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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medium and heavy hydrocarbons (including branched and unbranched paraffins and olefins.8) = e(O7’)” (I) For approximately 360 pure light..8) = -0. 1992): log (p + 0.008 (Mehrotra.b) by showing a linear correlation between the two parameters in Walther’s (1931) viscosity correlation. nonfused and fused-ring naphthenes and aromatics). 1987.8) = C ~i~~~ - log (pi + 0. In contrast. The available calculation methods for the viscosity of bitumens range from empirical correlations to those based on the corresponding states principle (Johnson et al. 1991a.-saturated or toluene-diluted bitumens is presented here. In addition. n-alkyl-branched cyclopentanes. log (p + 0.. 1989): log (~ + 0. f(r() = XX.: f( pi). boiling point.268 Equation (1) is a one-parameter viscosity-temperature equation that was obtained by Mehrotra (1991a. based on Equation (l). 1987. for the low viscosity of light gases at atmospheric pressure.b). 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. and (ii) to describe a method. Equation (1) was modified by inserting a negative sign (Mehrotra.8) and Xi as mole fraction Xi (Mehrotra et al. with the generalized constants for bitumens and bitumen fractions as 8 = 160 and Q = 0. 1988). Svrcek and Mehrotra.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. the following mixing rule is obtained for the viscosity of a bitumen-diluent mixture: .8) P C Uilog (pi + 0. 1992). a mixing rule approach for calculating the viscosity of CO. Equation (3) is obtained from a commonly used additive viscosity formula.1(0. by selecting f( p) = (A4)” log (p + 0.01 were found as optimum (generalized) for constants 8 and 9.8) (3) where Vi 3 xi(Mi/lM)” denotes the geometric mean of mass and mole fractions. parameter b was shown to follow systematic trends with other properties. By combining Equation (3) and the Grunberg (1954) formula. Equation (1) was shown to be applicable also for the viscosity of bitumens (from Canadian oil-sands). such as molar mass. cyclohexanes and aromatics. For each family of hydrocarbons. Recently. values of 100 and 0. Mehrotra and Svrcek. for predicting the viscosity of bitumens (from Canadian oil-sands) diluted with liquid and/or gaseous diluents over a wide range of conditions. respectively (Mehrotra. and pipeline calculations.

8) + c’ ci u.7853 -2. the molar mass of Cuts I to 5 ranges from 209 to 2500 g/mol.065 800 2500 0.6.8) = 2 ui e(WJbl + 2 ci ui uj B. it is clear that viscosities of bitumen fractions differ by several orders of magnitude.4.283 310 0. (1989).0444 . (1989) Correlation of viscosity data with Eq.2 8.9073 14. = Bii = 0 and B.3 14.941 0. Mixing Rule I: Mixing Rule II: log (cl + 0. ujBii (4) where Bii (B.990 0. + 0. (1): log (/J + 0. Equations (3) and (4) are combined with Equation (1) to obtain the following mixing rules based on the generalized one-parameter viscosity equation. Also. Cuts I and 2 were clear liquids with low viscosities. Figure 1.381 Mehrotra et al.259 log (i + 0. (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. The boiling point ranges for Cuts I and 2 are bp < 343°C and 343 c bp < SlO”C.3. .5 4. As indicated in Table 1. From viscositytemperature data for all five bitumen fractions.008T)b Parameter b AAD % . These five bitumen fractions (or “cuts”) were obtained by vacuum distillation of a Cold Lake bitumen sample.8) = 160(0. respectively. 1989). = Bji) is a binary viscous interaction term that could be determined from mixture viscosity data.999 1. Next.072 (g/m00 209 0. and Cut 5 was a glass-like solid with a softening temperature of approximately 100°C (Mehrotra et al..8 Cuts 1 to 4 of Cold Lake bitumen contained little or no asphaltenes whereas approximately 50 mass % of Cut 5 was asphaltenes.8) = c’ ui log (p. 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) 0.168 667 0.0234 .8) = 2 I+ @(W)“J log (G + 0.103 0.5 3. Cuts 3 and 4 had consistencies and viscosities much like the whole bitumen.9632 -4.879 0.

