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Fluid Phase Equilibria, 75 (1992) 257-268 Elsevier Science Publishers B.V.

, Amsterdam

257

A generalized viscosity equation for liquid hydrocarbons: Application to oil-sand bitumens
Anil K. Mehrotra
Department of Chemical and Petroleum Engineering, The Universityof Calgary, Calgary, Alberta T2N IN4 (Canada)

Keywords: viscosity- temperature equation, liquid hydrocarbon viscosity, gas viscosity, bitumen - diluent mixture viscosity

ABSTRACT A new method is presented for the correlation and prediction of the effect of temperature on viscosity of liquid hydrocarbons and their mixtures. A oneparameter viscosity- temperature equation is described that has been validated with data for approximately 360 pure liquid hydrocarbons, including paraffins, olefins, cyclopentanes, cyclohexanes, naphthenes and aromatics. The viscosity data for all hydrocarbons are represented well by: log (II + 0.8) = 0( a?“‘)*, where lo is in mPa s, T in kelvin, and 8 = 100; Q = 0.01 for pure hydrocarbons. For most compounds, parameter b follows systematic trends with several properties, such as molar mass, boiling point, critical temperature and acentric factor. The usefulness of the one-parameter equation is extended to the viscosity of oil-sand bitumens diluted with light gases or liquid diluents. This is accomplished by combining the viscosity equation with simple mixing rules. The predictions for mixture viscosity, spanning several orders of magnitude, are in excellent agreement with data over wide ranges of temperature and composition.

INTRODUCTION Numerous calculation methods and correlations for the effect of temperature on liquid viscosity are available in literature (Perry et al., 1984; Reid et al., 1986). Amongst the viscosity prediction methods, the approaches given by Ely and Hanley (1981), Teja and Rice (1981), and Pedersen et al. (1984) have been applied successfully for some liquid mixtures. In contrast, a relatively simple predictive approach is presented here.

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8) (3) where Vi 3 xi(Mi/lM)” denotes the geometric mean of mass and mole fractions. n-alkyl-branched cyclopentanes.b) by showing a linear correlation between the two parameters in Walther’s (1931) viscosity correlation.. log (p + 0. 1988).8) P C Uilog (pi + 0. 1991a. 1989): log (~ + 0. nonfused and fused-ring naphthenes and aromatics). 1987.8) = -0. by selecting f( p) = (A4)” log (p + 0. Recently. respectively (Mehrotra. In addition. parameter b was shown to follow systematic trends with other properties.268 Equation (1) is a one-parameter viscosity-temperature equation that was obtained by Mehrotra (1991a. Generalized mixing rules for viscosity prediction Viscosity of bitumens from the vast deposits of Alberta’s oil-sands is an important property that is needed in reservoir and process simulation. In contrast. boiling point.008 (Mehrotra. for the low viscosity of light gases at atmospheric pressure. Mehrotra and Svrcek. a mixing rule approach for calculating the viscosity of CO. the following mixing rule is obtained for the viscosity of a bitumen-diluent mixture: . such as molar mass.b).8) = C ~i~~~ - log (pi + 0. The available calculation methods for the viscosity of bitumens range from empirical correlations to those based on the corresponding states principle (Johnson et al. with the generalized constants for bitumens and bitumen fractions as 8 = 160 and Q = 0. cyclohexanes and aromatics.8) and Xi as mole fraction Xi (Mehrotra et al. and pipeline calculations.1(0. and (ii) to describe a method. 1992): log (p + 0. 1992). For each family of hydrocarbons. for predicting the viscosity of bitumens (from Canadian oil-sands) diluted with liquid and/or gaseous diluents over a wide range of conditions. Equation (1) was modified by inserting a negative sign (Mehrotra.: f( pi). Equation (3) is obtained from a commonly used additive viscosity formula.8) = e(O7’)” (I) For approximately 360 pure light. By combining Equation (3) and the Grunberg (1954) formula. Svrcek and Mehrotra. 1987. Equation (1) was shown to be applicable also for the viscosity of bitumens (from Canadian oil-sands).01 were found as optimum (generalized) for constants 8 and 9..-saturated or toluene-diluted bitumens is presented here. f(r() = XX. based on Equation (l). values of 100 and 0.015T)b (2) The objectives of this paper are: (i) to document the effectiveness of Equation (1) as a predictive equation for the viscosity of liquid hydrocarbons and their mixtures. critical temperature and acentric factor. medium and heavy hydrocarbons (including branched and unbranched paraffins and olefins.

