WAX, DEFINITION AND THERMODYNAMIC MODELLING

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WAX, DEFINITION AND THERMODYNAMIC MODELLING
INTRODUCTION The paraffin wax molecules are straight-chain alkanes that contain more than 15 carbon atoms and have very little branching. Under the most favourable conditions, n-paraffins form clearly defined orthorhombic crystals, but unfavourable conditions and the presence of impurities lead to hexagonal and/or amorphous crystallisation. The gelation characteristics are also affected the same way. Alex et al[DoPE1].1 have said that the crude oils with a high n-paraffin content are considered waxy. Rønningsen et al.2 [DoPE2] pointed out that wax may range from predominantly low molecular weight (M) n-alkanes (C20-C40) to high proportion of high M iso-alkanes.

Wax study has been going on for many years (since early 1900’s), mainly in the experimental aspect. Many wax deposition studies have been conducted and reported in the literature2-14. There are different methods for the determination of the onset temperature of wax crystallisation in petroleum fluids. These methods, depending on their capability, could measure wax appearance temperature (WAT), Cloud Point Temperature (CPT) some times called wax precipitation temperature (WPT) and wax disappearance temperature (WDT). The most common methods are as follows; Standard methods, Polarisation Microscopy, Differential Scanning Calorimetry (DSC), Viscometry and Quartz Crystal Microbalance (QCM). The standard methods are not considered good enough for the onset temperature measurement of black oils due to the limitation of the applied liquids.

Until Won15 presented his first thermodynamic model, almost all studies were aimed at experimentally determining the wax formation conditions and the influence of various parameters. Minchin3 had conducted a study on the properties of petroleum waxes in term of their

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compositions. In 1949, Mazee4 studied and discussed the properties of paraffin waxes in solid state. Bern et al.7 studied wax deposition in North Sea subsea crude-oil pipelines. Burger et al.8 investigated the mechanism of wax deposition in the Trans-Alskan pipeline (TAPS). They concluded that deposition occurs on the pipe wall as a consequence of the lateral transport of both dissolved and precipitated wax molecules during cooling of the flowing oil. Since Won15 many authors have developed wax models13-14, 16-20. Among these, Hansen and Co-workers16 have used polymer solution, and Lira et al.13 have considered the solidification of each component or pseudocomponent as an individual solid phase. Pedersen20 considered the ideal solid solution method.

In this study a new model was developed to predict wax appearance temperature (WAT) and the amount of wax precipitation. The fugacity coefficient of liquid was found by the cubic EOS for pure component, i at pressure and temperature of the system. Regular solution theory was used to perform the calculation of the solid phase, and a cubic (Valderama, PR or SRK) EOS was used for the calculation of liquid and vapour phases (if exists). The reported experimental values were used in this study to correlate the imperative parameters and validate the model. The binary mixtures are taken from phase diagram data reported by Peters et al.21-24, Puri and Kohan6, Mazee4 and Domanska et al.25-28. Regarding the multi-component systems, many mixtures representing solid (wax)-liquid have been reported14, 16, 29. As far as the three-phase (S-L-V) data are concerned, only a few experimental data are available.

WAX MODEL The essential step in determining the distribution of component i in solid phase is the calculation of fugacities of each component i in that phase and employing the concept of the equality of fugacities (Equation-2.27), the fugacity of solid ( by, ) of each component is defined

(1) where is the activity coefficient of component i, component i and superscript S is solid phase. is the mole fraction of component i and is standard state fugacity of

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In the following sections evaluations of aforementioned parameters are discussed and equations which are used in this study are presented. DEFINITION AND THERMODYNAMIC MODELLING Page 3 of 27 More detailed description of the wax model is discussed elsewhere30-31. solid fugacity). which was calculated by EOS. Besides.htm 1/21/1998 . Fusion Temperature. These properties are fusion temperatures ( ). mk:@MSITStore:E:\Csearch. Equation-2 is used for n-paraffin when .e. latent heat of fusion ( ). In this study a regular solution theory. solubility parameters (δi) and heat capacity of fusion (∆Cpi).WAX. Tf The fusion temperature plays an important part in calculating the solid (wax)-liquid equilibria (i.chm::/2045. In order to calculate the fugacity of each component in the solid phase. Won15 has suggested the following forms. Hence. using the data reported by Broadhurst32. in this study correlations were developed for normal alkanes of different (odd/even) carbon numbers. the standard state fugacity of pure components as liquid phase was required. Therefore. Equation-3 is used for and Equation-4 is used for non-paraffinic hydrocarbons. is considered for the solid phase. Others have presented different correlations Study conducted by different authors32-35 indicated that the characteristics of n-alkanes according to their carbon numbers (odd/even) significantly differ from one another. in order to perform wax calculation a number of properties are requisite to be evaluated. (2) (4) (3) where M is the molecular weight of each component and T is in Kelvin. its accurate estimation is vital to the calculations of wax solid formation.

