Phase Behavior Data of (CO2 + Toluene + Phenanthrene) and (CO2 +

Article pubs.acs.org/jced

Phase Behavior Data of (CO2 + Toluene + Phenanthrene) and (CO2 + (Methanol + Phenanthrene) Systems at High Pressure Arthur J. O. Braga,† Rafael P. do Carmo,‡ Papa M. Ndiaye,†,‡ and Frederico W. Tavares*,†,‡ †

Escola de Química, Universidade Federal do Rio de Janeiro Centro de Tecnologia Av. Athos da Silveira Ramos, 149 Ilha do Fundão, Rio de Janeiro, CEP 21941-909, Brazil ‡ Programa de Engenharia Química/COPPE - Universidade Federal do Rio de Janeiro, Cidade Universitária, Rio de Janeiro, RJ CEP: 21949-972, Brazil ABSTRACT: In this work, the phase equilibrium data of the ternary systems (CO2 + toluene + phenanthrene) and (CO2 + methanol + phenanthrene) at high pressure are reported. The static synthetic method, with a new design of a variable-volume view cell, was used to obtain the vapor liquid (VL) and solid− liquid (SL) transition data in a temperature range of (274 to 363) K and pressures up to 16 MPa. For the ternary system (CO2/toluene/phenanthrene), the mole fractions of carbon dioxide varied from (0.6 to 0.90) with two toluene to phenanthrene molar ratios of (6/1) and (12/1). For the system (CO2/ methanol/phenanthrene) the CO2 molar fractions varied from 0.33 to 0.75 with methanol to phenanthrene molar ratios of (150/1) and (250/1). For these two ternary systems, (vapor + liquid), and (solid + liquid) transitions were observed. Results shows that carbon dioxide acts as antisolvent for the system toluene/ phenanthrene and as cosolvent for the systems methanol/phenanthrene.

1. INTRODUCTION Phenanthrene is a polycyclic aromatic hydrocarbon (PAH) with a condensed structure of three aromatic benzene rings.1 The PAHs are found in petroleum fluids at low levels in finished petroleum products (such as gasoline, diesel, kerosene) and, at relatively high levels, in crude oil heavy fractions such as asphaltene, waxes and bitumen residues.2 The study and the understanding of the phase behavior of heavy petroleum fractions, especially in the presence of low molecular weight compounds such as methane and CO2, is a key step for the petroleum fluids production and refining processes due to wax and asphaltene precipitation.2,3 The mechanism of asphaltene precipitation in crude oil has been the subject of much controversy in the literature, such as the importance or not of the association.3−5This controversy is especially due to the lack of robust and reliable techniques for the characterization of petroleum heavy fractions in terms of physicochemical properties3 (molecular weight, critical properties, density etc.). In this context, the use of a representative molecule with well-defined thermodynamic properties can contribute significantly to better understanding of the real mechanism of wax and asphaltene precipitation in crude oils.2,6Because phenanthrene is well characterized, the knowledge of its phase behavior in an industrial solvent such as toluene and methanol in the presence of carbon dioxide or methane can be used as a representative system to infer information concerning the precipitation of asphaltenes and waxes in the presence of carbon dioxide. Several studies report the phase behavior of systems involving phenanthrene and carbon dioxide.7−10 These studies © 2017 American Chemical Society

showed that phenanthrene is poorly soluble in CO2. The pressure required to completely solubilize phenanthrene in carbon dioxide, even at low phenanthrene concentration and at high temperature, is in the order of 10 MPa.7 This fact justifies the use of carbon dioxide as an antisolvent in gas antisovent systems processes when phenanthrene is present.8 Knowledge of the phase behavior is a key step for the modeling, design, and optimization of separation processes controlled by equilibrium.11−14 Some studies showing the phase behavior of systems with phenanthrene containing cosolvents are available in the literature.15 However, none of these papers reported phase equilibrium data for systems with phenanthrene and CO2 in methanol and toluene. Here, we provide the vapor−liquid (VL) and solid−liquid (SL) phase transitions at high pressures of ternary systems involving phenanthrene, CO2, toluene, and methanol.