Next. From viscositytemperature data for all five bitumen fractions. (5) (6) Data used for validating the viscositypredictions Data for the viscosity of a Cold Lake bitumen and its five fractions were reported by Mehrotra et al. respectively.283 310 0. = Bji) is a binary viscous interaction term that could be determined from mixture viscosity data.7853 -2.8) = 160(0.9632 -4.072 (g/m00 209 0.5 3. These five bitumen fractions (or “cuts”) were obtained by vacuum distillation of a Cold Lake bitumen sample.8 Cuts 1 to 4 of Cold Lake bitumen contained little or no asphaltenes whereas approximately 50 mass % of Cut 5 was asphaltenes.4. ujBii (4) where Bii (B.0444 .2 8. Mixing Rule I: Mixing Rule II: log (cl + 0.8) = 2 I+ @(W)“J log (G + 0. + 0. and Cut 5 was a glass-like solid with a softening temperature of approximately 100°C (Mehrotra et al. As indicated in Table 1.259 log (i + 0. Figure 1. it is clear that viscosities of bitumen fractions differ by several orders of magnitude. TABLE 1 Data and viscosity correlation for the five fractions of Cold Lake bitumen ’ Sample Cut1 Cut2 Cut3 Cut4 Cut5 ‘Data from Mass fraction Molar mass Density (g/cm3) 0. Cuts 3 and 4 had consistencies and viscosities much like the whole bitumen. The boiling point ranges for Cuts I and 2 are bp < 343°C and 343 c bp < SlO”C.103 0.008T)b Parameter b AAD % .941 0.065 800 2500 0.9073 14.3. Also. .6.879 0.8) = 2 ui e(WJbl + 2 ci ui uj B. (1): log (/J + 0.990 0. Cuts I and 2 were clear liquids with low viscosities.999 1.0234 .168 667 0.. (1989) Correlation of viscosity data with Eq.381 Mehrotra et al.5 4. the molar mass of Cuts I to 5 ranges from 209 to 2500 g/mol.8) = c’ ui log (p. = Bii = 0 and B. Equations (3) and (4) are combined with Equation (1) to obtain the following mixing rules based on the generalized one-parameter viscosity equation. (1989).3 14. 1989).8) + c’ ci u.

temperature-composition data for 12 reconstituted binary blends of bitumen fractions were presented by Eastick and Mehrotra (1990).260 \ -b 0 cut 6.150°C and at pressures up to 10 MPa (Eastick et al. by use of Equation (1) or (2). The calculations for the viscosity of CO. Viscosity of the five fractions of Cold Lake bitumen (data from Mehrotra et al. 1989). i.-solubility of the five bitumen fractions and the whole bitumen were collected at temperatures of 25 . Results are also described for the viscosity of toluene-diluted bitumen and bitumen fractions. Data for the viscosity and CO. These data are used for evaluating the Cut i-Cut j binary interactions and for validating the calculation approach. for the individual components. binaries are used to obtain Bii each pair. bitumen fractions.-saturated bitumen fractions. the calculation procedure is used for . are described next. The data for the viscosity of the reconstituted blends of bitumen fractions are used to obtain Cut i-Cut j interaction parameters. The data for CO. and gases. ‘C Fig. The data for the five Cut i-CO. RESULTS AND DISCUSSION Results are presented first for the correlation of viscosity with temperature. Finally. 4 and 5 as well as the whole bitumen were reported by Mehrotra (1990). The viscosity. pure liquid hydrocarbons. These data are used for obtaining the viscous interaction term (B. 1992). 1..-saturated Cold Lake (whole) for bitumen are used for further validation of the viscosity calculation approach.e. to validate Equations (5) and (6) for binary mixtures. Viscosity data for mixtures of toluene and Cuts 3.) for Cut iCut j pairs. Cut 2 1 10’ 0 cut v cut !& - 3 4 0 cut 5 Equation (1) i 250 100 I 0 50 100 I 150 I 200 Temperature..

-saturated and toluene-diluted results are compared to the measured values.5 (l/T/. the optimum values of parameter b in Equation (1) were given by Mehrotra (1991a. Fig. and the For approximately 360 pure liquid hydrocarbons.b). medium and heavy hydrocarbons as a function of boiling temperature. namely molar mass. Dependence of parameter b on normal boiling point of light and medium hydrocarbons.261 predicting the viscosity of CO.) 103. Figures 2 and 3. the value of parameter b in Equations (1) is -6.')X 103. 1991a. Dependence of parameter b on boiling temperature (at 10 mmHg) of heavy hydrocarbons. X K-l (l/T. 3. was found to be satisfactorily correlatable with the molar mass (A4 in g/mol) and the density at 25°C (P in g/cm’) : . Parameter b for bitumen fractions. Correlation and prediction of component viscosities bitumen. Similar consistent trends for parameter b were also noted with other properties.0 2. present the variation of parameter b for light. for example. 2. K-' Fig. Table 1. critical temperature and acentric factor (Mehrotra. -3 -4 -6 Branched -6 -4 -5 Non-fused Aromatics -6 Paraffins and Olefins -3 D b z -5 g u” a -5 -6 Fused ring Aromatics -6 E z rz -3 Non-fused Nophthenes -7 -4 -5 Fused ring Naphthenes 2.0853. For toluene (the liquid diluent).b).

