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GPC and ICP MS Detection. A 20 µL sample was injected and isocratically eluted at a THF flow rate of 1 mL/min for 120 min. A post-column splitter was used to divide the flow between a low-flow outlet of 50 µL/min to feed the ICP MS and a high-flow outlet of 950 µL/min that was discarded. The sensitivity of the columns during the separation was evaluated using a mixture of polystyrene (PS) standards and a refractive index detector. A Microsoft Excel program was used to deconvolute the chromatograms by summing the Gaussian curves. RESULTS AND DISCUSSION Percentage Distributions of V, Ni and S. The total concentration in each crude oil and residue evaluated is presented in Table 1 along with the mass balances and the partitions of the three studied elements in the SARA fractions. Note that approximately 40-60% of the V and Ni content present in the crude oil or residue is concentrated in the asphaltene fraction, whereas the remaining content (between 60 and 40%) is in the resins. The differences between the samples are attributed to the nature of the crude oil. The percentage of sulfur was mainly distributed between the resin and aromatic fractions, indicating that S compounds with medium polarity predominate in crude oil. In contrast, the V and Ni compounds that are present in the fractions have a higher polarity (resins and asphaltenes).8,9 In all samples evaluated, the concentration of V was greater than that of Ni. Size Distributions of V, Ni and S Compounds. Trimodal size distributions were observed for the V compounds in CO1, its resins and asphaltenes. These distributions are shown in Figure 1 and are labeled as HMW, MMW and LMW compounds, consistent with the nomenclature previously used.2 For Ni (Figure 2) and S (Figure 3), a less pronounced trimodal distribution was observed; in some fractions, a simple monomodal distribution occurred (Ni in aspahltenes and S


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in saturades, aromatcis and asphaltenes), whereas others showed bimodal (S in resins) or trimodal (Ni in resins) distributions. The analysis time was 120 min; however, the equivalent in seconds of elution time (between 18 and 35 min) is displayed. The integration boundaries were chosen according to the trimodal distribution of the V compounds. Molecular Weight of the Different Zones. Because of a lack of standards for V with a HMW, estimations for the HMW compounds were not attained. By contrast, through a comparison of the elution with the reference standards 2,3,7,8,12,13,17,18-octaethyl-21H,23Hporphine vanadium(IV) oxide (V600) and vanadyl 2,9,16,23-tetraphenoxy-29H,31Hphthalocyanine (V948), we estimate that the previously reported free MPs10-13 are in the LMW zone and partially in the MMW zone (Figure 4). Percentage distributions of HMW, MMW and LMW compounds of V and S. The exact size distributions of V in the different crude oils and residues evaluated as well as in their resins and asphaltenes are shown in Figure 5. As shown, the LMW V compounds represent between 13 and 22% of the total V present in the crude oils and residues, with the remainder similarly distributed between MMW (30-40%) and HMW (40-50%) compounds. It is important to note that the resin fraction was clearly dominated by MMW compounds, whereas the asphaltenes were dominated by HMW compounds. Similar results were obtained for Ni; therefore, its distribution is not presented. For the S compounds, the distributions in the crude oils and residues evaluated and in the resins, asphaltenes and aromatics are shown in Figure 6 (the distribution in saturades has been omitted). In the crude oils, residues, resins and aromatics, MMW compounds predominated, whereas HMW compounds predominated in the asphaltenes. Because of the high sensitivity of


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the method used, V and S compounds with HMW, MMW and LMW were identified in all fractions. Effect of the Dilution of Asphaltene on the Profile Obtained Using GPC-ICP HR MS According to the literature, the HMW components of asphaltenes are a consequence of aggregation.34,39 However, according to different models, this aggregation occurs naturally in crude oil.21,22,24-26 In fact, 90 wt% of the asphaltenes are self-associated nanoaggregates with an average diameter ranging from 5 to 9 nm and a maximum size of up to 20 nm.40 Additionally, according to Dechaine and Gray,41 1) the interchange of material between the aggregates and free solution was extremely low, 2) an increase in the temperature enhanced the asphaltene mobility but did not reduce the size of the asphaltene structures below 5 nm, 3) a decrease in the concentration to 0.1 g/L (100 ppm) did not result in a decrease in size and 4) the origin of the asphaltenes (Athabasca, Safaniya, and Venezuela) did not substantially influence the observed behavior. To evaluate the effect of dilution on the asphaltene distribution from our results and detection system, we determined the size distribution of the asphaltene fraction obtained from CO4 because of its high concentration of V (3700 ppm). As shown in Figure 7, the ratio between HMW V compounds and V total is relatively stable even at concentrations higher than 100 mg/kg of asphaltenes in THF (Figure 7). At concentrations under 100 mg/Kg, HMW compounds of V (Figure 8) and S (Figure 9) even after dilution of the asphaltene solution by 40,000. Based on these results, we speculate that these compounds may occur naturally in crude oil and may be similar to the nanoaggregates reported by Dickie and Yen22 and Mullins et al.25 or to a supramolecular assembly of molecules.26,27


