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, 3–6 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

.......... The regular solution theory of Scatchard and Hildebrand......... at a given temperature and pressure. (1) V L S 1 RT ∫T Ti f (C L pi −C S pi ) dT ..... Tif the melting temperature. which assumes regularity (sE=0) and isometric mixing (vE=0) at constant temperature and pressure........................ which is based on a quasi-crystal lattice and a statistical mechanical theory. From experimental results of heat capacities of the liquid and solid phase for the components n-C8................. By combining the equations (4)..................................................... respectively......... the vaporliquid K-value.... fiV in the vapor phase........ is developed for the mixture of non-polar liquid with similar size of molecules... Both the gas and liquid phases are described by the use of an equation of state.......... is developed for the mixture of non-polar liquid with significantly different size and shape of molecules. they can be expressed as follows: where ∆ Hif is the melting enthalpy....... Liangtian Sun SPE 56675 organic compounds of wax........... and R the gas constant...... CPiL and CPiS the liquid heat capacity and solid heat capacity of component i........... 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 ... Lei Sun................... (2) V L f i L = f i S .... 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 = φ iOL P .................. (4) f i L = xiLφ iL P .. KiVL can be expressed as: VL i L xiV φ i = L = V ... (6) and (3)...............2 Haiyan Mei....... (5) In these two equations..... Xiangyan Kong........ the liquid-solid K-value. xiV and xiL are the molar fractions of component i in the vapor and liquid phases... (10) f iV = xiV φ iV P .... The polymer solution theory..... P is the pressure... 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 ......... (6) where xiS is the molar fraction of component i...... 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................ (5) and (2).. Maolin Zhang... (9) ∫T Ti f C L pi Equation (1) equates the following two equations: f i = f i .. 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...................... By combining the equations (5)....... respectively....... respectively.............. asphaltene and resin. the fugacities of component i...... Thermodynamic Model According to the thermodynamic equilibrium principle........................... There are two thermodynamic solution models which are widely adopted in the modelling of the solid precipitation from oil and gas systems........ 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 ..... n-C25 and n-C33............... KiSL is given by: SL i K φ iL P xiS = L = S OS ...... riS the activity coefficient of component i and fiOS the standard state fugacity of component i in the solid phase........ (7) φi xi K The vapor and liquid phase fugacity coefficients • iV and • iL are obtained from an equation of state............ (3) When an equation of state is applied to calculate the fugacities fiV and fiL of component i in the vapor and liquid phases. (8) xi ri f i By considering the heat capacity difference between the solid and liquid phases.............. n-C18.... (11) where φiOL is the liquid phase standard state fugacity ....................... The regular solution theory is employed to account for the non-ideality of the solid phase mixture...... a5 are the constants.......... Although a lot of research has been done considerably on the nature of heavy organic compounds and the mechanism of solid deposition........... Shilun Li.......... The solid phase where Mi is the molecular weight of component i and a4 ........ In this work.................... the regular solution theory is employed to formulate the activity coefficient for the solid phase only... ιiV and φiL are the fugacity coefficients of component i in the vapor and liquid phases...............