2. EXPERIMENTAL SECTION 2.1. Material. Table 1 shows the chemicals and their mole fraction purity used in this work. All chemicals were used without further purification. 2.2. The Modified Equilibrium Cell. The equilibrium cell used here has an important improvement over cells used in previous works.16−18 The cell is stainless steel (316 L) and has an internal diameter of 20 mm and length of 113 mm with a Special Issue: Memorial Issue in Honor of Ken Marsh Received: February 1, 2017 Accepted: August 9, 2017 Published: August 23, 2017 2812

DOI: 10.1021/acs.jced.7b00126 J. Chem. Eng. Data 2017, 62, 2812−2818

Journal of Chemical & Engineering Data

Article

thermal fluid (water) flowing through the shell. The sample is enclosed inside the tube. The improved equilibrium cell is very efficient for solid−liquid onset transition measurements, which are very sensitive to temperature change. Figure 3 shows a

Table 1. Chemical Used in This Work chemical name

source

mole fraction purity

phenanthrene methanol toluene carbon dioxide

Sigma-Aldrich Sigma-Aldrich Sigma-Aldrich Air liquid

0.992 0.999 0.999 0.999

usable volume of 35 mL. The cell is provided with an internal piston whose purpose is to control the sample pressure. The cell has two upper inlets connected respectively, to the thermocouple and the feed valve (V6). A bottom outlet allows an eventual sampling of the heavy phase. Two lateral sapphire windows symmetrically arranged and aligned allow the illumination of the samples inside the cell and the eventual connection of external measuring devices such as a spectrophotometer. The cell front is equipped with a sapphire window in contact with a digital microscope device that allows real-time monitoring of the sample. Phase transitions are detected instantly with a magnification up to 150 times the actual size using the digital microscope. Figures 1 and 2 show a

Figure 3. Transversal and longitudinal cut of the equilibrium.

transversal and a longitudinal cut of the cell with the longitudinal holes inside the cell through which the water from a thermal bath circulates to maintain the sample temperature at a determined value. 2.3. Experimental Procedure. The experimental scheme used here is based on the static−synthetic method shown in Figure 4 and described in more details in previous papers.16 The experimental procedure begins by loading CO2 into the syringe pump chamber. Because at room temperature (298 K) CO2 is a gas, the mere opening of V1 is not sufficient to move enough amount of carbon dioxide into the syringe pump (ISCO model 260 D) chamber. Usually, with the cylinder valve V1 opened for about 30 min and V2 closed, the temperature of the syringe pump chamber is reduced and kept at 290 K using a thermal jacket (ISCO) connected to a water circulating bath. This arrangement allows a natural flow from the gas cylinder at room temperature up to the chamber of syringe pump kept at 290 K as shown in Figure 4. The cell is then loaded with a known quantity of phenanthrene, toluene/methanol, and carbon dioxide using the following procedure: First, accurate known quantities of phenanthrene and a solvent (Toluene or Methanol) are weighed with a high precision balance with an accuracy of 0.0001 mg, to produce a known mole ratio of phenanthrene/solvent. The cell is then closed and connected to the process line. The next step is to inject a known mass of carbon dioxide previously calculated to reproduce a known global composition. Keeping valves V1, V5, V6, and V7 closed, valves V2, V3, and V4 are opened. The entire line process is pressurized and stabilized at 15 MPa and 290 K using the syringe pump. At this condition, carbon dioxide is liquid with a known density (0.92074 g/L). The stabilization of the system (zero pump flow) requires about 30 min, and should be done carefully because any trace of flow observed in the syringe pump controller may lead to systematic errors on the determination of the volume of liquid CO2 to be injected. Once the system is stabilized, the volume of CO2 inside the syringe pump chamber is recorded and a given volume of liquid CO2 corresponding to the referred mass is injected into the cell through the micrometric valve V6. It is important to emphasize that the during the carbon dioxide injection, the syringe pump chamber and the line process are kept to 15 MPa and 290 K. 2.4. Vapor−liquid Measurements Procedure. Once the CO2 injection process is concluded, V6 is closed and for safety,

Figure 1. Global view of the equilibrium cell used.

