SPE 56675 A Thermodynamic Modelling Method for Organic Solid Precipitation

Haiyan Mei, Xiangyan Kong, Maolin Zhang, University of Science and Technology of China; Lei Sun, Shilun Li, Liangtian Sun, South-West Petroleum Institute, China

Copyright 1999, Society of Petroleum Engineers Inc. This paper was prepared for presentation at the 1999 SPE Annual Technical Conference and Exhibition held in Houston, Texas, 36 October 1999. 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, as presented, have not been reviewed by the Society of Petroleum Engineers and are subject to correction by the author(s). The material, as presented, does not necessarily reflect any position of the Society of Petroleum Engineers, its officers, or members. Papers presented at SPE meetings are subject to publication review by Editorial Committees of the Society of Petroleum Engineers. Electronic reproduction, distribution, or storage of any part of this paper for commercial purposes 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 where and by whom the paper was presented. Write Librarian, SPE, P.O. Box 833836, Richardson, TX 75083-3836, U.S.A., fax 01-972-952-9435.

Abstract A gas and oil system contains a certain amount of heavy organic substances, such as wax, resin and asphaltene which precipitate as a solid phase, causing serious problems to production for oil and gas fields, when thermodynamic conditions are changed. In this paper, a thermodynamic model of the gas-liquidsolid three-phase equilibrium for an oil and gas hydrocarbon system is presented, based on the regular solution theory, an equation of state and the phase equilibrium principle of fluid thermodynamics. A flash calculation model for the gas, liquid and solid three phases is developed, being combined with a material conservative equation. An equation of state is used to describe both gas and liquid phases, and a regular solution theory is only used to account for the non-ideality of the solid mixture, which can reflect the effects of temperature, pressure and composition of system on solid precipitation. The influence of the heat capacity difference between the liquid and the solid on the solid precipitation is taken into consideration. Some adjustable parameters and a tuning function are introduced in this model because of uncertainty of heavy component properties. It is shown that the model has a good convergency and stability, and the calculated values by this model are in good agreement with the experimental data. Introduction Organic solid precipitation in the oil and gas system has always been a serious problem, which has confronted with the petroleum industry for many years. The solid precipitation problem can take place in several locations of oil production and processing, such as the formation, wellbore, well tubing, transfer pipeline, surface equipment, storage tank, and refining

process equipment. When it happens in the reservoir, for example, in the miscible flooding, these deposits can cause severe formation damage, including the pore plugging, the porosity and permeability decreasing. In addition, the reservoir wettability can be altered by the adsorption of organic chemicals on the rock surface, which can lead to lowering the ultimate oil recovery and decreasing the gas injection efficiency. When the solid precipitation occurs in the wellbore, well tubing and transfer pipeline, it results in plugging the flowing channel, increasing the fluid pressure gradient and decreasing the well productivity. In many oilfields, a huge expense has to be costed on the removal of these deposits in order to maintain normal production and operation. It is significantly important to do more research on the gasliquid-solid three-phase equilibrium and the phase behavior calculation, both in theory and application. The main causes of solid precipitation are the changes of the thermodynamic equilibrium conditions, such as the temperature, pressure and composition of the system. The phase behavior modelling calculation on the gas, liquid and solid three phases can determine the thermodynamic conditions in which the solid precipitation begins to occur and can predict the amount of the solid phase in different conditions. It can provide a theory basis and an evaluation technique for directing oil and gas production and processing in order to prevent and mitigate the solid precipitation problem. The fluid phase equilibrium theory on the gas-liquid and the liquid-liquid has been broadly conducted for many years and obtained considerable achievement. In contrast, the attention of the research on the gas-liquid-solid three-phase equilibrium has been attracted only in recent decade. The critical and difficult point for the study on the gas-liquid-solid three-phase equilibrium is how to describe the characteristics of the solid phase. There are two ways to achieve this purpose. One is to describe the phase behavior for all phases, gas, liquid and solid, by the use of an equation of state. The other is to calculate the gas and liquid phases using an equation of state, and to treat the liquid and solid phases in terms of the solution theory, such as the regular solution and the polymer solution. Because, at present, it is improper to describe the solid phase behavior with an equation of state, many investigators adopt the latter. The precipitated solid usually constitutes the heavy