Our correlations have been extrapolated up to C100 for normal paraffins. The comparison between measured and predicted Tf for these correlations is shown in Figures-1 and 2.WAX. d. b.19. Coefficients a. Won15 presented the following equation for the heat of fusion. The following equation was also developed for aromatics. The latent heat of fusion of low molecular weight hydrocarbons depends very much on their number of carbon atoms as well as on the parity of the carbon numbers. DEFINITION AND THERMODYNAMIC MODELLING Page 4 of 27 (5) where Cn is the carbon number.14. c. (7) Other authors presented similar equation for the heat of fusion11. These correlations are mostly valid for carbon numbers above C10 to around C45.1). therefor we developed the following equations for the heat of fusion based on the odd/even carbon numbers of n-paraffins. Also a similar equation was correlated for iso-paraffins and naphtenes with one less coefficient (Table-.htm 1/21/1998 . For instance. by lumping all phase transition heats into one latent heat of fusion.chm::/2045. e and f are listed in Table-1. The above equation-(5) was correlated for even carbon numbers from nC4 and for odd carbon numbers from C9. as for the teradecane is 10772 cal/g-mole. (6) Latent Heat of Fusion. Experimental data used for the correlation of these equations were taken from mk:@MSITStore:E:\Csearch. Since the characteristics of the odd and even carbon numbers differ from each other and their accurate values could lead to better results. the latent heat of fusion for undecane is 5330 cal/g-mole.

Solubility Parameter of Solid. Using different binary mixtures thefollowing equation was developed for δS. (10) mk:@MSITStore:E:\Csearch. al11 was used in this study for this model and for the Pan model. δS One of the parameters involved in calculating the fugacity of a component in the solid phase is the solubility parameter. (9) where δs is the solubility parameter of solid (wax) (cal/cc)1/2. B. the latent heat of fusion was the best fitted as compared to the other correlations. As it can be seen using the odd/even method. which was recommended by the author. D and E are given in Table-2. (8) where the values for coefficients A.chm::/2045. The comparisons of the aforementioned correlations have been shown in Figure-3.htm 1/21/1998 . A good approximation of the solubility parameters could very well lead to a better prediction of the WAT. DEFINITION AND THERMODYNAMIC MODELLING Page 5 of 27 Broadhurst32. The correlation proposed by Pedersen et. The fit of the above mentioned equations were about 99% for both cases. Different authors have presented different correlations for δS.WAX. C.

C6-C18. using odd/even correlation. C6-C20. We have also generated the following equation for the molar volume of the solid (wax) components.WAX. C2-C20 and Cyclopentane-C16 . and M is molecular weight. There seems to be more discrepancies as the mole fraction of Cyclopentane increases and Hexadecane decreases Tabel-4 represents the percent average absolute deviation between experimental and predicted WAT using this model. C6C20 and C2-C20 with a very good accuracy. the model has been able to predict the WAT for C6-C16.htm 1/21/1998 . (11) VALIDATION OF THE MODEL In order to validate the model. Other binary mixtures to predict WAT were C6-C16. As an example Figure-4. One chosen sample was C21H42C23H48 n-alkanes for which the liquid-solid phase envelope has been reported37. mk:@MSITStore:E:\Csearch.chm::/2045. C6C18. the developed model shows significant deviations from the experimental values for mixture (Figure-4) . These include binary mixtures as well as multicomponent mixtures for Solid (Wax)-Liquid hydrocarbon (S-L2) and Solid (Wax)-Liquid hydrocarbon-Vapour (S-L2-V).K) and T is in K. based on the density correlation given by Warth36. When binary mixture of Cyclopentane-C16 was used. DEFINITION AND THERMODYNAMIC MODELLING Page 6 of 27 where ∆Cp is in cal/(gmole. Binary Mixtures Sets of different binary mixtures were chosen and the model was tested against the experimental data. different fluids were taken according to the availability of the data.