Figure 2. Internal cut of the equilibrium cell used in this work.

global view and an internal cut of the equilibrium cell used in this work. The main improvement of the equilibrium cell concerns the temperature control. An efficient system of longitudinal holes uniformly distributed through the cell allows a rigorous temperature control with an accuracy of 0.1 K. This arrangement is similar to that of a heat exchanger with the 2813



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Figure 4. Scheme of the experimental unit used in this work.

Table 2. Experimental Vapor−Liquid Transitions for CO2/ Methanol Obtained in This Work for a Carbon Dioxide Molar Fraction Equal to 0.4213 System

CO2 (1) + Methanol (2)

x1

T/K

ua (T)/K

P/MPa

ua (P)/MPa

0.4215

303.1 313.2 323.1 333.3 343.2 353.1

0.1 0.1 0.1 0.1 0.1 0.1

5.12 6.19 7.49 8.40 9.76 10.69

0.05 0.05 0.04 0.04 0.03 0.03

a

u(P) and u(T) are standard uncertainties for pressure and temperature respectively u(x1) = 0.0003.

the pressure inside the equilibrium cell is reduced to 5 MPa to retract the cell piston pneumatically controlled by the syringe pump controller. Keeping V1, V7, and V5 closed, V2, V3, V4, and V5 are opened. A sequence of procedures aiming to obtain a monophasic system is then started. Contents of the cell are continuously stirred while the pressure within the cell is increased up to 20 MPa. At this condition, a single phase is observed and this is checked via the front sapphire view window with ×150 magnification by the digital microscope. Using a high precision pressure transducer (Swagelok S- model with an error 0.5% of the span limit) the VL saturation pressure is then measured at the controlled cell temperature (through a water circulating bath connected to the cell), with the precise amount of phenanthrene now dissolved in the precise amount of solvent (methanol or toluene) in the presence of a known quantity of carbon dioxide, to establish the reported global compositions. For this purpose, the cell pressure, initially at 20 MPa, is gradually reduced though the syringe pump controller at a rate of 0.01 MPa per minute. This rate of

Figure 5. Comparison of experimental bubble points of the CO2/ methanol obtained with those from the literature at carbon dioxide molar fraction equal to 0.4213.

pressure reduction is sufficient to minimize the mass transfer resistance. The phase transition is detected by the digital microscope connected to a computer with magnification up to 150 times. After completion of the measurement at a given pressure, the cell temperature was adjusted to a new value and the vapor liquid measurement procedure was repeated. For the experimental run at one global composition, a series of VL measurements at seven temperatures (363, 353, 343, 333, 323, 313, and 303 K) were performed. This procedure was repeated at least three times for each fixed global composition. After VL measurements, the cell pressure is then reduced up to 5 MPA, and the exhausting valve V7 is opened. The cell is then disconnected from the process line and cleaned. 2814



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2.5. Solid−Liquid Measurement Procedure. For solid− liquid transitions, phenanthrene, toluene (or methanol), and carbon dioxide were loaded into the cell to give a global known composition, according to the procedure described in section 2.3. The desired pressure was set and the temperature was slowly decreased at a rate of 0.1 K per minute, until the beginning of a solid phase formation was detected instantly by the digital microscope. To avoid kinetic effect, the experimental procedure adopted here for solid−fluid transition measurements was similar to that presented by Ferreira et al.17 The cell is then emptied, cleaned, and the procedure is repeated three times for each global composition.

Table 4. Experimental Data of Vapor−Liquid (VL) and Solid−Liquid (SL) Transitions for the System {CO2 (1) + Toluene (2) + Phenanthrene (3)} for Molar Ratio Toluene to Phenanthrene Equal to 12/1. Here, x1 and x2 Are Mole Fractions of CO2 (1) and Toluene (2), respectively T/K

