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Comparison of Hansen solubility parameter of asphaltenes extracted from bitumen produced in different geographical regions. Takashi Sato, Sadao Araki, Masato Morimoto, Ryuzo Tanaka, and Hideki Yamamoto Energy Fuels, Just Accepted Manuscript • Publication Date (Web): 10 Jan 2014 Downloaded from http://pubs.acs.org on January 10, 2014

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Comparison of Hansen solubility parameter of asphaltenes extracted from bitumen produced in different geographical regions. Takashi Sato, * Sadao Araki,* Masato Morimoto, ** Ryuzo Tanaka, *** and Hideki Yamamoto* *Department of Chemical, Energy and Environmental Engineering Faculty of Environmental and Urban Engineering, Kansai University, 3-3-35 Yamate-cho, Suita-shi, Osaka, Japan **Advanced Fuel Group, Energy Technology Research Institute, National Institute of Advanced Industrial Science and Technology, 3-9 Toranomon 4-tyome, Minato-Ku, Tokyo, Japan ***Advanced Technology and Research Institute, Japan Petroleum Energy Center, 16-1 Onogawa, Tsukuba-Shi, Ibaragi, Japan KEY WORDS asphaltene, Hansen solubility parameter, dynamic light scattering, aggregation, organic solvent, mixed solvent. ABSTRACT The Hansen solubility parameters (HSPs) of asphaltenes extracted from oil sand bitumen samples produced at Athabasca in Canada and also from a vacuum residue fraction (VR) produced in the Middle East were determined by the Hansen solubility sphere method. For

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calculation of HSPs, the solubilities of asphaltenes were determined using a dynamic light scattering (DLS) method by dissolving or dispersing the asphaltenes in various solvents and measuring the particle size distributions thereof. The particle diameters of asphaltenes in good solvents were lower than its detection limit (< 1 nm). It was demonstrated in the present study that asphaltenes differing in elemental composition had different HSP values corresponding to dispersion, dipole interaction, and hydrogen-bonding forces (δd, δp, and δh, respectively). Experimental results suggested that the differences in HSP values of the asphaltenes were influenced by the H/C ratio, oxygen content, and average asphaltene molecular weight. 1. INTRODUCTION In order to more effectively utilize precious oil resources and take appropriate consideration of their environmental loads, it is important to analyze the physical properties and reactivities of oils based on their molecular structure and composition. Asphaltenes, a constituent of crude and heavy oils, are highly complex mixtures of polycyclic organic compounds with large variations in skeletal structure. It is considered that the sizes and stabilities of asphaltenes aggregation had an influence on the physical properties and reactivities of the heavy oils. The aggregation behaviors of asphaltenes are complicated, since the size and shape of the aggregates vary significantly, depending on the kind of crude oil and solvent temperature used during processing. Asphaltene aggregation proceeds mainly through π stacking interactions (π–π interactions) between polycyclic aromatic clusters; the number of rings as well as the number and properties of the substituted aliphatic side-chain/polar functional groups of the compounds determines the cohesive force of these interactions. For effective suppression of asphaltene aggregation, identification of the various intermolecular interactions among the molecules is required.