0112. aromatic for the Mixture-1. predicted results showed a good unanimity with the reported data. • • • • Stock thank oils with one WAT reported for each. The over all percent average error in predicting the S-LHc phase boundary was less than 1 K and in predicting S-L2-V phase boundary was about 2 K. live oils (volatile. Then the flash calculation below the WAT temperatures. Figures. The S-L2 phase boundary was at 0. Using this mixture. Stock Tank Oil Three of these samples had reported WAT at 1 atm and the amount of wax precipitated as the temperature was reduced below the WAT point16.3969 mole fraction of C34H70 at different pressures. a synthetic oil. the change of WAT point with pressure is small. the S-L2-V phase boundary represents points of intersection between two and three-phase equilibrium at different compositions. paraffinic Mixture-2 and waxy oil for the Mixture-3. Also in the same figure. The developed model was used to predict the WAT. DEFINITION AND THERMODYNAMIC MODELLING Page 7 of 27 C3H8-C34H70 was another binary mixture of which the solid (wax) phase boundary was reported by Peters et al.chm::/2045. lighter and heavy) with reported WAT at different pressures.htm 1/21/1998 . in general it over predicted the amount of wax build up. all at 1 atm was carried out. but the model is quite capable of predicting the effect.is an example of the result of the flash calculation for two-phase (S-L2). Mixtures with different characteristics were used in this study are as follows. This is especially true after the early stages of mk:@MSITStore:E:\Csearch. Figures-5 represents the phase boundary comparison for this mixture. These fluids are reported to be biodegraded.3696 to = 0. ranging between = 0. Multi-component Mixtures In order to test the model against the actual fluids.WAX. As it can be seen. As it can be seen even though the model was able to predict the WAT with a very good accuracy. a North Sea gas condensate mixture. several multi-component systems were chosen. Solid (wax)-Liquid hydrocarbon (S-L2) and Solid (Wax)-Liquid hydrocarbon-Vapour (S-L2-V) phase boundaries were predicted by using two and three-phase boundary calculations. As it can be seen. The characterisation of the heavy part of these systems was described in using a continuous function.18.

DEFINITION AND THERMODYNAMIC MODELLING Page 8 of 27 the temperature drop.htm 1/21/1998 . The Pan model under predicted the WAT. For this mixture. the suggested model has been able to predict the WAT with a very good accuracy. Reservoir Oil These mixtures were light.14. Table-5 represents the average absolute deviation between experimental and predicted using all three models. the phase boundary of S-L2 and S-L2-V were reported. by about 5. volatile and heavy oil samples. As shown the model developed in this study was able to predict the phase envelope with a good accuracy. The Pan model has under predicted the WAT for the first oil. The developed model has predicted the WAT with a very good accuracy for the second oil. Also Table. As it can be seen. but the method of calculations were similar to the one used for this study.presents the reported and predicted values for the WAT using the developed model. Figures-11 presents the amount of wax precipitated for a three-phase (S-L2-V) system.61 atm and the developed model predicted a value of 314 K. Synthetic Oil A synthetic oil mixture of C1-C10-Heavy fraction37. This North Sea gas condensate mixture was reported to have the WAT of around 309 K at 13.chm::/2045. North Sea Gas Condensate (GC) Another mixture used in this study was a North Sea gas condensate with reported value of the WAT and the amount of wax precipitated when temperature was lowered38. the Won and the Pan models.WAX. Figure-6 presents the comparison of the measured and predicted two-phase (L2-V and S-L2) and three-phase (S-L2-V) phase boundary. It has to be pointed out that the same characterisations were implemented using all three models. Figures-7 to 10 compare the predicted values for these oils using the developed model. with the heavy included components from n-C18 to n-C30 was the other chosen mixture. The amount of wax build mk:@MSITStore:E:\Csearch. which were used in defining their correlations. The Won model has over predicted the WAT in all three cases. while slightly over predicted the WAT for the first and third mixtures. The WAT was measured and reported at different saturation pressures for each mixture 14. while over predicted the WAT for the third oil. It has to be noted that these data has been reported by Pan et al. the Won and the Pan models.4 K while the Won model has over predicted by more than 15 K. It has to be noted that for both the Won and the Pan models only parameters that have been presented by the respected authors were used. which was a volatile oil. and shows a very good prediction of WAT for the second oil.

