Predicting the Viscosity of Hydrocarbon Mixtures and Diluted Heavy

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Predicting the Viscosity of Hydrocarbon Mixtures and Diluted Heavy Oils Using the Expanded Fluid Model Francisco Ramos Pallares, Florian F Schoeggl, Shawn David Taylor, Marco A Satyro, and Harvey William Yarranton Energy Fuels, Just Accepted Manuscript • DOI: 10.1021/acs.energyfuels.5b01951 • Publication Date (Web): 09 Oct 2015 Downloaded from http://pubs.acs.org on October 9, 2015

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Predicting the Viscosity of Hydrocarbon Mixtures and Diluted Heavy Oils Using the Expanded Fluid Model F. Ramos-Pallares1, F.F. Schoeggl1, S.D. Taylor2, M.A. Satyro3, H.W. Yarranton1 1. Department of Chemical and Petroleum Engineering, University of Calgary, 2500 University Dr. NW, Calgary, AB, Canada, T2N 1N4. 2. DBR Technology Center, Schlumberger Canada Limited, 9450 17th Avenue NW, Edmonton, Alberta, Canada T6N 1M9. 3. Department of Chemical and Biomolecular Engineering, Clarkson University, 8 Clarkson Ave., Potsdam, New York, United States, 13699. ABSTRACT The Expanded Fluid (EF) viscosity model was recently developed for petroleum applications. While petroleum fluids can be modeled as a single component fluid, process calculations often require that the fluid be treated as a mixture of pseudo-components. For mixtures, the EF model mixing rules require binary interaction parameters, αij, between each component pair in the mixture, which are fitted to experimental data. In this study, a generalized correlation is developed for these interaction parameters as a function of the specific gravity and hydrogen-to-carbon ratio of the mixture components. The proposed correlation was developed based on a dataset which included viscosity and density literature data for pure hydrocarbon pairs at room temperature and atmospheric pressure and new data for pseudo-pairs heavy oil/solvent at temperatures from 21 to 175°C, pressures up to 10 MPa, and solvent contents up to 40 wt%. The correlation was assessed on a distinct test dataset which included viscosity data for pure hydrocarbon mixtures from the literature, new data for deasphalted crude oils diluted with paraffinic and aromatic solvents, and new data for crude oils diluted with similar solvents. The viscosities of the development and test datasets were predicted with an overall average absolute relative deviation (AARD) of 13% and 10%, respectively, compared to 36% and 50% respectively when ideal mixing, αij =0, was assumed. Finally, the correlation was tested on an independent dataset from the literature including viscosity data for crude oils diluted with a variety of solvents. The viscosities of the independent dataset were predicted with an overall average absolute relative deviation (AARD) of 14%, compared to 30% when ideal mixing, αij =0, was assumed. The deviations obtained with the correlated αij are almost as low as those obtained when fitting the data by adjusting the αij.

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Introduction A defining characteristic of heavy oil and bitumen is their viscosity, which can be as high as one million mPa.s at room temperature. This high viscosity must be reduced for recovery, transportation, and processing; for example, in cyclic steam stimulation, steam-assisted gravity drainage, solvent-based processes, steam-solvent recovery processes, dilution for pipeline transport, and refinery blending. Viscosity reduction is typically achieved by chemical conversion methods such as visbreaking or by increasing the temperature, diluting the crude oil with hydrocarbon solvents, decreasing the pressure, or a combination of these variables. Viscosity prediction is important in many of these applications; for instance, to optimize the amount of diluent added to dilbit rail cars and to model, design, and optimize in situ heavy oil recovery processes. Hence, an accurate method to determine viscosity over a wide range of temperatures, pressures, and compositions is required.

There are several methods available for the estimation of viscosities of pure hydrocarbons and crude oils which can be classified as either theoretical or empirical. Theoretical models are based on statistical mechanics; for example the Erying (Glasstone et al., 1941) and the Chapman-Enskog (Chapman et al., 1970) models. These models work satisfactorily for hydrocarbon gases and their mixtures at low pressure; however, they are challenging to apply and provide unsatisfactory results for liquid hydrocarbons (Poling et al., 2000). Empirical correlations are based on experimental observations and capture the behavior of viscosity through adjustable parameters which are tuned to fit experimental data. Empirical correlations have been used in reservoir simulators to predict the viscosity behavior of petroleum fluids which are generally treated as single components; for example, the Walther correlation (Walther, 1931), the Vogel correlation (Vogel, 1921), and the Andrade correlation (Andrade, 1934). These correlations are intended for single-phase liquids far from their critical point (Yarranton et al., 2013).

Mixing rules are generally used to extend empirical models to mixtures. Either the viscosity of the individual components or model parameters are combined by means of their molar, mass or volume fraction to calculate the viscosity or model parameters for the mixture. The simplest types of mixing rules are the Arrhenius rule, an average of the logarithm of the component viscosities (Arrhenius, 1887), and the power law rule, an average of the component viscosities elevated at an 2 ACS Paragon Plus Environment

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experimentally determined exponent (Barrufet et al., 2003). These mixing rules do not produce accurate results for diluted heavy oils and bitumen (API, 1977; Centeno et al., 2011); hence viscosity binary interaction parameters, a viscosity blending index, or another adjustable value must be introduced to improve the accuracy of the predictions.

Several approaches have been proposed in order to predict the viscosity of diluted crude oils using mixing rules. Comprehensive reviews of these mixing rules are provided elsewhere (Centeno et al., 2011; Mehrotra et al., 1996) and are summarized here. Cragoe (1933) developed a universal equation for binary heavy oil-solvent blends that is a function of the viscosity of the components and their mass fraction, however, its results are not satisfactory for all possible combinations heavy oil and solvent (Shu, 1984) and for high viscosity bitumen (Nourozieh et al., 2014). Lederer (1933) formulated a logarithmic mixing rule which is a function of the volume fraction of the components of the mixture and includes an adjustable parameter that varies between 0 and 1. Shu (1984) proposed a correlation to calculate the adjustable parameter for Lederer’s mixing rule as a function of pure component densities and viscosities at a given temperature and pressure. However, this correlation covers a limited range of temperature (Barrufet et al., 2003). Mehrotra (1991) presented a set of logarithmic mixing rules to calculate the viscosity of mixtures bitumen-solvent as a function of the mole fraction, molecular weight, and a temperature dependent binary interaction parameter. Yarranton et al. (2013) developed mass fraction based mixing rules for the Walther correlation applicable to dead and live conventional oils and bitumens diluted with solvents over a broad range of temperatures and pressures. This approach is promising for liquid conditions, including diluted bitumens far from the critical point, but does not encompass the entire phase diagram.

Semi-empirical viscosity correlations that apply to the entire phase diagram are: the corresponding states approach (Pedersen and Fredenslund, 1987, Aasberg-Petersen et al., 1991), Friction Theory (Quinones-Cisneros et al., 2000), and the Expanded Fluid model. The discussion here is focused on the Expanded Fluid (EF) model which was developed for heavy oils (Yarranton and Satyro, 2009). This semi-empirical correlation provides reliable and accurate fit for the viscosity of pure hydrocarbons and single pseudo-component dead and live heavy oils and bitumens. The use of mass based mixing rules allows the correlation to predict viscosity of binary mixtures, including 3 ACS Paragon Plus Environment

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dead and live heavy oils and bitumens with hydrocarbon solvents and condensate. The mixture predictions may be improved by the introduction of a binary interaction parameter to tune the model to available data; however, to date, the value of the binary interaction parameter must be fitted for each specific system. (Yarranton and Satyro, 2009; Oldenburg et al., 2010, Motahhari, 2013).

The main objective of this study is to develop a generalized correlation for the viscosity binary interaction parameters in the EF model in order to improve the accuracy of the model predictions. To do so, a development density and viscosity dataset was compiled from the literature which included pure hydrocarbon binaries with components from different chemical families including n-alkanes, branched alkanes, cyclics and aromatics. In addition, experimental viscosity and density data for the pseudo-binaries of heavy oil with different types of solvents (n-alkanes, cyclohexane, toluene and 1-methylnaphthalene) were collected at temperatures, pressures and solvent content up to 175°C, 10 MPa and 50 wt%, respectively. The viscosity interaction parameters were calculated for each pair of components by fitting the EF to the binary and pseudo-binary mixture data. The calculated viscosity binary interaction parameters, αij, were then correlated to specific gravity and the hydrogen-to-carbon ratio of the component fluids. Finally, the proposed correlation was assessed against a test dataset (other pure hydrocarbon mixtures from the literature, diluted crude oils, and diluted deasphalted oil from this study) and an independent dataset (diluted crude oils from the literature).

Experimental Methods Materials The following gas free samples were used in this study: WC-B-B1 (B1 in figure legends), WC-BB2 (B2), CO-B-A1 (B3) and ME-CV-A1 (CV1). WC, CO, and ME indicate Western Canada, Colombia, and Middle East, respectively, B and CV indicate bitumen and conventional oil; and the third terms indicates the source reservoir and sample number. An additional sample (Blend1) was prepared by mixing ME-CV-A1 with deasphalted WC-B-B2 (WC-B-B2-DAO) in a 30 to 70 mass ratio, respectively. Selected physical properties and the asphaltene and toluene insoluble contents of the samples are summarized in Table 1.


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Table 1. Pentane-precipitated (C5) asphaltene and toluene insoluble (TI) contents, hydrogen-tocarbon atomic ratio, specific gravity (SG) at 15.6°C, and viscosity at 20°C of the oil samples used in this study. Legend

C5 Asphaltene Content wt%

TI Content wt%

H/C Ratio

SG @15.6°C

Viscosity @20°C mPa.s

WC-B-B1

B1

17

0.63

1.473

1.012

89,200

WC-B-B2

B2

21

1.27

1.470

1.020

437,000

CO-B-A1

B3

27

1.00

1.440

1.106

2,800,000

CV1

3.8

0.03

1.756

0.872

18.1

Blend1

1.4

0.009

1.624

0.953

1,085

DAO

0

0

1.568

0.989

3,050

Sample

ME-CV-A1 Blend1 WC-B-B2-DAO

The solvents used for the preparation of the diluted bitumen samples were ethane (purity of 99%), propane (purity of 99.5%), n-butane (purity of 99.5%), n-pentane (purity of 99.5%), n-heptane (purity of 99.5%), n-dodecane (purity of 99.5%), n-eicosane (purity of 99.5%), toluene (purity of 99.5%), cyclohexane (purity of 99%), and 1-methylnaphthalene (purity of 99%). Pressurized ethane, liquid propane, and liquid n-butane were purchased from Praxair Canada Inc. Liquid atmospheric n-pentane, n-heptane, n-dodecane, toluene and cyclohexane were obtained from VWR. Solid n-eicosane and liquid 1-methylnaphthalene were obtained from Sigma-Aldrich.

Preparation of Deasphalted Bitumen and Asphaltene and Toluene Insoluble Contents Asphaltenes were precipitated from bitumen using a 40:1 ratio (mL/g) of n-pentane/bitumen. The mixture was sonicated in an ultrasonic bath for 60 minutes at room temperature and left to settle without disturbing for a total contact time of 24 hours. The supernatant was filtered through an 8 µm pore size Whatman filter paper until approximately 20% of the solution remained in the beaker. A total of 10% of the original volume of solvent was added to the remaining asphaltenes in the beaker, and then sonicated for 60 minutes before being left to settle overnight for a contact time of approximately 18 hours. The remaining mixture was filtered through the same filter paper. The filter cake was washed using 25 mL of n-pentane each time at least three times a day until the 5 ACS Paragon Plus Environment

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effluent from the filter was almost colorless and then dried for 8 days. All the filtrate was place in a rotary evaporator and the solvent was evaporated to recover the maltenes. To eliminate remnant solvent the maltenes were placed in an oven at 40°C until no change of mass was observed, typically 35 days. The final product of this process is termed here deasphalted bitumen. The filter cake contains the asphaltenes and any co-precipitated toluene insoluble material and is here termed asphaltenes-TI. The asphaltene-TI content is the mass of the filter cake divided by the mass of the bitumen.