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CONCLUSIONS The V and Ni compounds present in the crude oils and residues evaluated are partitioned similarly between the resins (40-60%) and asphaltenes (40-60%). By contrast, the S compounds are mainly concentrated in the aromatics and resins (75-90%), and only 10-25% are present in asphaltenes. With regard to size distribution, HMW, MMW and LMW compounds of V, Ni and S were observed in the crude oils and residues evaluated. A comparison of the LMW compounds with the V standards in the chromatograms indicates that these compounds have a molecular weight that is typical of simple MPs and do not represent more than approximately 22% of the total V present in the crude oil. This result may explain the low percentage of the extraction of metalloporphyrins by several methods cited in the literature.18 The remaining V is equally partitioned between MMW (30-40%) and HMW (40-50%) compounds. We speculate that these compounds are similar to nanoaggregates or trapped or larger molecules. MMW compounds were predominant in resins and HMW compounds in asphaltenes. HMW compounds were even observed in an asphaltene solution that was diluted by 40,000-fold (25 mg/kg).

AUTHOR INFORMATION Corresponding Author *Telephone: +33 559 407 752. Fax: +33 559 407 674. E-mail: [email protected]. Notes The authors declare no competing financial interest.


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ACKNOWLEDGMENTS The financial support of the Conseil Régional d’Aquitaine (20071303002PFM) and FEDER (31486/08011464) is acknowledged.


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(10) McKenna, A. M.; Purcell, J. M.; Rodgers, R. P.; Marshall, A. G. Energy Fuels 2009, 23, 2122-2128. (11) Qian, K.; Mennito, A. S.; Edwards, K. E.; Ferrughelli, D. T. Rapid Commun. Mass Spectrom. 2008, 22, 2153-2160. (12) Qian, K.; Edwards, K. E.; Mennito, A. S.; Walters, C. C.; Kushnerick, J. D. Anal. Chem. 2010, 82, 413-419.


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(13) Zhao, X.; Liu, Y.; Xu, C.; Yan, Y.; Zhang, Y.; Zhang, Q.; Zhao, S.; Chung, K.; Gray, M. R.; Shi, Q. Energy Fuels 2013, 27, 2874-2882. (14) Reynolds, J. G. In Asphaltenes and Asphalts, 2. Developments in Petroleum Science, 40 B; Yen, T. F.; Chilingarian, G. V., Eds.; Elsevier: Amsterdam, The Netherlands, 2000. (15) Crouch, F. W.; Sommer, C. S.; Galobardes, J. F.; Kraus, S.; Schmauch, E. H.; Galobardes, M.; Fatmi, A.; Pearsall, K.; Rogers, L. B. Sep. Sci. Technol. 1983, 18, 603-634. (16) Fish, R. H.; Komlenic, J. J.; Wines, B. K. Anal. Chem. 1984, 56, 2452-2460. (17) Biggs, W. R.; Fetzer, J. C.; Brown, R. J.; Reynolds, J. G. Liq. Fuels Technol. 1985, 3, 397-421. (18) Dechaine, G. P.; Gray, M. R. Energy Fuels 2010, 24, 2795-2808. (19) Grigsby, R. D.; Green, J. B. Energy Fuels 1997, 11, 602-609. (20) Goulon, J.; Retournard, A.; Friant, P.; Goulon-Ginet, C.; Berthe, C.; Muller, J. F.; Poncet, J. L.; Guilard, R.; Escalier, J. C.; Neff, B. J. Chem. Soc., Dalton Trans. 1984, No.6, 1095-1103. (21) Acevedo, S.; Guzmán, K.; Labrador, H.; Carrier, H.; Bouyssiere, B.; Lobinski, R. Energy Fuels 2012, 26, 4968-4977. (22) Dickie, J. P.; Yen, T. F. Anal. Chem. 1967, 39, 1847-1852. (23) Marcano, F.; Flores, R.; Chirinos, J.; Ranaudo, M. A. Energy Fuels 2011, 25, 2137-2141. (24) Schulze, M.; Lechner, M. P.; Stryker, J. M.; Tykwinski, R. R. Org. Biomol. Chem. 2015, 13, 6984-6991. (25) Mullins, O. C. Energy Fuels 2010, 24, 2179-2207. (26) Gray, M. R.; Tykwinski, R. R.; Stryker, J. M.; Tan, X. Energy Fuels 2011, 25, 31253134. (27) Murgich, J.; Abanero, J. A.; Strausz, O. P. Energy Fuels 1999, 13, 278-286.