3. RESULTS AND DISCUSSION 3.1. CO2/Methanol System. Table 2 shows the experimental bubble points for binary system CO2/methanol obtained here, and Figure 5 shows a comparison with those reported in the literature. As can be observed the experimental Table 3. Experimental Data of Vapor−Liquid (VL) and Solid−Liquid (SL) Transitions for the System {CO2 (1) + Toluene (2) + Phenanthrene (3)} for Molar Ratio Toluene to Phenanthrene Equal to 6/1. Here, x1 and x2 Are Mole Fractions of CO2(1) and Toluene(2), Respectively T/K

ua (T)/K

363.2 353.4 343.6 333.9 323.7 313.5 303.7 298.9 297.7 295.9 291.8 290.8 290.0

0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.2 0.3 0.3

363.0 353.3 343.4 334.0 323.7 313.7 307.6 306.4 306.4 306.0 306.0

0.1 0.1 0.1 0.1 0.1 0.1 0.2 0.1 0.1 0.2 0.2

358.5 353.4 348.6 343.7 338.9 334.1 329.5 324.9

0.1 0.1 0.1 0.1 0.1 0.1 0.2 0.2

P/MPa

ua (P)/MPa

x1 = 0.6128 and x2 = 0.3319 9.34 0.34 8.48 0.33 7.53 0.33 6.59 0.32 5.68 0.31 4.76 0.30 3.95 0.29 3.52 0.29 3.33 0.28 3.22 0.28 4.00 0.29 5.00 0.30 6.00 0.31 x1 = 0.7807 and x2 = 0.1880 11.35 0.36 10.04 0.35 8.99 0.34 7.73 0.33 6.58 0.32 5.53 0.31 6.50 0.32 7.00 0.32 8.00 0.33 9.00 0.34 10.00 0.35 x1 = 0.9047 and x2 = 0.0187 15.19 0.40 13.92 0.39 13.53 0.39 12.46 0.37 11.86 0.37 11.27 0.36 11.00 0.36 13.00 0.38

transition type VL VL VL VL VL VL VL VL VL VL SL SL SL

ua (T)/K

363.2 353.4 343.6 333.5 323.7 313.5 303.7 298.7 277.3

0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.2 0.3

362.7 353.2 343.6 333.8 323.4 313.6 303.5 298.6 292.8 291.4 290.6 289.4 289.0 288.8

0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.2 0.2 0.1 0.2 0.1

352.5 343.3 333.5 323.6 315.2 309.8

0.1 0.3 0.1 0.1 0.1 0.1

P/MPa

ua (P)/MPa

x1 = 0.5994 and x2 = 0.3698 8.97 0.34 8.18 0.33 7.39 0.32 6.56 0.32 5.62 0.31 4.81 0.30 4.16 0.29 3.68 0.29 4.00 0.29 x1 = 0.7710 and x2 = 0.2114 11.29 0.36 10.10 0.35 8.91 0.34 7.70 0.33 6.60 0.32 5.56 0.31 4.67 0.30 4.15 0.29 3.54 0.29 4.00 0.29 5.00 0.30 6.00 0.31 7.00 0.32 8.00 0.33 x1 = 0.8998 and x2 = 0.0925 13.41 0.38 12.96 0.38 11.27 0.36 9.95 0.35 9.00 0.34 11.00 0.36

transition type VL VL VL VL VL VL VL VL SL VL VL VL VL VL VL VL VL VL SL SL SL SL SL VL VL VL VL SL SL

a u(P) and u(T) are standard uncertainties for pressure and temperature, respectively. u(x1) = 0.0003; u(x2) = 0.0003.

VL VL VL VL VL VL SL SL SL SL SL VL VL VL VL VL VL SL SL

Figure 6. P−T diagram of the system CO2/toluene/phenanthrene with molar ratio toluene to phenanthrene equal to 6. WCO2 is the carbon dioxide overall mass fraction.

a

u(P) and u(T) are standard uncertainties for pressure and temperature, respectively. u(x1) = 0.0003; u(x2) = 0.000. 2815



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procedure is adequate and the modified equilibrium cell used is able to reproduce literature data with great accuracy. 3.2. CO2/Toluene/Phenanthrene System. Table 3 shows the experimental equilibrium data obtained in this study for the system {CO2 (1) + toluene (2) and phenanthrene (3)} for a molar ratio toluene to phenanthrene of (6/1). Table 4 shows the result of the same system for molar ratio toluene to phenanthrene of (12/1). These tables present the results in terms of pressure transition, temperature transition, and the phase transition type. In Figure 6, the P−T projection is presented for several carbon dioxide compositions for the ternary system {CO2 (1) + toluene (2)+ phenanthrene (3)} at fixed toluene to phenanthrene molar ratio of (6:1). For a fixed temperature, the increase of CO2 concentration causes an increase in the pressure of both vapor−liquid and solid−liquid transitions. Solid−liquid transitions have a high sensitivity to the CO2 concentration. For example, at 6 MPa, the solid−liquid transition temperature changes from 289 to 308 K when the