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

0853.-saturated and toluene-diluted results are compared to the measured values. Correlation and prediction of component viscosities bitumen. namely molar mass. 1991a.b).b). the value of parameter b in Equations (1) is -6. present the variation of parameter b for light. the optimum values of parameter b in Equation (1) were given by Mehrotra (1991a. Dependence of parameter b on boiling temperature (at 10 mmHg) of heavy hydrocarbons. and the For approximately 360 pure liquid hydrocarbons.5 (l/T/. K-' Fig. -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. Similar consistent trends for parameter b were also noted with other properties. Parameter b for bitumen fractions. 2.) 103. Dependence of parameter b on normal boiling point of light and medium hydrocarbons. was found to be satisfactorily correlatable with the molar mass (A4 in g/mol) and the density at 25°C (P in g/cm’) : . for example. Table 1. For toluene (the liquid diluent). critical temperature and acentric factor (Mehrotra.0 2.')X 103.261 predicting the viscosity of CO. Figures 2 and 3. medium and heavy hydrocarbons as a function of boiling temperature. X K-l (l/T. 3. Fig.

0.CO. Equation (5) is written as: log (cl + 0.01 . binary mixture. Viicosity prediction of bitumen fraction -diluent (binary) mixtures For a Cut i .0.998) b = -40. CAH.5Bi6 (10) Calculations to obtain Bi6 for each data point were performed with Equation (10).0899 0. as is indicated in Table 2.95 + 58.01 -0.008T)bi]+ u6 [ -O.015T)b Parameter 6 AA.u (%) (g/mol) 28.07 . Note that.0791 1.1 and 0.8 28.l(O.CO2 binary mixture becomes: log (i + 0.0087Jbi] + ug [-0. values were regressed. the results indicated an improvement in viscosity predictions from Equation (10) over those obtained from Equation (9).015.0157)b6] + 2 Ui u. Cut i) and the second for CO. 1992).9 (2): N2 co CH‘I CO.04 .8) = -0.1(0.23 + 13. in Equation (2) for gases.990) b = -27.0568 0. the values of 8 and Q are -0.9 16. For each Cut i-CO. The predicted viscosities were found to be well within one order of magnitude of the data by Eastick et al. TABLE 2 Correlation Gas of viscosity of five light gases at 0-200°C Molar mass Correlation of viscosity data with Equation log (/J + 0.9 30. respectively (Mehrotra.e.8) = Ui [160(0.0632 0.886 [log iWJ2 With Density (p at 25°C): ( It-1 = 0.21. (1992)..O15l)“6] (9) where the first term is for a bitumen fraction (i.74 p .1(0.67 p2 (7) (8) Calculations with the one-parameter equation for the viscosity of gases also yielded an excellent match of the data.01 .0. Equation (6) for a Cut i .6 44.56 [log M] . linearly with temperature and the results are summarized in Table 3 and plotted in Figure 4. pair.0908 0. .1. the B. Overall.8) = I+ [160(0.262 With n4ozar ie7ss (M): ( Ir 1 = 0.0.

.19 -0.0037 0.0037 0.) (Bib) .T correlations for Cut i-EQ.79 @Iii) in Equation A.53 -0.0155 0.0101 0.1.81 . 0.19 0.09 2. Cut 5-co. Cut i-Cut j and Cut i.0 0.51 9.263 TABLE 3 Correlations J Binary pair atz cut’ Cut . Cut 2-co.17 .09 . Cut 3-co* Cut 4-co.) (B& (B.1.14 .toluene binary pairs.0101 -0.0233 (6) 4 5 3 4 5 (BM) (Bj7) (B4.0065 0.toluene Cut 5 .T correlation: Ao (B& (BJ (B. Cut 1 -Cut Cut 1 -Cut Cut 2-Cut Cut 2 -Cut Cut f:Cut Clltz co Cut I-Cd.1.toluene Cut 4 .15 -0.LCu:. The Bil.28 -1.) (B& ne Cut 3 .toluene B25/Wh /kdBz4 857 NW/B47 Fig. *for binary viscous interaction parameters i Bc .19 -1.0100 0.28 4. 4.0085 0.0136 0.1.0.0204 0.1.0192 0.0136 .) (B...

