SPE 136966 Thermodynamics Prediction of Wax Precipitation Using the Patel-Teja Equation of State

K.K. Farayola, Y.B. Adeboye, and O.A. Adekomaya, Petroleum and Gas Engineering Programme, Department of Chemical Engineering, University of Lagos; and A.O. Olatunde, Department of Chemical Engineering, University of Lagos
Copyright 2010, Society of Petroleum Engineers This paper was prepared for presentation at the 34th Annual SPE International Conference and Exhibition held in Tinapa Calabar, Nigeria, 31 July7 August 2010. This paper was selected for presentation by an SPE program committee following review of information contained in an abstract submitted by the author(s). Contents of the paper have not been reviewed by the Society of Petroleum Engineers and are subject to correction by the author(s). The material does not necessarily reflect any position of the Society of Petroleum Engineers, its officers, or members. Electronic reproduction, distribution, or storage of any part of this paper without the written consent of the Society of Petroleum Engineers is prohibited. Permission to reproduce in print is restricted to an abstract of not more than 300 words; illustrations may not be copied. The abstract must contain conspicuous acknowledgment of SPE copyright.

Abstract
Flow assurance is a problem which plagues the petroleum industry. The purpose of this study is to predict wax precipitation in crude oil pipelines. The industry spends millions of dollars to remediate this problem. As a result, ways are being sought to reduce the occurrence of the phenomenon by predicting as accurately as possible, the wax appearance temperature, which is a very important parameter when analysing the problem of wax precipitation. Experimental methods have been employed in times past, but in recent times, thermodynamic modeling of wax formation allows better prediction of wax deposition in pipelines. A three parameter equation of state, the Patel-Teja EOS is used to describe the non-ideality of the liquid phase (oil) while the UNIQUAC model is used to describe the solid phase (wax). Solid precipitation is measured as temperature drops below the wax appearance temperature. The introduction of the third parameter increases the accuracy of results. The results from this study are in agreement with observations made by Pedersen et al. (1995) and Lira Galeana et al. (1996). This study has shown that the Patel-Teja EOS gives better predictions of wax precipitation when compared with the Peng Robinson EOS. This paper is based on theoretical data only. Accurate prediction of wax precipitation reduces loss time, maintenance cost and production loss due to shut-in. Although a kinetic model is required to estimate the wax deposition rate, accurate thermodynamics model is a key requirement for both wax deposition and precipitation calculations as the kinetics is being controlled by the thermodynamics driving force. The thermodynamic model proves successful and compares favourably with results obtained from the experimental data.

Introduction
The most common channels of transporting oil and gas are the pipelines. There are several problems associated with transportation of crude oil. One of these is the problem of wax formation. Drops in temperature can cause waxes to precipitate out of crude oil, thereby forming waxy and elongated crystals. Wax precipitation from petroleum fluids could be predicted at high pressures (reservoir conditions) and low pressures (stock tank oil). Wax formation may occur in surface pipelines, production tubings, surface equipments or reservoir formation. Light and intermediate hydrocarbons (paraffins, aromatics, naphthenes, etc.) and heavy organic compounds (resins, asphaltenes, diamondoids, etc.) are the main constituents of a waxy crude oil. The heavier fractions are the first to precipitate when the temperature of a waxy crude oil drops. A stage is reached when the waxy crude oil becomes so thick that it does not pour. The temperature at which this happens is the pour point. Crystallization commences as soon as cloud point or wax appearance temperature (WAT) is reached. Several authors have described wax precipitation by using experimental data; they predicted too high cloud point temperatures and thereby overestimated the amount of wax at temperatures below the wax appearance temperature (WAT). There are losses of light hydrocarbons from crude oil system as a result of decrease in temperature and or pressure. These result in the oil having decreased ability to hold the paraffins molecules in the crude oil and precipitation of paraffin then result from the crude oil. Galeana et al. (1996) have suggested that in typical real systems, the carrying capacity of the light fraction of the oil keeps hydrocarbons with molecular weights ranging from 100