The toluene insoluble (TI) are mineral material, such as sand, clay, ashes and adsorbed organics that precipitates along with the asphaltenes without affecting the onset or percentage of precipitated asphaltenes (Mitchell and Speight, 1973). To remove the TI, 10 kg/m³ of asphaltenesTI were mixed with toluene at room temperature. The mixture was sonicated in an ultrasonic bath for 20 minutes or until all the soluble material was dissolved, and then the solution was settled for 60 minutes. The mixture was centrifuged at 4000 rpm for 6 minutes. The residue in the centrifuge tubes was dried and weighed. The TI content is the mass of TI divided by the original mass of crude oil. The asphaltenes content is the asphaltenes content less the TI content all divided by the original mass of the bitumen. The asphaltene and TI contents of the samples used in this study are summarized in Table 1. Note that all the bitumen viscosity experiments were conducted on bitumen that still contained the asphaltenes and TI. The contents are provided to facilitate in the comparison of data from different samples.

Diluted Bitumen Preparation Mixtures of the dead bitumen and liquid solvents (n-pentane, n-heptane, toluene, cyclohexane and 1-methylnaphthalene) were prepared at ambient temperature and atmospheric pressure. A known mass of dead oil and solvent (approximately 350 g in total) were placed in a beaker equipped with a lid and mixed continuously in a rotary mixer at 6 rpm until a homogenous mixture was observed. The mixture was considered homogeneous when its density was no longer changing with mixing time, typically after 12 hours. Mixtures of n-eicosane, which is solid at room temperature, and dead bitumen were prepared at 50°C where the n-eicosane was a liquid. Once the mixture was homogeneous, its final mass was determined in order to recalculate the solvent concentration to


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take into account any evaporation (usually less than 1 wt%) which was assumed to be only from solvent losses. Mixtures of the dead bitumen and gaseous solvents (ethane, propane and n-butane) were prepared using an in-house mixing apparatus. Details of the apparatus and procedure are provided elsewhere (Motahhari et al., 2011a). Briefly, this apparatus consists of a horizontal cylindrical vessel with two moving pistons on either sides of a perforated disk fixed in the middle of the vessel. To prepare each mixture, a known mass of the pressurized solvent (determined by direct measurement) was filled into the pre-evacuated volume of the cylinder. Then, the required mass of the bitumen to reach the intended composition of the mixture was injected into the cylinder. The bitumen and solvent were mixed by displacing the pistons back and forth forcing the sample to flow through the perforated plate for 2 to 3 days at 10 MPa and 50°C. A Quizix SP-5200 pump system with hydraulic oil as the working fluid was used to move the pistons. Temperature was controlled to within ±0.5 °C using heating tapes. The mixture was assumed to be completely mixed and equilibrated when there was no longer any pressure and volume change. The mixture was then displaced to the transfer vessel for the density and viscosity measurements.

Density and Viscosity Measurements Viscosity was measured in two apparatus: 1) a capillary viscometer with an in-line Anton Paar DMA HPM density meter; 2) a cone and plate rheometer. A second Anton Paar DMA 4500M oscillating U-tube density meter was used to determine the density of the samples tested with the cone and plate apparatus. Viscosity and density data for samples WC-B-B1 and WC-B-B2 were measured at temperatures and pressures up to 175°C and 10 MPa in the capillary viscometer apparatus which requires of 350 mL of sample. Viscosity and density of the remaining samples were determined using a cone and plate rheometer and an oscillating U-tube density meter, respectively, (approximately 8 mL of sample is required for this approach) at temperatures up to 100°C at atmospheric pressure. The amount of sample available was determining factor in selecting the device to measure viscosity and density.

Capillary Viscometer This device consists of two transfer vessels and two capillary tubes in a temperature controlled oven, Figure 1. The apparatus is also equipped with an Anton Paar DMA HPM density meter with 7 ACS Paragon Plus Environment

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an external Anton Paar mPDS 2000V3 evaluation unit. Hydraulic oil is used as the displacement fluid and pressure in the apparatus is controlled using a back pressure regulator (BPR) on the return line of the hydraulic oil. The set pressure of the regulator is maintained using compressed air and is monitored with a Bourdon pressure gauge with a precision of 0.05 MPa. The temperature of the air bath is controlled within ±0.05°C of the intended measurement temperature, except for the room temperature experiments. The room temperature varied within a range of ±0.25°C. The capillary tubes were calibrated at temperature range of 20 to 175°C using Cannon Instruments certified viscosity standards. The density meter was calibrated using pure nitrogen and distilled water at temperature range of 20 to 175°C and pressures up to 10 MPa. The measured viscosity and density reproduced the calibration data, as well as some other test fluids such as n-heptane and toluene, to within ±3% and ±0.5 kg/m³, respectively. Density and viscosity measurements were taken simultaneously for each fluid at the test pressure and temperature. Prior to the measurements, the fluid was flowed back and forth through the apparatus to ensure homogeneity, which was confirmed when the density and pressure drop through capillary tubes were consistent for the entire displacement. To collect the required data for the viscosity measurement, the fluid was flowed from one vessel to other though one of the installed capillary tubes at 5 different fixed flow rates. Once the flow reached a steady state condition at each flow rate, the pressure difference between its inlet and outlet was recorded. The viscosity of the fluid was then calculated from the slope of the differential pressures versus flow rate and the calibration constant of the capillary tube. To measure density, the flow rate through the capillary tube was set at 0.001 cm³/min to maintain the test pressure set by BPR throughout the apparatus. Once the flow reached a steady state condition, the density was measured. Measurements on the diluted bitumen samples were undertaken from room temperature up to 175°C in steps of 25°C. At each temperature, the data were collected at pressures well above the bubble point pressure of the fluid up to 10 MPa in steps of 2.5 MPa.


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PT1

Pressure Transducers PT2

BLUE M Air Bath Capillary Tube #1

Hydraulic Oil Reservoir Capillary Tube #2 Back Pressure Regulator

T

P

Transfer Vessel

Density-meter Thermometer

Transfer Vessel T

Pump

Temperature Controller

Compressed Air Bottle

Figure 1. Schematics of the capillary viscometer and in-line density-meter apparatus.

Cone and Plate Rheometer An Anton Paar MCR-52 cone and plate rheometer equipped with an Anton Paar Peltier P-PTD 200 mechanism for temperature control was used in this study. The viscosity is determined from the slope of the shear stress versus shear rate line. The instrument was calibrated using Cannon Instruments certified viscosity standards at atmospheric pressure and temperatures up to 150°C. After calibration, the measured viscosities were within ± 2% of the reported viscosity of the standards. Viscosity measurements were performed up to 100°C, although for bitumen/solvent mixtures containing more volatile solvents the measurements were done at temperatures below 50°C in order to avoid solvent evaporation. Solvent loss could be detected as an increment of viscosity at constant temperature. All the mixtures tested in this study were found to be Newtonian in the range of temperatures and shear rate range (from 1 to 750 s-1) at atmospheric pressure.

Density Meter The densities of the samples tested in the cone and plate rheometer were determined using an Anton Paar DMA 4500M oscillating U-tube density meter at atmospheric pressure and 9 ACS Paragon Plus Environment

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temperatures up to 75°C. Temperature of the sample cell was controlled to within ±0.01°C by a Peltier mechanism enabling measurements from 0°C to 90°C. Pure component samples were injected directly into the apparatus and their density was measured once thermal equilibrium was reached at a set temperature. For the mixtures of bitumen and solvent, the sample was first sonicated at 20°C until homogeneous. The mixture was considered homogeneous when its density was no longer changing with mixing time, typically after 12 hours. The instrument was calibrated using reverse-osmosis water and nitrogen. The precision and repeatability of the density measurements were ±0.01 kg/m³ and ± 0.05 kg/m³ respectively.

Quality Check of Viscosity Data Walther (1931) demonstrated that, for liquids, the double log of viscosity is linearly related to the log of the absolute temperature. Others (Butler, 1997; Yarranton et al., 2013) have confirmed that heavy oils and bitumens also follow this relationship. Hence, one check on the quality of any liquid viscosity data is to confirm its linearity when plotted in these coordinates. This condition was satisfied for all the data measured in this study or obtained from the literature.

Modeling Expanded Fluid Viscosity Correlation Details of this correlation and its development are given elsewhere (Yarranton and Satyro, 2009). Briefly, the correlation is based on the empirical observation that the viscosity of the fluid decreases as it expands from a compressed state of infinite viscosity. The viscosity of the fluid (μ) in mPa.s, is formulated as a departure from dilute gas viscosity (μo): 𝜇𝜇 − 𝜇𝜇𝑜𝑜 = 0.165(𝑒𝑒𝑒𝑒𝑒𝑒(𝑐𝑐2 𝛽𝛽) − 1)

(1)

where c2 is a parameter specific for each fluid which determines the response of the viscosity of the fluid to the expansion from the compressed state. β is the correlating parameter between the density and viscosity and is related to the expansion of the fluid as follows:

β=

1  ρ * 0.65  exp  s  − 1 − 1  ρ  

(2)

where ρs* is pressure dependent compressed state density of the fluid given by:


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ρ so ρ = exp(−c3 P) * s

(3)

where ρso is the compressed state density of the fluid in vacuum, c3 is the fluid-specific pressure dependency constant in kPa-1, and P is pressure in kPa.

The inputs to the EF correlation are the pressure, density, and dilute gas viscosity of the fluid. The dilute gas viscosity of the components was estimated using the following empirical correlation (Yaws, 2008):

µo =Ao + BoT + CoT 2

(4)

where Ao, Bo, and Co are fitting parameters specific for each pure component and usually defined at 1 atm. The fluid-specific parameters: c2, c3 and ρso are fitted using the available viscosity data. Mixing Rules The EF correlation treats a mixture as one single fluid with fluid-specific parameters calculated from those of the components of the mixture with following mixing rules (Motahhari et al., 2011b): 𝑛𝑛𝑛𝑛 𝑜𝑜 𝜌𝜌𝑠𝑠,𝑚𝑚𝑚𝑚𝑚𝑚 = �∑𝑛𝑛𝑛𝑛 𝑖𝑖 ∑𝑗𝑗 𝑐𝑐2,𝑚𝑚𝑚𝑚𝑚𝑚

𝑜𝑜 𝜌𝜌𝑠𝑠,𝑚𝑚𝑚𝑚𝑚𝑚

𝑛𝑛𝑛𝑛 = ∑𝑛𝑛𝑛𝑛 𝑖𝑖 ∑𝑗𝑗

c3,mix

𝑤𝑤𝑖𝑖 𝑤𝑤𝑗𝑗 2

1

1

𝑠𝑠,𝑖𝑖

𝑤𝑤𝑖𝑖 𝑤𝑤𝑗𝑗 𝑐𝑐2,𝑖𝑖

𝑐𝑐

𝑠𝑠,𝑗𝑗

�𝜌𝜌𝑜𝑜 + 𝜌𝜌2,𝑗𝑗 𝑜𝑜 � �1 − 𝛼𝛼𝑖𝑖𝑖𝑖 �

2

−1

�𝜌𝜌𝑜𝑜 + 𝜌𝜌𝑜𝑜 � �1 − 𝛼𝛼𝑖𝑖𝑖𝑖 �� 𝑠𝑠,𝑖𝑖

 nc w  =  ∑ i =1 i   c3,i  

𝑠𝑠,𝑗𝑗

(5) (6)

−1

(7)

where nc is the number of components in the mixture and wi is the mass fraction of the component “i” in the mixture. αij is the viscosity binary interaction parameter currently with a default value of zero. The binary interaction parameter can be used to tune the correlation when experimental viscosity data for the mixture are available.

The dilute gas viscosity of the mixture (µo,mix) is calculated using Wilke’s method (1950) as follows:

µo,mix = ∑ i

xi µo,i

∑ x jϕij

(8)

j


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where:

(

) (

1 + µ / µ 0.5 MW / MW o ,i o, j j i  ϕij =  0.5 8 1 + MWi / MW j   

(

)

)

0.25 

2



(9)

and where xi, µo,i and MWi are the mole fraction, dilute gas viscosity and molecular weight of the component “i” of the mixture.