9 16.0.0.e. as is indicated in Table 2. binary mixture.886 [log iWJ2 With Density (p at 25°C): ( It-1 = 0.0632 0.07 . For each Cut i-CO.0791 1. the values of 8 and Q are -0.l(O.0899 0. linearly with temperature and the results are summarized in Table 3 and plotted in Figure 4.8 28.0.67 p2 (7) (8) Calculations with the one-parameter equation for the viscosity of gases also yielded an excellent match of the data.0568 0.CO2 binary mixture becomes: log (i + 0. TABLE 2 Correlation Gas of viscosity of five light gases at 0-200°C Molar mass Correlation of viscosity data with Equation log (/J + 0. 1992).9 30.01 . Note that.CO.0.1.1(0. The predicted viscosities were found to be well within one order of magnitude of the data by Eastick et al.015. the B.. the results indicated an improvement in viscosity predictions from Equation (10) over those obtained from Equation (9). pair. Cut i) and the second for CO.6 44.8) = -0.8) = Ui [160(0.015T)b Parameter 6 AA.01 -0.21. values were regressed. CAH.008T)bi]+ u6 [ -O. in Equation (2) for gases.9 (2): N2 co CH‘I CO.262 With n4ozar ie7ss (M): ( Ir 1 = 0. . Equation (5) is written as: log (cl + 0. respectively (Mehrotra.u (%) (g/mol) 28. Overall.1 and 0.04 .8) = I+ [160(0.0087Jbi] + ug [-0.74 p .O15l)“6] (9) where the first term is for a bitumen fraction (i. Viicosity prediction of bitumen fraction -diluent (binary) mixtures For a Cut i .23 + 13.0908 0. Equation (6) for a Cut i .1(0.01 .0157)b6] + 2 Ui u. (1992).5Bi6 (10) Calculations to obtain Bi6 for each data point were performed with Equation (10).998) b = -40.56 [log M] .95 + 58.990) b = -27.

0 0. 4.T correlations for Cut i-EQ.. Cut 3-co* Cut 4-co.toluene Cut 5 .51 9.28 -1.19 -0. Cut i-Cut j and Cut i. 0. The Bil.LCu:.09 2.14 . Cut 1 -Cut Cut 1 -Cut Cut 2-Cut Cut 2 -Cut Cut f:Cut Clltz co Cut I-Cd. *for binary viscous interaction parameters i Bc .0101 -0. Cut 2-co.0085 0.1.) (B.0233 (6) 4 5 3 4 5 (BM) (Bj7) (B4.79 @Iii) in Equation A. .1.1.53 -0.28 4.1.0155 0.19 0.T correlation: Ao (B& (BJ (B.0101 0.) (B& ne Cut 3 .0204 0.0136 0.0100 0.0136 .0065 0.toluene B25/Wh /kdBz4 857 NW/B47 Fig.81 .0037 0.) (B& (B.toluene binary pairs.toluene Cut 4 .0037 0. Cut 5-co.) (Bib) .0192 0.19 -1.1.09 .263 TABLE 3 Correlations J Binary pair atz cut’ Cut .15 -0..17 .0.