SPE 136964

(C7) to around 400 (C25) dissolved in the liquid phase (oil), in agreement with the wax analysis by Bishop and Phillip (1994). The solid solution models predict the presence of light hydrocarbons in the solid wax (Won, 1989). The heaviest aromatic compounds do not contribute much to the formation of wax. This study focuses on the prediction of wax appearance temperature (WAT) using Patel Teja EOS. When WAT is reached, the molar ratio of the first precipitation in the crude oil system is greater than zero but it is still very small, in the order less than 10-8. C7+ fraction have been classified into wax forming and non wax forming parts. The difficulty in identifying components increases with carbon number for the C7+ fraction. Pedersen et al. (1995) have suggested that the non wax forming components could be assigned very high fugacity coefficients in the wax phase so that the non wax forming components are avoided in the wax phase. While the heaviest components do not contribute much to wax formation, they are very important in the calculation of the cloud point temperatures as demonstrated in this work.

During formation of wax, some components undergo a solidification process. When wax disappears, the wax phase components undergo a melting process. For the phase transition of a pure component i from solid to liquid form, the thermodynamics is the melting of component i. Application of the phase equilibrium criteria is achieved by considering the wax phase as a homogeneous solid solution which exists in equilibrium with a liquid solution. At equilibrium between oil phase and wax phase, the fugacity (fi) for component i in both phases must be the same. That is:

fi = fi

(2)

The change in Gibbs free energy is considered to determine the thermodynamic favorability of the phase transition. An expression for the change in Gibbs free energy as a result of melting of component i is given by:
G =H TS

(3)

For a given temperature T, the total enthalpy change associated with the transition from solid to liquid is:
Ti f H = H i f + C p dT T

Theoretical background
An accurate thermodynamic relationship is required to accurately model the equilibrium between oil and wax phase. An equilibrium relationship exists which relates the fugacity of the liquid phase (oil) and the fugacity of the solid phase (wax) with thermo physical properties and is given by:
f H f ln l = i f s RT f i

(4)
f 1 i (C pl C p s )dT + R T T f C l C s p p dT T

Equation 2 then becomes:

G H i = RT RT f

1 T 1 Ti Ti f RT T

(5)

Ti f 1+ Hitr Titr 1 s C p ln T + Ti f 1 T RTitr T R Ti f T (1)

The second solid phase transition from rotator to orthorhombic phase occurs at slightly lower temperature given by Ttr. Equation 5 then becomes:
G Hi = RT RT f

Several researchers have used the above relationship as a basis for the development of mathematical models. All researchers in this field of study made use of the general fugacity equation for solid-liquid equilibrium given by equation 1. Differences however exist in the equations used to model the solid and liquid phases as can be seen on the left hand side of the equation, and the choice of thermo physical correlations. While some researchers have used free energy models (e.g. the UNIFAC model) which works well at low pressures, others have used equations of state, which suitably models high pressure scenarios and have proved more reliable in describing the non ideality of the liquid phase. Various models also exist and have been used to model the solid phase. Models like the UNIQUAC, WILSON, etc have been used to describe the non ideality of the solid phase. In this study, the Galeana et al (1996) model is modified by using the Patel-Teja three parameter equation of state to model the non-ideality of the liquid phase. The assumptions made in the development of this model include; lightest component that can be found in the wax phase is C7, wax crystals are orthorhombic, and only straight chain paraffins are present.

1 T + Htr 1 T Ti f RT Tr

[ ]

l s T f T f 1 i 1 i C p C p l s dT C p C p dT + RT T R T T

(6) The relationship between change in Gibbs free energy and change in fugacity of a pure component i is given by:
f s Gi f = RT ln i fil

(7)

Combining equations (6) and (7) and expressing the result in terms of activity coefficient give:
ln f f ,i l s C p tr i tr ,i x s s i f ,i + 1 1 1 + = ln l l f ,i R R f , i Rtr ,i x

[ ] [ ]

(8) Liquid Non-Ideality The Patel-Teja equation of state will be used to predict liquid non-ideality instead of the Peng Robinson EOS or the UNIFAC method. This makes possible the

SPE 136964

incorporation of a third parameter c, which improves the accuracy of the equation of state. The fugacity of a pure compound may be expressed as follows:
ln = ( Z 1 ) ln Z + 1 v RT P dv RT v