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One possible tool for prediction of properties of asphaltene is solubility parameters or other cohesion parameters. The Hildebrand solubility parameter (δt) is commonly used for the evaluation of cohesion energies of substances. The solubility parameter, a physical property demonstrating the cohesion energy density of a substance, is useful for evaluation of the compatibility, wettability, and cohesiveness/dispersibility between substances. Hansen further defined the Hildebrand solubility parameter as comprising three factors based on the kind of molecular interaction involved: namely, dispersion forces (δd), intermolecular dipole interactions (δp), and hydrogen-bonding interactions (δh). The Hansen solubility parameter (HSP) has recently attracted attention as a means for evaluating the aggregation behavior of asphaltenes quantitatively, with several reports on the HSPs of asphaltene appearing in the literature.1-4 Acevedo et al. reported the HSP values of asphaltenes that were treat by the p-nitrophenol method. Redelius calculated the HSPs of asphaltenes and maltenes separated from Venezuelan and other bitumens.2 Further, Acevedo et al. and Redelius3 compared HSPs of the components separated from heavy oils and bitumens. In these literature reports, the solubilities and solubility parameters of the asphaltenes were calculated from the Hansen solubility spheres thus obtained. When preparing the Hansen solubility sphere, information on the solubility or dispersibility of the desired substance in some solvents is essential. Previous reports in which the HSPs of asphaltenes were calculated have used a number of methods to determine the solubility of asphaltenes in each solvent examined: particle size distributions of asphaltenes have been determined by the measurement of aggregation point (Laux et al.),3 visual and microscopic observations (Redelius),2 and high-definition microscopic imaging (Acevedo et al.).1 In the present study, a dynamic light scattering (DLS) method was employed for determination of asphaltene solubility. Yudin et al.5 and Mansur et al.6 have previously described a DLS method


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for asphaltene solubility determination; Yudin et al. measured the particle diameter of asphaltene in a mixture of toluene and heptane over time, while Mansur et al. studied the influences of various parameters on asphaltene solubility using DLS measurements, including asphaltene concentration, thermodynamic properties of solvents, addition of an asphaltene-dispersing agent, dispersion temperature, the period of exposure of asphaltenes to model solvents, and others. As described above, the HSPs of asphaltenes extracted from the same bitumen samples using different treatments have already been reported. However, the HSPs of asphaltenes extracted from bitumen samples produced in different geographical locations using the same treatment methods have not been examined. Waldo et al. reported that the sulfur and oxygen contents as determined by elemental analysis vary significantly between bitumens produced at different sites in California, Texas, Canada, Kuwait and France.7 Klein et al. reported that the heteroatom content and aromaticity fluctuate significantly when the production site varies.8 In addition, the efficiency of asphaltene sedimentation inhibitor depends on the kind of oil used; currently a suitable inhibitor is used, and is selected in preliminary laboratory tests for each oil. As described above, aggregation depends on the structural properties of the organic compounds comprising asphaltene, namely, the number of rings as well as the number and properties of the substituted aliphatic side-chain/polar functional groups, and thus, the aggregation behavior of asphaltenes differs with variation in production site; consequently, the magnitude of interaction forces between the asphaltenes and solvent is also expected to vary. In other words, the HSPs of the asphaltenes extracted from bitumens produced in different sites are likely to vary. Accordingly, determination of HSPs of various asphaltenes and elucidation of the relationship of HSP value with asphaltene properties would be helpful for a more detailed understanding of asphaltene aggregation behaviors.


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The first objective of this study was to determine the HSPs of asphaltenes extracted from raw materials produced in different sites. In this study, the HSPs of asphaltenes extracted from oil sand bitumen samples produced at Athabasca in Canada and a VR fraction produced in the Middle East were experimentally determined. The HSPs and the properties of the asphaltenes thus ascertained will be described in this report. 2. EXPERIMENTAL 2.1. Theory of the Hansen solubility parameter. The solubility parameter δt [(MPa)1/2] used in solubility evaluation is defined by Equation (1), using liquid cohesion energy E [J] and molar volume V [cm3/mol] (Hildebrand et al.):9 δt = (E/V)1/2

(1)

Hansen divided the cohesion energy E [J] of the Hildebrand solubility parameter into three factors, i.e., dispersion interactions Ed [J], dipole interactions Ep [J] and hydrogen-bonding interaction Eh [J], which can be expressed by the following:10 E = Ed + Ep + Eh

(2)

δd = (Ed/V)1/2, δp = (Ep/V)1/2, δh = (Eh/V)1/2

(3)

δt2 = δd2 +δp2 + δh2

(4)

where, δd [(MPa)1/2], δp [(MPa)1/2], and δh [(MPa)1/2] are the dispersion force factor, the dipole interaction force factor, and the hydrogen-bonding force factor of the HSP, respectively. Quantitative evaluation of solubility can be represented by using Ra [(MPa)1/2] value meaning the distance of HSPs for both of substances.