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(28) Strausz, O. P.; Mojelsky, T. W.; Lown, E. M. Fuel 1992, 71, 1355-1363. (29) Reynolds, J. G.; Biggs, W. R. Fuel Sci. Technol. Int. 1986, 4, 749-777. (30) Park, J. I.; Al-Mutairi, A.; Marafie, A. M. J.; Yoon, S. H.; Mochida, I.; Ma, X. J. Ind. Eng. Chem., 2016, 34, 204-212. (31) Behrouzi, M.; Luckham, P. F. Energy Fuels 2008, 22, 1792-1798. (32) Gutierrez Sama, S..; Desprez, A.; Krier, G.; Lienemann, C. P.; Barbier, J.; Lobinski, R.; Barrere-Mangote.; Giusti, P.; Bouyssiere, B. Energy Fuels 2016, 30, 6907-6912. (33) Peramanu, S.; Pruden, B. B.; Rahimi, P. Ind. Eng. Chem. Res. 1999, 38, 3121-3130. (34) Mullins, O. C.; Martínez-Haya, B.; Marshall, A. G. Energy Fuels 2008, 22, 1765-1773. (35) Ancheyta-Juarez, J.; Maity, S. K.; Betacourt-Rivera, G.; Centeno-Nolasco, G.; RayoMayoral, P.; Gómez-Pérez, M. T. Appl. Catal., A 2001, 216, 195-208. (36) Ali, M. F.; Abbas, S. Fuel Process. Technol. 2006, 87, 573-584. (37) Reynolds, J. G. Fuel Sci. Technol. Int. 1991, 9, 613-634. (38) Caumette, G.; Lienemann, C. P.; Merdrignac, I.; Paucot, H.; Bouyssiere, B.; Lobinski, R. Talanta 2009, 80, 1039-1043. (39) Goncalves, S.; Castillo, J.; Fernández, A.; Hung, J. Fuel 2004, 83, 1823-1828. (40) Yarranton, H. W.; Ortiz, D. P.; Barrera, D. M.; Baydak, E. N.; Barré, L.; Frot, D.; Eyssautier, J.; Zeng, H.; Xu, Z.; Dechaine, G.; Becerra, M.; Shaw, J. M.; McKenna, A. M.; Mapolelo, M. M.; Bohne, C.; Yang, Z.; Oake, J. Energy Fuels 2013, 27, 5083-5106. (41) Dechaine, G. P.; Gray, M. R. Energy Fuels 2011, 25, 509-523.


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TABLES Table 1. Percentage Distributions of V, Ni and S in Crude Oils, Residues and Their SARA Fractions. Saturates Sample

Info

Total (mg/Kg, %)

% SARA CO1

VR

AR

ppm (mg/Kg, %)

ppm (mg/Kg%)

19

23

39

17

Mass balance %

1.4 (0.1)

2.5 (0.1)

553 (49.2)

1306 (50.6)

105.2

Ni

102.2

0.6 (0.1)

2.9 (0.6)

141 (49.9)

319 (49.4)

107.6

S

34500

2772 (1.6) 40018 (28.8)

42374 (51.6)

33866 (18.0)

109.7

22

30

34

12

V

472.8

2.3 (0.1)

0.3 (0.0)

802 (53.5)

1967 (46.3)

107.7

Ni

100.8

0.6 (0.1)

2.5 (0.7)

185 (55.8)

408 (43.4)

111.8

S

35000

2603 (1.7) 42093 (38.2)

44967 (46.2)

38351 (13.9)

94.5

31

34

29

7

V

432.4

2.2 (0.1)

1.7 (0.1)

980 (61.1)

2561 (38.6)

107.5

Ni

57.4

0.6 (0.3)

1.3 (0.7)

127 (60.1)

341 (38.9)

106.9

S

26260

2595 (3.2) 33808 (45.2)

36478 (41.6)

36156 (10.0)

111.1

% SARA CO4

ppm (mg/Kg,%)

