Fluid Phase Equilibria 149 1998.

191207

Liquidsolid equilibria in a decane q multi-paraffins system

J. Pauly, C. Dauphin, J.L. Daridon
)

Laboratoire Haute Pression, Centre Uniersitaire de Recherche Scientifique, Uniersite de Pau, Aenue de lUniersite, 64000 Pau, France Received 18 December 1997; accepted 13 May 1998

Abstract Measurements, performed at atmospheric pressure on mixtures made up of decane plus various distributions of heavy normal paraffins from octadecane to triacontane, were carried out to provide information on wax content amount and composition. as function of temperature. At various temperatures below the wax appearance temperature, liquid and solid phases in partially frozen mixtures were separated by isothermal filtration and analyzed by gas chromatography. Amount and composition of both phases were then deduced from mass balance after correction of the entrapped liquid in the solid residue. Furthermore, the LS equilibrium data obtained are compared with the values predicted by means of several models. q 1998 Elsevier Science B.V. All rights reserved.
Keywords: Experimental method; Data; Solidfluid equilibria; Heavy hydrocarbons

1. Introduction Certain petroleum fluids, such as paraffinic crudes, contain heavy hydrocarbons which, when they are present in significant proportions, can precipitate during production or during transport through a pipeline traversing cold regions. Accumulation of these solid deposits, which clog up filters and obstruct pipelines if the phenomenon is not treated, represents a major risk of deterioration for this kind of equipment. In order to prevent this process, which is linked to changing pressure and temperature conditions and fluid composition caused by bringing the well into production, it is essential to be able to predict the phase behavior of the reservoir fluid by means of thermodynamic models. To develop models or to test the validity of existing models, it is useful to have experimental liquidsolid phase equilibrium data for systems whose composition is precisely identified. With this

Corresponding author. Tel.: q33-5-59-92-30-54; Fax: q33-5-59-80-83-82; E-mail: jean-luc.daridon@univ-pau.fr

0378-3812r98r$19.00 q 1998 Elsevier Science B.V. All rights reserved. PII: S 0 3 7 8 - 3 8 1 2 9 8 . 0 0 3 6 6 - 5

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aim in mind, we performed w1x liquidvapor and liquidsolid phase transition measurements under pressure on synthetic mixtures whose composition was close to those encountered in natural fluids. Thus, the phase envelope and the temperatures of appearance of solid paraffins with different mixtures made up of a methaneq decane solvent in equimolar distribution and a heavy fraction made up of a series of alkanes between C 18 and C 30 were determined experimentally up to 50 MPa. Unfortunately, these measurements give no data about the composition or the quantity of the emerging solid phase. In order to make up this lack of information, we characterized experimentally in this paper the solid deposits created by determining the composition and the quantity deposited vs. temperature at atmospheric pressure. To ensure consistency with previously studied mixtures, we maintained the same heavy fractions; however, because the mixed solvent was completely degassed at atmospheric pressure, it was replaced by pure decane. The equilibrium data were then compare with the values calculated by various predictive models. The first model tested is the regular solution model of Won w2x in which both liquid and solid phases are assumed regular. The second model, developed by Hansen et al. w3x, is based on the generalized

Fig. 1. Scheme of the transparent cell for liquidsolid separation. 1. Piston. 2. Transparent cylinder. 3. Heat conducting liquid. 4. Two-phase system. 5. Transparent cell. 6. Filter. 7. Valve. 8. Septum.

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polymer solution theory of Flory w4x for the description of the liquid state and the solid phase is regarded as ideal. Whereas in the third model proposed by Coutinho et al. w5,6x, the solid state is described by a local composition model. Finally, the experimental data have been used to test the prediction capacities of the approach which rest on the hypothesis that each component of the heavy fraction can crystallize pure w7x, thus leading to several solid phases.

2. Experimental technique The method generally used to characterize equilibria between fluid phases vs. temperature consists of taking and then analyzing a micro-sample of each of the phases present in equilibrium at all the temperatures investigated. In the case of liquidsolid equilibrium, where the solid phase is made up of an amalgam of crystals which is not necessarily homogeneous, sampling cannot be considered representative of the composition of the solid phase. In this context, to determine accurately the composition of the solid phase, it has to be completely isolated from the rest of the system and then analyzed as a whole. To do this, the mixture of heavy compounds is initially prepared in substantial quantity by weighing and then diluted in the solvent until the desired overall composition is reached. The system obtained is then heated until complete dissolution of the paraffins and then homogenized. At this stage, the mixture is broken down into several samples, of an average capacity of 3 to 4 cm3, to allow for investigation at different temperatures.