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Ra = {4(δd1 - δd2)2 + (δp1 - δp2)2 + (δh1 - δh2)2}1/2

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(5)

Smaller Ra value means higher solubility for each substance, because an interaction force acting between the molecules are similar. On the other hand, it can be estimated that the substances with large Ra value shows low solubility. Results of the solubility evaluations can be visualized by plotting the results of δd, δp, and δh measurements in a three-dimensional graph. When the solubility parameters of good and poor solvents for a desired substance are plotted in such a three-dimensional figure, those data points of good solvents gather in a particular region in the form of a sphere called the Hansen solubility sphere. In the solubility sphere, good solvents for a desired substance are plotted to the interior of the sphere, while poor solvents are plotted to the exterior of the sphere. The HSP of the desired substance is at the center of the sphere.1, 2, 11-14 The radius of the sphere is called the interaction radius R0 [(MPa)1/2]. Generally, HSP is calculated according to the molecular group contribution method.15 However, in the case of substances such as C60 fullerene and TiO2, of which the solubility parameters cannot be calculated by the group contribution method, it is possible to calculate HSP by determining the solubility or dispersibility of these substances in solvent and thus forming a Hansen solubility sphere.11, 12 The relative energy difference (RED) [-] is represented using R0 and Ra [(MPa)1/2] in the form of Equation (6). When RED is ≤ 1, the solvent is a good solvent, while when RED is > 1, it is a poor solvent. Thus, RED can be used as an indicator of solubility. RED = Ra/R0

(6)

The solubility parameter of a mixed solvent is calculated by the following equation:


6

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δi = ϕ1δi1 + ϕ2δi2

(7)

where ϕ is the volume fraction of each of the mixed solvents and the lower subscripts 1 and 2 represent components 1 and 2, respectively. The lower subscript i represents d, p or h (i.e., δi represents dispersion interaction, dipole interaction, or hydrogen-bonding interaction factors). 2.2. Materials. Asphaltenes used in this study were extracted from oil sand bitumen samples produced at Athabasca in Canada and from a VR fraction produced in the Middle East. Asphaltenes were extracted in the following manner: asphalt particles with diameters of 2.8 mm or less and heptane of a 20 fold larger volume were placed in an extraction tank and the mixture was then heated gradually at an initial pressure of 0.3 MPa under a nitrogen atmosphere. After about 40 min when the mixture was heated to 373 K, the internal pressure was increased to 1 MPa and the mixture was left in that state for 1 h. After cooling to about 303 K, the mixture was passed through a polytetrafluoroethylene (PTFE) filter having a pore diameter of 0.8 μm. The recovered cake and heptane in the amount equivalent to that first added were placed in the extraction tank and the extraction operation was repeated once again. In the description below, the asphaltenes extracted from the oil sand bitumen samples produced at Athabasca in Canada and a VR fraction produced in the Middle East are referred to as CaAs and ArAs1, respectively. The results of elemental analyses, H/C ratios, and average molecular weights of CaAs and ArAs1 are shown in Table 1. Elemental analysis of carbon, hydrogen and nitrogen in asphaltenes were determined by CHNS elemental analyzer (Thermoquest Co. Ltd., EA-1110CHNS-O). Analyses of amount of sulfur and oxygen in asphaltenes were carried out by combustion-ion chromatography and by JIS M8813, respectively. The amount of nickel and vanadium was analyzed by the inductively coupled plasma atomic emission spectrophotometry