= 0.329032 0.076799 + 0.0211947

(21)

(9)

The Valderrama modification of the PT-EOS can be introduced to calculate ac , b and c The critical compressibility factor can be obtained by solving the following quadratic equation:
m = 0 .452413 +1 .30982 0 .295937 2

For the Patel-Teja equation of state, P is given by:

ac RT P= + v b v( v + b ) + c( v b )

(22)
2

m = 0.46283 + 3.58230 c + 8.19417( c )

(23)

(10)

In terms of compressibility factor z, the fugacity coefficient is related to the Patel-Teja, the three parameter equation of state as follows:
ln =( 1) ln

ln 2 + + C C + ln 2 ++C

)]

Experimental results are required to obtain the composition of the paraffin, which will then be used to describe the phase behaviour. For proper description of phase behaviour, data from the pure physical components are required. However, since these data may not be readily available, approximate results should be expected. Solid Non-Ideality The predictive UNIQUAC model as proposed by Coutinho et al. (2001) will be used to predict the nonideality of the solid phase.
ln i s =ln

(11) Where:

A=

aP (RT) 2

(12)

b = R

(13) (14)

i +1 i Z q ln i x s x s 2 i i i i

(( ) ) ( )
n +1 i +qi qi ln j ij i j =1

Where,

C=

c R

ij =exp

ji ii
qi RT

(24)

(25)

The three parameters of the equation of state may be expressed as:

R2T 2 ac = ac c Pc

i =

xi qi x jq j j

(26)

(15)

i =

xi ri x jrj j

(27)

RT b= b c Pc
RT c= c c Pc
ac = 3 2 + 3( 1 2 ) b + b 2 ( 1 3 )

Here, (16) (17)

i , ji and denote the area fraction, segment

fraction and interaction energies respectively. The interaction energy is related to the heat of sublimation of a pure orthorhombic crystal by:
ii =
2 ZC

( sub Hi RT )

(28)

(18) (19) (20)

b = 0 . 3249 0 . 022005

c =1 3

ZC, the coordination number has a value of 6 for orthorhombic crystals. Since the model requires the pure component of thermophysical properties for its calculations, it is said to be highly predictive. The heat of sublimation can be calculated using the melting temperature of the pure component and the heat of vaporization as follows:

SPE 136964

sub H = vap H + fus H + tr H

Crude Oil Applications

The experimental data for 16 North Sea oils have been presented by Ronningsen et al. (1991) and Pedersen et al. Four of the sixteen oils have been selected in this study and their brief description is given in Table 1. Table 1: Brief Description of Oils used in this study
Oil No. 1 2 5 8 Type of Oil Biodegraded, aromatic oil Paraffinic oil Waxy oil Paraffinic oil

Hydrocarbons with less than 7 carbon atoms, C6- fraction can be identified by standard compositional analytical methods. However, the difficulties in identification increase as the carbon number increases for heavier hydrocarbon, C7+ fraction. Pedersen et al. (1995) observed that heavy hydrocarbons do not contribute much to wax formation. The predicted wax appearance temperatures using the Patel Teja EOS for oils 1, 2, 5 & 8 are given in Table 2. These compared favourably well with the experimental data and calculated cloud point temperatures given by Galeana et al. (1996). The results obtained in this study give better predictions than predictions by Lira Galeana et al. (1996). At the wax appearance temperatures, very small amount of wax precipitation occurs and becomes negligible at greater temperatures. Table 2: Experimental and Predicted Wax Appearance Temperatures
Oil No. 1 2 5 8 Exp. K Peng Robinson, K 305.9 311.8 312.4 308.2 Patel Teja, K 305 312 313 310 Exp.-Peng Robinson, K -1.75 0.35 0.75 2.95 Exp.Patel Teja, K -0.85 0.15 0.15 1.15

are shown in Table 2. The molar ratio of the first precipitating component of the crude oil system is between zero and 10-8, Galeana et al. (1996). This also means that weight percent of wax as shown in Figure 1 is a very small number greater than zero. It can be observed that at the predicted wax appearance temperatures, such as 305K for oil 1, a very small amount of wax precipitates and this becomes difficult to determine at higher temperatures. Solid composition based on the number of carbon atoms follows the same pattern for oils 1, 2, 5 & 8 as shown in Figures 3 6. For the oil mixture used, the C15+ components will form stable wax. A stability analysis has been carried out to determine the smallest components that will form stable wax. The C15+ components are added to compute the total solid composition and therefore the individual solid composition for oils 1, 2, 5& 8 in Figures 3 6 are based on C15+ components.