Fluid Specific Parameters The fluid specific parameters of the EF correlation for pure solvents used in this work were taken from Yarranton and Satyro (2009) and Motahhari et al. (2011b, 2013), and are summarized in Appendix A. The numerical values of the constants in Equation 4 for each pure component were taken from Yaws (2008). The crude oils used here were characterized as single components for the purpose of viscosity modeling. The fluid-specific parameters of the EF model for the bitumens were determined by logarithmic least squares fitting of their viscosity data, using the measured density as an input. The dilute gas viscosity of bitumen was estimated using the parameters of the n-paraffin compounds of the same molecular weight. The contribution of the dilute gas viscosity to the total viscosity of the dead bitumen was negligible at the conditions in this study. The dilute gas viscosity of the mixtures was determined according to Equations 8 and 9.

The EF fluid-specific parameters for the crude oils used in this study are provided in Table 2. The EF model fit the viscosity data for these fluids to within a maximum deviation of 17% with an overall average absolute relative deviation (AARD) of 5%. Table 2. Fluid specific EF correlation parameters for the crude oils used in this study. Parameter c3 was only determined when high pressure viscosity and density data were available. Sample WC-B-B1 WC-B-B2 CO-B-A1 ME-CV-A1 ME-CV-A2* Blend1 WC-DAO-B2

ρso kg/m3 1076.9 1072.1 1064.4 979.6 985.6 1024.2 1043.8

c2 0.522 0.505 0.544 0.397 0.380 0.450 0.422

c3 x106 kPa-1 0.15 0.16 0.32

* second sample from ME-CO-A oil 12 ACS Paragon Plus Environment

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Results and Discussion Data Collected in This Study Viscosity and density data for the WC-B-B1 bitumen (B1 in legends) and its pseudo-binaries with ethane, propane, n-butane, n-pentane and n-heptane were measured in the capillary viscometer (CapVis) at temperatures from 21 to 175°C and pressures up to 10 MPa. The same device was used to measure the viscosity and density of bitumen WC-B-B2 (B2), its pseudo-binaries with neicosane, toluene, and cyclohexane, and its pseudo-ternary with heptol (a mixture of 50 wt% nheptane and 50 wt% toluene).

The viscosity of CO-B-A1 (B3), ME-CV-A1 (CV1) and Blend1 were measured in the cone and plate rheometer (C&P) at temperatures up to 100°C at atmospheric pressure. The cone and plate rheometer was also used to measure the viscosity of the pseudo-binaries CO-B-A1/toluene, MECV-A1/toluene, ME-CV-A1/1-methylnaphthalene (MN), WC-B-B2/1-methylnaphthalene, and the pseudo-ternaries of Blend1 (ME-CV-A1/WC-B-B2-DAO) with n-tetradecane and with 1methylnaphthalene. Those viscosities were measured at temperatures up to 50°C at atmospheric pressure; the temperature was kept below 50°C to avoid evaporation of solvent. Density was determined in the U-tube oscillating density meter at temperatures up to 50°C at atmospheric pressure. Viscosity and density of the pseudo-binary ME-CV-A2/n-pentane was measured in the capillary viscometer.

The maximum solvent content considered in this study was 50 wt%. Higher solvent contents were not examined because most of the viscosity reduction was observed to occur at solvent contents below 50 wt%. For some solvents, such as ethane, the maximum solvent content was set lower in order to avoid the onset of asphaltene precipitation.

Density and viscosity data for one multi-component hydrocarbon mixture (10 wt% n-pentane, 20 wt% n-heptane, 5 wt% n-octane, 6 wt% n-pentadecane, 29 wt% cyclohexane, and 30 wt% toluene) were also measured using the CapVis. All of the experimental data are tabulated in Appendix B.


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Development Dataset The samples in this study were divided into two groups: a development dataset from which the viscosity binary interaction parameter correlation was developed and a test dataset that was used to evaluate the proposed correlation. The test dataset included Western Canadian bitumen from one source reservoir (WC-B-B1 and WC-B-B2) with a variety of solvents and over a wide range of conditions, Table 3. The sample properties and asphaltene content were provided in Table 1, and their EF fluid-specific parameters in Table 2.

Viscosity and density data for 67 different pure hydrocarbon binaries (3850 data points) from the literature reported at 25°C and 0.1 MPa (Chevalier, et al., 1990; Al Gherwi, et al., 2006; Queimada, et al., 2003) were also included in the development dataset. These mixtures consisted of components from different chemical families including n-alkanes, branched alkanes, cyclic and aromatics, and spanned the entire range of composition.

Table 3. Samples, measurement method and conditions for the data measured in this study for the development dataset. MN stands for 1-methylnaphthalene. NP is number of data points. Mixture

Method

NP

B1/ethane B1/ propane B1/n-butane B1/n-pentane B1/n-heptane B1/toluene B2/n-eicosane B2/cyclohexane B2/MN

CapVis CapVis CapVis CapVis CapVis CapVis CapVis CapVis C&P

18 39 61 53 53 95 54 62 15

Temp. °C 20-175 20-175 20-175 20-175 20-175 20-175 20-175 20-175 10-50

Range of Conditions Pressure Solvent Content MPa wt% 0.1-10 5.2 0.1-10 7-16 0.1-10 7-15 0.1-10 15-30 0.1-10 15-30 0.1-10 5-50 0.1-10 5.8-25 0.1-10 5-40 0.1 5-50

Test Dataset The samples and conditions from this study that were included in the test dataset are presented in Table 4. This dataset included pseudo-binary mixtures of solvent with oils from two different geographic regions; a Colombian bitumen, CO-B-A1 (B3), and a Middle Eastern conventional oil, ME-CV-A1 (CV1). Three pseudo-ternary mixtures were also included, one with a single oil and 14 ACS Paragon Plus Environment

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Energy & Fuels

two solvents and the others with a blended oil and one solvent. Finally, three pseudo-binary mixtures prepared with the deasphalted oil (DAO) from WC-B-B2 (B2) were added to the dataset. The sample properties and asphaltene content of the original oils were provided in Table 1 and their EF fluid-specific parameters in Table 2.

Table 4. Samples, measurement method and conditions for the data measured in this study for the test dataset. MN stands for 1-methylnaphthalene and NP is the number of data points. Mixture Binary – Whole Oil B3/toluene B3/MN CV2/n-pentane CV1/toluene CV1/MN Ternary - Whole Oil B2/heptol Blend1/n-tetradecane Blend1/MN Binary - DAO B2-DAO/n-octane B2-DAO/n-dodecane B2-DAO/toluene

Range of Conditions Pressure Solvent Content MPa wt%

Method

NP

Temp. °C

C&P C&P CapVis C&P C&P

18 12 25 32 40

20-35 25-50 21-150 0-15 10-25

0.1 0.1 0.1-10 0.1 0.1

5-10 14.3 10 6-10 2-8

CapVis C&P C&P

94 28 28

20-175 0-50 0-50

0.1-10 0.1 0.1

5-39 1.8-5 5-8

C&P C&P C&P

15 16 30

20-40 25-50 20-50

0.1 0.1 0.1

12 5-18 2-10.2

Viscosity and density literature data (Al-Gherwi et. al., 2006; Baylaucq et al., 1997a, 1997b; Bonet et al., 2003; Canet et al., 2001; Dauge et al., 1999; Iloukhani and Rezaei-Sameti, 2005; Nhaesi and Asfour, 2005; Queimada et al., 2003; Silva et al., 2009; Wang et al., 2007 ) for 8 binaries, 8 multi-component hydrocarbon mixtures (with the number of components ranging between 3 and 6) were included in the test dataset (772 data points). These mixtures featured asymmetric components and included data at temperatures from 20 to 80°C and pressures up to 100 MPa. The six component hydrocarbon mixture measured in this study was added to this dataset.

Independent Dataset Viscosity and density data (a total of over 1500 data points) were compiled from the literature for 5 different diluted Western Canada bitumens (4 from the Athabasca region and 1 Cold Lake) and 15 ACS Paragon Plus Environment

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one diluted Canadian heavy oil (MacKay River), Table 5. The diluents included pure hydrocarbons such as n-pentane, n-hexane, n-decane, n-tetradecane, toluene and xylene. The dataset includes 9 pseudo-binaries and 2 pseudo-ternaries at temperatures from 20 to 200°C, pressures up to 10 MPa, and solvent contents up to 50 wt%. The pseudo-ternaries were prepared from McKay River bitumen diluted with two different n-hexane/toluene mixtures: Mixture1 (75 wt% n-hexane) and Mixture2 (25 wt% n-hexane).

Table 5. Samples and conditions for the independent dataset. Range of Conditions Mixture

NP

Athabasca 1/toluene Athabasca 1/xylene Athabasca 2/pentane Athabasca 3/decane Athabasca 4/tetradecane Cold Lake /toluene McKay River/hexane McKay River/decane McKay River/toluene McKay River/Mixture1 McKay River/Mixture2

Ref.

300

Temp. °C 25-71

Pressure MPa 0.1-10

Comp. %wt 5-50

Guan, 2013

300 28 300 300 30 140 145 145 67 70

25-71 50-200 25-71 25-71 25-100 25-71 25-71 25-71 25-71 25-71

0.1-10 1 0.1-10 0.1-10 0.1 1-10 1-10 1-10 1-10 1-10

5-50 5-10 5-50 5-50 1-10 5-35 35-50 5-50 5-50 5-50

Guan, 2013 Arguelles, 2012 Nourozieh, 2013 Kariznovi, 2013 Mehrotra, 1990 Khan, 2014 Khan, 2014 Khan, 2014 Khan, 2014 Khan, 2014

Determination of Binary Interaction Parameters The first step was to model the viscosity of all the mixtures presented in the development dataset to confirm that binary interaction parameters are required to fit the data and to determine their values. The mixture viscosities were calculated from the measured density and known pressure using the EF model with the mass-based mixing rules (Equations 5 to 7). Two approaches to calculating the mixture viscosity were evaluated: 1) ideal mixing rules, i.e. the viscosity binary interaction parameter was set to zero (αij=0), and; 2) non-ideal mixing rules, i.e. a non-zero viscosity binary interaction parameters was fitted to the mixture data. The former approach provides a baseline against which to compare the model performance with non-zero interaction parameters. The latter approach demonstrates the improvement in model accuracy when binary


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interaction parameters are used and provides the αij values that will be used to develop a binary interaction parameter correlation.

Ideal Mixing Rules Figures 2a and 2b show the measured and predicted viscosity for mixtures of pure hydrocarbons. Predictions calculated assuming ideal mixing have lower deviations for mixtures of hydrocarbons that belong to the same chemical family but it increases for components from different chemical families, as demonstrated in Figure 2 for the binaries n-octane/n-tetradecane and cyclohexane/toluene. In general, the absolute average relative deviation (AARD) and maximum absolute relative deviation (MARD) for the EF model predictions for pure hydrocarbons, calculated assuming ideal mixing, were 3% and 17%, respectively. A summary of the deviations of pure hydrocarbon pairs is presented in Table 6.

2.5

1.2 Exp. Data predicted - ideal fitted

1

Viscosity, mPa.s

2

Viscosity, mPa.s

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

1.5

1

0.5

0.8 0.6 0.4 Exp. Data predicted - ideal fitted

0.2

(a)

(b)

0

0 0

0.25 0.5 0.75 n-Octane Mass Fraction

1

0

0.2 0.4 0.6 0.8 Cyclohexane Mass Fraction

1

Figure 2. Experimental and predicted viscosities at 25°C and 0.1 MPa of pure hydrocarbon binaries: a) n-octane/n-tetradecane (Chevalier et al., 1990); b) cyclohexane/toluene (Silva et al., 2009).


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Table 6. Summary of the deviations of the calculated viscosities of pure hydrocarbon binaries in the development data set. NB is number of binaries. Binary

NB

Mixing Rules with Fitted αij

Ideal Mixing Rules (αij=0)

Mixing Rules with Correlated αij

AARD, %

MARD, %

AARD,%

MARD,%

AARD,%

MARD,%

Alkane/Alkane

16

0.4

4

0.7

6

1

7

Alkane/Branched

11

0.6

2

2

7

3

8

Aromatic/Aromatic

6

0.3

1

1

3

3

9

Aromatic/Alkane

10

0.9

2

6

17

4

15

Aromatic/Cyclic

5

0.5

1

5

10

2

6

Cyclic/Alkane

5

0.7

3

3

5

1

4

Figure 3a and 3b show experimental viscosity and predictions for WC-B-B1 and WC-B-B2 bitumen diluted with hydrocarbon solvents. In general, the deviations are highest for the lower carbon number solvents where the viscosity reduction is greatest. The deviations also increase as the solvent content increases and this trend is observed at all temperatures and pressures, as shown for toluene diluted bitumen in Figure 4. The higher deviations at higher solvent contents suggest that the ideal mixing rules do not accurately describe the mixtures. Similar results were obtained for the other mixtures and a summary of the deviations is presented in Table 7. The predictions are within an order of the magnitude of the measured values with overall AARD and MARD of 36% and 225%, respectively.