volatile oil. 6. “Determination of Cloud Point for Waxy Crudes Using a Near-Infrared/Fiber Optic Technique. δs and V were developed in this study. 5. DEFINITION AND THERMODYNAMIC MODELLING Page 9 of 27 up was over predicted by both this model and the Won model. 543-601. 895-908. Mazee W. Crystallization and Dissolution Temperatures..A. The model and the developed expressions were validated using several binary and muti-component mixtures.16. (1970). Minchin S. The developed correlations and wax parameters were tested against those of other models and showed their superiority in predicting the WAT and the amount of wax precipitated. Fuhr B. Jr. Bjørndal B. The Pan model has under predicted the wax precipitation at the early stages but with only three Kelvin inside the wax zone it over estimated the wax build up. American Chemical Society. These mixtures were chosen within different categories of reservoir fluids that would potentially form waxes.J. “An Account of Some Solid Properties of Petroleum Waxes in Terms of Their Composition. Petrol. and Newtonian and Non-Newtonian Flow Properties.WAX. ∆hf.. mk:@MSITStore:E:\Csearch. (1963). and Pedersen W. Section VI. synthetic oil. that is Tf. “Wax Precipitaion from North Sea Crude Oils. 15. and Huston. Inst. No. pp.” Proc. i.. 5.” Energy & Fuels. and Kohn J.P. Alex R.” J. 5. and Klein L.B. Puri S..B.T. Bostwick L.chm::/2045. (1991). gas condensate. 1948). Rønningsen H.P.. No. 21.M. As can be seen the developed model was able to predict the WAT and the amount of wax predicted for this oil with a fairly good accuracy. 1. 97-102.G. 35.htm 1/21/1998 . The above fluids enabled us to evaluate the model for two-phase (S-L2) and three-phase (S-L2-V) systems. 296. REFERENCES 1. Hansen A.” Journal of Chemical and Engineering data. 4. “Some Studies on the Physics of Paraffin Wax and Wax/Polymer Systems. (1949) “On the Properties of Paraffin Wax in the Solid State. CONCLUSIONS Expressions to determine the parameters of the wax model. 34. 3. 4. black oil and dead oil. Barmby D. J..S.e. 3. The overall results indicate that the developed model is capable of predicting the WAT and wax deposition with a good accuracy.F. “Solid-Liquid-Vapor Equilibrium in Methane-n-Eicosane and Ethane-n-Eicosane Binary Systems.L.5. (Aug. 2. . pp.” Energy & Fuel. (1991).” Journal of Institute of Petroleum. 6th World Petroleum Congress.

Hansen A. (Dec. “Studies of Wax Deposition in the Trans Alaska Pipeline. 12. Larsen E. European Offshore Petroleum Conference & Exhibition.H.M. 13. “A Thermodynamic Model for Predicting Wax Deposition From Crude Oils”.. (June 1981).D.C. Inc. Lira-Galeana C.H. “Thermodynamic Measurement and Prediction of Paraffin Precipitation in Crude Oil”. AIChE. 15. and Cairns R. Precipitation and Dissolution of Wax studied by Differential Scanning Calorimetry... 4. 1994). Chung F. 69th SPE Annual Technical Conference.” SPE 28480. “Wax Precipitation from North Sea Crude Oils. Hansen A. DEFINITION AND THERMODYNAMIC MODELLING Page 10 of 27 7.J. Burger E. Larsen E. 14.. “Wax Precipitaion from North Sea Crude Oils.htm 1/21/1998 . (Sept.chm::/2045. and A. mk:@MSITStore:E:\Csearch. Thermodynamic Modelling.S.. Solid-Phase Content as function of Temperature Determined by Pulsed NMR. 2. 255-279. “Pressure and Composition Effect on Wax Precipitation: Experimental Data and Model Results. 1988). NIPER-555. 1993). 9. Nielsen A.B.S.. (1980).P. (1995) “Thermodynamics of Wax Precipitation in Petroleum Mixtures”.” SPE 36740. 10. 3..P.D. (1991). “Thermodynamics for Solid solution-Liquid-Vapour Equilibria: Wax phase Formation from Heavy Hydrocarbon Mixtures”.. Won K. 16. (1986). Pan H. Santamaria M. “Wax Precipitaion from North Sea Crude Oils. 11. and Rønningsen H.B.B. Firoozabadi A. and Prausnitz J.M.T.P. and Rønningsen H. (1992)..A.WAX. V. and Striegler J.P.” EUR 206. Niesen.G. Narayana L. “Modelling Heavy Organic Deposition”. 239. Firoozabadi (1996).” American Chemical Society. No. 34.. Withers V.J. Leontarities and Darby R.K.H. Hansen J.P.R.B. and Brubaker J. Core Laboratory Division.” American Chemical Society. (1991).. Bern P.” Journal of Petroleum Technology. and Rønningsen H.. 19. 17. Fredenslund Aa. 1993). Brown (Oct. Skovborg P. Pedersen K. 8. 12. Perkins T. 42.. “Wax Deposition in Crude Oil Pipelines. and Rønningsen H.W. “A Thermodynamic Model for Predicting Wax Formation in Crude Oils”. Hsu J.” American Chemical Society. “Wax Deposition of Waxy Live Crudes Under Turbulent Flow Conditions.B. (Jan. Pedersen W..S. Fluid Phase Equilibria. Nielsen A. Pedersen W. Pedersen K. SPE 26604. (1991). Erickson D. 18.B. Western Atlas Division. and T. 30.R. AIChE Journal.