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(ICP-AES). Average molecular weights of the asphaltenes were determined by gel permeation chromatography (JASCO Corporation, Gulliver) equipped with a refractive index detector (Shodex, RI-104) and a column (Shodex, KF-403HQ, inside diameter 4.6mm, exclusion limits 70,000). Temperature of column was 313 K and the eluent was tetrahydrofuran. Retention time of asphaltene for the GPC measurement was converted to the molecular weight based on the retention time of polystyrenes (several molecular weight), decacyclene (molecular weight 451) and 2, 9, 16, 23-tetra-t-butyl-29H, 31H-phtalocyanine (molecular weight 739). 2.3. Experimental Method. In this study, the particle diameters of the asphaltenes in 30 or more solvents were determined for evaluation of their solubilities. Average particle size of asphaltenes in solvents was measured by dynamic light scattering particle analyzer (Otsuka Electronics, FPAR-1000). Solubility evaluations based on particle size distribution were aimed at grouping the solvents for CaAs and ArAs1 into good and poor solvents. The many solvents were used to be located around the surfaces of the Hansen solubility sphere as much as possible, in order to improve the accuracy in preparing the Hansen solubility sphere. A mixture of solvent and an asphaltene was ultrasonicated in a desktop ultrasonic cleaning machine (Branson Ultrasonics, Emerson Japan, Ltd., B3510J-DTH) for 10 min, left to stand for 24 h, and ultrasonicated for an additional 5 min prior to measurement of particle size distribution. Average particle size of asphaltenes in solution after the ultrasonic treatment was measured using dynamic light scattering at 298 K and atmospheric pressure. The particle diameters of CaAs and ArAs1 were measured for 3 min (about 80 times of the cumulated number) at 298 K under atmospheric pressure. In the case of CaAs, the particle size distributions were determined


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at several concentrations. In addition, the particle size distributions of CaAs in toluene + pentane and toluene + cyclohexane solvent systems were determined. The HSPs of asphaltenes were calculated by the Hansen solubility sphere created by the commercial software named the Hansen solubility parameters in practice (HSPiP). 3. RESULT AND DISCUSSION 3.1. Measurement of Asphaltene Particle Size by DLS. The particle size distributions of CaAs in 36 solvents were determined at an asphaltene concentration of 1 g/L; DLS observations indicated the absence of particles having a diameter of 1 nm or more in 15 solvents including toluene. The particle diameter of CaAs could be determined in a total of 21 solvents. According to a report by Mansur et al., the particle diameters of asphaltenes in toluene were 12, 14, 14, and 22 nm at concentrations of 0.01, 0.017, 0.02 and 0.025 w/v%, respectively. The particle size distribution of CaAs in toluene could not be successfully determined at a concentration of 0.017 g/L, which is equivalent to the concentration reported by Mansur et al. Because the DLS instrumentation used in this study was a high-sensitivity system (FPAR-1000), particle diameters in the range of 1–5000 nm would be measurable. For solvents in which the particle diameter could not be determined, the particle diameter of CaAs was considered to be not more than the detection limit (< 1 nm). The above results differed from those previously reported, likely because the differences in raw materials and purification method employed may also exert a significant influence on the particle diameter of asphaltene. According to Anisimov et al., asphaltene aggregation proceeds by reaction-limited aggregation (RLA) in the early phase of particle growth after which time the aggregation mechanism changes to diffusion-limited aggregation (DLA).5 CaAs was considered to be in the RLA state in solvents