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1000 B2+C20 B1+C7 B1+C5 B1+C4 B1+C3 B1+C2 predicted - ideal

100

B1+C7 B1+TOL B2+CyC6 predicted - ideal

Viscosity, mPa.s

Viscosity, mPa.s

1000

10

100

10

(b)

(a) 1

1 0

0.1 0.2 0.3 Solvent Mass Fraction

0

0.4

0.2 0.4 Solvent Mass Fraction

0.6

Figure 3. Measured and predicted viscosities (αij = 0) of bitumens WC-B-B1 (B1) (closed symbols) and WC-B-B2 (B2) (open symbols) at 100°C and 5MPa diluted with: a) n-alkanes; b) n-heptane, cyclohexane (CyC6), and toluene (Tol).

100000

10000

B1 Tol 5 wt% Tol 25 wt% Tol 50 wt% Tol fitted-fluid predicted-mixture

1000

B1 Tol 5 wt% Tol 25 wt% Tol 50 wt% Tol fitted-fluid predicted-mixture

1000

Viscosity, mPa.s

10000

Viscosity, mPa.s

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

100

100 10

10

1

1

(b)

(a) 0.1 0

50

100 150 Temperature, °C

200

0.1 0

2

4 6 Pressure, MPa

8

10

Figure 4. Measured and predicted viscosities (αij = 0) of Bitumen WC-B-B1 (B1) diluted with toluene (Tol): a) at 5MPa; b) at 50°C.


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Table 7. Summary of the deviations of the calculated viscosities of diluted crude oils in the development dataset. Mixture

Mixing Rules with Fitted αij

B1/ethane B1/ propane B1/n-butane B1/n-pentane

αij -0.0520 -0.0460 -0.0160 -0.0154

AARD,% 12 19 12 9

MARD,% 32 52 54 24

B1/n-heptane B1/toluene B2/n-eicosane B2/cyclohexane B2/MN

-0.0037 +0.0211 +0.0193 +0.0077 +0.0213

10 8 11 12 0.5

47 30 34 27 1

Ideal Mixing Rules (αij=0) AARD,% MARD,% 20 48 43 76 21 63 21 44 14 33 38 17 103

52 125 126 41 225

Mixing Rules with Correlated αij αij

AARD,%

MARD,%

-0.0625 -0.0316 -0.0177 -0.0101

18 28 11 13

45 62 53 30

-0.0013 +0.0210 +0.0127 +0.0114 +0.0210

12 7 14 13 1

50 30 51 30 2

Non-Ideal Mixing Rules Since the ideal mixing rules did not accurately describe the mixture viscosities in all cases, the EF model was fit to the data using non-zero values for αij. To preserve the simplicity and generality of the correlation, the αij values were assumed to be independent of temperature, pressure, and composition for each pseudo-binary. The optimum values of αij for each component pair in the development group were calculated by minimizing the deviations of the EF predictions from the measured viscosity data of the binary or pseudo-binary mixtures.

Figure 2 shows that using binary interaction parameters improves the viscosity predictions for pure hydrocarbon mixtures, particularly for mixtures of species of different chemical family. The calculated αij values for the pure hydrocarbon mixtures in the development group as well as the average and maximum deviations for each pseudo-binary are summarized in Table 6. The use of binary interaction parameters reduced the overall AARD and MARD for pure hydrocarbons to 0.6% and 9%, respectively (compared with 3% and 17%, respectively, with αij=0).

Similarly, the use of binary interaction parameters improved the viscosity predictions for solvent diluted bitumen, Figures 5a and 5b. The improvement was observed at all temperatures (and pressures) as shown for toluene diluted bitumen in Figure 6. A single value of αij (+0.0221) for 20 ACS Paragon Plus Environment

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the pair bitumen WC-B-B1/toluene, independent of temperature, pressure and composition, was sufficient to fit all the experimental data with an AARD and MARD of 4% and 12%, respectively. A similar result was obtained for the other mixtures. The calculated αij values for the bitumen/solvent pseudo-pairs in the development group as well as the average and maximum deviations for each pseudo-binary are summarized in Table 7. The use of binary interaction parameters reduced the overall AARD and MARD for the diluted bitumens to 11% and 54%, respectively (compared with overall AARD and MARD of 34% and 225% with αij = 0). The maximum deviations were generally found at low temperature. Figures 4a and 6a show that, at low temperature, the viscosity changes significantly with small changes in temperature. The density of the fluid approaches the ρso value at lower temperatures; hence, small deviations in the input density can cause high deviations in the viscosity prediction at low temperature.

1000

1000

B2+C20

B1+C7

B1+C7

B1+TOL

B1+C5

B2+CyC6

B1+C4

fitted

B1+C3

100

B1+C2

Viscosity, mPa.s

Viscosity, mPa.s

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

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fitted

10

100

10

(a)

(b)

1

1 0


0.4

0

0.2 0.4 Solvent Mass Fraction

0.6

Figure 5. Measured and fitted viscosities (αij = 0) of bitumens B1 (closed symbols) and B2 (open symbols) at 100°C and 5MPa diluted with: a) n-alkanes; b) n-heptane, cyclohexane (CyC6), and toluene (Tol).


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100000

10000

B1 Tol 5 wt% Tol 25 wt% Tol 50 wt% Tol fitted-fluid fitted-mixture

1000

B1 Tol 5 wt% Tol 25 wt% Tol 50 wt% Tol fitted-fluid fitted-mixture

1000

Viscosity, mPa.s

10000

Viscosity, mPa.s

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

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100

100

10

10

1

1

(b)

(a) 0.1 0

50


200

0.1 0

2

4 6 Pressure, MPa

8

10

Figure 6. Measured and predicted viscosities (αij = +0.0221) of Bitumen B1 diluted with toluene (Tol): a) at 5MPa; b) at 100°C.

Generalization of Viscosity Binary Interaction Parameters The second step was to develop a generalized correlation for the viscosity binary interaction parameters based on the calculated αij values for the development dataset mixtures. Since viscosity can be correlated to density, it is plausible that there is some relationship between viscosity binary interaction parameters and density binary interaction parameters. Saryazdi et al. (2013) found that the binary interaction parameters for the density of mixtures of bitumen and solvent correlated to the normalized specific gravity defined as: ∆𝑆𝑆𝑆𝑆𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛 =

2�𝑆𝑆𝑆𝑆𝑖𝑖 −𝑆𝑆𝑆𝑆𝑗𝑗 � 𝑆𝑆𝑆𝑆𝑖𝑖 +𝑆𝑆𝑆𝑆𝑗𝑗

(10)

where SG is the specific gravity of the components “i” and “j”. Therefore, the αij values were plotted against the normalize difference of specific gravity of the paired components, Figure 7a.


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0.06

0.05

bitumen/alkane bitumen/aromatic bitumen/cyclic alkane/alkane alkane/branched aromatic/aromatic alkane/aromatic alkane/cyclic cyclic/aromatic αij°

0.04 0.02 0 -0.02

bitumen/alkane bitumen/aromatic bitumen/cyclic alkane/alkane alkane/branched aromatic/aromatic alkane/aromatic alkane/cyclic aromatic/cylic departure function

0.04 0.03 0.02

Δαij

Binary Interaction Parameter, αij

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

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0.01

-0.04

0

-0.06 -0.08

-0.01

(a)

(b)

-0.1 0

0.2

0.4

0.8 0.6 ΔSGnorm

1

1.2

-0.02 0

0.2

0.4 0.6 Δ(H/C)norm

0.8

1

Figure 7. (a) Viscosity binary interaction parameter, αij, versus ΔSGnorm. Solid and open symbols corresponds to pseudo-binaries bitumen WC-B-B1(B2)/solvent or pure hydrocarbon pairs respectively. (b) Departure term, Δαij, versus Δ(H/C)norm for the pseudo-binaries and binaries in the developing data set.

Figure 7a provides two notable observations: 1) the bitumen/solvent αij are constant below ΔSGnorm= 0.165 and decrease linearly above this value, and; 2) the pure hydrocarbon αij appear to cluster according to differences in chemical family. These observations suggest that the viscosity binary interaction parameters can be determined from a reference function to ΔSGnorm and a departure function that accounts for the differences in chemical family: 𝑜𝑜 𝛼𝛼𝑖𝑖𝑖𝑖 = 𝛼𝛼𝑖𝑖𝑖𝑖 − Δ𝛼𝛼𝑖𝑖𝑖𝑖

(12)

where αijo is the reference value and ∆αij is the departure function. The bitumen/solvent trend was selected as a reference function and the bitumen/solvent data of Figure 7a were fitted to obtain the following expression: ΔSGnorm ≤ 0.165: ΔSGnorm > 0.165:

𝑜𝑜 𝛼𝛼𝑖𝑖𝑖𝑖 = 0.021 𝑜𝑜 𝛼𝛼𝑖𝑖𝑖𝑖 = 0.038304 − 0.10478Δ𝑆𝑆𝑆𝑆𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛

(13) (14)

Figure 7b shows that the departure from the reference function (the difference between the fitted binary interaction parameter and the reference value, ∆αij) correlates to the normalized difference in hydrogen-to-carbon ratio of the paired components defined as:


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Δ(𝐻𝐻 ⁄𝐶𝐶 )𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛 =

2�(𝐻𝐻⁄𝐶𝐶 )𝑖𝑖 −(𝐻𝐻⁄𝐶𝐶 )𝑗𝑗 � (𝐻𝐻⁄𝐶𝐶 )𝑖𝑖 +(𝐻𝐻⁄𝐶𝐶 )𝑗𝑗

Page 24 of 56

(15)

where (H/C) is the hydrogen to carbon ratio of components “i” and “j”. The data in Figure 7b were fitted to obtain the following expression for the departure function: Δ(H/C)norm ≤ 0.25: Δ(H/C)norm > 0.25: where αii = αjj = 0.

Δ𝛼𝛼𝑖𝑖𝑖𝑖 = 0.02756 − 0.1103Δ(𝐻𝐻 ⁄𝐶𝐶 )𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛 Δ𝛼𝛼𝑖𝑖𝑖𝑖 = 0

(16) (17)

The viscosity binary interaction parameter for each pair in the development dataset was calculated using Equations 12 to 17 and then used to calculate the mixture viscosities. The correlated αij values for the bitumen/solvent pseudo-pairs in the development group as well as the average and maximum deviations for each pseudo-binary are summarized in Table 7. The overall AARD and MARD for the pure hydrocarbon binaries were only reduced slightly to 2.4% and 15%, respectively (compared with 3% and 17%, respectively, with αij=0). However, the overall AARD and MARD for the bitumen/solvent pseudo-binaries were reduced significantly to 13% and 62%, respectively (compared with overall AARD and MARD of 34% and 225% with αij = 0). The improvement in accuracy with the generalized correlation was only slightly less than that obtained using fitted values (overall AARD and MARD of 12% and 136% with fitted αij). Assessment of the Binary Interaction Parameter Correlation- Test Dataset The validity of the proposed correlation for αij was assessed against the test dataset which included independent data for hydrocarbon mixtures, diluted crude oils, and diluted deasphalted oils. The viscosity predictions with the correlated and zero αij are compared for each type of mixture below. Hydrocarbon Mixtures The correlated αij and deviations of the viscosity predictions for the hydrocarbon mixtures in the test dataset are listed in Table 8. For binaries, the overall AARD and MARD were of 4% and 16%, respectively, when correlated αij were used compared with 6% and 21% respectively when αij was set to zero. The results demonstrate that a single correlated value of αij is sufficient to reasonably predict the viscosity of the mixtures regardless temperature, pressure, and composition, Figure 8. The improvement was more significant for the more asymmetric mixtures, Figure 8a. 24 ACS Paragon Plus Environment

Page 25 of 56

For multi-component hydrocarbon mixtures, the overall AARD and MARD were 3.7% and 12%, respectively, for viscosity predictions calculated using correlated αij values compared with 4.3% and 22%, respectively, with ideal mixing rules. Binary pair interactions alone were sufficient to predict the viscosity of multi-component mixtures at any temperature, pressure, or composition, Figure 8b.