CO2 mass fraction varies from 0.4 to 0.6. This phenomenon can be explained by the fact that CO2 is a good solvent for toluene at low temperatures and moderate pressures and a poor solvent for phenanthrene. Because toluene is a good solvent for phenanthrene, the addition of carbon dioxide in the binary mixture causes an antisolvent effect. In Figure 7, the P−T projection of the same mixture is presented; however, at a molar ratio toluene to phenanthrene equal to 12. The phase behavior exhibited is similar to that shown in Figure 5. For a fixed temperature, as the molar ratio toluene to phenanthrene increases, the transition pressure for the vapor−liquid equilibrium region remains unchanged for the same carbon dioxide fraction. This is in contrast to the liquid− solid equilibrium region, where the increase of the toluene to phenanthrene molar ratio decreases the temperature at which the precipitation occurs, as can be observed in Figure 8. Table 5. Experimental Data of Vapor−Liquid (VL) and Solid−Liquid (SL) Transitions for the System {CO2 (1) + Methanol (2) + Phenanthrene (3)} for Molar Ratio Methanol to Phenanthrene Equal to 150/1. Here, x1 and x2 Are Global Mole Fractions of CO2 (1) and Methanol (2), Respectively T/K

Figure 7. P−T diagram of the system CO2/toluene/phenanthrene with molar ratio toluene to phenanthrene equal to 12. WCO2 is the carbon dioxide overall mass fraction.

Figure 8. Comparison of the molar ratio toluene to phenanthrene influence on bubble points and solid−liquid transitions. WCO2 is the carbon dioxide overall mass fraction.

ua (T)/K

362.8 353.0 343.3 333.7 323.2 313.2 303.2 297.7 295.9 2923 291.2 288.7 287.7

0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.2 0.1 0.1 0.1 0.1 0.1

363.2 353.5 343.7 334.0 323.7 313.8 304.0 287.0 287.9 289.9 291.9

0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.2 0.2 0.1 0.2

314.0 304.1 294.2 284.2 284.2 280.8 280.6 277.2

0.1 0.1 0.1 0.1 0.1 0.2 0.3 0.2

P/MPa

ua (P)/MPa

x1 = 0.3334 and x2 = 0.6622 8.42 0.33 7.72 0.33 6.91 0.32 6.14 0.31 5.35 0.30 4.64 0.30 3.98 0.29 4.50 0.30 5.00 0.30 6.00 0.31 7.00 0.32 8.00 0.33 9.00 0.34 x1 = 0.5295 and x2 = 0.4674 11.51 0.37 10.55 0.36 9.45 0.34 8.28 0.33 7.08 0.32 5.97 0.31 4.99 0.30 9.00 0.34 7.00 0.32 6.00 0.31 4.00 0.29 x1 = 0.7500 and x2 = 0.2483 6.16 0.31 5.05 0.30 4.12 0.29 3.28 0.28 3.42 0.28 5.00 0.30 6.00 0.31 8.00 0.33

transition type VL VL VL VL VL VL VL SL SL SL SL SL SL VL VL VL VL VL VL VL SL SL SL SL VL VL VL VL SL SL SL SL

a u(P) and u(T) are standard uncertainties for pressure and temperature, respectively. u(x1) = 0.0003; u(x2) = 0.0003.

