Comparison of Different Methods To Determine the Surface Wettability

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Comparison of Different Methods to Determine the Surface Wettability of Fine Solids Isolated from Alberta Oil Sands Cheng Wang, Mirjavad Geramian, Qi Liu, Douglas G. Ivey, and Thomas H. Etsell Energy Fuels, Just Accepted Manuscript • DOI: 10.1021/ef502709r • Publication Date (Web): 27 Apr 2015 Downloaded from http://pubs.acs.org on May 4, 2015

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Comparison of Different Methods to Determine the Surface Wettability of Fine Solids Isolated from Alberta Oil Sands Cheng Wang, Mirjavad Geramian, Qi Liu, Douglas G. Ivey, Thomas H. Etsell* Department of Chemical and Materials Engineering, University of Alberta, Edmonton, AB, Canada T6G 2V4

ABSTRACT The wettability of fine solids in Alberta oil sands is one of the most important factors affecting non-aqueous bitumen extraction and subsequent solvent recovery from the extraction gangue. However, there is some controversy as to which method is most suitable for wettability determination of fine solids isolated from the oil sands. In this paper, four different methods, i.e., particle partition, static sessile drop contact angle coupled with penetration time, Washburn capillary rise, and film flotation, were investigated and compared in order to find suitable methods to determine the wettability of these fine solids. Two model samples, high purity kaolinite (hydrophilic) and bitumen treated kaolinite (hydrophobic), were used to investigate the suitability of the above four methods. These methods were then used to measure the surface wettability of fine solids isolated from the oil sands (marine clay) after toluene extraction, either untreated or heated at 400℃ for two hours. The results showed that the Washburn capillary rise method was not applicable. In addition, the particle partition and static sessile drop contact angle coupled with penetration time methods had some deficiencies and were not very suitable to determine the wettability of fine solids isolated from the oil sands. Film flotation method was determined to be the

*

Corresponding author: T. H. Etsell, E-mail: [email protected], Tel.: +1 780 492 5594; fax: +1

780 492 2881 1

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most appropriate method. It was sufficiently sensitive to distinguish solid surface hydrophilicity and hydrophobicity, it could quantify the hydrophilicity and hydrophobicity based on the measured “mean critical surface tension”, and could determine the surface heterogeneity of the solids based on the standard deviation of the measurements. By using film flotation method, the mean critical surface tensions of fine solids was higher than 68.1 mN/m while that of the heat treated solids was higher than 72.0 mN/m, and the standard deviation of floating particles (0-25.9 wt%) for fine solids was 40.5 mN/m, which indicated that heat treatment made the fine solids to be more hydrophilic and the hydrophobicity of the fine solids were heterogeneous. In addition to direct application of the four standard methods, we have further developed the methods and gained some new insights into the methods. Keywords: oil sands; fine solids; kaolinite; wettability; wettability determination.

1. Introduction Fine solids in the oil sands of Alberta, Canada, i.e., particles that are below 2 µm and consist mainly of clay minerals [1], have a deleterious effect on both water-based and solvent-based (non-aqueous) bitumen extraction. It has been shown [2] that bitumen has a greater tendency to detach from larger particles than from smaller ones, and that the detachment of bitumen from silica is easier than from illite or kaolinite during hot water extraction of bitumen from the oil sands. During non-aqueous solvent extraction, the fine solids can migrate into the recovered bitumen due to their high hydrophobicity, and thus degrade the quality of the bitumen product [3]. The fine solids remaining in the extraction gangue also affect solvent recovery, making the solvent extraction process more costly and less environmentally desirable. Wettability property is one of the most important factors in petroleum investigation and application [3-8]. The reservoir wettability affects both the 2