Haiyan Mei, Xiangyan Kong, Maolin Zhang, Lei Sun, Shilun Li, Liangtian Sun

SPE 56675

organic compounds of wax, asphaltene and resin. Although a lot of research has been done considerably on the nature of heavy organic compounds and the mechanism of solid deposition, the accurate prediction of solid precipitation has been impeded because of the complexity of the solid compounds in hydrocarbon systems at the current limitation of experimental techniques. There are two thermodynamic solution models which are widely adopted in the modelling of the solid precipitation from oil and gas systems. Both the regular solution theory [1][3][4] and the polymer solution theory [2][6] are used to estimate the activity coefficient for the liquid or the solid phase. The regular solution theory of Scatchard and Hildebrand, which assumes regularity (sE=0) and isometric mixing (vE=0) at constant temperature and pressure, is developed for the mixture of non-polar liquid with similar size of molecules. The polymer solution theory, which is based on a quasi-crystal lattice and a statistical mechanical theory, is developed for the mixture of non-polar liquid with significantly different size and shape of molecules. In this work, the regular solution theory is employed to formulate the activity coefficient for the solid phase only. Both the gas and liquid phases are described by the use of an equation of state. Thermodynamic Model According to the thermodynamic equilibrium principle, at a given temperature and pressure, the fugacities of component i, fiV in the vapor phase, fiL in the liquid phase and fiS in the solid phase are equal at thermodynamic equilibrium:

fugacity of component i is expressed as:

f i S = x iS ri S f i OS ....................................................... (6)
where xiS is the molar fraction of component i, riS the activity coefficient of component i and fiOS the standard state fugacity of component i in the solid phase. By combining the equations (4), (5) and (2), the vaporliquid K-value, KiVL can be expressed as:
VL i L xiV i = L = V ...................................................... (7) i xi

The vapor and liquid phase fugacity coefficients iV and iL are obtained from an equation of state. By combining the equations (5), (6) and (3), the liquid-solid K-value, KiSL is given by:
SL i

iL P xiS = L = S OS ................................................ (8) xi ri f i

By considering the heat capacity difference between the solid and liquid phases, the following expression of the relationship between the standard state fugacity of solid phase and the standard state fugacity of liquid phase is derived [4]:
f i OS = f i OL exp[ + 1 R H RT C T
S pi f i

(1 dT ]

T Ti
f

)+

f i = f i = f i .......................................................... (1)
V L S

1 RT

Ti

(C

L pi

S pi

) dT

... (9)

Ti

L pi

Equation (1) equates the following two equations:

f i = f i .................................................................... (2)
V L

f i L = f i S ..................................................................... (3)
When an equation of state is applied to calculate the fugacities fiV and fiL of component i in the vapor and liquid phases, they can be expressed as follows:

where Hif is the melting enthalpy, Tif the melting temperature, CPiL and CPiS the liquid heat capacity and solid heat capacity of component i, respectively, and R the gas constant. From experimental results of heat capacities of the liquid and solid phase for the components n-C8, n-C18, n-C25 and n-C33, the function of heat capacity difference with temperature and molecular weight is [4]:
L S C Pi = C Pi C Pi = a 4 M i + a 5 M i T .............. (10)

f iV = xiV iV P ........................................................... (4)

f i L = xiL iL P ........................................................... (5)
In these two equations, xiV and xiL are the molar fractions of component i in the vapor and liquid phases, respectively. iV and iL are the fugacity coefficients of component i in the vapor and liquid phases, respectively. P is the pressure. The regular solution theory is employed to account for the non-ideality of the solid phase mixture. The solid phase

where Mi is the molecular weight of component i and a4 , a5 are the constants. The liquid standard state fugacity of component i is taken as the pure component fugacity at the system temperature and pressure, and is expressed as follows:

f i OL = iOL P ........................................................... (11)