Cutj interaction parameters from Equation (12). The viscosity predictions for those data from Mixing Rule I.8) = ui [160(0. log (G + 0. density and viscosity of Cold Lake bitumen were reported by Eastick et al.008ZJbj]+ 2 ui uj Bq (12) The resulting Biis were regressed linearly with temperature and the results are presented in Table 3. in terms of its five fractions (Mehrotra et al. = B. the Bqs for the blends involving Cuts 3 and 4 are identical. The values of parameter b for the six components were taken from Tables 1 and 2. The temperature and pressure ranges for these data were 23. .264 Viscosity of reconstituted binary blerxis of bitumen fractions As mentioned previously.0087’)bi]+ uj [160(0. Equation (5). viscosity data over a range of temperatures for twelve binary blends of bitumen fractions (prepared by mixing Cuts I or 2 with Cuts 3. which does not involve any binary interaction term.. 4 or 5) were provided by Eastick and Mehrotra (1990). the CO. Obviously..5 MPa.-saturated bitumen.10... i. values for the five Bg and six B. it was assumed that B. together with the CO.8) = ui [160(0. 1992) were used to calculate all ui terms. Calculations for the viscosity of CO. would involve 15 binary interaction terms. The bitumen composition. = B3. have a positive slope... except for B.100°C and 0. The remaining four Cut i-Cut j interaction terms are B. Of these. are remarkably close to the experimental viscosities with an AAD of 23.. These B..-saturated (whole) bitumen In the following calculations.. Note that all BV. an adequate prediction of these data is an important test of the viscosity calculation procedure outlined here. (1992). rewritten as Equation (ll).for which no binary-mixture viscosity data were available.T lines. Equation (6). Calculations were first performed with Mixing Rule I. and Bd5.. Sixteen data points for the CO.e. log (i + 0. = B. B. Bj4. The calculated viscosities for all binary blends were in good agreement with the data (AAD typically less than 10%). plotted in Figure 5. It was reasoned that these four BVs would be small owing to the similar viscosities of both components in each case. were found to be well within one order of magnitude. respectively. The predicted viscosities of CO..-saturated (whole) bitumen is modeled as a 6-component mixture comprising the five bitumen fractions and CO* as the sixth component.6%.2.008Y’)bj] (11) Next. 1989)..s are given in Table 3. = B.-saturated bitumen with Mixing Rule II. That is.-solubility data (Eastick et al. = 0. B13 = B. and B. Prediction of the viscosity of CO.-solubility. Also.0087’)*i]+ uj [160(0.T correlations are plotted in Figure 4. the binary blend data were used to evaluate the Cut i .

Comparison of predicted and experimental viscosity of CO. Fig. indeed.?a ‘PI ? cl t >. In contrast.8%.265 The viscosity predictions from Equation (6) for CO. it was noted that the term for the Cut 5 -CO. The AAD for the sixteen data points was 61.-saturated (whole) bitumen were higher than the measured data. 5. Mixing Rule II should be viewed as a semi-predictive method. In Figure 5. 1 “. mPa. Hence.103: . (a gas) to Cut 5 (a glass-like solid).“.s Experimental viscosity. Comparison of predicted and experimental viscosity of toluene-diluted Cold Lake (whole) bitumen. Thus. nevertheless. Mixing Rule I is a truly predictive method for the viscosity of CO. is 9. Of the eleven B+s in the double-summation of Equation (6).““n “. ‘“.s Fig. and (ii) the gas solubility for each Cut i-CO.-saturated Cold Lake (whole) bitumen.e E : o Mixing 0 Mixing Experimental Viscosity..“I . Both sets of results. the value of B. acceptable in view of the fact that the calculations involved a mixture of six widely different components.I . “‘.I ““.‘. as is shown in Figure 5.-saturated bitumen may require additional data for the viscosity of CO.-saturated (whole) bitumen from Mixing Rule I are slightly lower than the data.s. the use of Mixing Rule II for another CO. These predictions are. .-saturated bitumen.19 which is much larger than all other Bi8.. mPa. In Table 2. &) had a dominant effect on the viscosities calculated from Mixing Rule II. 104.“.-saturated bitumen fractions and Cut i-Cut j blends to obtain the B. 6.. Comparison of predictions j?om Mixing Rules I and II The information required for using Mixing Rule I consists of (i) parameter b in Equation (1) or (2) for each constituent. are within one-half to two-times the data.I . which have very different viscosities spanning several orders of magnitude. the predictions for the viscosity of CO. from CO. interaction (i.e. mixture. while those from Mixing Rule II are higher.