10

0.7

Viscosity, mPa.s

x1=0.125, T=30°C x1=0.500, T=40°C x1=0.875, T=80°C prediction αij = 0 prediction αij ≠ 0

8

Viscosity, mPa.s

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

6

4

P=10MPa prediction αij=0 prediction αij≠0

0.6

0.5

0.4

2

(b)

(a)

0.3

0 0

20 40 Pressure, MPa

60

20


80

Figure 8. (a) Viscosity versus pressure of the binary (1) 1-methylnaphthalene/(2) 2,2,4,4,6,8,8heptamethylnonane (Canet et al., 2001). (b) Viscosity versus temperature of the mixture pentane(10.5wt%)/heptane(20wt%)/octane(5wt%)/pentadecane(3.5wt%)/cyclohexane(29wt%)/ toluene (29wt%) (this study).


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Table 8. Summary of the deviations of the calculated viscosities for the pure hydrocarbon mixtures in the test dataset. EtBz, HMN, MCyC6, HBz and CyC6 stand for ethylbenzene, 2,2,4,4,6,8,8heptamethylnonane, mehtylcyclohexane, heptylbenzene and cyclohexane respectively. Ideal Mixing Rules (αij=0) AARD, MARD, % %

Mixture Binary C7/C24 Tol/C5 EtBz/C8 EtBz/CyC6 C7/MN CyC6/Decalin MN/C13 MN/HMN Multicomponent C8/C9/HBz C7/MCyC6/MN Tol/C8/EtBz/C14 Tol/C8/EtBz/C16 Tol/EtBz/C14/C16 C8/EtBz/C14/C16 Tol/C8/C14/C16 C13/HMN/MCyC6/HBz/MN C5/C7/C8/C15/CyC6/Tol

Mixing Rules with Correlated αij AARD, MARD, % %

8 10 2 4 0.5 1 7 11

11 18 4 8 1 3 13 21

8 9 2 3 0.8 4 1 4

10 16 4 6 3 6 3 10

4 2 5 1 4 3 1 13 5

6 7 16 6 8 10 6 23 12

6 1 3 4 4 4 2 5 3

8 7 7 8 8 12 5 10 7

Diluted Crude Oils First consider the pseudo-binary test data from this study, which are summarized in Table 4. The two crude oils in this dataset (CO-B-A1 from Colombia and ME-CV-A1 from the Middle East) are from different geographical locations than the Western Canadian bitumen (WC-B-B2) used to develop the αij correlation and have significantly different density and viscosity, Table 1. Figure 9a shows that using the αij correlation improves the accuracy of the predicted viscosity for both oils despite the difference in their properties and asphaltene content. The improvement was observed for all three solvents considered (n-heptane results are not shown on the figure because the data are very similar to the toluene data). Figure 9b shows that the predictions are improved over the full range of temperatures and pressures considered. A summary of the deviations is 26 ACS Paragon Plus Environment

Page 27 of 56

presented in Table 9. The overall AARD and MARD were 10% and 32%, respectively, with correlated αij compared with 57% and 282%, respectively, with ideal mixing rules.

Note, the properties of the sample ME-CV-A2 (CV2) used to prepare the pseudo-binary with npentane were slightly different from the ME-CV-A1 sample used previously, see Table 2. Its viscosity was only measured at atmospheric pressure and therefore the parameter c3 could not be determined from the data and was instead calculated from a correlation developed by Motahhari (2013): 2.8∗10−7

𝑐𝑐3 = 1+3.23𝑒𝑒𝑒𝑒𝑒𝑒(−1.54∗10−2 𝑀𝑀𝑀𝑀)

(17)

where c3 is in kPa-1 and MW is the molecular weight. The molecular weight of the ME-CV-A2 crude oil was 475 g/mol (Powers, 2014) and c3=2.8 10-7 kPa-1.

4

100000

T=50°C T=125°C T=150°C prediction, αij = 0 prediction, αij ≠ 0

10000

Viscosity, mPa.s

3

Viscosity, mPa.s

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

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1000

100 B3+MN 14.3wt% B3+Tol 9.6wt% CV1+MN 2.0wt% CV1+Tol 9.8wt% prediction, αij = 0 prediction, αij ≠ 0

10

(a)

2

1

(b)

1

0 0

20


80

0

2

4 6 Pressure, MPa

8

10

Figure 9. (a) Viscosity versus temperature at 0.1 MPa for CO-B-A1 (B3 in legend) and ME-CVA1 (CV1 in legend) diluted with toluene (Tol) and 1-methylnaphthalene (NM). (b) Viscosity versus pressure for the mixture of 90 wt% ME-CV-A2 and 10 wt% n-pentane.


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Table 9. Summary of deviations of calculated viscosities of diluted crude oils in the testing group. Ideal Mixing Rules (αij =0) AARD,% MARD,%

Mixture

Mixing Rules with Correlated αij AARD,% MARD,%

Binaries B3/toluene B3/MN CV2/n-pentane

76 200 4

117 282 9

10 24 3

26 32 6

CV1/toluene

22

18

5

13

CV1/MN

31

47

13

30

Blend1 Ternaries B2/heptol Blend1/n-tetradecane Blend1/MN

10

36

7

16

18 30 56

146 66 103

10 11 9

68 25 20

Viscosity and density data for three pseudo-ternary mixtures was collected at the conditions shown in Table 4. Recall that heptol is an equimass mixture of n-heptane and toluene and that Blend 1 is a mixture of 30 wt% ME-CV-A1 with 70 wt% deasphalted WC-B-B2. Figure 10a shows the measured and modeled viscosity for ternaries made from heptol. Figure 10b shows the measured and modeled viscosity for Blend1 and a pseudo-ternary made from Blend1. A summary of the deviations is provided in Table 9. The overall AARD and MARD for Blend1 were 7 and 16%, respectively, with correlated αij values compared with 10 and 36%, respectively, for αij set to zero. The overall AARD and MARD for the ternaries were 10 and 68%, respectively, with correlated αij values and 35 and 146%, respectively, for αij set to zero. While the use of correlated αij improve the viscosity predictions, the MARD is still quite high. The high MARD occurs at 20°C where the data are least reliable and the assumption of Newtonian behavior in the bitumen may begin to break down.


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10000

1000000

10000

Viscosity, mPa.s

B2 fitted Heptol 5wt% Heptol 25wt% Heptol 40wt% prediction, αij ≠ 0 prediction, αij = 0

100000

Viscosity, mPa.s

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

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1000 100

1000

100 Blend 1 Blend 1/MN 5wt% prediction, αij = 0 prediction, αij ≠ 0

10

(b)

(a) 1

10

0

50


200

0

10


40

50

Figure 10. Viscosity versus temperature of: a) WC-B-B2 (B2) diluted with heptol (50 wt% heptane and 50 wt% toluene) at 10 MPa; b) Blend 1 and Blend 1/1-methylnaphthalene (MN) 5 wt% at 0.1 MPa.

Deasphalted Oil/Solvent Mixtures Deasphalted bitumen has significantly lower density and viscosity than the source bitumen (Table 1) and therefore provides a test of the robustness of the correlation. Also, a comparison of deasphalted versus whole bitumen viscosity allows us to evaluate if the contribution of asphaltenes, which self-associate, alters the EF and αij correlations. For example, at low temperatures, asphaltenes are known to contribute to non-Newtonian behavior (Abivin et al., 2012, Bazyleva et al., 2010) and the EF correlation would no longer apply. It is possible that the previous fitting to diluted bitumen data was skewed. If so, the correlation would deviate for oils with little or no asphaltenes. On the other hand, if the EF correlation with the proposed interaction parameter correlation can be used to predict the viscosity of mixtures with deasphalted bitumen, then it suggests that the contributions from asphaltene association/structure formation can be neglected over the temperatures considered in this study (that is, at temperatures above the expected range of non-Newtonian behavior).

The viscosity of mixtures of deasphalted WC-B-B2 bitumen with n-octane, n-dodecane and toluene are shown in Figure 11. The EF fluid specific parameters of deasphalted bitumen were 29 ACS Paragon Plus Environment

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determined by fitting the correlation to the undiluted deasphalted bitumen data. Then, the viscosity of the mixtures was predicted with the binary interaction parameters set to zero and with the correlated binary interaction parameters, Figure 11. The average and maximum deviations are summarized in Table 10. In general, using the correlated interaction parameters improves the viscosity prediction (overall AARD and MARD of 7% and 30%, respectively) compared with no interaction parameters (overall AARD and MARD of 12% and 40% respectively). The EF correlation provides similar quality predictions for the deasphalted oil mixtures as for the whole bitumen mixtures. Hence, it appears that any structural contributions of the asphaltenes to the viscosity can be neglected at temperatures above 21°C for bitumens and lighter oils, where nonNewtonian behavior is neglible. 10000

10000

B2-DAO fitted 1wt% Tol 5wt% C12 12wt% C8 prediction, αij=0 prediction, αij≠0

Tol C12 prediction, αij=0 prediction, αij≠0

Viscosity, mPa.s

Viscosity, mPa.s

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

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1000

1000

(b)

(a) 100

100

20

30


60

0


0.2

Figure 11. Effect of temperature (a) and dilution at 25°C (b) on the viscosity of deasphalted bitumen WC-B-B2 (B2-DAO in legends) diluted with n-octane (C8), n-dodecane (C12) and toluene (Tol) at 0.1 MPa. Table 10. Summary of deviations of calculated viscosities for dilute deasphalted bitumen WC-BB2 (B2-DAO).

Mixture

Ideal Mixing Rules

Mixing Rules with

(αij =0)

Correlated αij

NP

AARD,%

MARD,%

αij

AARD,%

MARD,%

B2-DAO/octane

15

5

11

+0.0038

5

13

B2-DAO/dodecane B2-DAO/toluene

25 30

17 13

37 40

+0.0107 +0.0210

3 12

6 30


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Assessment of the Binary Interaction Parameter Correlation - Independent Dataset The validity of the proposed correlation for the viscosity binary interaction parameters was also assessed against the viscosity data of diluted bitumens from the literature. A total of over 1500 data points were compiled from different diluted Western Canada bitumens and one diluted Canadian heavy oil for a variety of diluents and conditions, Table 6. The calculated EF fluidspecific parameters for the bitumens as well as some of their physical properties are shown in Table 11. The parameter c3 was only calculated when high pressure data was available. Recall that the inputs to calculate αij values are the specific gravity and hydrogen-to-carbon ratio of the mixture components. When the value of the hydrogen-to-carbon ratio was not known, it was calculated using the relation found by Sanchez (2015): (𝐻𝐻 ⁄ 𝐶𝐶)𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏𝑏 = 3.4388 − 1.9327𝑆𝑆𝑆𝑆

(18)

where (H/C)bitumen and SG are the bitumen hydrogen-to-carbon atomic ratio and specific gravity respectively.