where iOL is the liquid phase standard state fugacity

SPE 56675

A Thermodynamic Modelling Method for Organic Solid Precipitation

coefficient which is obtained from an equation of state. Therefore, combining equation (10) and (9), the solid phase standard state fugacity is derived as: f i OS = f i OL exp[ ln a M T H i T (1 f ) + 4 i ( i 1 RT R T Ti ..... (12)
f f

expression [7]:
M i 48 .2273 ))) 7.62 + 2.8a 2 (1 exp( 5.9751( 628 .....(19 M i 450 = 10 .30 + 1.7823 10 3 a ( M 394 .77 ) i 2 M i 450

iS

Ti f a M (T f ) 2 + T 2Ti f )] )+ 5 i ( i T T 2R

) The form of f(Mi) is:

f ( M i ) = a 3 + (1 a 3 )( 0.5 arctan(( M i 16) / 14 6) / 3.1416 ) ... (20)

The non-ideality of the solid mixture is taken into account in terms of the regular solution theory. The solid phase activity coefficient is expressed as follows:

ln ri S =

V i (
S

S m

S i

RT

.................................... (13)

These adjustable model factors c1, c2, a2, a3, a4 and a5, which are used to correct the uncertainty of heavy components, are obtained by the matching calculation with the experimental data. Three-Phase Flash Model For a given system with n components, the feed molar number is 1 mole. At thermodynamic equilibrium, the normalized criteria of composition are needed:

where the iS is the solid phase solubility parameter, ViS the solid phase molar volume of component i. mS is the solubility parameter of the solid phase mixture, which is determined by:

S m

= iS

S i

.................................................. (14)

V + L + S = 1 .......................................................... (21)

where iS is the solid phase volume fraction of component i:

VxiV + LxiL + SxiS = Z i ......................................... (22) xiV = xiL = xiS = Z i = 1 ............................... (23)
where Zi is the molar composition of component i of the feed, V the vapor phase molar fraction, L the liquid phase molar fraction and S the solid phase molar fraction. The three-phase flash model is derived in terms of the normalized criteria, combined with the definitions of K-values of each phase, which is:

S i

x iS V = x iS V

S i S i
f

...................................... (15)

The melting temperature Ti , the melting enthalpy Hif of component i are obtained from the standard chemical handbook for light components, less than C7. Because of the uncertainty of the parameters of the heavy components, C7 plus, some adjustable factors are introduced in the Won's expressions [1] to determine the Tif and Vif of component i, therefore:
T i f = c 1 ( 374 . 5 + 0 . 02617 M Vi S = c 2 [ M i
i

20172 / M i ) ...... (16)

V (K

VL i

Zi = 1 ...................... (24) 1) + S ( K iSL 1) + 1 Z i K iVL = 1 ..................... (25) 1) + S ( K iSL 1) + 1 Z i K iSL = 1 ..................... (26) 1) + S ( K iSL 1) + 1

( 0.8155 + 0 .6272 10 4 M i 13 .06 / M i )] .... (17)

f

In the calculation of solid precipitation, Hi is a main factor affecting the cloud point temperature and the amount of precipitated solid phase. A weight function is introduced in the Won's expression [1] to ensure the continuity of components, then:

V ( K iVL

V ( K iVL

f i

= f ( M i ) * 0 . 1426 M i T i f ................... (18)

The iS of component i is determined by Thomas's

The set of equations (24), (25) and (26) is solved by the Newton-Raphson iteration method to determine the phase molar fractions, L, V, and S, and the molar composition xiV, xiL and xiS for each phase. At the beginning of the three-phase flash calculation, the initial K-values are needed to estimate. The initial K-values