.... (12) f f expression [7]: M i − 48 ..... a3..... A weight function is introduced in the Won's expression [1] to ensure the continuity of components. (25) − 1) + S ( K iSL − 1) + 1 Z i K iSL = 1 .. the normalized criteria of composition are needed: where the δiS is the solid phase solubility parameter.....9751( 628 .. some adjustable factors are introduced in the Won's expressions [1] to determine the Tif and Vif of component i....7823 × 10 − 3 a ( M − 394 .... The three-phase flash model is derived in terms of the normalized criteria...6272 × 10 −4 M i − 13 ............................ (25) and (26) is solved by the Newton-Raphson iteration method to determine the phase molar fractions.....8a 2 (1 − exp( − 5. which is determined by: δ S m = ΣΦ iS δ S i ....30 + 1.. (24) − 1) + S ( K iSL − 1) + 1 Z i K iVL = 1 .....(19   M i 〈 450 = 10 ... Because of the uncertainty of the parameters of the heavy components........... (20) The non-ideality of the solid mixture is taken into account in terms of the regular solution theory...... V the vapor phase molar fraction.. (21) where δiS is the solid phase volume fraction of component i: VxiV + LxiL + SxiS = Z i ... (26) − 1) + S ( K iSL − 1) + 1 ( 0............ which are used to correct the uncertainty of heavy components..... 1426 M i T i f .. which is: Φ S i x iS V = Σ x iS V S i S i f .. (22) ΣxiV = ΣxiL = ΣxiS = ΣZ i = 1 .. V. are obtained by the matching calculation with the experimental data..... c2........... δmS is the solubility parameter of the solid phase mixture........... the melting enthalpy ∆Hif of component i are obtained from the standard chemical handbook for light components.... a2.5 − arctan(( M i − 16) / 14 − 6) / 3..SPE 56675 A Thermodynamic Modelling Method for Organic Solid Precipitation 3 coefficient which is obtained from an equation of state...................... therefore: T i f = c 1 ( 374 ...... 02617 M Vi S = c 2 [ M i i − 20172 / M i ) .2273  ))) 7........... (18) The δiS of component i is determined by Thomas's The set of equations (24)......... The solid phase activity coefficient is expressed as follows: ln ri S = V i (δ S S m −δ S i ) 2 RT ........ Therefore..... (14) V + L + S = 1 ...... L the liquid phase molar fraction and S the solid phase molar fraction......... and the molar composition xiV.... 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 ............... then: V ( K iVL Σ V ( K iVL ∆H f i = f ( M i ) * 0 ..... the initial K-values are needed to estimate. (15) The melting temperature Ti .... (16) Σ V (K VL i Zi = 1 .. (23) where Zi is the molar composition of component i of the feed...... ViS the solid phase molar volume of component i. At the beginning of the three-phase flash calculation.... (17) f Σ In the calculation of solid precipitation.............1416 ) ....06 / M i )] ...8155 + 0 ..... C7 plus..... The initial K-values .......62 + 2.. L..............77 ) i 2   M i ≥ 450  δ 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........... ∆Hi is a main factor affecting the cloud point temperature and the amount of precipitated solid phase... the feed molar number is 1 mole........... 5 + 0 ........ Three-Phase Flash Model For a given system with n components.. a4 and a5......... and S.... (13) These adjustable model factors c1....... combining equation (10) and (9).... xiL and xiS for each phase. At thermodynamic equilibrium........ combined with the definitions of K-values of each phase............ less than C7.

Figure 3 shows the wax precipitation curve at 1 atm for system 2. respectively. the cloud point temperature (313°K).450 mole % and the solid phase from 0. The composition of system 4 is shown in table 6. 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 .501 mole %. Table 5 gives a comparison of the cloud point temperatures between experimental value and those calculated by Won.4 Haiyan Mei. The composition [5] and parameters for system 3 are shown in table 4. calculated also by Wilson's formula. SWEOS and LHSS-EOS [8] are included in this model. 73 mole % by Narayanan et al [5] and 57 mole % by this model. which can reflect the effects of the temperature. and 250°K. But in this research. Five equations of state.15°K. 313°K by Hansen et al. Figure 7 and 8 show the equilibrium compositions of liquid and solid phases at 1 atm. Lei Sun. and the solid phase from 1. KiSL is equal to the reciprocal of the value. The composition[5] and parameters for system 2 are given in table 3. 308°K by Narayanan et al[5] and 305°K by this model. while the liquid phase decreases from 4.821 mole % to 88. liquid. while the vapor phase decreases from 96. 307°K. 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. The initial K-values for the solid-liquid phase. Some adjustable parameters are introduced in this model to improve the matching effect.8°C at 1 atm. and solid phases vs pressure at a fixed temperature. Hansen et al. c1. The current research [3][4][9] indicates that only part of the heavy components participated in the solid phase precipitation for wax. a4. System 3. respectively. Xiangyan Kong. a3.042 mole %. the solid precipitation modelling calculation on the PuBei Oil Field of China is also conducted. The experimental cloud point temperature by Laser test technique is 48. 