Anda di halaman 1dari 6


Ruben Oliveira Chiavone Abstract

Askarel oil represents a threat to environment, even that its commercialization has been prohibited it is still used and its discard may contaminate the soil. Several methods to decontaminate soil and samples from askarel oil have been used. However, one effective method is the supercritical fluid extraction (SFE). In order to design an effective SFE project the determination of contaminant solubility is crucial. This work focused on predictive method using equation of state (EoS) to determinate solubility and results were compared to available experimental data. Keywords: askarel oil, supercritical fluid extraction, PCBs and equation of state.

Processes based on SFE have a wide area of application including environment control and it has been proposed as an analytical technique for polluted environmental sites and samples. SFE is also a cleanup technology (Anitescu and Tavlarides, 1999). The oil Askarel (mixture of polychlorinated biphenyls, PCBs) is a high toxicity substance; though its commercialization on Brazil has been prohibited many electrical generators still use PCBs as a dielectric fluid being allowed up until its shelf life. Throwing away such equipment can contaminate the environment with PCBs that is the importance of SFE on PCB remediation. The composition of Askarel oil is basic a mixture of 75% of PCBs congeners and 25% mass of tetrachlobenzene, which is the largest percentage on chlorobenzene of the oil (Vale, 2008). Table 1 shows the PCBs composition on Askarel.

Table 1 Composition of PCBs congers of the Askarel oil.

PCB formula 100 w (%, m/m) MW(g/mol) tri chlorated C12H7Cl3 tetra chlorated C12H6Cl4 penta chlorated C12H5Cl5 hexa chlorated C12H4Cl6 hepta chlorated C12H3Cl7 octa chlorated C12H2Cl8 nona chlorated C12HCl9















w = mass fraction; MW = molecular weight. Data from Silva (2011).

The determination of solubility (expressed as mole fraction) in the modeling of phase equilibrium involving the system oil Askarel (as a solid matrix) plus supercritical fluid (ScF) is the most important property to design an effective SFE process (Prausnitz et al, 1999).To determinate this property it has been used a thermodynamic analysis based on equation of state. This work focused on Soaves modification of Redlich-Kwong (SRK) EoS using modified second order Huron-Vidal (MHV2) mixing rule and UNIFAC activity coefficients (Holderbaum and Gmehling, 1990).

Carbon dioxide (CO2) was chosen to be the ScF for the modeling. CO2 is a convenient solvent for SFE. Among others, CO2 has the advantage of allowing extractions at temperatures close to room temperature (the CO2 critical temperature is 304.25 K) and its major advantage of derives from its environmentally-friendly properties: it is not toxic; it does not burn or explode; it is easily vented into atmosphere; and it is inexpensive (Prausnitz et al, 1999).

The method for predicting Askarel Oil solubility was based on use of the software SPECS V5.60x (2009) provided by Denmark Technical University (DTU) to estimate fugacity coefficient of each species with the SRK EoS, MHV2 mixing rule and UNIFAC activity coefficients (which it was all specified on SPECS). Then with programming language FORTRAN run routines repeatedly for calculating solubility along with solid solute vapor pressure and molar volume values as it will be discussed. According to Sandler (1989) the solubility of a solid in a ScF is given by equation (1).
( )( ) ( *
( )


Where ( ) is usually unity, because vapor pressure of solid is generally small. This equation must be solved by iteration since the solute mole fraction appears in the fugacity coefficient ( ). However, it was considered infinite dilution (10-5) for the solute in order to avoid the iteration process. Soaves modification of Redlich-Kwong EoS is given by equation (2). Holderbaum and Gmehling (1990) considered SRK EoS a simple and precise equation and along with a reasonable mixing rule it has a likely predictive capacity for mixtures like PCBs.
( ) ( )

(2) (3)

( ) ( )( )


MHV2 mixing rule at pressure zero is like a reference state which is given by equation 5 (q1 = 0.478 and q2 = -0.0047, Orbey and Sandler, 1997).

( )

(5) (6) (7)

This work used UNIFAC model to calculate the fugacity coefficient on SPECS software. PCBs, tetrachlorobenze and CO2 have been used the following subgroups: ACCl (54), ACH (10), AC (11) and CO2 (113) each which was picked from Magnussen (1981). For each pair of groups was

used 2 parameters, though the parameters ACClCO2 and CO2ACCl was regressed with solubility data from monochlorobezene and CO2 supercritical (Wang et al, 2006). Both vapor pressure and molar volume equation was picked from DIPPR (Daubert and Danner, 1989) data bank. The expression of vapor pressure was given by equation (8). The parameters of the equation for each compound are described on table 2. Table 2 Vapor pressure parameters. congener hexachlorobiphenyl heptachlorobiphenyl heptachlorobiphenyl heptachlorobiphenyl Pressure range (bar) 100-300 100-300 100-300 100-300 Temperature range (K) 313-333 313 323 333 Parameter A -4775 -4847 -4848 -4850 Parameter B 12.85 12.23 12.56 12.86 (8)

Parameters A and B based on values presented by Site (1996).

Tetrachlorobenzene was calculated using another equation (9) which was selected from DIPPR: ( ) ( ) (9)

Volume of solute has been calculated by modified Rackett equation (10) (Spencer and Danner, 1972). A correction factor of 0.867 (this correction was made considering experimental data) was applied in the equation because Rackett equation evaluates liquid volume, but the interest volume is the solid volume.