Haiyan Mei, Xiangyan Kong, Maolin Zhang, Lei Sun, Shilun Li, Liangtian Sun

SPE 56675

for the vapor-liquid phase, KiVL is calculated by the Wilson's formula. The initial K-values for the solid-liquid phase, KiSL is equal to the reciprocal of the value, calculated also by Wilson's formula. Modelling Results and Discussion Modelling Research on four oil and gas systems is conducted in order to test the accuracy and stability of the model above. Five equations of state, PR-EOS, SRK-EOS, PT-EOS, SWEOS and LHSS-EOS [8] are included in this model. But in this research, PR-EOS is chosen to simulate the vapor and liquid phases. System 1. The composition[1] and parameters for system 1 are provided in table 1, which is a typical gas condensate system. Figure 1 shows the molar fractions of vapor, liquid and solid phases vs temperature at a given pressure, 1 atm. When the temperature rises from 240K to 300K, the vapor phase increases from 93.474 mole % to 97.174 mole %, while the liquid phase decreases from 4.544 mole % to 2.711 mole %, and the solid phase from 1.709 mole % to 0.141 mole %. At the cloud point temperature, 307K, no solid phase exists. Figure 2 demonstrates the molar fractions of vapor, liquid, and solid phases vs pressure at a fixed temperature, 293.15K. When the pressure rises from 1 atm to 30 atm, the liquid phase rises from 2.867 mole % to 11.501 mole %, while the vapor phase decreases from 96.821 mole % to 88.450 mole % and the solid phase from 0.312 mole % to 0.042 mole %. Table 2 gives the compositions of vapor, liquid, and solid phases at 1 atm, 307K (cloud point temperature), and 20 atm, 280K, respectively. It is shown from this modelling example that the threephase flash calculation procedure is stable and 7 to 10 iterations can meet the given accuracy. System 2. The composition[5] and parameters for system 2 are given in table 3. The experimental cloud point temperature is 308K. The calculated cloud point temperatures are 355K by Won, 304K by Hansen et al, 308K by Narayanan et al[5] and 305K by this model. Figure 3 shows the wax precipitation curve at 1 atm for system 2. The calculated maximum precipitated wax is nearly 100 mole % by Hansen et al, 87 mole % by Narayanan et al [5] and 63 mole % by this model. Figure 4 and 5 depict the equilibrium compositions of liquid and solid phases at 1 atm, the cloud point temperature (305K), and 250K, respectively. System 3. The composition [5] and parameters for system 3 are shown in table 4. The experimental cloud point temperature is 314K. The calculated cloud point temperatures are 361K by Won, 313K by Hansen et al, 314K by Narayanan et al [5] and 313K by this model. Figure 6 describes the wax precipitation curve at 1 atm for system 3. The calculated maximum precipitated wax is 100 mole % by Hansen et al, 73 mole % by Narayanan et al [5] and 57 mole % by this model. Figure 7 and 8 show the equilibrium compositions of liquid and solid phases at 1 atm, the cloud point temperature

(313K), and 250K, respectively. Table 5 gives a comparison of the cloud point temperatures between experimental value and those calculated by Won, Hansen et al, Narayanan et al [5] and this model. From the discussion above, the variation of the calculated cloud point temperature with the experimental data by this model is lower than those by Won and Hansen et al and the maximum calculated amount of precipitation is the least. System 4. Besides the modelling research on the literature samples, the solid precipitation modelling calculation on the PuBei Oil Field of China is also conducted. The composition of system 4 is shown in table 6. The experimental cloud point temperature by Laser test technique is 48.8C at 1 atm. The calculated cloud point temperature by this model is 49.0C which has good agreement with the experimental value. The current research [3][4][9] indicates that only part of the heavy components participated in the solid phase precipitation for wax. The parameters Tif and Hif of the non-precipitated part are much less than those precipitated. This paper adopts this concept. The comparison of the amount of precipitated wax between the experimental and the calculated is given in table 7 and figure 9. Conclusions 1. A thermodynamic model is proposed for the vapor-liquidsolid phase equilibrium, based on an equation of state and the regular solution theory. 2. Some adjustable parameters are introduced in this model to improve the matching effect, modelling accuracy and flexibility of the model because of the scarcity of characteristic parameters of heavy compounds. 3. The predicted cloud point temperatures are in good agreement with the experimental data. 4. Both the vapor and liquid phases are calculated by an equation of state, which can reflect the effects of the temperature, pressure and composition of system on the phase behaviors as well as can ensure the thermodynamic consistency for checking the equality of the phase fugacities in the equilibrium calculation. Nomenclature a2, a3, a4, a5, c1, c2 CP f f(MI) H K L M P r R S T V Vi = adjustable parameters = heat capacity = fugacity = adjustable function = enthalpy = equilibrium coefficient = mole fraction of liquid phase = molecular weight = pressure = activity coefficient = gas constant = mole fraction of solid phase = temperature = mole fraction of vapor phase = mole volume of component