. DEFINITION AND THERMODYNAMIC MODELLING Page 11 of 27 20. and Jolanta Rolinska (1984). and Adrian C. SPE 54006. Tabatabaei. Presented at the Third International Conference on Gas Hydrate. “Measurements and Calculations of Phase Equilibria in Binary Mixtures of ethane+eicosane: Part 3: Three-Phase Equilibria. 31. Elsharkawy A. 32. 69. Todd (1999). Peters C.R. 69. 276. 72. 28. 68. “Solid-Liquid Equilibria in Some Binary Mixtures.J.” J. and de Swaan Aron J.” Fluid Phase Equilibria. Al-sahhaf T. “Three-Phase Equilibria in (ethane-pentacosane). held in Salt Lake City. “Prediction of Cloud Point Temperature and Amount of Wax Precipitation”. (1991). “Correlation of the Solubility of Hexacosane in aliphatic alcohols. de Roo J. de Roo J. 22.L. Ali R. SPE Production & Facilities.J. (1991). 194-206. (1962).M.L. Domanska U. Phase Behaviour Modelling of Petroleum Wax and Hydrate PhD Dissertation. Peters C. 269- 26. “An Analysis of the Solid Phase Behaviour of the Normal Paraffins. de Roo J.” Fluid Phase Equilibria. 3. Pedersen K.” International Data Series.A.J. “Determination and Prediction of Wax Deposition from Kuwaiti Crude Oils”.51-66.. 23.chm::/2045. 265-272 24. 103-11. (1987). (1987).” Journal of Research of the National Bureau of Standard.. Peters C.L. 30. “Solid-Liquid Equilibria in Some Binary Mixtures.. Domanska U.L. and K. No.” International Data Series. themodynamics. de Roo J.htm 1/21/1998 . and Lichtenthaler R. (1990). Domanska U. 2. Domanska U.135-143. 1995). Peters C. Fahim M. 4. S.” Fluid Phase Equilibria. 21.S. and Kniaz K. 29. and de Swaan Aron J.A. 18-22. Domanski (1991). Danesh. (April 1999). Tabatabaei-nejad (1999).. 83-93. (1990). Utah. and Alzabbai W. Broadhurst M.N.N. and Lichtenthaler R. 27.A.” Fluid Phase Equilibria. 66. 19.” International Data Series. 3. mk:@MSITStore:E:\Csearch. (Feb.J. “Solid-Liquid Equilibria in Some Binary Mixtures. “A Consistent Thermodynmic Model for Predicting Combined Wax-Hydrate in Petroleum Reservoir Flyuids”. “Measurements and Calculations of Phase Equilibria in Binary Mixtures of propane+teratriacontane.WAX.. “Measurements and Calculations of Phase Equilibria in Binary Mixtures of ethane+eicosane: Part 2: Solid+Liquid Equilibria. Chem.G. Ali. and Kniaz K. Bahman Tohidi. 251-266 25.