Critical Properties are available on literature (table 3). These properties are fundamental to estimate solubility with EoS. Table 3 Thermodynamic properties of PCBs congeners. property Tb (K) Tc (K) Pc (bar) MW tetrachlorobenzene 511.0 749.05 36.46 0.420 214.02 hexachlorobiphenyl 643.15 866.0 24.51 0.705 360.82 heptachlorobiphenyl 653.15 869.21 23.29 0.759 395.27 askarel oil 596.61 823.66 28.67 0.626 316.13

Tb: boiling temperature; Silva (2011).

: critical temperature;

: critical pressure;

: acentric factor. Data from

The validation process was done for a series of aromatics system plus CO2 supercritical using the SRK EoS, MHV2 mixing rule and UNIFAC model. The following 4-7 tables represent the results on those systems.

Table 4 Naphtalene (solid) in CO2 supercritical solubility data prediction. T (K) 308.15 328.15 333.55 338.50 P (atm) 85.7 to 252 81.1 to 284 107 to 287.6 149.8 to 271.4 No. of points 9 16 19 10 GARD 0.005351 0.017599 0.047432 0.114530

0.006768 0.034785 0.076745 0.302270

Experimental solubility from McHugh and Paulaitis (1980).

Table 5 Biphenyl (solid) in CO2 supercritical solubility data prediction. T (K) 308.95 318.55 322.65 328.35 P (atm) 104.6 to 435.4 151.5 to 442.5 153.6 to 469 109.2 to 484 No. of points 8 8 8 15 GARD 0.006540 0.014138 0.022088 0.049769

0.007516 0.017112 0.026241 0.168880

Experimental solubility from McHugh and Paulaitis (1980).

Table 6 Monochlorobenzene (liquid) in CO2 supercritical solubility data prediction. T (K) 323.15 328.15 333.15 P (atm) 84.38 to 92.38 84.88 to 98.99 85.37 to 105.4 No. of points 4 6 7 GARD 0.007505 0.010627 0.011566

0.014241 0.022067 0.027408

Experimental solubility from Wang et al (2006).

Table 7 Naphtalene and Phenanthrene (both solids) in CO2 supercritical solubility data prediction. T (K) 308.20 P (atm) 80.7 to 279 No. of points 11 GARD 0.007316 for Naphtalene 0.000284 for Phenanthrene

0.008863 for Naphtalene 0.000727 for Phenanthrene

Experimental solubility from Liu and Nagahama (1996). GARD (geometric average relative deviation) = (( ) ) ( ) ; (maximum deviation)

Results and Conclusions

These results showed that the method proposed was working and should be applicable reasonable on solids matrixes like Asakarel oil. The results for PCBs congeners was plotted (Figure 1) and was compared to experimental data. Since the error with the relative experimental data was considered low (maximum deviation was 0.003) the method applied may be considered feasible for operational and design purposes of the SFE unity.

Figure 1 Hexachlorobiphenyl and heptachlorobiphenyl solubility calculated using the model presented on this work and experimental data from literature.

Experimental data from Anitescu and Tavlarides (1999).

ANITESCU, G.; TAVLARIDES, L. L. Solubility of individual polychlorinated biphenyl (PCB) congeners in supercritical fluids: CO2, CO2/MeOH and CO2/n-C4H10. J. Supercrit. Fluids.14 1999, 197-211. DAUBERT, T. E.; DANNER, R. P. Data Compilation Tables of Properties of Pure Compounds, AIChE/DIPPR, New York, 1989. HOLDERBAUM, T.; GMEHLING, J. PSRK: A group contribution equation of state based on UNIFAC, Fluid Phase Equilib., 70, 1991, 251-265. LIU, G.-T; NAGAHAMA, K. Solubility of organic solid mixture in supercritical fluids. J. Supercrit. Fluids. 9, 1996, 152- 160. MAGNUSSEN, T. IVC-SEP Phase-Equilibria and Separation Processes MAN 8101 1997, 1981 latest revision by E. Pretel. ORBEY, H.; SANDLER, S.I. A comparison of Huron-Vidal type mixing rules of mixtures of compounds with large size differences, and a new mixing rule. Fluid Phase Equilib., 132 (1-2), 1997, 1-14. PRAUSNITZ, J.M.; LICHTENTHALER, R.N; AZEVEDO, E. G. Molecular Thermodynamics of FluidPhase Equilibria. 3rd Edition. Prentice Hall, New Jersey, 1999. SANDLER, S. I. Chemical and Engineering Thermodynamics. 2nd ed. Wiley, New York, 1989. SANDLER, S. I. Chemical, Biochemical, and Engineering Thermodynamics. 4th ed. Wiley, New Jersey, 2006.

SILVA, D. J. Aplicao da equao Soave-Redlich-Kwong para predio dos dados da extrao de PCBs com CO2 supercrtico. Anais do VI Congresso Brasileiro de Termodinmica Aplicada. Volume 107, 2011, p 1-10. SITE, A. D. The Vapor Pressure of Environmentally Significant Organic Chemicals: A Review of Methods and Data at Ambient Temperature. J. Phys. Chem. Ref. Data (26) (1), 1997, 157-193. VALE, L. A. S. Hidrodesclorao Cataltica de BifenilasPolicloradas (PCBs), Dissertao deMestrado, Instituto de Qumica, Universidade de So Paulo, So Paulo, 2008. WANG, B.; HE, J.; SUN, D.; ZHANG, R.; HAN, B. Solubility of chlorobutane, ethyl methacrylate and trifluoroethyl acrylate in supercritical carbon dioxide. Fluid Phase Equilib. (239), 2006, 6368.