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in which the particle diameter could not be determined, and in the DLA state in solvents in which the particle diameter could be determined. When conducting solubility evaluations for preparation of the Hansen solubility sphere, solvents in which particle diameters could not be determined were indicated as “good” solvents with a score of 1, while the solvents in which the particle diameter could be determined were indicated as “poor” solvents with a score of 0, which lead to aggregation. The particle diameters of CaAs were determined in 36 pure solvents at an asphaltene concentration of 1 g/L for solubility evaluation; the results are summarized in Table 2. Score of “-” means no measurement. The particle diameters of CaAs were determined in some solvents at asphaltene concentrations of 0.05 g/L and 5 g/L (Table 2). The particle solubilities in the examined solvents at asphaltene concentrations of 0.05, 1, and 5 g/L were the same at each concentration. The solubility of the CaAs used in this study, as determined by DLS, was apparently the same at a concentration in the range of 0.05–5 g/L. The particle diameters of ArAs1 in 33 pure solvents at an asphaltene concentration of 1 g/L were determined for solubility evaluation; the results are summarized in Table 3. The particle diameters of ArAs1 could not be measured, similarly to CaAs, in 14 of the solvents, including toluene, among the 33 solvents examined. The particle size distribution of ArAs1 in toluene could not be successfully determined at a concentration of 0.017 g/L, which is equivalent to that reported by Mansur et al. The particle diameter of ArAs1 was considered, similarly to that of CaAs, to be not more than the detection limit ( 1. According to the prediction based on the HSP of CaAs, RED is 1 when the solvent is close to toluene + pentane (Toluene = 0.72). Both RED and solubility evaluation based on particle diameter measurements agreed well, except in the case of toluene + pentane (Toluene = 0.75); RED was 0.97, which is considered to be mostly in agreement. The slight difference may be due to the interaction force between toluene and pentane. RED was 1 when the solvent was close to toluene + cyclohexane (Toluene = 0.45). Although there were some errors in RED in the cases of toluene + cyclohexane (Toluene = 0.45, 0.40), REDs were 1.00 and 1.03, respectively, which are considered to be mostly in agreement. Thus, it would be possible to estimate the agglomeration states of DLA and RLA in mixed solvents using the HSPs of asphaltenes. 4. CONCLUSION HSP values of two asphaltenes, CaAs extracted from oil sand bitumen samples produced at Athabasca in Canada and ArAs1 extracted from a VR fraction produced in the Middle East, were determined. Solubility evaluations of asphaltenes in organic solvents were performed using DLS for the determination of HSPs. There were some solvents, such as toluene, in which the particle


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diameter of CaAs could not be measured. No difference in the solubility of CaAs was observed for particle diameter measurements determined at asphaltene concentrations of 0.05, 1, and 5 g/L. The HSP of CaAs were as follows: δd = 19.1 ± 0.1 (MPa)1/2, δp = 4.2 ± 0.1 (MPa)1/2, δh = 4.4 ± 0.1 (MPa)1/2, δt = 20.1 ± 0.1 (MPa)1/2, R0 = 6.1 (MPa)1/2. The HSP of ArAs1 were as follows: δd = 19.4 ± 0.1 (MPa)1/2, δp = 3.4 ±0.1 (MPa)1/2, δh = 4.2 ±0.1 (MPa)1/2, δt = 20.1 ± 0.1 (MPa)1/2, R0 = 4.4 (MPa)1/2. It was found that asphaltenes differing in composition have different HSP values. It was observed that a decrease in H/C of asphaltenes led to an increase in δd. In addition, asphaltenes containing larger oxygen content exhibited greater δp and δh values. In particular, the amount of oxygen seemed to have a greater influence on the δp and δh of asphaltene than sulfur. Thus, for estimations using the HSPs of asphaltenes, care should be given to the components contained therein. Asphaltene solubilities in mixed solvents were examined using the HSP of CaAs determined in the present study. The solubilities of CaAs in toluene + pentane and toluene + cyclohexane solvent mixtures were mostly in good agreement with the REDs. ACKNOWREDGEMENT This research was supported by the Japan Petroleum Energy Center (JPEC) as a technological development project entrusted by Ministry of Economy, Trade and Industry. ABBREVIATIONS TCE, tetrachloroethane; THF, tetrahydrofuran; MIBK, methyl isobutyl ketone; MEK, methyl ethyl ketone; NMP, N-methyl-2-pyrrolidone; PGME, propylene glycol monomethyl ether. NOMENCLATURES