Table 1 Feed composition mass %. of the C 10 qdistribution of paraffins systems Mixture A Feed composition % of n-C 10 % of heavies 64.73 35.27 Mixture B 47.76 52.24 13.72 12.27 10.98 9.87 8.86 7.96 7.12 6.35 5.69 5.06 4.58 3.99 3.54 0.858 310.17 Mixture C 65.02 34.98 10.15 10.15 10.17 10.15 10.09 10.03 9.96 9.86 9.76 9.68 0.951 311.83 References Aldrich Purity )99.0

Heay fraction (mass %) % of n-C 18 % of n-C 19 % of n-C 20 29.21 % of n-C 21 20.97 % of n-C 22 15.01 % of n-C 23 10.74 % of n-C 24 7.66 % of n-C 25 5.46 % of n-C 26 3.88 % of n-C 27 2.76 % of n-C 28 1.95 % of n-C 29 1.38 % of n-C 30 0.98 a 0.684 MW grmol. 310.51

Fluka Aldrich Aldrich Fluka Aldrich Aldrich Fluka Fluka Aldrich Fluka Fluka Fluka Aldrich

)99.0 99.0 99.0 )98.0 99.0 99.0 )99.0 )98.0 )99.0 )98.0 )98.0 )99.5 )99.0

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The phase separation, which is obtained by compression of the two-phase liquidsolid system through a filter, is carried out in a transparent cell Fig. 1. , thermoregulated at the desired temperature with an accuracy of 0.02 K. . When the filtration is complete, the two phases recovered are weighed and then analyzed on a Hewlett-Packard 6890 gas chromatograph. Based on precise knowledge of the total mass of the sample and the quantity of matter present in the two phases, we were able to estimate by means of a mass balance that the quantity of the chemical retained in the filtration system, valve or on the cell walls was less than 1% for all the tests performed. At this stage, only the composition of the liquid phaseL. is determined accurately. The solid phaseS., which is made up of a myriad of micro-crystals, tends to keep part of the liquid, coating the crystals during compression filtering. So, the filtration residueSR. corresponds in fact to the superimposition of the solid phaseS. and of the trapped liquidLT.. Given the nature of the systems studies,

Table 2 Amount of solid deposit and composition of liquid and solid phases as a function of temperature for system A T K. 290.85 288.15 283.15 14.86 13.33 16.59 16.8 14.84 11.74 8.7 6.48 4.55 3.22 2.23 1.52 77.13 10.33 5.64 2.93 1.55 0.86 0.52 0.35 0.25 0.19 0.15 0.12 278.25 22.16 18.04 19.38 17.03 13.61 10.02 7.19 5.3 3.72 2.65 1.87 1.28 83.46 8.53 3.87 1.73 0.88 0.51 0.33 0.23 0.17 0.13 0.10 0.08 273.25 23.71 21.18 20.47 16.57 12.56 9.13 6.51 4.8 3.4 2.43 1.75 1.2 88.04 6.57 2.62 1.14 0.61 0.37 0.23 0.16 0.10 0.07 0.05 0.04 268.25 28.33 25.05 21.41 15.91 11.55 8.24 5.82 4.26 3.01 2.16 1.54 1.06 93.26 4.27 1.23 0.49 0.28 0.18 0.11 0.07 0.05 0.03 0.02 0.01 Amount of solid deposit (mass %) 2.46 6.80 Composition of the solid phase (mass %) C 20 4.09 7.26 C 21 6.9 11.04 C 22 10.2 14.00 C 23 13.1 15.19 C 24 14.36 14.07 C 25 13.56 11.63 C 26 12.11 9.3 C 27 9.54 6.78 C 28 7.31 4.91 C 29 5.3 3.44 C 30 3.52 2.38 Composition of the liquid phase (mass %) C 10 67.14 70.48 C 20 10.93 10.93 C 21 7.37 7.01 C 22 4.98 4.39 C 23 3.36 2.72 C 24 2.21 1.65 C 25 1.43 1.01 C 26 0.97 0.67 C 27 0.64 0.44 C 28 0.44 0.31 C 29 0.31 0.23 C 30 0.21 0.17