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3.3. CO2/Methanol/Phenanthrene System. Tables 5 and 6 show the experimental data obtained for the {CO2 (1) + methanol (2) + phenanthrene (3)} ternary system. Table 5 shows the vapor−liquid (VL) and solid−liquid (SL) experimental transitions for molar ratio methanol to phenanthrene equal to 150/1, while Table 6 shows VL and SL transitions for the molar ratio methanol to phenanthrene equal to 250/1. Table 6. Experimental data of Vapor-Liquid (VL) and SolidLiquid (LS) Transitions for the System {CO2 (1) + Methanol (2) + Phenanthrene (3)} for Molar Ratio Methanol to Phenanthrene Equal to 250/1. Here, x1 and x2 Are Mole Fractions of CO2(1) and Methanol(2), Respectively T/K

ua (T)/K

363.1 353.2 343.4 334.1 323.5 313.6 303.8 293.7

0.1 0.1 0.3 0.1 0.1 0.1 0.1 0.1

363.1 354.1 344.2 334.5 324.1 303.9 303.9 294.0

0.2 0.2 0.1 0.1 0.1 0.1 0.1 0.1

333.7 323.9 313.9 304.0 294.1 284.4

0.1 0.1 0.1 0.1 0.1 0.1

P/MPa

ua (P)/MPa

x1 = 0.3308 and x2 = 0.6665 8.27 0.33 7.55 0.33 6.78 0.32 6.00 0.31 5.80 0.31 4.56 0.30 3.86 0.29 3.06 0.28 x1 = 0.5265 and x2 = 0.4716 10.96 0.36 10.14 0.35 9.13 0.34 8.03 0.33 6.92 0.32 5.78 0.31 4.78 0.30 3.76 0.29 x1 = 0.7478 and x2 = 0.2512 9.69 0.35 8.19 0.33 6.47 0.31 5.02 0.30 4.12 0.29 3.18 0.28

transition type VL VL VL VL VL VL VL VL

Figure 9. P−T diagram of the system CO2/methanol/phenanthrene with molar ratio toluene to phenanthrene equal to 150/1. wCO2 is the carbon dioxide overall mass fraction.

VL VL VL VL VL VL VL VL VL VL VL VL VL VL

a

u(P) and u(T) are standard uncertainties for pressure and temperature, respectively. u(x1) = 0.0003; u(x2) = 0.0003.

Figure 10. P−T diagram of the system CO2/methanol/phenanthrene with molar ratio toluene to phenanthrene equal to 250/1. wCO2 is the carbon dioxide overall mass fraction.

For the system (CO2 + methanol + phenanthrene), Figures 9 and 10 present the P−T diagram for the molar ratios methanol to phenanthrene of 150/1 and 250/1, respectively. The liquid− vapor transition region shows a similar behavior to that of the CO2/phenanthrene/toluene system where the liquid−vapor transition pressure increases with the CO2 concentration at constant temperature. In the solid−liquid region, the transition temperature decreases as the CO2 concentration increases for a given pressure. This behavior is in contrast to that observed for CO2/toluene/phenanthrene system. Because methanol is a poor solvent for phenanthrene, carbon dioxide can enhance considerably the solubility of phenanthrene in methanol (Figure 9). For the molar ratio methanol to phenanthrene equal to 250/1, no liquid−solid transition was observed for the temperature range investigated here, even at high carbon dioxide concentration and low temperature (Figure 10).

experimentally measured at several conditions. Vapor−liquid and solid−liquid transition data were obtained, showing two antagonistic behaviors when carbon dioxide is present. For the ternary system CO2/toluene/phenanthrene, the increase of carbon dioxide concentrations increase the solid− liquid transition temperatures. In other words, carbon dioxide acts as an antisolvent for the toluene/phenanthrene system. In contrast, CO2 acts as cosolvent in the methanol/ phenanthrene system, where for a given pressure the addition of carbon dioxide greatly reduces the solid−liquid transition pressures.

■

AUTHOR INFORMATION

Corresponding Author

*E-mail: tavares@eq ufrj.br. Tel.: +55 2139387650.

4. CONCLUSIONS The transition pressures of two systems involving carbon dioxide and toluene, methanol, and phenanthrene were

ORCID

Frederico W. Tavares: 0000-0001-8108-1719 2817



Article

Funding

Progesterone + Propane, and Progesterone + n-Butane Systems at Elevated Pressures. J. Supercrit. Fluids 2008, 45, 161−170.

The authors thank CNPq, CAPES, FAPERJ, ANP, Brazilian agencies INCT-Midas and PETROBRAS for the scholarships and financial support. Notes

The authors declare no competing financial interest.

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REFERENCES

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Phase Behavior Data of (CO2 + Toluene + Phenanthrene) and (CO2 +

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