Table 11. Physical properties and EF parameters for the bitumens in the independent data set. Calculated (H/C) ratios inside parenthesis. Crude Oil

SG

H/C Ratio

Athabasca 1

1.010

Athabasca 2

1.015

Athabasca 3 Athabasca 4

1.009 1.010

Cold Lake

1.000

McKay River

1.008

(1.49) 1.50 (1.48) (1.49) (1.49) 1.59 (1.51) (1.49)

ρso

c3

Viscosity at 25°C, mPa.s 185000

kg/m³ 1060.4

0.5075

x10 kPa-1 0.24

540000

1062.5

0.5168

-

125000 184000

1062.1 1060.2

0.5070 0.5064

0.24 0.21

54500

1055.9

0.5100

-

87000

1065.0

0.5290

0.1

c2

-6

The independent dataset was modeling using both non-ideal mixing rules and mixing rules with correlated binary interaction parameters (Equations 12-17). A summary of the deviations is presented in Table 12. As expected, the use of correlated interaction parameters improved the viscosity prediction (overall AARD and MARD of 14 and 73%, respectively) compared with no interaction parameters (overall AARD and MARD of 30 and 200% respectively). As with the test dataset, the maximum deviations were found at room temperature where the potential error in the data is highest and the fluid may exhibit non-Newtonian behavior (Bazileva et al., 2010). 31 ACS Paragon Plus Environment

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Table 12. Summary of deviations of viscosity predictions for diluted bitumens from the independent dataset. Ideal Mixing Rules

Mixing Rules with

(αij =0)

Correlated αij

Mixture Athabasca 1/toluene Athabasca 1/xylene Athabasca 2/pentane Athabasca 3/decane Athabasca 4/tetradecane Cold Lake /toluene McKay River/hexane McKay River/decane McKay River/toluene McKay River/Mixture1 McKay River/Mixture2

AARD,% 43

MARD,% 60

AARD,% 6

MARD,% 16

33 17 8 24 17 19 22 68 17 34

50 37 35 48 53 37 48 200 34 74

10 12 9 9 10 16 24 37 16 19

22 26 38 32 25 25 53 73 28 38

Finally, the viscosity model was tested on the pseudo-ternary bitumen/solvent/solvent mixtures, Figure 12. Both zero and correlated αij values predict the viscosity of the pseudo-ternary with similar accuracy. This result is not surprising considering that Mixture 1 is composed by 75 wt% of n-hexane and the correlated interaction parameter between this component and the McKay River bitumen has a numerical value of -0.0047 which is too small to significantly alter the viscosity predicted with ideal mixing. The other correlated interaction parameters for the pairs McKay River bitumen/toluene and n-hexane/toluene are +0.021 and +0.0098, respectively. Therefore, it is expected that as the mass composition of toluene in the mixture increases, the deviation from ideal behaviour also increases as can be seen in Figure 12b with Mixture 2 (25 wt% n-hexane). Using the correlated interaction parameters again improved the viscosity prediction (overall AARD and MARD of 18 and 40%, respectively) compared with no interaction parameters (overall AARD and MARD of 25 and 74% respectively). A summary of the deviations is presented in Table 12.


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1000000

1000000

Mixture 1, 5wt% Mixture 1, 10wt% Mixture 1, 50wt% prediction, αij=0 prediction, αij≠0

100000

Mixture 2, 5wt% Mixture 2, 10wt% Mixture 2, 50wt% prediction, αij=0 prediction, αij≠0

100000 10000

Viscosity, mPa.s

10000

Viscosity, mPa.s

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

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1000 100

1000 100 10

10 1

1

(a)

(b)

0.1

0.1 20


80

20


80

Figure 12. Effect of temperature and solvent content on the viscosity of dilute Mc Kay River bitumen (Khan et al. 2014): a) diluent: Mixture 1, n-hexane/toluene (75% wt n-hexane) at 3MPa; b) diluent: Mixture 2, n-hexane/toluene (25% wt n-hexane) at 10MPa.

Conclusions The binary interaction parameter for the EF model mixing rules, αij, was found to be independent of temperature, pressure, and solvent content. In addition, binary interaction parameters were found to be sufficient to model the viscosity of multi-component mixtures.

The viscosity binary interaction parameter was correlated to the specific gravity and hydrogen-tocarbon ratio of paired components. The correlation was developed from a dataset of the density and viscosity of pure hydrocarbon binaries from the literature and pseudo-binaries of bitumen and solvent from this study. The data for the bitumen/solvent pseudo-binaries were collected at temperatures from 21 to 175°C, pressures up to 10 MPa, and solvent contents up to 50 wt%. Paraffinic, cyclic and aromatic solvents were included.

The proposed correlation was assessed on a test dataset which included pure hydrocarbon binaries and multi-component mixtures from the literature, as well as bitumen/solvent pseudo-binaries and pseudo-ternaries, and deasphalted bitumen/solvent pseudo-binaries from this study. The data for 33 ACS Paragon Plus Environment

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pure hydrocarbon mixtures were reported at temperatures from 20 to 80°C and pressures up 100 MPa over the entire range of composition. The data for the bitumen/solvent mixtures were collected at temperatures from 20 to 175°C, pressures up to 10 MPa, and solvent contents up to 40 wt%. The proposed correlation was also assessed on an independent dataset from the literature which included Western Canada bitumens diluted with paraffinic and aromatic solvents. These data were reported at temperatures from 20 to 200°C, pressures up to 10 MPa, and solvent contents up to 50 wt%. Table 13 compares the AARD and MARD of the viscosities calculated with fitted αij and predicted with αij set to zero (ideal mixing rule) and with correlated αij. The use of correlated αij provides a modest improvement over the ideal mixing rules for the prediction of the viscosity of hydrocarbon mixtures and a significant improvement for diluted bitumens. The deviations obtained with the correlated αij are almost as low as those obtained with the fitted αij. Table 13. Comparison of deviations of viscosity predictions for development, test, and independent datasets. Dataset Development – Hydrocarbons Development – Diluted Oils Test – Hydrocarbons Test – Diluted Oils Independent – Diluted Oils

Mixing Rules with Fitted αij AARD,% MARD,% 0.6 9 11 54 1.5 12 6 22 13 48

Ideal Mixing Rules (αij=0) AARD,% MARD,% 3 17 36 225 5 23 50 282 30 200

Mixing Rules with Correlated αij AARD,% MARD,% 2.4 13 3.7 10 14

15 62 16 68 73

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Nhaesi, A.; Asfour, A. Densities and Viscosities of the Regular Quinary System: Toluene (1) + Octane (2) + Ethylbenzene (3) + Tetradecane (4) + Hexadecane (5) and Its Quaternary Subsystems at (308.15 and 313.15) K. J. Chem. Eng. Data. 2005, 50, 149-153. Nourozieh, H., Kariznovi, M., Guo Guan, J., Abedi, J. Measuring of Thermophysical Properties and Modeling of Pseudo-Binary Mixtures of n-Decane and Athabasca Bitumen. Fluid Phase Equilib. 2013, 347, 62-75. Oldenburg, T. B. P., Yarranton, H. and Larter, S. R. 2010. The Effect of Low Molecular Weight. 2010 Canadian Unconventional Resources and International Petroleum Conference. Calgary, Alberta, Canada. Pedersen K. S., Fredenslund, A. An improved Corresponding States Model for the Prediction of Oil and Gas viscosities and Thermal Conductivities. Chem. Eng. Sci. 1987, 42, 182-186. Poling, B. E., Prausnitz, J. M., O’Conell, J. P. The Properties of Gases and Liquids. 5th ed.; New York, 2000. Powers, D. P. Characterization and Asphaltene Precipitation Modeling of Native and Reacted Crude Oils. Ph. D. Thesis University of Calgary, Calgary, Canada, 2014. Queimada, A.J.; Quinonez-Cisneros, S.E.; Marrucho, I.M.; Coutinho, J.A.P.; Stenby, E.H. Viscosity and Liquid Density of Asymmetric Hydrocarbon Mixtures. Int. J. Thermophys. 2003, 24, 1221-1239. Quinonez-Cisneros, S. E., Zeberg-Mikkelsen, C. K., Stenby, E. H. Friction Theory (F-Theory) for Viscosity Modeling. Fluid Phase Equilib. 2000, 169 (2), 249-276. Sanchez, M. C. Personal Communication, University of Calgary, Calgary, Alberta, Canada, March 2015. Saryazdy, F., Motahhari, H., Schoeggl, F., Taylor, S. D., Yarranton, H. W. Density of Hydrocarbon Mixtures and Bitumen Diluted with Solvents and Dissolved Gases.. Energy and Fuels. 2013, 27, 3666-3678. Shu, W. R. A Viscosity Correlation for Mixtures of Heavy Oil, Bitumen and Petroleum Fractions. SPE J. 1984, 24, 277-282. SPE-11280-PA. Silva, A.; Reis, R. A.; Paredes, M. L. L. Density and Viscosity of Decaline and Toluene Binary Mixtures at (283.15, 293.15, 303.15, 313.15, 323.15) K. J. Chem. Eng. Data. 2009, 54, 2067-2072. Vogel, H. Temperature Dependence of Viscosity of Melts. Phys. Z. 1921, 22, 645-646. Walther, C. The Evaluation of Viscosity Data. Erdol und Teer. 1931, 7, 382-384.


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Wang, Z.; Wang, L., Fan, T. Densities and Viscosities of Ternary Mixtures of Heptane, Octane, Nonane and Hexyl benzene from 293.15K to 313.15K. J. Chem. Eng. Data. 2007, 52, 1866-1871. Wilke, C. R.. A Viscosity Equation for Gas Mixtures. J Chem Phys. 1950, 18, 517-519. Yarranton, H., Satyro, M. Expanded Fluid-Based Viscosity Correlation for Hydrocarbons Ind. Eng. Chem. Res. 2009, 48, 3640-3648. Yarranton, H., van Dorp, J., Verlaan, M., Lastovka, V. Wanted Dead or Live: Crude Cocktail Viscosity-A Pseudo-Component Method to Predict the Viscosity of Dead Oils, Live Oils and Mixtures. J. Can. Pet. Techol. 2013, 52, 176-191. Yaws, C.L. Transport Properties of Hydrocarbons. William Andrew Inc. Norwich, NY, 2008.


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Energy & Fuels

Appendix A: Expanded Fluid Parameters of Pure Hydrocarbons Used in this Study

Compound ethane propane butane pentane heptane octane decane dodecane tridecane tetradecane pentadecane hexadecane eicosane tetracosane cyclohexane methylcyclohexane decaline 2,2,4,4,6,8,8heptamethylnonane toluene p-xylene o-xylene ethylbenzene hexylbenzene 1-methylnaphthalene

ρso kg/m³ 724.0 778.0 813.0 837.0 857.8 862.7 868.1 871.4 877.8 875.5 878.4 878.6 885.5 893.2 922.1 937.9 1010.0

0.1560 0.1740 0.1900 0.1980 0.2130 0.2210 0.2360 0.2490 0.2538 0.2650 0.2698 0.2780 0.3060 0.3350 0.2370 0.2505 0.2700

c3 x106 kPa-1 0.01 0.10 0.15 0.18 0.17 0.17 0.20 0.22 0.23 0.24 0.27 0.28 0.29 0.29 0.16 0.15 0.09

856.8

0.1921

0.25

1049.6 1045.5 1052.9 1042.4 975.2 1138.0

0.2155 0.2260 0.2320 0.2222 0.2159 0.2250

0.14 0.14 0.14 0.14 0.21 0.14

c2


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Appendix B: Density and Viscosity Data Collected in this Study Table B1. Density and viscosity of WC-B-B1 bitumen measured in a capillary viscometer (Motahhari, 2013). Temp. °C

Pressure MPa

Density kg/m³

Viscosity mPa.s

19.6 19.6 19.6 19.6 19.6 50.3 50.3 50.3 50.3 50.3 75.0 75.0 75.0 75.0 75.0 100.0 100.0 100.0 100.0 100.0 125.0 125.0 125.0 125.0 125.0 150.0 150.0 150.0 150.0 175.0 175.0 175.0 175.0

0.1 2.5 5.0 7.5 10 0.1 2.5 5.0 7.5 10 0.1 2.5 5.0 7.5 10 0.1 2.5 5.0 7.5 10 0.1 2.5 5.0 7.5 10 2.5 5.0 7.5 10 2.5 5.0 7.5 10

1013.3 1014.6 1015.7 1017.2 1018.7 992.8 994.0 995.5 996.9 998.2 976.1 977.6 979.1 980.6 981.9 959.4 961.3 962.8 964.4 966.0 940.5 942.7 944.5 946.2 948.1 925.1 927.4 929.2 931.0 907.0 909.1 911.4 913.4

70400 77800 88500 101000 114000 2800 2950 3260 3490 3770 385 443 496 562 624 112 120 127 136 141 37.1 40.0 44.5 46.6 51.0 20.2 21.2 21.9 22.9 10.6 11.0 11.4 12.1


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Table B2. Density and viscosity of WC-B-B2 bitumen measured in a capillary viscometer. Temp. °C 19.4 19.5 19.4 19.4 19.4 35.0 35.0 35.0 35.0 35.0 50.0 50.0 50.0 50.0 50.0 75.0 75.0 75.0 75.0 75.0 100.0 100.0 100.0 100.0 100.0 125.0 125.0 125.0 125.0 125.0 150.0 150.0 150.0 150.0 150.0 175.0 175.0 175.0 175.0