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E : cohesive energy, J/mol; Ed : cohesive energy of dispersion interaction, J/mol; Ep : cohesive energy of dipole interaction, J/mol; Eh : cohesive energy of hydrogen-bonding interaction, J/mol; V : molar volume, cm3/mol; δt : solubility parameter, MPa1/2; δd : Hansen solubility parameter of dispersion interaction, MPa1/2; δp : Hansen solubility parameter of dipole interaction, MPa1/2, δh : Hansen solubility parameter of hydrogen-bonding interaction, MPa1/2; Ra : distance between Hansen solubility parameter, MPa1/2; R0 : radius of Hansen solubility sphere, MPa1/2; RED: relative energy difference, -;  : volume ratio, -. REFERENCES (1) Acevedo, S.; Castro, A.; Vasquez, E.; Marcao, F.; Ranaudo, M. A. Energy Fuels 2010, 24, 5921-5933. (2) Redelius, P. Energy Fuels 2004, 18, 1087-1092. (3) Laux, H.; Rahimian; I.; Butz, T. Fuel Proccessing Technology 2000, 67, 79-89. (4) Mutelet, F.; Ekulu, G.; Solimando, R.; Rogalski, M. Energy Fuels 2004, 18, 667-673. (5) Yudin, I. K.; Nikolaenko, G. L.; Gorodetskii, E. E.; Kosov, V. I.; Melikyan, V. R.; Markhashov, E. L.; Frot, D.; Briolant, Y. J. Petroleum Sci. Eng. 1998, 20, 297-301 (6) Mansur, C. R. E.; de Melo, A. R.; Lucas, E. F. Energy Fuels 2012, 26, 4988-4994. (7) Waldo, G. S.; Mullins, O. C.; Penner-Hahn, J. E.; Cramer, S. P. Fuel 1992, 71, 53-57. (8) Klein, G. C.; Kim, S.; Rodgers, R. P.; Marshall, A. G. Energy Fuels 2006, 20, 1973-1979. (9) Hildebrand, J. H.; Scott, R. L.; The Solubility of Nonelectro-lytes, 3rd ed.; Dover Publications Inc.: 1950.


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(10) Hansen, C. M. Hansen Solubility Parameters: A User’s Handbook; CRC Press: 1999. (11) Hansen, C. M.; Smith A. L. Carbon 2004, 42, 1591-1597. (12) Wieneke, J. U.; Kommoß, B.; Gaer, O.; Prykhodko, I.; Ul-bricht, M. Ind. Eng. Chem. Res. 2012, 51, 327-334 (13) Launay, H.; Hansen, C. M.; Almdal, K. Carbon 2007, 45, 2859-2865 (14) Machui, F.; Abbott, S.; Waller, D.; Koppe, M.; Brabec, C. J. Macromol. Chem. Phys. 2011, 212, 2159-2165 (15) Stefanis, E.; Panayiotou, C. Int. J. Thermophys. 2008, 29, 568-585 (16) Sato, S. J. Jpn. Inst. Energy 2011, 90, 274-276 (17) Kumagai, H.; Takanohashi, T. J. Jpn. Inst. Energy 2007, 86, 778-785 AUTHOR INFORMATION Corresponding Author [email protected] Funding Sources This research was supported by the Japan Petroleum Energy Center (JPEC) as a technological development project entrusted by Ministry of Economy, Trade and Industry, Japan.


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Table 1 Chemical Properties of asphaltenes used in this work Elementalanalysis [wt%]

Asphaltene

H/C [-]

AMW [g/mol]

C

H

N

S

O

Ni

V

Others

CaAs

81.3

7.2

1.3

8.1

1.5

0.037

0.100

0.46

1.05

775

ArAs1

82.5

7.0

1.0

8.0

1.0

0.021

0.064

0.42

1.01

738

CaAs : Asphaltene extracted from bitumen produced from Canada ArAs1 : Asphaltene extracted from bitumen produced from Middle East


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Table 2 Solubility score of CaAs in some organic solvents and Hansen solubility parameters of used organic solvents. Score [-]

δd [(MPa)1/2]

δp [(MPa)1/2]

δh [(MPa)1/2]

δt [(MPa)1/2]