280°K.141 mole %. Table 2 gives the compositions of vapor. and 20 atm. The experimental cloud point temperature is 314°K. System 2.711 mole %. The experimental cloud point temperature is 308°K. Both the vapor and liquid phases are calculated by an equation of state. 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. no solid phase exists. Figure 1 shows the molar fractions of vapor. Figure 6 describes the wax precipitation curve at 1 atm for system 3. 87 mole % by Narayanan et al [5] and 63 mole % by this model. modelling accuracy and flexibility of the model because of the scarcity of characteristic parameters of heavy compounds. PR-EOS is chosen to simulate the vapor and liquid phases. The calculated cloud point temperatures are 355°K by Won. the vapor phase increases from 93. When the pressure rises from 1 atm to 30 atm. SRK-EOS. From the discussion above. which is a typical gas condensate system. Nomenclature a2. 3. The parameters Tif and • Hif of the non-precipitated part are much less than those precipitated. At the cloud point temperature. Maolin Zhang. Narayanan et al [5] and this model. 2. 307°K (cloud point temperature). 293. based on an equation of state and the regular solution theory. 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. The calculated cloud point temperatures are 361°K by Won. a5. 1 atm. 304°K by Hansen et al. KiVL is calculated by the Wilson's formula. PT-EOS.709 mole % to 0. A thermodynamic model is proposed for the vapor-liquidsolid phase equilibrium.0°C which has good agreement with the experimental value. System 4. System 1. liquid. The calculated cloud point temperature by this model is 49. PR-EOS. 314°K by Narayanan et al [5] and 313°K by this model. and 250°K. the liquid phase rises from 2. Conclusions 1. The comparison of the amount of precipitated wax between the experimental and the calculated is given in table 7 and figure 9. This paper adopts this concept. the cloud point temperature (305°K). and solid phases at 1 atm. Shilun Li. liquid and solid phases vs temperature at a given pressure.312 mole % to 0.174 mole %. 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.867 mole % to 11. Liangtian Sun SPE 56675 for the vapor-liquid phase. The calculated maximum precipitated wax is nearly 100 mole % by Hansen et al. The calculated maximum precipitated wax is 100 mole % by Hansen et al. 4. Figure 2 demonstrates the molar fractions of vapor.544 mole % to 2. respectively. The composition[1] and parameters for system 1 are provided in table 1. Figure 4 and 5 depict the equilibrium compositions of liquid and solid phases at 1 atm. When the temperature rises from 240°K to 300°K.474 mole % to 97. Besides the modelling research on the literature samples. The predicted cloud point temperatures are in good agreement with the experimental data.

P. References 1. K. JCPT. (1991). B. 6-9. for his technical recommendation in this project and Dr.S.: Experimental and Theoretical studies of Solids Precipitation from Reservoir Fluid. A. 7.. Narayanan. D.(1986). Pedersen.12. for their participation in this work. 4. (January 1992). March 28-April 1. 4 Thermodynamic Modelling. No. Fotland. Vol. S.: Pressure and Composition Effect on Wax Precipitation: Experimental Data and Model Results. and Pedersen. Firoozabadi. JCPT.: Prediction of Cloud Point Temperatures and Amount of Wax Precipitation.: A Thermodynamic Model for Predicting Wax Deposition from Crude Oils. Schou.10. Colorado. and Darby.A.SPE 56675 A Thermodynamic Modelling Method for Organic Solid Precipitation 5 x Z Greek Letters ∆ δ Φ Σ Superscripts f O V. Pan. 3.• Fredenslund. S Subscript i = mole fraction = overall(feed) mole fraction = difference operator = solubility parameter = volume fraction = sum operator = fusion-point index = standard state index = vapor. Oct. Li Shi Lun. K. Hansen. F.: Thermodynamics for Solid Solution--Liquid-Vapor Equilibria: Wax Formation from Heavy Hydrocarbon Mixtures. South-West Petroleum Institute.. U. 5• 924• 932. K. South-West Petroleum Institute. Pedersen. L. 2. and Ronningson. J. J. Vol. S. (Dec. F. solid phase index = component index Acknowledgments The authors thank Professor Daiyi Ying. Beijing. Denver. L. Energy & Fuels.: A Thermodynamic Model for Predicting Wax Formation in Crude Oils. Skovborg. AIChE 1993 Spring National Meeting. Bennion. Sun Lei et al: A Modified Cubic Equation of State and Its Application to Phase Equilibrium Calculations of Gas Condensate Fields. D. H. SPE Production & Facilities• (Feb. H.1996). Huang Yu. P. Zhou..35. (Dec.34• No. K.Vol 30. Thomas.pp265-279. Leontaritis.: Wax Precipitation from North Sea Crude Oils. R. liquid. 8. (1992). H. W. Thomas. 6. 9.1. K. Bennion. P. No. Won. 5. A. AIChE Journal. B. Vol 31.1988). W. X. B. SPE22418. .. paper SPE36740 presented at the 1996 SPE Annual Technical Conference and Exhibition.1995). Fluid Phase Equilibria.: Modelling of Solid Precipitation from Reservoir Fluid. Xingfan He and Min Li. (1993).