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distribution of reservoir fluids and the oil recovery [4-6]. Bitumen extraction and solvent recovery from hydrophobic solids are likely more difficult than from hydrophilic solids [7,8]. However, only a few studies [3,7-12] have been reported on the wettability determination of solids, especially fine solids isolated from the oil sands, let alone the effects of fine solid wettability on non-aqueous extraction and solvent recovery. There is some controversy as to which method is most suitable for wettability determination of fine solids isolated from the oil sands. The static sessile drop contact angle method, which directly measures the contact angle of a water droplet deposited on a compressed fine solids pellet, has been commonly employed, possibly due to its relative simplicity [3,10,11]. However, for powdered solids, contact angle values obtained on compressed pellets are somewhat different from those on a smooth specimen of the same solid due to surface roughness and porosity [13]. Xu et al [7,12] used static sessile drop contact angle, film flotation, hydrophilic/hydrophobic partitioning, and water drop penetration time (WDPT) to evaluate fine (106 µm and 72.0 mN/m), the mean critical surface tension of the total MC-fine solids should be higher than 68.1 mN/m. However, almost no MC-400 particles float on the solution (even in pure water), which indicates that the mean critical surface tension of MC-400 particles is higher than 72.0 mN/m. Upon comparing the mean critical surface tension of MC-fine with that of MC-400, the MC-400 particles appear to be more hydrophilic than the original untreated fine solids. Based on the obvious difference in film flotation curves and mean critical surface tension values for MC-fine and MC-400, it can be concluded that the film flotation method is sufficiently sensitive to distinguish solid surface hydrophilicity and hydrophobicity. In addition, the film flotation method can quantify hydrophilicity and hydrophobicity of solids, based on the “mean critical surface tension”, and determine 18


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the surface heterogeneity of the solids based on the standard deviation of the measurements. 3.2.5. Comparison of the four techniques and prospective application A comparison of the four wettability determination techniques is shown in Table 3. It appears that the Washburn method is unsuitable for the materials studied here, and the particle partition and static sessile drop contact angle coupled with penetration time methods have some deficiencies. The film flotation method is considered to be the most appropriate method to determine the wettability of fine solids isolated from the oil sands. Besides the quantitative wettability determination characteristic, film flotation method may have some potential advantages and applications in the oil sands studies, e. g. 1) the “mean critical surface tension” can be used to predict the bitumen content in the solids while “standard deviation” can be used to investigate the heterogeneity of bitumen contained in the solids, which based on the highly positive correlation of hydrophobicity and bitumen content in the solids; 2) “mean critical surface tension” and “standard deviation” can be used as an evaluation standard to determine and regulate the hydrophobicity of the oil sands solids, and further affect the bitumen extraction and solvent recovery; 3) film flotation method can be also used to investigate some fundamental questions, for an example, oil sands particles with different surface tension can be collected by film flotation method and this would help us to understand the composition and structures of the oil sands solids with different wettability properties.

4. Conclusions

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Particle partition, static sessile drop contact angle coupled with penetration time, Washburn capillary rise and film flotation methods were used for successively determining the wettability of pure kaolinite, bitumen treated kaolinite, and fine solids isolated from marine clay with and without heat treatment, in order to find suitable methods to determine the wettability of fine solids isolated from oil sands. The following conclusions have been obtained: (1) For the particle partition method, most of the KGa-2 particles are water-wetted and KGa-Bit particles are mineral oil-, cyclohexane- or carbon tetrachloride-wetted in Mo-W, Cy-W and Ct-W, respectively, and both KGa-2 and KGa-Bit particles are partitioned in the methylene chloride phase, which shows that the density of the solids has a negligible effect while the polarity of the solvent has a major effect on the partitioning of hydrophilic and hydrophobic particles. This method is effective in determining the wettability of solids and can effectively separate hydrophilic and hydrophobic particles by using two immiscible liquids consisting of water and a non-polar solvent. The amounts of water-wetted solids in Mo-W and Cy-W for MC-fine are 96.9% and 97.7%, respectively, while the amounts of water-wetted solids for MC-400 in Mo-W and Cy-W are 98.3% and 97.8%, respectively, which shows that this method is not sufficiently sensitive to determine and distinguish the wettability of samples with small wettability differences. (2) For static sessile drop contact angle coupled with penetration time method, the contact angle follows an approximately linear dependence with the concentration of KGa-Bit, while the penetration time follows a nonlinear dependence. The contact angle and penetration time of 20 mm pellets are 21.1° and 34.0 s for MC-fine, and 8.5° and 23.3 s for MC-400, while those of 10 mm pellets are 33.7° and 7.1 s for 20