0.05 g/L

1 g/L

5 g/L

Bromobenzene

19.2

5.5

4.1

20.4

-

-

1

TCE

18.8

5.1

5.3

20.2

-

1

-

Dichlorobenzene

19.2

6.3

3.3

20.5

-

1

-

Chlorobenzene

19.0

4.3

2.0

19.6

-

1

1

Chloroform

17.8

3.1

5.7

18.9

-

1

-

Quinoline

20.5

5.6

5.7

22.0

-

1

-

Benzaldehyde

19.4

7.4

5.3

21.4

-

1

-

Toluene

18.0

1.4

2.0

18.2

1

1

1

Xylene

17.8

1.0

3.1

18.1

-

1

1

Pyridine

19.0

8.8

5.9

21.8

-

1

1

Benzene

18.4

0.0

2.0

18.5

-

1

1

Ethyl benzene

17.8

0.6

1.4

17.9

-

1

1

Methylene dichloride

17.0

7.3

7.1

19.8

-

1

-

Carbon disulfide

20.2

0.0

0.6

20.2

-

1

-

THF

16.8

5.7

8.0

19.5

-

1

1

1,4-Dioxane

17.5

1.8

9.0

19.8

0

0

-

Tetrachloromethane

17.8

0.0

0.6

17.8

-

0

-

1-Chlorobutane

16.2

5.5

2.0

17.2

0

0

-

Nitrobenzene

20.0

10.6

3.1

22.8

0

0

-

Morpholine

18.0

4.9

11.0

21.7

0

0

-

2-Phenyl ethanol

18.3

5.6

11.2

22.2

0

0

-

Aniline

20.1

5.8

11.2

23.7

0

0

-

Ethyl acetate

15.8

5.3

7.2

18.2

-

0

-

Cyclohexane

16.8

0.0

0.2

16.8

0

0

-

MIBK

15.3

6.1

4.1

17.0

0

0

-

MEK

16.0

9.0

5.1

19.1

0

0

-

NMP

18.0

12.3

7.2

23.0

0

0

-

Acetone

15.5

10.4

7.0

19.9

-

0

-

PGME

15.6

6.3

11.6

20.4

-

0

-

Pentane

14.5

0.0

0.0

14.5

0

0

-

Dimethyl formamide

17.4

13.7

11.3

24.9

-

0

-

18

16.6

7.4

25.6

-

0

-

1-Butanol

16.0

5.7

15.8

23.2

-

0

-

Acetonitrile

15.3

18.0

6.1

24.4

-

0

-

Ethanol

15.8

8.8

19.4

26.5

-

0

-

Methanol

14.7

12.3

22.3

29.4

-

0

-

Solvents

γ-Butyrolactone

CaAs : Asphaltene extracted from bitumen produced from Canada 1 : Good solvents for CaAs 0 : Bad solvents for CaAs - : No measurement ACS Paragon Plus Environment

18

Page 19 of 22

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

Table 3 Solubility score of ArAs1 in some organic solvents and Hansen solubility parameters of used organic solvents. δd [(MPa)1/2]

δp [(MPa)1/2]

δh [(MPa)1/2]

δt [(MPa)1/2]

Score [-]