SPE 56675

A Thermodynamic Modelling Method for Organic Solid Precipitation

x Z Greek Letters Superscripts f O V, L, S Subscript i

= mole fraction = overall(feed) mole fraction = difference operator = solubility parameter = volume fraction = sum operator

= fusion-point index = standard state index = vapor, liquid, solid phase index = component index

Acknowledgments The authors thank Professor Daiyi Ying, South-West Petroleum Institute, for his technical recommendation in this project and Dr. Xingfan He and Min Li, South-West Petroleum Institute, for their participation in this work. References
1. Won, K. W.: Thermodynamics for Solid Solution--Liquid-Vapor Equilibria: Wax Formation from Heavy Hydrocarbon Mixtures, Fluid Phase Equilibria,Vol 30,pp265-279,(1986). 2. Hansen, J. H. Fredenslund, A. and Pedersen, K. S.: A Thermodynamic Model for Predicting Wax Formation in Crude Oils, AIChE Journal, Vol.34 No.12, (Dec.1988). 3. Pedersen, K. S.: Prediction of Cloud Point Temperatures and Amount of Wax Precipitation, SPE Production & Facilities (Feb.1995). 4. Pedersen, K. Schou, Skovborg, P. and Ronningson, H. P.: Wax Precipitation from North Sea Crude Oils. 4 Thermodynamic Modelling, Energy & Fuels, 5 924 932, (1991). 5. Narayanan, L., Leontaritis, K. J. and Darby, R.: A Thermodynamic Model for Predicting Wax Deposition from Crude Oils, AIChE 1993 Spring National Meeting, March 28-April 1, (1993). 6. X. Zhou, Thomas, F. B.: Modelling of Solid Precipitation from Reservoir Fluid, JCPT, Vol.35, No.10, (Dec.1996). 7. Thomas, F. B, Bennion, D. B, Bennion, D. W.: Experimental and Theoretical studies of Solids Precipitation from Reservoir Fluid, JCPT, Vol 31, No.1, (January 1992). 8. Li Shi Lun, Huang Yu, Sun Lei et al: A Modified Cubic Equation of State and Its Application to Phase Equilibrium Calculations of Gas Condensate Fields, SPE22418, Beijing, (1992). 9. Pan, H., Firoozabadi, A., Fotland, P.: Pressure and Composition Effect on Wax Precipitation: Experimental Data and Model Results, paper SPE36740 presented at the 1996 SPE Annual Technical Conference and Exhibition, Denver, Colorado, U.S.A., Oct. 6-9.

Haiyan Mei, Xiangyan Kong, Maolin Zhang, Lei Sun, Shilun Li, Liangtian Sun

SPE 56675

Table 1 Composition and Parameters for System 1

Mole Comp. % CO2 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 C26 C27 C28 C29 C30 C31 C32 C33 C34 C35 C36 C37 C38 C39 C40 9.160 68.800 8.430 5.110 5.110 1.050 0.630 0.830 0.950 0.520 0.260 0.200 0.170 0.160 0.150 0.110 0.086 0.078 0.068 0.054 0.045 0.037 0.031 0.026 0.022 0.018 0.015 0.012 0.010 0.0086 0.0071 0.0059 0.0049 0.0041 0.0034 0.0028 0.0024 0.002 0.0016 0.0014 0.0011 Mol. Wt. g/mol 44.01 16.043 30.07 44.097 58.124 72.151 86.178 100.25 114.232 128.259 142.286 156.313 170.34 184.367 198.394 212.421 226.448 240.475 254.502 268.529 282.556 296.583 310.610 324.637 338.664 352.691 366.718 380.745 394.772 408.799 422.826 436.853 450.880 464.907 478.934 492.961 506.988 521.015 535.042 549.069 563.096 Tc
K

Pc atm 72.8 45.4 48.2 41.9 37.5 33.3 29.3 27.0 24.5 22.8 20.8 19.4 18.0 17.0 16.0 15.0 14.0 12.8 11.9 11.0 10.5 10.4 10.2 10.03 9.9 9.8