Pressure MPa 0.1 2.5 5.0 7.5 10 0.1 2.5 5.0 7.5 10 0.1 2.5 5.0 7.5 10 0.1 2.5 5.0 7.5 10 0.1 2.5 5.0 7.5 10 0.1 2.5 5.0 7.5 10 0.1 2.5 5.0 7.5 10 2.5 5.0 7.5 10

Density kg/m³ 1013.9 1014.9 1016.0 1017.4 1018.9 1003.8 1004.7 1005.9 1007.4 1008.9 994.2 995.3 996.7 998.2 999.5 978.3 979.7 981.3 982.7 984.3 962.9 964.5 966.2 967.9 969.5 945.7 947.6 949.5 951.1 953.1 929.2 931.3 933.4 935.4 937.3 915.5 917.8 920.2 922.2

Viscosity mPa.s 212600 249000 285000 330000 381000 31400 35500 39400 43700 48200 6980 7570 8310 9100 10000 1100 1190 1280 1380 1450 289 308 327 348 370 109 116 121 128 135 52.3 54.4 57.1 59.9 62.6 30.9 32.3 33.6 34.9


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Table B3. Density and viscosity of WC-B-B1 bitumen diluted with 5.2 wt% ethane and measured in a capillary viscometer (Motahhari, 2013). Temp. °C 20 20 20 20 50 50 50 50 75 75 75 75 100 100 100 125 125 150

Pressure MPa 2.5 5.0 7.5 10 3.0 5.0 7.5 10 4.0 5.0 7.5 10 5.0 7.5 10 7.5 10 10

Density kg/m³ 956.2 957.6 959.3 961.0 935.6 937.0 938.8 940.5 918.4 919.2 921.0 922.9 901.0 903.2 905.4 884.7 887.2 869.6

Viscosity mPa.s 681 723 762 810 108 113 119 125 37.2 37.8 39.6 41.3 16.8 17.5 18.1 9.4 9.7 6.0


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Energy & Fuels

Table B4. Density and viscosity of WC-B-B1 bitumen diluted with propane and measured in a capillary viscometer (Motahhari, 2013). Temp. °C

Pressure MPa

19/20 19/20 19/20 19/20 50 50 50 50 75 75 75 75 100 100 100 125 125 125 150 150 175

2.5 5.0 7.5 10 2.5 5.0 7.5 10 2.5 5.0 7.5 10 5.0 7.5 10 5.0 7.5 10 7.5 10 10

8.0 wt% Propane Density Viscosity kg/m³ mPa.s 956.9 1030 958.2 1100 959.9 1180 961.8 1260 934.8 133 936.6 140 938.3 149 940.0 158 916.8 41.5 918.8 43.6 920.6 46.2 922.5 48.7 901.8 19.1 903.9 19.8 906.1 20.7 883.5 10.1 885.7 10.5 888.2 10.8 868.4 6.3 870.9 6.5 853.7 4.3

16 wt% Propane Density Viscosity kg/m³ mPa.s 897.3 76.3 898.9 79.5 900.8 83.2 903.0 86.9 873.3 19.3 875.4 20.2 877.5 21.0 879.7 22.1 853.6 9.0 856.0 9.3 858.4 9.6 860.6 10.0 836.4 5.0 839.2 5.2 842.0 5.4 819.3 3.3 822.7 3.4 799.0 2.2 802.8 2.3 -


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Table B5. Density and viscosity of WC-B-B1 bitumen diluted with 15 wt% n-butane and measured in a capillary viscometer (Motahhari, 2013). Temp. °C 20 20 20 20 50 50 50 50 75 75 75 75 100 100 100 100 125 125 125 125 150 150 150 150 175 175 175 175

Pressure MPa 2.5 5.0 7.5 10 2.5 5.0 7.5 10 2.5 5.0 7.5 10 2.5 5.0 7.5 10 2.5 5.0 7.5 10 2.5 5.0 7.5 10 2.5 5.0 7.5 10

Density kg/m³ 925.8 927.3 928.6 931.0 904.0 905.7 907.6 909.6 885.4 887.6 889.8 891.8 867.2 869.4 871.7 874.1 848.4 851.0 853.6 856.2 829.3 832.6 835.6 838.3 810.5 814.1 817.6 820.7

Viscosity mPa.s 145 151 157 167 33.6 35.1 36.3 37.9 14.3 14.8 15.5 16.0 7.5 7.7 8.0 8.3 4.5 4.7 4.9 5.0 3.0 3.1 3.2 3.3 2.1 2.2 2.3 2.4


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Table B6. Density and viscosity of WC-B-B1 bitumen diluted with n-pentane and measured in a capillary viscometer (Motahhari, 2013). Temp. °C

Pressure MPa

20 20 20 20 20 50 50 50 50 75 75 75 75 100 100 100 100 125 125 125 125 150 150 150 150 175 175 175 175

0.1 2.5 5.0 7.5 10 2.5 5.0 7.5 10 2.5 5.0 7.5 10 2.5 5.0 7.5 10 2.5 5.0 7.5 10 2.5 5.0 7.5 10 2.5 5.0 7.5 10

15 wt% n-Pentane Density Viscosity kg/m³ mPa.s 936.1 216 937.5 224 938.9 238 940.4 247 942.4 263 917.2 48.6 918.8 51.8 920.5 54.9 922.3 59.1 899.4 20.0 901.3 20.8 903.1 21.8 905.0 22.6 881.3 9.6 883.3 9.9 885.4 10.4 887.6 10.8 863.3 5.7 865.7 5.9 868.2 6.1 870.5 6.3 844.9 3.7 847.6 3.8 850.3 4.0 852.9 4.1 826.2 2.6 829.5 2.7 832.6 2.8 835.6 2.9

30 wt% n-Pentane Density Viscosity kg/m³ mPa.s 868.2 20.6 870.1 21.9 871.8 22.5 873.4 23.4 875.8 24.2 847.5 7.9 849.6 8.2 851.6 8.5 853.8 8.8 827.8 4.3 830.2 4.4 832.4 4.6 834.7 4.7 808.0 2.7 810.6 2.7 813.1 2.8 816.1 2.9 788.0 1.8 791.3 1.9 794.2 1.9 797.5 2.0 767.2 1.3 771.2 1.4 774.7 1.4 778.3 1.5 -


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Table B7. Density and viscosity of WC-B-B1 bitumen diluted with n-heptane and measured in a capillary viscometer (Motahhari, 2013). Temp. °C

Pressure MPa

20/19 20/19 20/19 20/19 20 50 50 50 50 50 75 75 75 75 75 100 100 100 100 100 125 125 125 125 125 150 150 150 150 175 175 175

0.1 2.5 5.0 7.5 10 0.1 2.5 5.0 7.5 10 0.1 2.5 5.0 7.5 10 0.1 2.5 5.0 7.5 10 0.1 2.5 5.0 7.5 10 2.5 5.0 7.5 10 5.0 7.5 10

15 wt% n-Heptane Density Viscosity kg/m³ mPa.s 952.2 587 953.4 634 954.7 683 956.2 737 957.9 794 930.4 90.7 931.8 96.2 933.5 102 935.2 107 936.9 113 913.8 31.6 915.5 32.9 917.4 34.5 919.1 36.3 920.9 37.9 896.5 14.5 898.4 15.2 900.4 15.8 902.4 16.5 904.3 17.2 878.3 8.0 880.6 8.3 882.9 8.6 885.0 9.0 887.3 9.3 863.5 5.2 866.1 5.3 868.6 5.6 871.0 5.7 848.9 3.6 851.9 3.7 854.4 3.8

30 wt% n-Heptane Density Viscosity kg/m³ mPa.s 893.9 41.1 895.4 42.7 896.7 44.5 898.4 46.8 900.6 48.6 872.8 12.7 874.7 13.1 876.6 13.7 878.6 14.3 854.8 6.4 857.0 6.7 858.9 6.9 861.0 7.2 837.3 3.8 839.5 4.0 841.8 4.1 844.3 4.2 818.9 2.5 821.5 2.6 824.2 2.7 826.8 2.8 -


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Table B8. Density and viscosity of WC-B-B2 bitumen diluted with n-eicosane and measured in a capillary viscometer. Temp. °C

Pressure MPa

50 50 50 50 50 75 75 75 75 75 100 100 100 100 125 125 125 125 150 150 150 150 175 175 175 175

0.1 2.5 5.0 7.5 10 0.1 2.5 5.0 7.5 10 2.5 5.0 7.5 10 2.5 5.0 7.5 10 2.5 5.0 7.5 10 2.5 5.0 7.5 10

6.0 wt% n-Eicosane Density Viscosity kg/m³ mPa.s 984.8 2320 986.0 2500 987.5 2740 988.9 2990 990.2 3190 969.0 400 970.6 415 972.2 437 973.6 466 974.9 503 953.9 114 955.6 120 957.1 127 958.8 133 937.5 43.3 939.3 45.4 940.9 47.7 942.8 50.1 921.4 20.7 923.6 21.5 925.4 22.5 927.2 23.5 905.0 11.5 907.2 11.9 909.6 12.4 911.4 12.8

24 wt% n-Eicosane Density Viscosity kg/m³ mPa.s 939.9 257 941.1 273 942.6 292 944.1 315 945.6 336 922.1 77.6 923.6 81.2 925.3 86.0 927.0 91.2 928.6 96.0 906.6 31.7 908.5 33.2 910.3 34.8 912.1 36.5 888.2 13.1 890.0 13.5 891.9 14.3 891.9 14.9 873.4 7.7 875.6 8.0 877.8 8.4 879.8 8.8 855.8 4.9 858.3 5.1 860.8 5.3 863.0 5.5


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Table B9. Density and viscosity of WC-B-B2 bitumen diluted with cyclohexane and measured in a capillary viscometer. Temp. °C

Pressure MPa

21 21 21 21 21 50 50 50 50 50 75 75 75 75 75 100 100 100 100 125 125 125 125 150 150 150 150 175 175 175 175

0.1 2.5 5.0 7.5 10 0.1 2.5 5.0 7.5 10 0.1 2.5 5.0 7.5 10 2.5 5.0 7.5 10 2.5 5.0 7.5 10 2.5 5.0 7.5 10 2.5 5.0 7.5 10

5.0 wt% Cyclohexane Density Viscosity kg/m³ mPa.s 1005.3 38000 1006.6 42200 1007.8 48000 1009.3 54200 1010.8 60600 985.4 1792 986.8 1986 988.2 2140 989.7 2320 991.1 2510 968.8 324 970.6 333 972.2 352 973.6 369 975.1 389 954.2 92.2 955.8 97.2 957.6 103 959.2 109 937.0 35.4 938.9 37.1 940.7 38.9 942.6 40.8 920.2 17.1 922.3 17.7 924.3 18.5 926.3 19.3 903.5 9.9 905.9 10.1 908.2 10.5 910.3 10.9

40 wt% Cyclohexane Density Viscosity kg/m³ mPa.s 902.7 35.2 904.2 36.6 905.8 38.7 907.4 41.1 909.5 43.1 881.5 12.1 883.3 12.6 885.2 13.1 887.0 13.7 888.9 14.4 861.9 5.9 864.0 6.0 866.3 6.3 868.3 6.5 870.3 6.7 843.6 3.5 845.9 3.6 848.2 3.7 850.8 3.8 822.8 2.2 825.6 2.3 828.2 2.4 830.8 2.4 801.0 1.5 804.6 1.6 807.7 1.6 810.8 1.7 779.8 1.1 783.8 1.2 787.4 1.2 790.9 1.2


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Table B10. Density and viscosity of WC-B-B1 bitumen diluted with toluene and measured in a capillary viscometer. Temp. °C

Pressure MPa

20 20 20 20 20 50 50 50 50 50 75 75 75 75 75 100 100 100 100 100 125 125 125 125 150 150 150 150 175 175 175 175

0.1 2.5 5.0 7.5 10 0.1 2.5 5.0 7.5 10 0.1 2.5 5.0 7.5 10 0.1 2.5 5 7.5 10 2.5 5.0 7.5 10 2.5 5.0 7.5 10 2.5 5.0 7.5 10