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Table 3 Amount of solid deposit and composition of liquid and solid phases as a function of temperature for system B T K. 293.15 290.85 288.05 8.15 0.01 0.18 0.40 1.00 2.79 6.05 9.84 12.55 14.27 15.08 13.80 12.47 11.58 70.22 5.09 4.76 4.40 3.79 3.31 2.82 2.04 1.32 0.85 0.56 0.37 0.27 0.19 283.15 12.92 0.10 0.41 1.25 2.93 5.60 9.11 11.55 12.27 12.80 12.78 11.80 10.28 9.13 72.60 5.61 5.16 4.56 3.66 3.23 2.06 1.25 0.70 0.41 0.29 0.19 0.16 0.11 277.55 21.58 0.25 2.13 5.28 8.33 10.52 11.55 11.04 10.11 9.56 9.27 8.27 7.22 6.47 77.99 6.56 5.59 4.14 2.46 1.34 0.75 0.42 0.25 0.16 0.13 0.08 0.07 0.06 268.95 28.03 4.34 8.85 11.01 10.50 9.75 9.15 8.37 7.39 6.96 6.80 6.30 5.53 5.06 90.74 4.84 2.44 0.95 0.41 0.25 0.18 0.11 0.08 0.00 0.00 0.00 0.00 0.00 Amount of solid deposit (mass %) 4.57 6.80 Composition of the solid phase (mass %) C 18 0.00 0.00 C 19 0.00 0.00 C 20 0.00 0.00 C 21 0.02 0.32 C 22 0.48 1.29 C 23 1.74 3.55 C 24 4.16 7.07 C 25 7.57 10.78 C 26 11.86 14.34 C 27 16.17 16.65 C 28 18.76 16.44 C 29 19.44 16.01 C 30 19.80 13.54 Composition of the liquid phase (mass %) C 10 64.63 66.96 C 18 5.00 5.25 C 19 4.72 4.90 C 20 4.43 4.50 C 21 3.93 3.93 C 22 3.62 3.52 C 23 3.36 3.16 C 24 2.80 2.48 C 25 2.21 1.76 C 26 1.72 1.24 C 27 1.34 0.87 C 28 0.97 0.60 C 29 0.72 0.47 C 30 0.56 0.35

which are all made up of a pure solvent much lighter than the heavy fraction, the proportion of liquid trapped in the solid phase can easily be determined from the quantity of solvent measured in the solid residue. Because the difference in length of chain between decane and the first distribution paraffin is substantial eight carbons., there cannot be any partial miscibility between heavy paraffins and decane w8x. Now, as the melting temperature of the solvent is 243 K, it cannot be crystallized in our range of investigation temperatures. So its presence in the solid phase is solely due to the existence of the trapped liquid: mSR s m LT C 10 C 10

1.

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As we know the exact composition in the liquid phase, it is possible to calculate the total amount of entrapped liquid by:
L mLT s mSR rXC 10 C 10

2.

which leads to the fraction Y LT of liquid trapped in the solid residue of filtration: Y LT s
SR XC 10 L XC 10

3.

SR L in which XC 10 and XC 10 correspond to the mass fraction of solvent analyzed in the two parts recovered after separation. The quantity of solid crystallized expressed in mass fraction. can thus be corrected by:

F S s F SR 1 y Y LT .

4.

where F SR and F S represent the mass fractions of the solid residue and the solid which has actually
Table 4 Amount of solid deposit and composition of liquid and solid phases as a function of temperature for system C T K. 293.05 288.15 283.05 14.97 0.07 0.28 0.98 2.81 6.43 11.62 15.86 18.29 20.64 23.03 72.94 4.43 4.58 4.57 4.09 3.34 2.48 1.53 0.91 0.63 0.50 278.15 20.33 0.10 0.37 1.23 3.23 6.84 11.72 15.43 17.86 20.26 22.96 82.72 3.64 3.60 3.31 2.58 1.75 1.06 0.58 0.33 0.23 0.19 272.95 22.80 0.58 1.92 4.65 8.02 11.16 13.66 14.40 14.49 15.00 16.12 82.71 4.62 4.32 3.47 2.20 1.21 0.64 0.34 0.21 0.16 0.13 267.85 27.03 1.23 3.46 6.86 9.65 11.46 12.90 13.20 13.06 13.58 14.59 85.93 4.74 3.94 2.60 1.30 0.62 0.34 0.20 0.13 0.10 0.10 Amount of solid deposit (mass %) 5.86 11.93 Composition of the solid phase (mass %) C 18 0.00 0.03 C 19 0.00 0.12 C 20 0.29 0.56 C 21 1.08 1.78 C 22 3.21 4.70 C 23 7.57 9.72 C 24 13.33 15.03 C 25 19.38 19.05 C 26 24.86 22.77 C 27 30.29 26.25 Composition of the liquid phase (mass %) C 10 60.08 69.49 C 18 3.94 4.15 C 19 4.12 4.31 C 20 4.25 4.38 C 21 4.15 4.13 C 22 4.16 3.76 C 23 4.26 3.27 C 24 4.01 2.42 C 25 3.64 1.70 C 26 3.64 1.30 C 27 3.75 1.10