Res. Agrawal K.htm 1/21/1998 .H... pp 639-670. No.598 - e 1287. (1996).886E-01 C -2. Eng. Coefficients of Equation (8).219 140.Phys. 63. R.. Ed.A Review.A.1238 0. (1993) “Phase-Transition Studies in n-Alkanes and Petroleum-Related Waxes.C.H. Turner W. Sec.370 * Iso-paraffins and Naphtanes Table-2. New York. Xans P. Montel F.M. (1971) “Normal Alkanes. Erdöl Kohle.401 B -16. 6.016E-04 D E 7. 54. 10.WAX. 36.01223 - d 690. Solids. Coutinho J. 38.871 -62. 241-248 39.chm::/2045. Affens.659 156. 918-925.M. Fluid Phase Equilibria.843 B 1.284E-01 mk:@MSITStore:E:\Csearch. Coefficients of Equation (5). Daridon J.M. and Joshi G. Carbon numbers Even Odd Iso-P& N* a -426. 88-93. Carbon numbers Even A -1. 543-547.” Ind. The chemistry and Technology of Waxes. “Predictive local composition models for solid-liquid and solid-solid equilibrium in n-alkanes: Wilson equation for multicomponent systems. Res. Dev...L. Chem.543 c 0.” Ind. S. Handoo J. Warth A.38 f 326... Reinhold publishing corporation. Table-1.670 -775. Srivastava S. N. (1956).469 76. 35. Fuel. 13. No.P. Chem. Eng.. 117. Hall J. 3. “Phase Boundary Measurement on a Methane+Decane+Multi-Paraffins System”. 37. (1960).A. Stenby E. Holt. 35.560 -2.086 -2. DEFINITION AND THERMODYNAMIC MODELLING Page 12 of 27 33. Prod. (1984). W. (1996).” J.R.P.and Hazlett. 34. Mazee W. Chem..

chm::/2045.13 even 0.53 new 0.88 Pan 0. Comparison of average absolute deviation (AAD) between experimental and predicted liquid and solid phase boundary using different models for C21H42-C23H48 Mixture(in K) . Average absolute deviation(AAD) between measured and predicted WAT for binary mixtures at different composition (in K).93 1.901 Table-3. Mixture C6H14-C16H34 C6H14-C18H38 C6H14-C20H42 C2H6-C20H42 AAD/K 0.10 odd 0.74 0.61 0.741E-01 -2. Table-4.79 0.520 3. LPB* SPB+ Won 0.WAX.52 1.90 * LPB is average deviation of liquid phase boundary.htm 1/21/1998 .903E-06 -2. + SPB is average deviation of solid phase boundary. DEFINITION AND THERMODYNAMIC MODELLING Page 13 of 27 Odd 4.28 0.66 0.18 0.23 mk:@MSITStore:E:\Csearch.317E-03 6.

Mix-1 Mix-2 Mix-3 308 314 289 Won 318 328 304 Pan 300 306 294 This Work 309 315 292 Table-6.22 2.88 Table-5. Experimental and predicted WAT points (in K) for three stock tank oil using different model.95 4. Average absolute deviation (AAD) between experimental and predicted WAT points for three oil mixtures using different models (in K) .18 3.54 4.94 15. Won Oil-1* Oil-2* Oil-3* * Pan 3.59 12.14 these data are reported by Pan et al.WAX. Exp.19 24.14 mk:@MSITStore:E:\Csearch.chm::/2045. DEFINITION AND THERMODYNAMIC MODELLING Page 14 of 27 Cyclopentane-C16H34 1.htm 1/21/1998 .94 This Work 10.

1026458740234375 1." Arial 12 None None 169..21840209960936 3835.P. and Klein L.3319030761722 3142..”.9853515625 1.chm::/2045.. 895-908 Cn Mw 1 2 Mw Tf Won Pan N-1 N-2 Mw Exp.62481689453125 FullPage Arial 10 0 0 7124.12 113. Energy & Fuel. DEFINITION AND THERMODYNAMIC MODELLING Page 15 of 27 [DoPE1] Alex R. Fuhr B.6 5 0. Hansen A.L. 5 [DoPE2] Rønningsen H. 1991.. American Chemical Society. 1991. and Newtonian and Non-Newtonian Flow Properties.9853515625 5009. Kcal/mole Kcal/mole DHF Cn Pan (WON) 58.12393066406253 363.B..103421 0 MinMax 1 MinMax Chart 1 -1 "Figure3. Crystallization and Dissolution Temperatures.htm 1/21/1998 .B.995219 1.F.56120361328124 62. Bjorndal B.1437866210936 630.J. “Wax Precipitaion from North Sea Crude Oils. “Determination of Cloud Point for Waxy Crudes Using a Near-Infrared/Fiber Optic Technique”.WAX.22393798828125 5762.3568267822265625 520.3 Comparison of the prediction of Tf for Non-Paraffinic using different models. 5.. Pedersen W. Energy & Fuels. 1..5133117675782 mk:@MSITStore:E:\Csearch.