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MC-fine, and 19.3° and 5.9 s for MC-400. The results show this method can be used to quantify the hydrophilic and hydrophobic nature of samples, and it is sensitive to samples with small wettability differences. However, this method suffers drawbacks related to surface roughness, water evaporation and penetration which result in a diminishing water droplet. The measured contact angle and penetration time are not static and their values could vary widely. (3) For the Washburn capillary rise method, the contact angles for KGa-2, 80% KGa-2/20% KGa-Bit, MC-fine and MC-400 are calculated as 83°, 89°, 86° and 83°, respectively. Comparison of the Washburn capillary rise results with the other three methods shows that this method is not suitable for determining wettability of clay samples and fine solids isolated from the oil sands. This is because clay minerals tend to cluster or swell causing the pore structures to change, which can result in misleading contact angle results. (4) For the film flotation method, the mean critical surface tensions of KGa-Bit and KGa-2 are 31.3 mN/m and >72.0 mN/m, respectively, and the standard deviation of KGa-Bit is about 8.8 mN/m. The mean critical surface tension of the MC-fine is higher than 68.1 mN/m and that of MC-400 is higher than 72.0 mN/m. The results show that this method can be used to assess the hydrophobicity and hydrophilicity of an assembly of particles with different surface tensions. It is sufficiently sensitive to distinguish solid surface hydrophilicity and hydrophobicity. Furthermore, it can be used to quantify hydrophilicity and hydrophobicity of solids based on the “mean critical surface tension” and determine the surface heterogeneity of solids based on the standard deviation of the measurements This method is considered the most

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appropriate method to determine the wettability of fine solids isolated from Alberta oil sands.

Acknowledgements The authors are grateful to the Institute for Oil Sands Innovation (IOSI) for providing research funding. The authors would also like to thank Dr. Xiaoli Tan, Mr. Jeremiah Bryksa and Ms. Lisa Brandt for assistance with the experiments.

Nomenclature Abbreviations Bitumen treated kaolinite = KGa-Bit Fine solids isolated from oil sand (marine clay) = MC-fine Heat treated solids at 400℃ = MC-400 Mineral oil-water = Mo-W Cyclohexane-water = Cy-W Carbon tetrachloride-water = Ct-W Methylene chloride-water = Mc-W Variables m= mass of penetrating liquid (g) t = penetration time of the liquid (s) c = capillary constant of the powder bed reff = effective radius or the equivalent radius of voids in the packed powders A = cross-section of the tube

γ c = mean critical surface tension (mN/m) 22


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γc = critical surface tension of the particles (mN/m) f(γc) = frequency distribution function

σ γ c = standard deviation of the frequency distribution function Greek Letters ρ = density of the liquid (g/cm3) σ = surface tension of the liquid (mN/m) η = viscosity of the liquid (mPa·s) ε = porosity of the packing in the tube

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[10] Darcovich, K.; Kotlyar, L. S.; Tse, W. C.; Ripmeester, J. A.; Capes, C. E.; Sparks, B. D. Energy and Fuels 1989, 3, 386-391. [11] Chen, F.; Finchi, J. A.; Xu, Z.; Czarnecki, J. Journal of Adhesion Science and Technology 1999, 13, 1209-1224. [12] Dang-Vu, T.; Jha, R.; Wu, S. Y.; Tannant, D. D.; Maliyah, J.; Xu, Z. H. Energy and Fuels 2009, 23, 2628-2636. [13] Chau, T. T. Minerals Engineering 2009, 22, 213-219. [14] Syncrude Research. Syncrude Canada Limited, 1979. [15] Galet, L.; Patry, S.; Dodds, J. Journal of Colloid and Interface Science 2010, 346, 470-475. [16] Dunstan, D.; White, L. R. Journal of Colloid and Interface Science 1986, 111, 60-64. [16] Kirdponpattara, S.; Phisalaphong, M.; Newby, B. Z. Journal of Colloid and Interface Science 2013, 397, 169-176. [14] Washburn, E. W. Physical Review 1921, 17, 273-283. [15] Fuerstenau, D. W.; Williams, M. C. Particle and Particle Systems Characterization 1987, 4, 7-13. [16] Fuerstenau, D. W.; Diao, J. L.; Williams, M. C. Colloids and Surfaces 1991, 60, 127-144. [17] Diao, J. L. and Fuerstenau, D.W. Colloids und Surfaces 1991, 60, 145-169. [18] Vhquez, G.; Alvarez, E.; Navaza, J. M. Journal of Chemical and Engineering Data 1995, 40, 611-614. [19] Bukka, K.; Miller, J. D.; Obladt, A. G. Energy and Fuels 1991, 5, 333-340. [20] Madejová, J. and Komadel, P. Clays and Clay Minerals 2001, 49, 410-432. 24