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crystallized in the whole system. Finally, the real composition of the solid phase X iS can be obtained using: X iS s

X iSR y Y LT X iL .
1 y Y LT .

5.

for any given i.

3. Measurements Measurements were made on three mixtures of different compositions of the decaneq heavy fraction system on which the liquidvapor and liquidsolid transition measurements had been previously performed by Daridon et al. w1x in the presence of methane. The molar proportion of decane 80%. and heavy fraction 20%. are the same in the three mixtures. Only the composition of the compounds present in the heavy fraction differs from one sample to the other Table 1.. These substances, which all belong to the n-alkanes, are distributed within the heavy fraction according to a decreasing distribution characterized by the recurrence relationship: x c nq1 s a x c n

6.

corresponding to a simplified representation of the heavy fractions found in paraffinic crudes. The coefficient a , which is different for the three mixtures studied, was defined so as to maintain the

Fig. 2. Temperature dependence of the amount of solid deposit for system C.

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Fig. 3. Composition mass %. of the solid phase vs. temperature for system B.

mean molar mass at 310.6 grmol which corresponds to the molar mass of docosane. However, the number of components must be different from one mixture to the other in order to keep the same average molar mass with different values of a coefficient. Thus, mixture A was prepared in order that the composition of the heavy fraction is continually decreasing from eicosane to triacontane while the heavy part of mixture B contains paraffins from octadecane to triacontane and mixture C is limited to heptacosane. Measurements were carried out every 5 K from the phase change temperature which is estimated at 293.35 and 299.35 K for systems A and B and 297.65 K for mixture C. The amount of solid deposit

Table 5 Percentages of paraffin crystallized vs. temperature for system A 290.85 K Overall percentage of paraffins crystallized Percentage of C 20 crystallized Percentage of C 21 crystallized Percentage of C 22 crystallized Percentage of C 23 crystallized Percentage of C 24 crystallized Percentage of C 25 crystallized Percentage of C 26 crystallized Percentage of C 27 crystallized Percentage of C 28 crystallized Percentage of C 29 crystallized Percentage of C 30 crystallized 7.13 0.94 2.31 4.91 8.95 14.07 19.30 24.01 27.33 29.51 30.17 29.45 288.15 K 19.81 4.62 10.29 18.86 28.96 38.42 45.69 50.47 52.90 53.50 52.30 50.42 283.15 K 43.02 18.23 36.69 49.72 62.20 70.22 74.36 76.15 76.18 74.87 72.66 69.32 278.25 K 63.25 37.60 58.80 73.66 81.33 84.85 86.20 86.66 86.29 85.79 84.85 82.77 275.25 K 72.21 50.05 70.80 81.90 86.47 88.60 89.71 90.44 90.98 91.53 91.36 90.71 268.25 K 85.37 69.82 87.28 92.80 94.07 94.61 95.22 95.74 95.91 96.76 97.10 97.02