TIf
K

Hif

Table 2 Equilibrium Mole Compositions of GASLiquid-Solid Phases for System 1

Comp. xiV CO2 C1 C2 C3 C4 C5 C6 C7 C8 C9 C10 C11 C12 C13 C14 C15 P 1 atm T 307K xiL xiS xiV P 20 atm T 280K xiL xiS

cal/mol 950.0 112.0 334.0 420.0 556.0 1004.0 1753.41 2514.70 3272.58 4034.37 4797.62 5562.35 6328.54 7096.20 7865.33 8635.93 9408.00

304.2 190.6 305.4 369.8 425.2 469.6 507.4 540.2 568.8 594.6 617.6 638.8 658.3 675.8 694 707 717 733.0 745.0 756.0 767.0 780.0 790.0 800.0 809.0 813.0 829.54

0.225 0.008 0.098 0.152 0.193 0.251 0.296 0.351 0.394 0.444 0.49 0.535 0.562 0.623 0.679 0.706 0.742 0.77 0.79 0.827 0.833 0.838 0.842 0.845 0.847 0.848

215.55 89.15 101.15 83.25 134.85 143.45 142.68 175.91 200.90 220.58 236.45 249.54 260.54 269.91 278.02 285.1 291.35 296.91 301.90 306.41 310.50 314.25 317.69 320.86 323.80 326.54 329.09 331.48 333.73 335.85 337.86 339.76 341.56 343.28 344.92 346.48 347.98 349.42 350.80 352.13 353.41

0.0945598 0.0245380 0.0208510 0.0954439 0.0354902 0.0140686 0.7199532 0.0556419 0.1332657 0.7373380 0.0658709 0.1776464 0.0863053 0.0320948 0.0102158 0.0864926 0.0458322 0.0088591 0.0492028 0.0606499 0.0047714 0.0457155 0.0928172 0.0093976 0.0412861 0.1654168 0.0188033 0.0310354 0.2345272 0.0354717 0.0056340 0.0716991 0.0027112 0.0029613 0.0814240 0.0043671 0.0016817 0.0655000 0.0018942 0.0006326 0.0599561 0.0026896 0.0008949 0.1037718 0.0055243 0.0002633 0.0844105 0.0074037 0.0003868 0.1272091 0.0115674 0.0000972 0.0983969 0.0153812 0.0000761 0.0714253 0.0092401 0.0000166 0.0540919 0.0126522 0.0000136 0.0360355 0.0061006 0.0000027 0.0270295 0.0087986 0.0000038 0.0278072 0.0060551 0.0000007 0.0207341 0.0092326 0.0000014 0.0236608 0.0065246 0.0000002 0.0175477 0.0106095 0.0000004 0.0222799 0.0078088 0.0000001 0.0164176 0.0134231 0.0000001 0.0208905 0.0092898 0.0000000 0.0152660 0.0169460 0.0000000 0.0153199 0.0085983 0.0000000 0.0110698 0.0167689 0.0000000 0.0119772 0.0085782 0.0000000 0.0085158 0.0179165 0.0000000 0.0108625 0.0104809 0.0000000 0.0075031 0.0238910 0.0000000 0.0094691 0.0125848 0.0000000 0.0062523 0.0308349 0.0000000 0.0075185 0.0143496 0.0000000 0.0046001 0.0371297 0.0000000 0.0062643 0.0168266 0.0000000 0.0034549 0.0440550 0.0000000 0.0051498 0.0173703 0.0000000 0.0025987 0.0446046 0.0000000 0.0043136 0.0189854 0.0000000 0.0019116 0.0465753 0.0000000 0.0036167 0.0206955 0.0000000 0.0013698 0.0471524 0.0000000 0.0030591 0.0225123 0.0000000 0.0009698 0.0464522 0.0000000 0.0025017 0.0233591 0.0000000 0.0006557 0.0427793 0.0000000 0.0020838 0.0234693 0.0000000 0.0004609 0.0386136 0.0000000 0.0016658 0.0240080 0.0000000 0.0002896 0.0336295 0.0000000 0.0013868 0.0256659 0.0000000 0.0001853 0.0299672 0.0000000 0.0011911 0.0284115 0.0000000 0.0001198 0.0271404 0.0000000 0.0009817 0.0302951 0.0000000 0.0000731 0.0233021 0.0000000 0.0008140 0.0326226 0.0000000 0.0000442 0.0199372 0.0000000 0.0006745 0.0337232 0.0000000 0.0000439 0.0163066 0.0000000 0.0005624 0.0362015 0.0000000 0.0000275 0.0139651 0.0000000 0.0004643 0.0385862 0.0000000 0.0000169 0.0117849 0.0000000 0.0003802 0.0409050 0.0000000 0.0000103 0.0098325 0.0000000 0.0003235 0.0451831 0.0000000 0.0000064 0.0085096 0.0000000 0.0002669 0.0485473 0.0000000 0.0000039 0.0071419 0.0000000 0.0002108 0.0500658 0.0000000 0.0000023 0.0057434 0.0000000 0.0001815 0.0564088 0.0000000 0.0000014 0.0050446 0.0000000 0.0001395 0.0569423 0.0000000 0.0000008 0.0039745