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[21] Reichardt, C. and Thomas, W. John Wiley & Sons, 2011. [22] Shang, J. Y.; Flury, M.; Harsh, J. B.; Zollars, R. L. Journal of Colloid and Interface Science 2008, 328, 299-307. [23] Zendehboudi, S.; Chatzis, I.; Mohsenipour, A.A.; Elkamel A. Energy Fuels, 2011, 25, 1731-1750. [24] Montgomery, D. C. John Wiley & Sons, 2008. [25] Shafiei, A.; Dusseault, M. B.; Zendehboudi, S.; Chatzis, I. Fuel, 2013, 108, 502-514.

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Appendix I: Statistical analysis of film flotation results Table A shows the statistical analysis of film flotation results for KGa-2(A-1), KGa-Bit(A-2), MC-fine(A-3c) and MC-400(a-4). The tables contain the number of replicates, mean values, standard deviations, lower limits and upper limits (confidence interval) of the data. It can be seen that film flotation results for the four solids show relatively low standard deviations and narrow confidence intervals, which indicates that film flotation experiments exhibit relatively good repeatability. In addition, MC-fine and MC-400 results appear to be less repeatable than those for KGa-2 and KGa-Bit, which can be attributed to the higher heterogeneity of the MC-fine and MC-400 samples.

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Table Captions Table 1 CHNS results for KGa-2, KGa-Bit, MC-fine and MC-400 (wt. %) Table 2 Density, surface tension, relative polarity and solubility of the solvents in water Table 3 Comparison of particle partition, static sessile drop contact angle coupled with penetration time, film flotation and Washburn capillary rise measurements Table A Statistical analysis of film floatation results for KGa-2 (A-1), KGa-Bit (A-2), MC-fine (A-3) and MC-400 (A-4)

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Table 1 Sample

Nitrogen Carbon Hydrogen Sulfur

KGa-2

0

0.0470

0.8252

0

KGa-Bit

0.1209

9.2822

2.3065

0.8002

MC-fine

0.0822

4.9245

0.6029

0.0630

MC-400

0.0790

3.9317

0.4536

0.0512

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Table 2

Solvent

Density (g/mL)

Water Mineral oil* Cyclohexane Methylene chloride Carbon tetrachloride

0.998 0.840 0.779 1.326 1.594

Surface tension (mN/m) 72.7 24.7 27.8 26.3

Relative polarity 1.0 0.006 0.309 0.052

Solubility in water (g/100g) 0.005 1.32 0.008

*Note: Mineral oil is composed mainly of alkanes and cyclic paraffins, related to petroleum jelly, which have low surface tension and polarity.

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Table 3

Advantage

Disadvantage

Suitability for fine solids

Particle partition

Can separate hydrophilic and hydrophobic particles.

Cannot quantify the wettability of fine solids; not sensitive for samples with small wettability differences.

Not very suitable

Static sessile drop contact angle coupled with penetration time

Convenient method and can quantify wettability of fine solids; sensitive for samples with small wettability differences.

Not very accurate due to surface roughness and porosity of pellets.

Not very suitable

Methods

Sufficiently sensitive to distinguish solid surface hydrophilicity and hydrophobicity; can quantify Critical surface hydrophilicity and tension hydrophobicity; can determine surface heterogeneity of the fine solids. Washburn capillary rise

-

Cannot determine wettability of clay samples and fine solids.