0206955 0.0085158 0.5 C17 10956.0051498 0.0256659 0.0062643 0.0000000 0.9 9.9 37.0002896 0.037 0.3 27.988 521.0658709 0.2 10.56 343.0034 0.0000000 0.0001198 0.0320948 0.0108625 0.160 0.0034549 0.0457155 0.556 296.0168266 0.4 18. % 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 9.00 304.0047714 0.0500658 0.151 86.2345272 0.0179165 0.93 9408.200 0.664 352.0086 0.0169460 0.0059 0.0000000 0.110 1.0056340 0.41 0.026 0.0102158 0.93709 1.772 408.8 • TIf °K * • Hif * Table 2 Equilibrium Mole Compositions of GASLiquid-Solid Phases for System 1 Comp.475 254.0 809.0 15.0094691 0.0000166 0.691 366.8 19.018 0.0337232 0.8 425.0360355 0.097 58.0036167 0.048 8.9 11.25 134.0163066 0.222 8.0284115 0.77 0.7 18787.152 0.0003802 0.010 0.043 30.11797 963.0000000 0. Liangtian Sun SPE 56675 Table 1 Composition and Parameters for System 1 Mole Comp.907 478.0928172 0.68 175.8 594.0000038 0.02 285.42589 1.50 314.386 8.002 0.799 422.58 236.0152660 0.0001815 0.110 5.0 16.07668 0.4 48.637 338.0386136 0.34937 0.718 380.4 C24 16422.800 8.0000000 0.62914 0.0 C19 12511. Xiangyan Kong.0085096 0.0002108 0.1332657 0.85 143.0188033 0.0025987 0.260 0.0 556.069 563.0167689 0.45 142.1 21165.58 4034.0000000 0.0006326 0.94299 0.1272091 0.0000000 0.0371297 0.0153199 0.286 156.55 89.5 22.0208905 0.3 24356.0000000 0.0354902 0.48837 0.0 1753.86 323.0092326 0.8 23556.950 0.0540919 0.80 352.0173703 0.015 535.0001853 0.07 44.0863053 0.0000000 0.0039745 C16 10181.5 10.0000014 0.3 675.0714253 0.06824 936.0000000 0.0043136 0.0019116 0.008 0.898 8.0000000 0.0945598 0.76 341.35 6328.853 450.0125848 0.112 7.706 0.0011911 0.86 339.0000000 0.0 780.0954439 0.2 C22 14853.803 9.150 0.0028 0.91 278.0000000 0.015 0.4 C21 14071.0009698 0.0207341 0.0556419 0. Wt.0 C20 13290.679 0.6 305.0302951 0.54 260.078 0.25 114.0 745.290 8.81106 1.770 8. .763 9.881 9.068 0.4 540.0458322 0.193 0.92438 849.6 26765.0000000 0.0117849 0.421 226.6 617.0139651 0.0085983 0.0000000 0.0008140 0.0000000 0.0000000 0.0000008 0.0000000 0.0134231 0.394 212.0599561 0.37 4797.13475 * calculated initial values.0000014 0.610 324.313 170.1 291.8 658.1776464 0.042 549.6809 1.0983969 0.0199372 0.98733 889.0143496 0.394 0.0000000 0.0234693 0.0000000 0.0002669 0.623 0.0409050 0.0001395 0.0000000 0.2 190.0000275 0.448 240.0092898 0.0075031 0.838 0.0020838 0.0000000 0.8 20.0027112 0.54 7096.01939 908.086 0.535 0.2 568.0 24.0569423 0.54 0.0222799 0.351 0.0078088 0.0000000 0.0465753 0.15 101.934 492.0164176 0.0002633 0.0000000 0.0016817 0.022 0.742 0.33 