C16 10181.5 C17 10956.5 C18 11733.0 C19 12511.0 C20 13290.4 C21 14071.2 C22 14853.6 C23 15637.4 C24 16422.7 C25 9.62914 0.90889 17209.4 17997.7 18787.4 19578.5 20371.1 21165.2 21960.8 22757.8 23556.3 24356.3 25157.7 25960.6 26765.0 27570.9 28378.2 C26 C27 C28 C29 C30 C31 C32 C33 C34 C35 C36 C37 C38 C39 C40 839.763 9.48837 0.92438 849.881 9.34937 0.93997 859.895 9.21214 0.95565 869.803 9.07668 0.97144 879.606 8.94299 0.98733 889.305 8.81106 1.00331 898.898 8.6809 1.01939

908.386 8.55251 1.03558 917.770 8.42589 1.05186 927.048 8.30104 1.06824 936.222 8.17795 1.08472 945.290 8.05664 1.1013

954.254 7.93709 1.11797 963.112 7.81931 1.13475

* calculated initial values.

SPE 56675

A Thermodynamic Modelling Method for Organic Solid Precipitation

Table 3 Composition and Parameters for System 2

Pseudo COMP.
P1 P2 P3 P4 P5 P6 P7 P8 P9

Mole %
0.03350 0.08952 0.12600 0.08128 0.06739 0.09582 0.06874 0.07161 0.36620

Mol. Wt. g/mol 70 90 110 140 158 200 230 258 426

Tc
K 488.81 539.32 578.06 627.05 674.46 715.00 738.26 765.43 836.32

Pc Atm 26.32 33.86 32.72 25.69 21.89 19.22 17.11 15.24 10.60

TIf

Hif

V apor

Sold i

Li d qui

0.3120 0.3162 0.3570 0.4543 0.5373 0.6113 0.6730 0.7437 1.0444

K 138.89 151.73 193.36 233.87 250.86 278.83 292.75 303.02 338.29

Cal/mol 934.36 1960.81 3043.89 4673.21 5654.47 7953.55 9603.87 11150.17 20550.85

Vapor-Phase Mole Fraction(%)

100 98 96 94 92 90 240

5 4 3 2 1 0 250 260 270 280 290 300

* calculated initial values.

Table 4 Composition and Parameters of System 3

Pseudo Comp.
P1 P2 P3 P4 P5 P6 P7 P8 P9

Temperature(K) Fi 1 M ol Fracton of V apor, qui and Sold vs g. e i Li d i Tem perat ure( m ) f Syst 1at or em 1

Mole %
0.13590 0.15780 0.16530 0.07652 0.07546 0.06126 0.04973 0.04204 0.23590

Mol. Wt. g/mol 70 90 110 140 158 200 230 258 426

Tc
K

Pc atm 25.03 30.78 30.31 24.59 20.81 18.35 16.91 15.07 10.11

TIf
K

Hif

cal/mol 934.36 1960.81 3043.89 4673.21 5654.47 7953.55 9603.87 11150.17 20550.85

* calculated initial values.