-

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Suitable

Unsuitable

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Table A-1 - KGa-2 Methanol aqueous solutions with different surface tensions 22.51 23.93 25.54 27.48 29.83 32.86 36.51 41.09 47.21 56.18 72.01

Number of replicates

Mean value for floating particles

Standard deviations

Lower 95%

Upper 95%

3 3 3 3 3 3 3 3 3 3 3

0 0 0 0 0 0 0 0 0 2.73 3.33

0 0 0 0 0 0 0 0 0 0.76 0.23

0 0 0 0 0 0 0 0 0 0.85 2.76

0 0 0 0 0 0 0 0 0 4.61 3.91

Table A-2 - KGa-Bit Methanol aqueous solutions with different surface tensions 22.51 23.93 25.54 27.48 29.83 32.86 36.51 41.09 47.21 56.18 72.01

Number of replicates

Mean value for floating particles

Standard deviations

Lower 95%

Upper 95%

3 3 3 3 3 3 3 3 3 3 3

0 0 0 2.20 30.27 78.73 96.80 98.33 100 99.27 98.00

0 0 0 2.03 3.72 3.20 1.56 2.08 0 0.81 3.46

0 0 0 -2.84 21.03 70.78 92.92 93.16 100 97.26 89.39

0 0 0 7.24 39.50 86.69 100.68 103.50 100 101.27 106.61

Table A-3 - MC-fine Methanol aqueous solutions with different surface tensions 22.51 23.93 25.54 27.48 29.83 32.86 36.51 41.09 47.21 56.18 72.01

Number of replicates 3 3 3 3 3 3 3 3 3 3 3

Mean value for floating particles 0 0 0 0 0 0 1.33 2.00 6.13 20.20 25.87

Standard deviations

Lower 95%

Upper 95%

0 0 0 0 0 0 0.23 1.83 2.47 2.80 1.22

0 0 0 0 0 0 0.76 -2.55 0 13.24 22.83

0 0 0 0 0 0 1.91 6.55 12.27 27.16 28.90

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Table A-4 - MC-400 Methanol aqueous solutions with different surface tensions 22.51 23.93 25.54 27.48 29.83 32.86 36.51 41.09 47.21 56.18 72.01

Number of replicates 3 3 3 3 3 3 3 3 3 3 3

Mean value for floating particles 0 0 0 0 0 0 3.27 3.47 1.13 0.73 1.47

Standard error

Lower 95%

Upper 95%

0 0 0 0 0 0 1.17 1.97 0.23 0.70 0.83

0 0 0 0 0 0 0.36 -1.43 0.56 -1.01 -0.60

0 0 0 0 0 0 6.18 8.37 1.71 2.48 3.54

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Figure Captions Figure 1 Apparatus for film flotation experiment Figure 2 Particle size distribution for KGa-2 and MC-fine. Figure 3 FTIR spectra for bitumen, KGa-2, KGa-Bit, MC-fine and MC-400. Figure 4 XRD patterns of KGa-2 and KGa-Bit, MC-fine and MC-400. Figure 5 Particle partition of KGa-2 and KGa-Bit in Mo-W, Cy-W and Mc-W immiscible liquids. Figure 6 Relationship between the amount of KGa-Bit and contact angle and penetration time. Figure 7 Penetration profiles for n-hexane through tubes packed with KGa-2, 80% KGa-2/20% KGa-Bit, MC-fine and MC-400. Figure 8 Penetration profiles for de-ionized water through tubes packed with KGa-2, 80%KGa-2/20%KGa-Bit, MC-fine and MC-400. Figure 9 Film flotation results for KGa-2 and KGa-Bit. Figure 10 Film flotation results for MC-fine and MC-400.

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Figure 1

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Figure 2

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Figure 3

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Figure 4

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Figure 5

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Figure 6

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Figure 7

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Figure 8

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Figure 9

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Figure 10

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Comparison of Different Methods To Determine the Surface Wettability

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