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Table 6 Percentages of paraffin crystallized vs. temperature for system B 293.15 K Overall percentage of paraffins crystallized Percentage of C 18 crystallized Percentage of C 19 crystallized Percentage of C 20 crystallized Percentage of C 21 crystallized Percentage of C 22 crystallized Percentage of C 23 crystallized Percentage of C 24 crystallized Percentage of C 25 crystallized Percentage of C 26 crystallized Percentage of C 27 crystallized Percentage of C 28 crystallized Percentage of C 29 crystallized Percentage of C 30 crystallized 11.92 0.00 0.00 0.00 0.024 0.63 2.42 6.63 14.10 24.82 36.62 48.08 56.38 62.87 290.85 K 18.11 0.00 0.00 0.00 0.59 2.61 7.59 17.23 30.90 45.78 58.29 66.67 71.31 73.85 288.05 K 22.97 0.01 0.34 0.79 2.29 6.96 16.00 29.97 45.76 59.83 70.50 76.80 80.39 84.39 283.15 K 35.13 0.28 1.16 3.91 10.62 20.44 39.61 57.81 72.23 82.24 86.74 90.21 90.50 92.49 277.55 K 55.55 1.04 9.48 25.99 48.22 68.36 80.90 87.85 91.75 94.27 95.15 96.60 96.59 96.74 268.95 K 80.79 25.89 58.55 81.87 90.89 93.83 95.19 96.74 97.30 100.00 100.00 100.00 100.00 100.00

vs. temperature is reported in Tables 24 and plotted as example in Fig. 2 for mixture C. Similarly, the compositions analyzed in the two phases are reported in Tables 24, and the distribution of paraffins within the solid phase is represented schematically in the histogram in Fig. 3 for mixture B. From the results obtained on the quantities and compositions of the phases present in equilibrium, it is possible to express the percentage of crystallized paraffins. These data are given in Tables 57 and in Fig. 4 for mixture B which display the percentages corresponding to the individual crystallized paraffins as a function of temperature. In Fig. 3 within which the paraffin content in solid phase of system B is plotted as a function of temperature and number of carbon atoms, it can be noticed that at the highest temperature, the solid phase is not composed of all the paraffins present in the mixture. The lightest, from C 18 to C 20 , only precipitate 5 to 10 K below the wax appearance temperature according to the system studied. It can

Table 7 Percentages of paraffin crystallized vs. temperature for system C 293.05 K Overall percentage of paraffins crystallized Percentage of C 18 crystallized Percentage of C 19 crystallized Percentage of C 20 crystallized Percentage of C 21 crystallized Percentage of C 22 crystallized Percentage of C 23 crystallized Percentage of C 24 crystallized Percentage of C 25 crystallized Percentage of C 26 crystallized Percentage of C 27 crystallized 13.48 0.00 0.00 0.42 1.60 4.58 9.96 17.14 24.88 29.82 33.44 288.15 K 30.74 0.08 0.38 1.71 5.52 14.47 28.72 45.69 60.29 70.37 76.37 283.05 K 39.41 0.28 1.06 3.63 10.78 25.30 45.20 64.60 77.93 85.19 89.09 278.15 K 59.64 0.71 2.59 8.65 24.20 49.92 73.85 87.18 93.24 95.67 96.92 272.95 K 63.07 3.56 11.60 28.33 51.83 73.21 86.30 92.61 95.39 96.56 97.25 267.85 K 72.48 8.79 24.55 49.47 73.36 87.29 93.34 96.11 97.37 98.01 98.22

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Fig. 4. Percentage of paraffins crystallized as a function of temperature for system B.

also be noted in Fig. 4, which shows the percentage of crystallized paraffin as a function of temperature for each component, that the slope of precipitation is especially large at the beginning of the crystallization for heavy paraffins.

4. Comparison of models Liquidsolid phase equilibria are reflected by equations of equality of fugacity which lead to the following expression of the distribution coefficient K i for each component present in both phases: Kis x iS x iL s

/ /
g iS
f iS o

g iL

f iL o

exp

HP

P
o

iL yiS RT

dP

7.

In this expression, the equilibrium ratio is defined by the sum of three terms. The first one, which characterises the nonideality of liquid and solid solutions, requires further hypotheses on the nature of the liquid and solid solutions to be evaluated. The second term, which takes into account the effects of temperature, can be evaluated w9x directly from determination of the change in Gibbs free energy between the pure solid and the pure subcooled liquid at pressure Po . The last term, which represents the pressure dependence, is generally little different from unity at low pressure and can be neglected as the volume change is small. Thus, when solidsolid transitionSS. occurs between temperature T and melting temperature T m , the equilibrium ratio can be written: Kis

g iL g iS

exp

D Him RT

1y

T Tim q

D HiSS RT

1y

T TiSS q

m DC P

1y

Tim T

q ln

Tim T

8.