Conclusions
The Patel Teja EOS has been used to predict wax appearance temperature in crude oil systems. The prediction was based on using Patel Teja EOS to describe liquid non ideality and the results were tested with experimental data. Prediction of wax precipitation in pipelines using Patel Teja EOS has given better results in terms of wax appearance temperature and amount of wax precipitated when compared with Peng Robinson EOS

304.15 312.15 313.15 311.15

Figure 1 shows an example of calculated wax precipitation curve, which means a curve of weight % wax of the total mixture as a function of temperature at atmospheric pressure. The Patel Teja EOS used in this study predicted the wax appearance temperature of 305 K which is very close to the experimental value, 304.15 K as shown in Table 2. This is a better prediction than prediction by Peng Robinson EOS. Figure 2 shows the curves of weight percent of wax precipitated for oils 1, 2, 5 & 8 as a function of temperature at atmospheric pressure. The predicted wax appearance temperature is given when initial substantial amount of solid was formed. The readings from Figure 2 for oils 1, 2, 5 & 8

SPE 136964

Table 3: Compositions and Properties of Oil Mixtures Oil No. Oil No. Comp. C1 C2 C3 C4 C5 C6 C7 C8 C9 C10 C11 C12 C13 C14 C15 C16 C17 C18 C19 C20 C21 C22 C23 C24 C25 1 1 Mol 0.01139 0.00507 0.00481 0.01197 0.01628 0.02003 0.05478 0.08756 0.07222 0.05414 0.05323 0.04571 0.0528 0.0472 0.04445 0.03559 0.03642 0.03104 0.02717 0.02597 0.01936 0.02039 0.01661 0.01616 0.01421 Mol. Wt. 16 30.1 44.1 58.1 72.2 86.2 90.9 105 117.7 132 148 159 172 185 197 209 227 243 254 262 281 293 307 320 333 2 2 Mol. Mol. Wt. 5 5 Mol. Mol. Wt. 8 8 Mol. Mol. Wt.

0.0911 0.1084 0.07413 0.06394 0.05649 0.0527 0.04541 0.04921 0.03903 0.02894 0.0342 0.02399 0.02737 0.00909 0.02207 0.01463 0.01226 0.00933 0.01327

92.3 105.9 120 133 148 163 177 190 204 217 235 248 260 269 283 298 310 322 332

0.06536 0.08607 0.04882 0.0283 0.03019 0.03119 0.03687 0.03687 0.03637 0.03079 0.03657 0.03289 0.03489

88.8 101 116 133 143 154 167 181 195 207 225 242 253

0.09933 0.1075 0.07179 0.06561 0.05494 0.04547 0.04837 0.037 0.0352 0.02922 0.03072 0.02124 0.02493

92.8 106.3 120 134 148 161 175 189 203 216 233 248 260

SPE 136964

Nomenclature
Cn Cp f G H MW P Q R S T x Z Zc n-alkane with n carbon number of atoms Specific heat capacity Fugacity Gibbs free energy Enthalpy Molecular weight Pressure UNIQUAC structural parameter UNIQUAC structural parameter Entropy Absolute temperature Molar fraction Compressibility factor Coordination number

Subscripts and superscripts

i j f l s tot tr vap Component i Component j Fusion Liquid Solid Total Solid phase transition Vaporisation