-solubility data (Eastick et al. values for the five Bg and six B..10.T correlations are plotted in Figure 4. together with the CO.-saturated (whole) bitumen is modeled as a 6-component mixture comprising the five bitumen fractions and CO* as the sixth component.100°C and 0.T lines. Note that all BV. That is. which does not involve any binary interaction term. Calculations for the viscosity of CO. B. Equation (5).8) = ui [160(0. . log (i + 0.0087’)*i]+ uj [160(0. except for B.-saturated bitumen. Also.-saturated bitumen with Mixing Rule II. The viscosity predictions for those data from Mixing Rule I. = B3.-saturated (whole) bitumen In the following calculations.. Equation (6).. the CO. in terms of its five fractions (Mehrotra et al. an adequate prediction of these data is an important test of the viscosity calculation procedure outlined here. The values of parameter b for the six components were taken from Tables 1 and 2. i. The calculated viscosities for all binary blends were in good agreement with the data (AAD typically less than 10%).6%.. were found to be well within one order of magnitude. plotted in Figure 5. 1992) were used to calculate all ui terms. respectively. Bj4.0087’)bi]+ uj [160(0. the Bqs for the blends involving Cuts 3 and 4 are identical.. = B. = 0. The remaining four Cut i-Cut j interaction terms are B.008ZJbj]+ 2 ui uj Bq (12) The resulting Biis were regressed linearly with temperature and the results are presented in Table 3. viscosity data over a range of temperatures for twelve binary blends of bitumen fractions (prepared by mixing Cuts I or 2 with Cuts 3. and Bd5.for which no binary-mixture viscosity data were available. rewritten as Equation (ll). log (G + 0. Prediction of the viscosity of CO. 1989)... 4 or 5) were provided by Eastick and Mehrotra (1990).5 MPa. The predicted viscosities of CO. and B. B13 = B. Sixteen data points for the CO. it was assumed that B.-solubility.8) = ui [160(0.264 Viscosity of reconstituted binary blerxis of bitumen fractions As mentioned previously. have a positive slope..Cutj interaction parameters from Equation (12). (1992). = B. density and viscosity of Cold Lake bitumen were reported by Eastick et al.008Y’)bj] (11) Next. These B... would involve 15 binary interaction terms. the binary blend data were used to evaluate the Cut i .s are given in Table 3. Of these. Calculations were first performed with Mixing Rule I. = B.2. It was reasoned that these four BVs would be small owing to the similar viscosities of both components in each case. Obviously. The bitumen composition..e. are remarkably close to the experimental viscosities with an AAD of 23. The temperature and pressure ranges for these data were 23..

6..“. Both sets of results. ‘“. which have very different viscosities spanning several orders of magnitude.I . . In Figure 5. nevertheless. mPa.-saturated bitumen fractions and Cut i-Cut j blends to obtain the B. 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. &) had a dominant effect on the viscosities calculated from Mixing Rule II. “‘. Comparison of predicted and experimental viscosity of CO. Mixing Rule II should be viewed as a semi-predictive method. as is shown in Figure 5. it was noted that the term for the Cut 5 -CO.s. The AAD for the sixteen data points was 61.265 The viscosity predictions from Equation (6) for CO.I . These predictions are.8%. acceptable in view of the fact that the calculations involved a mixture of six widely different components.-saturated bitumen may require additional data for the viscosity of CO.19 which is much larger than all other Bi8. the predictions for the viscosity of CO.“. interaction (i. indeed.-saturated (whole) bitumen were higher than the measured data. and (ii) the gas solubility for each Cut i-CO. mPa.-saturated (whole) bitumen from Mixing Rule I are slightly lower than the data. are within one-half to two-times the data. In Table 2.“I . while those from Mixing Rule II are higher.103: . is 9. the value of B.““n “. Of the eleven B+s in the double-summation of Equation (6).e E : o Mixing 0 Mixing Experimental Viscosity..s Fig..‘. In contrast. Comparison of predicted and experimental viscosity of toluene-diluted Cold Lake (whole) bitumen. Hence. 5. the use of Mixing Rule II for another CO. mixture.s Experimental viscosity. from CO.-saturated bitumen. 104.-saturated Cold Lake (whole) bitumen. Fig. 1 “. Thus. Mixing Rule I is a truly predictive method for the viscosity of CO.I ““.?a ‘PI ? cl t >. (a gas) to Cut 5 (a glass-like solid).e.

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

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

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

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