8635.880 464.232 128.49 0.0000000 0.0000000 0.0354717 0.0716991 0.0000000 0.827 0.0140686 0.90 306.0000000 0.031 0. Shilun Li.529 282.7 25960.160 68.30104 1.0 800.0564088 0.745 394.0000000 0.21214 0.48 347.69 320.0088591 0.170 0.2 21960.0000000 0.0000439 0.0 829. g/mol 44.0000000 0.1037718 0.0864926 0.42 350.0233021 0.0104809 0.25 317.305 8.0115674 0.0844105 0.91 200.03558 917.7373380 0.0 10.0 790.0238910 0.0278072 0.0057434 0.8 22757.0000002 0.41 2514.0055243 0.93997 859.97144 879.0271404 0.05186 927.13 353.8 694 707 717 733.0061006 0.0060551 0.444 0.0000001 0.0000000 0.0000000 0.80 326.0071419 0.7 C25 9.0 112.0074037 0.55251 1.826 436.45 249.0008949 0.4 10.35 296.0000027 0. xiV CO2 C1 C2 C3 C4 C5 C6 C7 C8 C9 C10 C11 C12 C13 C14 C15 P• 1 atm T• 307°K xiL xiS xiV P• 20 atm T• 280°K xiL xiS cal/mol 950.0050446 0.0000000 0.0492028 0.0000000 0.0189854 0.0000000 0.0000000 0.0 813.833 0.0043671 0. Maolin Zhang.0385862 0.895 9.0000000 0.0119772 0.0029613 0.0427793 0.0000000 0.0004643 0.1654168 0.178 100.7199532 0.0006557 0.830 0.0000000 0.01 16.0446046 0.251 0.0000000 0.5 20371.15 83.2 469.0336295 0.5 33.225 0.847 0.0 420.0464522 0.0451831 0.0011 Mol.95565 869.3 29.0326226 0.0208510 0.0062523 0.0049 0.0098325 0.0 1004.0110698 0.124 72.630 0.0000000 0.0087986 0.0016 0.41 310.0655000 0.0412861 0.0000000 0.0000007 0.0000064 0.90889 17209.85 337.98 349.6 638.296 0.03 9.0299672 0.0000000 0.502 268.0 767.0005624 0.0308349 0.09 331.54 269.0003868 0.961 506.367 198.1013 954.00331 898.0000731 0.0018942 0.0000000 0.0 14.0485473 0.5 C18 11733.0004609 0.70 3272.0440550 0.0014 0.0030591 0.90 220. Lei Sun.110 0.08472 945.0046001 0.0016658 0.0013868 0.254 7.0153812 0.0362015 0.20 7865.0606499 0.430 5.0000000 0.0000000 0.4 17997.0236608 0.3 25157.259 142.0245380 0.0075185 0.48 333.0 334.0270295 0.0000169 0.0225123 0.848 215.2 41.8 45.0233591 0.012 0.0175477 0.92 346.0106095 0.73 335.562 0.6 507.0093976 0.0000001 0.845 0.0471524 0.842 0.0240080 0.0026896 0.045 0.9 28378.0000136 0.34 184.0310354 0.0041 0.0092401 0.2 C26 C27 C28 C29 C30 C31 C32 C33 C34 C35 C36 C37 C38 C39 C40 839.0000442 0.0 17.0000972 0.0 27570.050 0.0065246 0.0000000 0.096 Tc °K Pc atm 72.62 5562.054 0.0000761 0.0003235 0.0000000 0.0 12.6 C23 15637.0013698 0.91 301.0 756.0000103 0.098 0.28 344.0071 0.4 369.79 0.0085782 0.0009817 0.8 11.05664 1.0006745 0.0814240 0.0000004 0.0000000 0.54 329.606 8.0024 0.0000000 0.81931 1.0025017 0.0000039 0.17795 1.0000000 0.4 19578.6 Haiyan Mei.0126522 0.0000023 0.520 0.583 310.0000000 0.