Asphaltenes C7

416.7

% SARA CO3

Resins

V

% SARA CO2

ppm (mg/Kg, %)

Aromatics

35

25

25

6

V

459.5

0.6 (0.0)

23.1 (1.2)

1019 (51.6)

3884 (47.2)

107.5

Ni

51.3

0.2 (0.2)

4.8 (2.2)

112 (52.2)

404 (45.4)

104.2

S

23250

2821 (4.3) 44962 (48.8)

32254 (35.0)

45991 (12.0)

99.1

% SARA

16

33

36

15

V

141.4

0.8 (0.1)

2.1 (0.5)

167 (41.8)

554 (57.7)

104.4

Ni

44.6

0.5 (0.2)

1.5 (1.1)

51.1 (41.0)

172.6 (57.7)

100.6

S

49470

1726 (0.7) 46735 (38.0)

43381 (38.5)

61672 (22.8)

103.1

% SARA

17

35

34

14

V

576.2

0.5 (0.0)

5.2 (0.3)

762 (41.5)

2596 (58.2)

108.4

Ni

125.2

0.2 (0.0)

4.5 (0.1)

183 (44.8)

534 (54.0)

110.6

S

41300

3851 (1.8) 48178 (45.8)

35819 (33.0)

51101 (19.4)

103.1

The parentheses show the repartition (in %) of the element between the SARA fraction with regard to the total in the crude oil.


15

Energy & Fuels

x 10000

FIGURES

Intensity 51V (cps)

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 16 of 24

25

HMW

MMW

LMW

20 15 10 5 0 1100

1300

1500

1700

Retention Time (sec) Crude Oil Asphaltenes

1900

2100 Resins

Figure 1. Size distributions of V in CO1 as well as its asphaltenes and resins.


16

3.5 3

HMW

MMW

LMW

2.5 Intensity 58Ni (cps)

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Energy & Fuels

x 10000

Page 17 of 24

2 1.5 1 0.5 0 1100

1300 Crude Oil

1500

1700

1900

Time (sec) Asphaltenes

2100 Resins

Figure 2. Size distributions of Ni in CO1 as well as its asphaltenes and resins.


17

Page 18 of 24

120

HMW

MMW

100

Intensity 32S (cps)

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

x 10000

Energy & Fuels

LMW

80 60 40 20 0 1100

1300

1500

1700

1900

2100

Retention Time (sec) Crude Oil Aromatics

Asphaltenes Saturades

Resins

Figure 3. Size distribution of S in CO1 and its SARA fractions.


18

Intensity 51V (cps)

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Energy & Fuels

x 10000

Page 19 of 24

25

HMW

20

MMW

LMW

15 10 5 0 1100

1300

1500

1700

1900

2100

Retention Time (sec) Crude Oil

Asphaltenes

V948

V600

Resins

Figure 4. Relative comparison of V standards to V in CO1 as well as its resins and asphaltenes.


19

Energy & Fuels

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 20 of 24

Figure 5. Percentages of HMW, MMW and LMW compounds of V in a) crude oils and residues, b) asphaltenes and c) resins.


20

Page 21 of 24

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Energy & Fuels

Figure 6. Percentages of HMW, MMW and LMW compounds of S in a) crude oils and residue, b) asphaltenes, c) resins and d) aromatics.


21

Energy & Fuels

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 22 of 24

Figure 7. Ratio of V HMW in asphaltenes of CO4 and concentrations in THF at different dilutions determined by SEC-ICP HR MS.


22

Page 23 of 24

30,000 Intensity 51V (cps) x 10000

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Energy & Fuels

200

20,000

180 10,000

160 140

0 1100

120

1400

1700

100 80 60 40 20 0 900

1100

1300

1500

1700

1900

2100

Time (sec) 100

200

500

1000

2500

5000

10000

20000

25000

30000

40000

Figure 8. Size distributions of V compounds with HMW in asphaltenes from CO4 at different dilutions in THF.


23

Page 24 of 24

40,000 35,000 30,000 25,000 20,000 15,000 10,000 5,000 0 1000

200 180 160 140

Intensity 51V (cps)

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

x 10000

Energy & Fuels

120

1300

1600

100 80 60 40 20 0

900

1100 1300 1500 1700 1900 2100 Time (sec)

100

200

500

1000

2500

5000

10000

20000

25000

30000

40000

Figure 9. Size distributions of HMW S compounds in asphaltenes from CO4 at different dilutions in THF.


24

Size Distributions of Sulfur, Vanadium and Nickel Compounds in

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