Tetrahydronaphthalene

19.6

2.0

2.9

19.9

1

Bromobenzene

19.2

5.5

4.1

20.4

1

TCE

18.8

5.1

5.3

20.2

1

1-Bromonaphthalene

20.6

3.1

4.1

21.2

1

Chlorobenzene

19.0

4.3

2.0

19.6

1

Dichlorobenzene

19.2

6.3

3.3

20.5

1

p-Chlorotoluene

19.1

6.2

2.6

20.2

1

Chloroform

17.8

3.1

5.7

18.9

1

Quinoline

20.5

5.6

5.7

22.0

1

Toluene

18.0

1.4

2.0

18.2

1

Xylene

17.8

1.0

3.1

18.1

1

Benzaldehyde

19.4

7.4

5.3

21.4

1

Benzene

18.4

0.0

2.0

18.5

0

Carbon disulfide

19.9

5.8

0.6

20.7

1

N-Methyl aniline

19.5

6.0

7.8

21.8

0

Ethyl Benzoate

17.9

6.2

6.0

19.9

0

Methyl Benzoate

18.9

8.2

4.7

21.1

0

Ethyl benzene

17.8

0.6

1.4

17.9

0

Pyridine

19.0

8.8

5.9

21.8

0

1,4-Dioxane

17.5

1.8

9.0

19.8

0

THF

16.8

5.7

8.0

19.5

1

Methylene dichloride

17.0

7.3

7.1

19.8

0

1-Chlorobutane

16.2

5.5

2.0

17.2

0

Cyclohexane

16.8

0.0

0.2

16.8

0

Nitrobenzene

20.0

10.6

3.1

22.8

0

Morpholine

18.0

4.9

11.0

21.7

0

Aniline

20.1

5.8

11.2

23.7

0

2-Phenyl ethanol

18.3

5.6

11.2

22.2

0

MIBK

15.3

6.1

4.1

17.0

0

MEK

16.0

9.0

5.1

19.1

0

Tetrachloromethane

16.1

8.3

0.0

18.1

0

NMP

18.0

12.3

7.2

23.0

0

Pentane

14.5

0.0

0.0

14.5

0

Solvents

ArAs1 : Asphaltene extracted from bitumen produced from Middle East 1 : Good solvents for ArAs1 0 : Bad solvents for ArAs1


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 22

Table 4 Solubility scores and RED values of CaAs for mixed solvents of toluene + pentane and toluene + cyclohexane

Solvents Toluene

δd [(MPa)1/2]

δp [(MPa)1/2]

δh [(MPa)1/2]

Average particle size [nm]

Score [-]

RED [-]

18.0

1.4

2.0

0.0

1

0.71

Toluene+Pentane (φ

Toluene=0.95)

17.8

1.3

1.9

0.0

1

0.76

Toluene+Pentane (φ

Toluene=0.90)

17.7

1.3

1.8

0.0

1

0.81

Toluene+Pentane (φ

Toluene=0.85)

17.5

1.2

1.7

0.0

1

0.86

Toluene+Pentane (φ

Toluene=0.80)

17.3

1.1

1.6

0.0

1

0.91

Toluene+Pentane (φ

Toluene=0.75)

17.1

1.1

1.5

315.9

0

0.97

Toluene+Pentane (φ

Toluene=0.70)

17.0

1.0

1.4

479.9

0

1.02

Pentane

14.5

0.0

0.0

-

0

1.82

Toluene

18.0

1.4

2.0

0.0

1

0.71

Toluene+Cyclohexane (φ

Toluene=0.50)

17.4

0.7

1.1

0.0

1

0.98


Toluene=0.45)

17.3

0.6

1.0

0.0

1

1.00


Toluene=0.40)

17.3

0.6

0.9

0.0

1

1.03


Toluene=0.35)

17.2

0.5

0.8

195.5

0

1.06

16.8

0.0

0.2

3804.4

0

1.24

Cyclohexane

CaAs : Asphaltene extracted from bitumen produced from Canada 1 : Good solvents for CaAs 0 : Bad solvents for CaAs


20

Page 21 of 22

：Good solvent ：Bad solvent

25.0 20.0

δp [(MPa)1/2]

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

15.0 10.0

5.0 0.0 5.0 10.0 15.0 20.0 25.0

15.0 17.5 20.0 22.5 25.0 27.5

Figure 1 Hansen solubility parameter of CaAs in 3D diagram with solubility parameters of organic solvents used in this work. : Blue balls are the “good” solvents, and red cubes are the “bad” solvents.


21

Energy & Fuels

：Good solvent ：Bad solvent

25.0

20.0

δp [(MPa)1/2]

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 22

15.0 10.0 5.0 0.0 5.0

10.0 15.0 20.0 25.0

15.0 17.5 20.0 22.5 25.0 27.5

Figure 2 Hansen solubility parameter of ArAs1 in 3D diagram with solubility parameters of organic solvents used in this work. : Blue balls are the “good” solvents, and red cubes are the “bad” solvents.


22

Comparison of Hansen Solubility Parameter of ... - ACS Publications

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