chm::/2045.XLS] Sheet1'!$C$7:$C$31 0 '[FIG-1.XLS]Sheet1'! $C$7:$C$31 0 '[FIG1.2244 15 Solid Narrow None Arial 11 Scatter Marker None 0 1 3 -1 " Exp.htm 1/21/1998 .2494995117188 6 1.WAX. " Exp.XLS] Sheet1'!$D$7:$D$31 1 -1 "Pan" Pan 25 Solid Narrow None 0 '[FIG-1.XLS]Sheet1'! $H$5:$H$26 0 '[FIG1.XLS] Sheet1'!$F$7:$F$31 Bottom 0 0 -1 "Mw/ g/mol" Arial 11 None None 1 Arial 11 0 Value Left 1 1 -1 "Tf/K" Arial 11 None None 0 Arial 11 0 Value Horizontal Custom 4043.XLS] Sheet1'!$C$7:$C$31 0 '[FIG-1.2138 227.07125 -89. None Circle 6 31 31 0 '[FIG-1.32 60.631942 mk:@MSITStore:E:\Csearch.XLS]Sheet1'! $E$7:$E$31 2 -1 "This work" This work 0 Dot Wide None 0 '[FIG-1. DEFINITION AND THERMODYNAMIC MODELLING Page 16 of 27 3 50 -215.XLS]Sheet1'! $I$5:$I$26 0 -1 "Won " Won 24 DashDotDot Medium None 0 '[FIG-1.4291870117186 1881.752649 1.

37317 11.1333 298.976337 5.848 75 -9.35431 2.328 13 184.9903 209.2 147 192.172 7 100.51152 3.4809 330.813209 9.232 114.4 278 282 290 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 2.42332 20.48241 17.0097 70.96231 18.38 15 212.69655 13.98275 15.5237 251.562 22 310.513 280.276 11 156.151 86.232 128.205 114.8295 550 346.076 208.458 18 254.83462 27 31.15084 11.84 155.966 344.2567 450 334.232 114.4 138.71 319.432 17 240.7 164 152.4824 150 196.78575 19.484 19 268.62505 28 34.351 210.5515 256.406 16 226.6108 250 279.99612 18.28913 14.50977 13.864426 8.86689 21.chm::/2045.796 31 436.6015 336.29466 23.8581 500 341.6982 322.1 269. DEFINITION AND THERMODYNAMIC MODELLING Page 17 of 27 1920 820 Arial 10 4 58.4733 330.324 182.00317 mk:@MSITStore:E:\Csearch.033615 4.2185 300 299.85226 15.5 149.198 8 114.6951 19.73508 16.75595 23.7061 248.297 168.htm 1/21/1998 .77 30 422.14719 20.20795 17.822 32 450.6686 312.03 400 325.354 14 198.205 100.859897 3.2978 324.95546 11.63602 16.42 257.WAX.146 6 86.7 113.593529 10.9143 279.095335 7.30883 202.95897 22.2615 350 314.1996 600 351.72524 6.796852 5.51 20 282.54 107.245066 4.57685 20.296 200 248.135 72.07974 26 27.421 210.3459 202.5825 202.336 283.46331 14.4824 100 93.12 5 72.36943 21.3274 29 408.0838 127.55439 24.9467 301.242 128.224 9 128.7789 279.421 252.22486 17.286 154.6296 52.5834 264.7891 329.537248 4.4052 239.033862 8.21333 112.58264 22.536 21 296.168 327.22545 14.92555 12.16347 21.561548 6.588 23 24 25 25.6375 341.486971 7.257582 8.6252 229.73188 12.221438 2.3 119.9 104.242 142.297 154.6052 219.327709 7.8 171 206 224 215 220 229 251.8933 217.634985 9.286 266.135 70.06996 14.271839 4.368 312.407007 10.1805 10.302 12 170.25 10 142.42125 17.178 100.2275 272.

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