In this formulation, the phase equilibrium ratio K i is connected only to the melting and solidsolid transition properties of pure components and to the ratio of activity coefficients. The properties of

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pure components can be correlated to molecular weight, while evaluation of the activity coefficients ratio requires models which can describe the properties of mixture in both states. In order to identify the most appropriate activity models combination for predicting the liquidsolid equilibria of this kind of mixtures, and in particular the amount and the composition of the solid phase as a function of temperature, a comparative study of the predictive abilities of various models has been performed with reference to the data measured. The models selected for these tests are listed below. 4.1. The model of Won Won w2x has introduced two simplifications in Eq. 8. . Firstly, the variation of heat capacity is neglected as it provides only a slight contribution in the exponential function. Secondly, the melting temperatures and solidsolid transition temperatures are considered as equal since they are generally very close, which leads to the following expression: Kis

g iL g
S i

exp

D HimqSS RT

1y

T Tim

9.

in which pure n-paraffin properties are estimated from correlation functions. Moreover, Won w2x has proposed to use the regular solution theory of ScatchardHildebrand in order to model the nonideality of liquid and solid phases. 4.2. The model of Pedersen et al. Pedersen et al. w10x have also proposed to use a regular solution model. However, two modifications were introduced in Wons model: the heat capacity difference was taken into account in the equilibrium ratio and correlation functions were given to express the solubility parameters as function of carbon number of components. 4.3. The model of Hansen et al. The basis of the model of Hansen et al. w3x is identical to Wons model since both use Eq. 9. to express the equilibrium ratio K i ; however, unlike Won w2x, Hansen et al. w3x have assumed the solid phase as homogeneous ideal. Whereas nonideality in the liquid phase is described by the polymer solution theory of Flory w4x, Hansen et al. w3x have also proposed a new correlation for estimating the melting temperature of heavy components of crude oils. However, as the mixtures studied contain only n-paraffins, this correlation was replaced by that of Won w2x for these tests. 4.4. The model of Coutinho et al. In order to take into account the significant difference in size between molecules in liquid state, Coutinho et al. w5x have proposed to use a free-volume model to describe the nonideality of the liquid phase. Moreover, for describing the nonideality of the solid phase, Coutinho et al. w6x have developed a predictive version of the local composition model of Wilson w11x in which interaction energies are related to the coordination number Z and to the enthalpy of sublimation of pure alkanes.

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4.5. The model of Ungerer et al. Ungerer et al. w7x have proposed another approach which rests on the assumption that each heavy component crystallizes pure, thus leading to several solid phases. In this method, the condition of equilibrium is given for each component which may precipitate, by the following expression: f iL s f iSo

10.

where fugacity of the pure component i in the solid state is determined from the fugacity of the same substance in subcooled liquid state. When the melting and solidsolid transition temperatures are assumed equal and the change of heat capacity is neglected, the equilibrium condition can be expressed by the following relationship: f iL s f iL o exp y

D HimqSS RT

1y

T Tim

11.

In this expression, the fugacity of the component i in the liquid solution and the pure liquid fugacity are calculated from the cubic PengRobinson w12x equation of state using original mixing rules. 4.6. The ideal solution model Moreover, the simple model in which both phases are assumed ideal has also been tested. Assuming, furthermore, the heat capacity change as negligible and the melting and solidsolid transition temperatures as equal, the equilibrium ratio is expressed by the following relation: K i s exp

D HimqSS RT

1y

T Tim

12.

in which it is connected only to the pure component properties. To appreciate the respective abilities of these models to predict the LS transition temperatures, the deviations between the calculated and the experimental values which correspond to the temperature of disappearance of the last solid part. were listed in Table 8. On the other hand, as the error on the
Table 8 Deviation DT between experimental and calculated wax appearance temperatures DT K. Mixture A Texp K. 293.35 Ideal model Won w2x Hansen et al. w3x Pedersen et al. w10x Coutinho et al. w5,6x Ungerer et al. w7x q7.0 q7.2 q5.0 q5.1 q1.0 y3.1 299.35 q4.1 q4.3 q2.1 q2.2 q0.6 y0.1 297.35 q4.0 q4.1 q2.0 q2.6 q0.8 y0.6 Mixture B Mixture C

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Fig. 5. Amount of paraffins crystallized calculated with various models for system A.

temperature of phase change introduces a shift of the solid deposits curves along temperature axis, the deviation between calculated and experimental quantities amount and composition. cannot be used to test the capacities of these models to represent the behavior of solid deposits. It was because of this difficulty that graphical representation Figs. 59. was used to compare the models. The deviations listed in Table 8 show that all activity models overestimate the solid appearance temperatures; nevertheless, this overestimation keeps slight, the deviation never exceeding 4 K. In

Fig. 6. Percentage of hexacosane crystallized calculated as a function of temperature for system C.