99 713.3135 0.85 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.75 303. qui and Sold vs g.55 9603. 15K ) f Syst or em 1 Wax Precipitated.02 338. Table 5 Comparison of Experimental and Predicted Cloud Point Temperatures.3162 0. Wt.08128 0.3244 Wax Weight % Experimental 0 0.9304 3.81 3043.03 669.02 338. P1 P2 P3 P4 P5 P6 P7 P8 P9 Temperature(K) Fi 1 M ol Fracton of V apor.06126 0.5074 0.4653 0.06874 0.89 4673.4 0.29 Cal/mol 934.06 0.5373 0.63 764.03 30.06 627.2453 4.87 11150. °K Syste Texp TWon THanse TNarayanan TThis Model m No.72 25.0235 0.07 10. Mole Comp. 4 0.24 10.81 539.78 30.4604 2. qui and Sold vs g. P1 P2 P3 P4 P5 P6 P7 P8 P9 Mole % 0.6730 0. 5 0.0013 12.89 151.1576 0.11 • TIf °K * • Hif * cal/mol 934.3570 0.83 292.8588 0.5500 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.04204 0. 1 0 Vaopr-Liquid Phases Mole Fraction(%) Pressure(atm) Fi 2 M ol Fract on of V apor.55 9603. e i Li d i Pressure( 293.1660 1. g/mol 70 90 110 140 158 200 230 258 426 Tc °K 488. n 2 308 355 304 308 305 3 314 361 313 314 313 Table 6 Composition and Parameters for System 4 Mole Comp.81 18.3631 15.32 33.36 1960. 3 0.59 20.31 24.2197 C20 C21 C22 C23 C24 C25 C26 C27+ % 1.8633 Comp.36 233.13590 0.17 20550.6 0.60 • TIf * • Hif * V apor Sold i Li d qui 0.11 15.12600 0.1198 1.21 5654.86 278.1953 2.36620 Mol.6270 0. 2 0.6753 0.89 4673.3711 0.0519 5. pi at m or Syst em 2 Solid Phase Mole Fraction(%) 325 482.00 738.43 836.23590 Mol. Wt.7324 1.4943 2.32 Pc Atm 26. Table 4 Composition and Parameters of System 3 Pseudo Comp.85 * calculated initial values.7483 1.86 32.07652 0.05 674.04973 0.16530 0.87 11150.3801 5.3573 1.15780 0.75 303.36 233.7437 1.4543 0.3120 0.1968 3.0645 1.73 193. Moles/Mole of Feed Table 7 Comparison of Experimental and Calculated for System 4 Temperature (°C ) 49 35 20 Calculated 0 0.89 151.0444 °K 138.SPE 56675 A Thermodynamic Modelling Method for Organic Solid Precipitation 7 Table 3 Composition and Parameters for System 2 Pseudo COMP.1096 138.9321 2.6047 0.06739 0.03350 0.09582 0.22 17.81 3043.9848 5.4536 1.91 15.3314 0.42 575. C2 C3 IC4 NC4 IC5 NC5 C6 C7 C8 C9 % 0.1788 0.8 0.07161 0.8330 C10 C11 C12 C13 C14 C15 C16 C17 C18 C19 % 6. e i Li d i Tem perat ure( m ) f Syst 1at or em 1 Mole % 0.6113 0.87 250.36 1960.47 7953.35 16.25 879.87 250.46 715. g/mol 70 90 110 140 158 200 230 258 426 Tc °K Pc atm 25.83 292.17 20550.29 Li d qui V apor Sold i Liquid-Solid Phase Mole Fraction(%) .8497 14.21 5654.05 535.73 193.4258 0.08952 0.32 578.7207 0.89 19.69 21.86 278.3556 1 0.47 7953.07546 0. Mole 100 80 60 40 20 0 0 5 10 15 20 25 30 0.00 626.00 734.26 765.

8 Liquid Solid 0.4 0.4 0.4 0.8 0.4 0. 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.8 0. tons ofLi d and Sold at250K and qui i 1at f Syst 2 m or em Fig.8 Wax Weight 175 Fig. Maolin Zhang.7 0. 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 0.1 0 150 Wax Precipitate Moles/Mole of Fe 1 Calcutated Experimental 0.2 200 225 250 275 300 325 0 10 20 30 40 Temperature.6 0.C 50 60 Temperature. Xiangyan Kong.9 Wax Precipitation Curve at 1atm for System 4 .8 Haiyan Mei.3 0.6 0.8 0. K Wax Precipitation Curve at 1atm for System 3 Fig.2 0 P1 P2 P3 Solid Moles/MOle of Fee 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.2 0. Shilun Li.2 0 P1 P2 P3 P4 P5 P6 P7 P8 P9 Pseudo-Component Fi 4 C om posi i g. Liangtian Sun SPE 56675 Liquid Moles/mole of Feed Soild Moles/Mole of Feed 1 0.2 0 P1 Liquid Solid 1 0.4 0.6 0. Lei Sun.6 0.6 0.6 0.8 0.4 0.5 0.6 0.9 0.8 Compositions of Liquid and Solid Phases at 250K and 1atm for System 3 1 0.

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