Greek symbols Activity coefficient Fugacity coefficient

ji

Pair interaction energies Accentric factor Area fraction Segment fraction

6. Lira-Galeana C., Firoozabadi A. and Prausnitz J.M. (1996), Thermodynamics of Wax Precipitation in Petroleum Mixtures, AIChEJ. 42(1), 239-247. 7. Pedersen, K.S., (1995), Prediction of Cloud Point Temperatures and Amount of Wax Precipitation, SPE Production and Facilities 27629, 46-47. 8. Pedersen, W.B., Hansen A.B., Larsen E., Nielsen A.B. and Ronningsen H.P.,(1991), Wax Precipitation from North Sea Crude Oils; 2 Solid-phase Content as Function of Temperature Determined by Pulsed NMR, Energy and Fuels, 908. 9. Pedersen K.S., Lindskou P., (2005), Phase Behavior of Petroleum Reservoir Fluids. CRC Press, 229, 240242. 10. Pedersen K.S., Skovborg P. and Ronningsen H.P., (1991) Wax Precipitation from North-Sea Crude Oils; Thermodynamic Modeling, Energy and Fuels, 5, 924. 11. Ronningsen, H.P., B. Bjorndal, A.B. Hansen, and W.S. Pedersen, Wax Precipitation from North Sea Crude Oils: I. Crystallization and Dissolution Temperature, and Newtonian and Non-Newtonian Flow Properties, Energy and Fuel, 5, 895 (1991) 12. Smith J.M., Van Ness M.M. and Abbott, (2002) Introduction to Chemical Engineering Thermodynamics 6th ed. 2004. 13. Won, K.W., (1986), Thermodynamics for Solid Solution-Liquid-Vapour Equilibria: Wax Phase Formation from Heavy Hydrocarbon Mixtures, Fluid Phase Equilibria 30, 265. 14. Won, K.W., (1989), Thermodynamic Calculation of Cloud point Temperatures and Wax Compositions of Refined Hydrocarbon Mixtures, Fluid Phase Equilibria, 53, 377.

4% 3%
WaxWeight

Oil1

References
1. Banki R. and Firoozabadi A.(2002), Modeling of Wax Deposition in Pipelines from Irreversible Thermodynamics. Paper SPE 77571, presented at Annual Technical Conference and Exhibition, San Antonia. 2. Banki R., Hoteit H., Firoozabadi A. (2008), Mathematical Formulation and Numerical Modeling of Wax Deposition in Pipelines from Enthalpy-Porosity Approach and Irreversible Thermodynamics. International Journal of Heat and Mass Transfer. 3. Coutinho, J.A.P., Beryl, E., Morwood, T., Sczzepanski, R. and Zhang, X. (2002), paper SPE 78324, presented at the 13th European Petroleum Conference, Aberdeen, Scotland. 4. Coutinho J.A.P., Pauly J. and Daridon J., Modeling Phase Equilibria in Systems with Organic Solid Solutions. 5. Hansen J.H., Fredenslund Aa., Pedersen K.S. and Ronningsen H.P. (1988), A Thermodynamic Model for Predicting Wax Formation in Crude Oils, AIChEJ., 34(12), 1937.

2% 1% 0% 230 250 270 290 310 330

Temperature,K

Figure1:Calculatedwaxappearance temperaturesforoil1

SPE 136964

4%

Oil1
3% WaxWeight

Oil2 Oil5 Oil8

2%

1%

0% 230 250 270 290 310 330

Temperature,K

Figure2:Calculatedwax appearance temperaturesforoils1,2,5& 8

IndividualSolidComposition

1.3E06 1.0E06 7.5E07 5.0E07 2.5E07 0.0E+00 230 250 270 290 310 Temperature,K 330
c16 c17 c18 c19 c20 c21 c22

IndividualSolidComposition

1.0E06

5.0E07

c16 c17 c18 c19 c20 c21 c22

Figure 4:Solidcompositionforoil2

0.0E+00 230 250 270 290 310 330

Temperature,K

Figure3:Solidcompositionforoil1
IndividualSolidComposition

2.5E07 2.0E07 c16 1.5E07 1.0E07 5.0E08 0.0E+00 230 250 270 290 310 330 Temperature,K c17 c18 c19

1E09 IndividualSolidComposition 8E10 c16 c17 c18 c19 6E10 4E10 2E10 0 230 280 Temperature,K 330

Figure6:Solidcompositionforoil8

Figure5:Solidcompositionforoil5