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Fig. 7. Percentage of tricosane crystallized calculated as a function of temperature for system C.

particular, the deviations observed with the model proposed by Coutinho et al. w5,6x are for the three systems of the order of 1 K. This performance is all the more remarkable, as the model is used in its original form, in other words, without any adjustment of parameters. On the other hand, the pure paraffin crystallisation model underestimates the liquidsolid transition temperatures. Still there, the values predicted by the model are not so far from experimental values.

Fig. 8. Percentage of eicosane crystallized calculated as a function of temperature for system C.

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Fig. 9. Mass fraction of eicosane calculated as a function of temperature for system A.

Study of solid deposit curves shows that Wons model and ideal solution model lead to similar prediction. This result comes from values of regular activity coefficients which are nearly similar in both phases. Thus, as for ideal solution, the g i ratios are close to unity and the equilibrium ratios become only function of pure components parameters. On Fig. 5, which represents the amount of solid deposits as a function of temperature for mixture A, it can be observed that the improvements of Pedersen et al. w10x solely bring about a translation of curves calculated by Wons model. These three models, as well as Hansen et al. w3x, overestimate the crystallisation rate at the wax appearance temperature. This is particularly true for mixtures B and C which contain more light components C 18 , C 19 .. Actually, all these models, which are based on the assumption that heavy components precipitate in one solid solution, predict that all components heaviest as well as lightest. of the heavy fraction are present in the first solid bulk, whereas measurements Tables 24. show that the lightest do not precipitate at the wax appearance temperature. This means, as it can be seen on Figs. 6 and 7, that the models can predict the heaviest component content in solid phase but give a poor representation of composition of lightest components Fig. 8. . Unlike these models, the approach of Ungerer et al. w7x always underestimates the slope of solid deposit vs. temperature. Actually, as the model assumes a pure component crystallisation, it predicts that only the heaviest component precipitates at the solid appearance temperature, and thus minimises the amount of solid deposit at the beginning. Consequently, the percentage corresponding to the individual paraffins crystallized as a function of temperature is better represented for heaviest component than for lightest. However, despite the assumption made, representation is not aberrant and the deviations observed by reference to experimental data are not higher than those observed with solid solution models. Finally, as it can be observed on Fig. 5, the curves predicted by the procedure of Coutinho et al. w5,6x show a good fit with experimental points. In particular, the model predicts an inflection point which is also experimentally observed on curves corresponding to the individual paraffins crystallized

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as a function of temperature Figs. 68. . Comparison of calculated and experimental solid phase composition Fig. 9. is more convincing of the quality of the model. So, a correct description of solid solutions is a necessary condition for a satisfactory representation of solidliquid equilibrium of many component systems. Nevertheless, as all other models, this model gives a better representation of heaviest Fig. 6. than lightest components Fig. 8. .

5. Conclusion Experimental equipment of solidliquid filtration and measurement procedure have been developed in order to study the solid precipitation in synthetic mixtures. The apparatus was used to perform new experimental measurements on mixtures made up of decane plus various distributions of heavy normal paraffins from octadecane to triacontane. These measures, which concern the amount and the composition of solid precipitate as a function of temperature on synthetic complex systems, provide a detailed characterization of the solid precipitation in synthetic systems. The numerical verifications performed on database demonstrate that the procedure proposed by Coutinho et al. w5,6x leads to a satisfactory representation of the liquidsolid equilibria of these multi-component systems.

6. List of symbols CP f Fj H K m P R T V xi Xi Yj Greek letters a g Superscripts L LT m Heat capacity fugacity mass fraction of phase j in the whole system enthalpy equilibrium ratio mass pressure ideal gas constant temperature volume mole fraction of i mass fraction of i mass fraction of phase j in the solid residue of filtration

distribution coefficient activity coefficient

liquid trapped liquid melting

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207

S SR SS Subscripts i n o

solid solid residue solidsolid transition

component carbon number pure component at reference pressure

Acknowledgements The authors wish to thank Doctor J. Coutinho for helpful discussions.

References
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