Table 5 Comparison of Experimental and Predicted Cloud Point Temperatures, K Syste Texp TWon THanse TNarayanan TThis Model m No. n 2 308 355 304 308 305 3 314 361 313 314 313 Table 6 Composition and Parameters for System 4
Mole Comp. C2 C3 IC4 NC4 IC5 NC5 C6 C7 C8 C9 % 0.1660 1.1198 1.1953 2.0519 5.9848 5.0013 12.3631 15.8497 14.2453 4.8330 C10 C11 C12 C13 C14 C15 C16 C17 C18 C19 % 6.3801 5.9304 3.1968 3.4943 2.9321 2.4604 2.0645 1.7324 1.4536 1.2197 C20 C21 C22 C23 C24 C25 C26 C27+ % 1.0235 0.8588 0.7207 0.6047 0.5074 0.4258 0.3573 1.8633 Comp. Mole Comp. Mole

100 80 60 40 20 0 0 5 10 15 20 25 30

0. 5 0. 4 0. 3 0. 2 0. 1 0

Vaopr-Liquid Phases Mole Fraction(%)

Pressure(atm) Fi 2 M ol Fract on of V apor, qui and Sold vs g. e i Li d i Pressure( 293. 15K ) f Syst or em 1

Wax Precipitated, Moles/Mole of Feed

Table 7 Comparison of Experimental and Calculated for System 4

Temperature (C ) 49 35 20 Calculated 0 0.1788 0.3244 Wax Weight % Experimental 0 0.1576 0.3556

1 0.8 0.6 0.4 0.2 0 150

175

200

225

250

275

300

Temperature(K) Fi 3 W ax Preci t ed C urve at 1at f g. pi at m or Syst em 2

Solid Phase Mole Fraction(%) 325

482.05 535.42 575.00 626.03 669.99 713.00 734.63 764.25 879.06

0.3135 0.3314 0.3711 0.4653 0.5500 0.6270 0.6753 0.7483 1.1096

138.89 151.73 193.36 233.87 250.86 278.83 292.75 303.02 338.29

Li d qui

V apor

Sold i

Liquid-Solid Phase Mole Fraction(%)

Haiyan Mei, Xiangyan Kong, Maolin Zhang, Lei Sun, Shilun Li, Liangtian Sun

SPE 56675

Liquid Moles/mole of Feed

Soild Moles/Mole of Feed 1 0.8 0.6 0.4 0.2 0 P1

Liquid

Solid

1 0.8 0.6 0.4 0.2 0 P1 P2 P3 P4 P5 P6 P7 P8 P9 Pseudo-Component Fi 4 C om posi i g. t ons of Li d and Sold Phases qui i at C l oud Poi Tem perat nt ure( 305K ) and 1at f m or Syst em 2

P2

P3

P4

P5

P6

P7

P8

P9

Pseudo-Component Fi 7 C om posi i g. t ons of Li d and Sold at C l qui i oud Poi Tem perat nt ure?313K ?and 1at f Syst m or em 3

Liquid Moles/Mole of Feed 1 0.8 0.6 0.4 0.2 0 P1 P2 P3

Solid

Moles/MOle of Fee

0.8
Liquid Solid

0.6 0.4 0.2 0 P1 P2 P3 P4 P5 P6 P7 Pseudo-Component P8 P9

P4

P5

P6

P7

P8

P9

Pseudo-Component Fi 5 C om posii g. tons ofLi d and Sold at250K and qui i 1at f Syst 2 m or em

Fig.8 Compositions of Liquid and Solid Phases at 250K and 1atm for System 3

1 0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0 150

Wax Precipitate Moles/Mole of Fe

1
Calcutated Experimental

0.8 Wax Weight

175
Fig.6

0.6 0.4 0.2

200

225

250

275

300

325

0 10 20 30 40 Temperature,C 50 60

Temperature, K
Wax Precipitation Curve at 1atm for System 3

Fig.9 Wax Precipitation Curve at 1atm for System 4