involving binary viscous interaction terms that are determined empirically.14 (Mehrotra. Three Cut i . All remaining interactions were neglected due to a lack of binary-mixture data. 1990). ACKNOWLEDGEMENTS Financial support was provided by the Natural Sciences and Engineering Research Council of Canada (NSERC). 1990) and are given in Table 3. = B.. i. i. Mixing Rule II. Subsequently.e. CONCLUSIONS A generalized one-parameter equation was presented for predicting the viscosity of pure hydrocarbons.10 (Mehrotra. bitumen fractions. only the significant results are given. i. Of these. B. The single parameter in this generalized viscosity equation is correlated well with other hydrocarbon properties. hence. = 0. Mixing Rule I was demonstrated to predict viscosities that are well within one order of magnitude of the data. plotted in Figure 6.were evaluated from the data for Mixtures 1. especially for Mixtures 12 and 13. In Figure 6.e. Equation (6). Of the two mixing rules for the viscosity of CO. the mixture is modeled as a 6-component mixture.toluene interaction terms. and gases. = BN = Bj5 = Bd5 = B. Calculations for the viscosity of toluene-diluted bitumen with Mixing Rule II. B3.-saturated or toluene-diluted bitumens. five bitumen fractions along with toluene (denoted by subscript 7) as the sixth component. % single viscosity parameter binary viscous interaction term . the viscosity equation was used to predict the mixture viscosity of diluted Cold Lake bitumen which was modeled as a 6-component mixture. The calculation steps with Walther’s (1931) two-parameter correlation have been described elsewhere (Mehrotra.266 Prediction of the viscosity of toluene-diluted (whole) bitumen For calculating the viscosity of toluene-diluted (whole) bitumen. NOMENCLATURE b Bfi average absolute deviation. The calculated viscosities. again involved 15 binary interaction terms. show remarkable agreement with the experimental viscosities. six Bus for Cut i-Cut j interactions are given in Table 3. = B0 and B57. 1990) from Equation (5) are in fair agreement with the data.. the predicted viscosities of Mixtures ll. is shown to yield improved viscosity predictions.e.

1987. Ind. 70: 159-164.. 1990.M. Fuel Processing Technology.. g/cm’ generalized viscosity constant geometric mean of mass and mole fractions Subscripts i j l-5 6 7 component i component j Cuts 1 to 5 (bitumen fractions) CO2 (gaseous diluent) toluene (liquid diluent) REFERENCES Eastick. The viscosity of regular solutions. g/m01 correlation coefficient absolute temperature. 1990. R. 1992. Svrcek. AK.. Viscosity data and correlation bitumen fractions. W.Y. and Hartley.F. Res... mPa s generalized viscosity constant density at 25”C. AK. g/m01 average (mixture) molar mass. and Mehrotra. W. AK. Res. J. Phase behaviour fractions. National Bureau of Standards. Can. Faraday Sot. A Computer Program for the Prediction of Viscosity and Thermal Conductivity in Hydrocarbon Mixtures. 30: 420-427. Trans. Chem.J. 26: 25-37. Svrcek. Eng. for mixtures of of CO. . L. Johnson.R. AK. S. 68: 839-848. Eng. Mehrotra. Eng.261 M M !I x molar mass.R.. J. Washington. R.-bitumen Ely.. A generalized viscosity equation for pure heavy hydrocarbons.E. H. Chem. Mehrotra. DC. Eastick. Chem. Development of mixing rules for predicting the viscosity of bitumen and its fractions blended with toluene... Chem. A. 50: 1293-1303. Viscosity prediction of Athabasca bitumen using the extended principle of corresponding states. 26: 2290-2298.Y. Ind. 1981. J. mPa s predicted mixture viscosity... 1954. and Mehrotra. Gnmberg. K mole fraction Greek symbols dynamic viscosity. Eng. NBS 1039. and Mehrotra. Can..K. 1991a.

. AK.. W. Eng.. A. Teja. Svrcek. 7: 382-384. Chapter 9. D. 1981. 1988. Pedersen. Generalized corresponding states method for the viscosities of liquid mixtures. KS.. Eng..L. McGraw-Hill. 6th ed. 39: 1011-1016.. 1931. and Poling.Mehrotra. Chem.O.. Generalized one-parameter viscosity equation for light and medium hydrocarbons.R. McGraw-Hill.. Mixing rules for predicting the viscosity of bitumens pure gases. saturated with Mehrotra.. J. P. 20: 77-81. Perry. Can. AK. Chem.Y. R. 1991b. Mehrotra. Fundam. Chem. 66: 323-327. and Rice. Prausnitz. Christensen. Viscosity of crude oils.. Chem. Chapter 3.. Green. Sci. Res. 70: 165-172. 1992. 26(5): 60-66. A. 1984. Des. 4th ed. Chem. Eng. 1986. and Mehrotra. C. Perry’s Chemical Engineers’ Handbook. Ind. correlation for bitumen viscosity. Eng.H. 1984. W. R.. Fredensland.. R. and Maloney.K. The Properties of Gases and Liquids.. Res. 67: 1004-1009.C. Ind.Y.. The evaluation of viscosity data. and Svrcek.S..W. Walther. J. J. and Thomassen. Pet. Viscosity of Cold Lake bitumen and its fractions. Technol. W. .. A. J. AK. J.. Eng. Mehrotra. One parameter Chem..M.Y. 1989. P. Eng. 1987. Reid. Can. and Svrcek. B.. Corresponding states method for calculating bitumen viscosity. Erdiil und Teer.. Eastick. AK. 30: 1367-1372. Can.E. P.