5.0 wt% Toluene Density Viscosity kg/m³ mPa.s 1004.2 8780 1005.5 9820 1006.5 10700 1007.9 11900 1009.0 13000 984.2 681 985.5 741 987.2 780 988.4 834 989.7 895 968.0 164 969.3 171 970.9 180 972.3 190 973.7 201 951.1 54.7 952.7 57.6 954.3 60.3 956.0 63.5 957.6 66.3 935.1 25.0 937.0 26.0 938.8 26.7 940.6 27.8 916.7 11.8 918.9 12.2 920.9 12.6 922.9 13.0 898.1 6.9 900.5 7.1 903.0 7.4 905.2 7.7

25 wt% Toluene Density Viscosity kg/m³ mPa.s 972.4 78.6 973.7 82.3 975.2 85.8 976.8 90.3 978.2 95.3 949.7 23.3 951.2 24.2 952.9 24.9 954.7 25.8 956.3 26.8 931.9 11.3 933.6 11.6 935.4 12.0 937.1 12.4 938.8 12.7 914.6 6.4 916.6 6.6 918.6 6.8 920.5 7.1 894.8 3.9 897.1 4.1 899.3 4.2 901.5 4.4 873.7 2.6 876.4 2.7 879.0 2.7 881.2 2.8 853.5 1.9 856.6 2.0 859.6 2.0 862.5 2.1

50 wt% Toluene Density Viscosity kg/m³ mPa.s 933.9 5.5 935.2 5.6 937.1 5.7 939.1 5.8 941.0 6.0 908.0 2.9 909.7 2.9 911.4 3.0 913.3 3.1 915.1 3.1 889.6 1.9 891.7 1.9 893.7 1.9 895.6 2.0 897.5 2.0 866.8 1.3 869.5 1.4 871.6 1.4 873.8 1.4 876.2 1.5 845.4 1.0 847.8 1.0 850.6 1.1 853.3 1.1 822.5 0.80 825.9 0.82 828.8 0.84 831.8 0.86 796.1 0.63 800.2 0.65 804.0 0.67 807.5 0.68


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Table B11. Density and viscosity of WC-B-B2 bitumen diluted with 1-methylnaphthalene (MN) at 0.1 MPa and measured in a cone and plate viscometer. Temp. °C 20 25 35 45 50

5.0 wt% MN Density Viscosity kg/m³ mPa.s 1014.6 41900 1011.2 20800 1004.4 6290 997.7 2340 994.3 1510

25 wt% MN Density Viscosity kg/m³ mPa.s 1019.4 1380 1016.0 898 1009.1 420 1002.2 220 998.7 165

50 wt% MN Density Viscosity kg/m³ mPa.s 1022.1 82.8 1018.6 64.0 1011.5 40.4 1004.5 27.0 1001.0 22.5


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Table B12. Density and viscosity of WC-B-B2 bitumen diluted with heptol (50 wt% n-heptane + 50 wt% toluene) and measured in a capillary viscometer. Temp. °C 21 21 21 21 21 50 50 50 50 50 75 75 75 75 75 100 100 100 100 100 125 125 125 125 150 150 150 150 175 175 175 175

Pressure MPa 0.1 2.5 5 7.5 10 0.1 2.5 5 7.5 10 0.1 2.5 5 7.5 10 0.1 2.5 5 7.5 10 2.5 5 7.5 10 2.5 5 7.5 10 2.5 5 7.5 10

5.0 wt% Heptol Density Viscosity kg/m³ mPa.s 1002.7 13200 1004.0 14400 1005.3 15800 1006.7 17100 1008.3 19900 982.7 921 984.1 995 985.6 1060 987.0 1130 988.5 1230 966.1 196 967.8 208 969.4 220 970.9 234 972.4 249 949.4 62.5 951.2 65.9 953.0 69.1 954.7 72.8 956.4 76.3 934.1 26.9 935.9 28.0 937.8 29.3 939.7 30.5 916.4 13.4 918.6 13.9 920.7 14.5 922.6 14.9 897.5 7.4 900.0 7.7 902.4 8.0 904.6 8.3

25 wt% Heptol Density Viscosity kg/m³ mPa.s 946.0 95.7 947.4 103 948.7 108 950.3 113 951.4 117 923.8 26.5 925.3 27.5 927.0 28.5 928.7 29.6 929.7 30.4 905.4 12.0 907.3 12.3 909.2 12.7 911.0 13.1 911.9 13.5 889.3 6.7 891.2 6.9 893.3 7.1 894.4 7.3 871.0 4.2 873.3 4.3 875.5 4.4 876.8 4.5 852.0 2.8 854.8 2.9 857.4 3.0 858.9 3.0 832.9 2.0 836.2 2.1 839.2 2.2 840.9 2.2

40 wt% Heptol Density Viscosity kg/m³ mPa.s 908.4 16.4 910.1 17.0 911.7 17.7 913.4 18.4 915.4 18.9 884.9 6.9 886.8 7.1 888.6 7.2 890.4 7.4 892.2 7.6 866.1 3.9 867.9 4.0 870.1 4.1 871.9 4.2 873.9 4.3 848.9 2.6 851.2 2.7 853.4 2.8 855.9 2.9 828.8 1.7 831.7 1.8 834.4 1.9 837.0 1.9 808.9 1.4 812.2 1.4 815.2 1.4 818.0 1.5 789.8 1.0 793.4 1.1 796.8 1.1 800.1 1.2


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Table B13. Density and viscosity of CO-B-A1 bitumen at 0.1 MPa measured in a cone and plate viscometer. Temp. °C 20 25 35 40 50 60 75 90

Density kg/m³ 1013.5 1011.0 1005.1 996.2 972.8

Viscosity mPa.s 104853 29793 11567 2985 -

Table B14. Density and viscosity of CO-B-A1 bitumen diluted with toluene at 0.1 MPa and measured in a cone and plate viscometer. Temp. °C 0 10 15 20 25 35 50

4.5 wt% Toluene Density Viscosity kg/m³ mPa.s 1003.1 57003 997.0 17992 -

9.6 wt% Toluene Density Viscosity kg/m³ mPa.s 3260 1250 1000.8 997.6 536 994.5 194 -

Table B15. Density and viscosity of CO-B-A1 bitumen diluted with 14.3 wt% 1-methylnaphthalene at 0.1 MPa and measured in a cone and plate viscometer.

Temp. °C 25 35 50

Density kg/m³ 1013.7 1007.2 997.4

Viscosity mPa.s 16600 5550 1540


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Energy & Fuels

Table B16. Density and viscosity of ME-CV-A1 bitumen at 0.1 MPa measured in a cone and plate viscometer. Temp. °C 10 15 20 25 50

Density kg/m³ 876.6 873.0 869.1 865.8 847.9

Viscosity mPa.s 28.0 21.8 18.1 16.1 -

Table B17. Density and viscosity of ME-CV-A1 bitumen diluted with 10 wt% n-pentane and measured in a capillary viscometer. Pressure MPa 0.1 2.5 5 7.5 10 2.5 5 7.5 10 2.5 5 7.5 10 2.5 5 7.5 10 2.5 5 7.5 10 2.5 5 7.5 10

Temp. °C 21 21 21 21 21 50 50 50 50 75 75 75 75 100 100 100 100 125 125 125 125 150 150 150 150

Density kg/m³ 836.5 838.3 839.9 841.7 844.0 816.9 818.8 820.7 822.9 799.5 801.8 803.9 806.0 779.7 782.2 784.5 787.1 761.0 764.0 766.6 769.5 742.1 745.6 748.8 751.9

Viscosity mPa.s 4.85 5.02 5.22 5.39 5.60 2.66 2.75 2.85 2.94 1.76 1.81 1.87 1.93 1.25 1.29 1.33 1.37 0.95 0.98 1.01 1.04 0.75 0.77 0.80 0.82


Energy & Fuels

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Table B18. Density and viscosity of ME-CV-A1 bitumen diluted with toluene at 0.1 MPa and measured in a cone and plate viscometer. Temp. °C 0 5 10 15

6.0 wt% Toluene Density Viscosity kg/m³ mPa.s 886.7 37.0 882.9 25.8 879.1 20.5 875.3 17.4

10 wt% Toluene Density Viscosity kg/m³ mPa.s 886.4 26.4 882.7 18.8 878.9 15.2 875.2 13.6

Table B19. Density and viscosity of bitumen ME-CV-A1 diluted with 1-methylnaphthalene (1MN) at 0.1 MPa and measured in a cone and plate viscometer. Temp. °C 5 8 10 15 20 25

2.0 wt% 1-MN Density Viscosity kg/m³ mPa.s 877.4 24.1 873.6 19.0 869.9 16.2 866.1 13.6

5.0 wt% 1-MN Density Viscosity kg/m³ mPa.s 881.2 22.3 877.4 17.9 873.8 870.1 12.9

8.0 wt% 1-MN Density Viscosity kg/m³ mPa.s 889.1 27.9 886.9 24.3 885.4 20.8 -

Table B20. Density and viscosity of Blend1 (70 wt% WC-B-B2 + 30 wt% ME-CV-A1) at 0.1 MPa and measured in a cone and plate viscometer. Temp. °C 10 25 30 35 40 50 60 70

Density kg/m³ 945.0 936.8 930.3 923.8 918.3

Viscosity mPa.s 2888.8 754.1 497.7 340.3 -


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Energy & Fuels

Table B21. Density and viscosity of Blend1 diluted with n-tetradecane at 0.1 MPa and measured in a cone and plate viscometer. Temp. °C 0 10 20 35 40 50 60

2.0 wt% n-Tetradecane Density Viscosity kg/m³ mPa.s 5496 1977 825.3 298.3 932.8 926.3 919.8 -

5.0 wt% n-Tetradecane Density Viscosity kg/m³ mPa.s 3259 1250 535.8 194.2 926.0 919.4 912.9 -

Table B22. Density and viscosity of Blend1 diluted with 1-methylnaphthalene (MN) at 0.1 MPa and measured in a cone and plate viscometer. Temp. °C 0 10 20 35 40 50 60

5.0 wt% MN Density Viscosity kg/m³ mPa.s 4350 1534 673.5 239.3 940.3 933.7 926.8 -

8.3 wt% MN Density Viscosity kg/m³ mPa.s 2887 1079 454.7 167.8 942.6 936.0 929.1 -

Table B23. Density and viscosity of WC-B-B2-DAO (deasphalted WC-B-B2 bitumen) at 0.1 MPa and measured in a cone and plate viscometer. Temp. °C 20 25 50 90 100

Density kg/m³ 983.2 980.0 964.3 939.2 -

Viscosity mPa.s 5455 3193 425.5 32.4


Energy & Fuels

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Table B24. Density and viscosity of WC-B-B2-DAO diluted with 12 wt% n-octane at 0.1 MPa and measured in a cone and plate viscometer. Temp. °C 20 25 30 35 40

Density kg/m³ 950.6 947.2 943.8 940.4 937.0

Viscosity mPa.s 497.7 343.5 242.0 173.8 130.0

Table B25. Density and viscosity of WC-B-B2-DAO diluted with n-dodecane at 0.1 MPa and measured in a cone and plate viscometer. Temp. °C 25 35 50 75

5.0 wt% n-Dodecane Density Viscosity kg/m³ mPa.s 965.9 1170 959.5 520 949.9 184 933.8 -

10 wt% n-Dodecane Density Viscosity kg/m³ mPa.s 950.8 430 934.4 90.1 918.0 -

18 wt% n-Dodecane Density Viscosity kg/m³ mPa.s 930.7 142 913.9 38.5 897.1 -

Table B26. Density and viscosity of WC-B-B2-DAO diluted with toluene at 0.1 MPa and measured in a cone and plate viscometer. Temp. °C 20 25 35 50

2.0 wt% Toluene Density Viscosity kg/m³ mPa.s 980.7 2680 977.5 1660 971.1 690 961.6 247

4.5 wt% Toluene Density Viscosity kg/m³ mPa.s 977.4 1420 974.0 916 967.6 439 957.8 169

10 wt% Toluene Density Viscosity kg/m³ mPa.s 970.0 415 966.6 299 959.9 155 949.8 81.0


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