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L. P. R. de Andrade1 ,Luis A. M. Rutledge1, E.L. Moreno2, I. Hovell2, Krishnaswamy Rajagopal3

Copyright 2012, Instituto Brasileiro de Petrleo, Gs e Biocombustveis - IBP Este Trabalho Tcnico foi preparado para apresentao na Rio Oil & Gas Expo and Conference 2012, realizado no perodo de 17 a 20 de setembro de 2012, no Rio de Janeiro. Este Trabalho Tcnico foi selecionado para apresentao pelo Comit Tcnico do evento, seguindo as informaes contidas no trabalho completo submetido pelo(s) autor(es). Os organizadores no iro traduzir ou corrigir os textos recebidos. O material conforme, apresentado, no necessariamente reflete as opinies do Instituto Brasileiro de Petrleo, Gs e Biocombustveis, Scios e Representantes. de conhecimento e aprovao do(s) autor(es) que este Trabalho Tcnico seja publicado nos Anais da Rio Oil & Gas Expo and Conference 2012.

H um interesse crescente em estudar as propriedades fsicas de misturas binrias e dos fluidos multicomponentes com dixido de carbono supercrtico (CO2) ao longo de uma vasta gama de temperatura e presso. A estimativa de propriedades tais como densidade, viscosidade, presso de saturao, compresso, solubilidade e tenso superficial de misturas so importantes no projeto, operao e controle, bem como otimizao de processos qumicos, especialmente em extraes, separaes, reaes catalticas e enzimticas. O comportamento de fase de misturas binrias e multicomponentes com CO2 supercrtico tambm importante na produo de petrleo e de refinao onde as misturas de parafinas, naftenos e aromticos com fluidos supercrticos so frequentemente encontrados. Fluidos de petrleo podem apresentar um comportamento de fase complexo na presena de CO 2, onde duas fases (VLE e LLE) e trs regies de fase (VLLE) podem ocorrer dentro de gamas de condies supercrticas de temperatura e presso. O objetivo deste estudo desenvolver uma metodologia experimental para medir o comportamento de fase de misturas contendo CO 2 em regies supercrticas, utilizando equipamentos de alta presso comercial.

There is a growing interest in studying physical properties of binary and multicomponent fluid mixtures with supercritical carbon dioxide (CO2) over an extended range of temperature and pressure. The estimation of properties such as density, viscosity, saturation pressure, compressibility, solubility and surface tension of mixtures is important in design, operation and control as well as optimization of chemical processes especially in extractions, separations, catalytic and enzymatic reactions. The phase behaviour of binary and multicomponent mixtures with supercritical CO 2 is also important in the production and refining of petroleum where mixtures of paraffin, naphthene and aromatics with supercritical fluids are often encountered. Petroleum fluids can present a complex phase behaviour in the presence of CO2, where two-phase (VLE and LLE) and three phase regions (VLLE) might occur within ranges of supercritical conditions of temperature and pressure. The objective of this study is to develop an experimental methodology for measuring the phase behaviour of mixtures containing CO2 in supercritical regions, using commercial high-pressure equipment.

1. Introduction
There is a growing interest in the use of supercritical fluid mixtures in a wide range of chemical processes, including supercritical fluid extraction, (McHugh, 1986), water power generation (Ber, 2007) and Biodiesel production, (Bunyakiat et al., 2006), high pressure and supercritical state to complex mixtures (Penedo et al., 2009) just to name a few, and the study of vapor-liquid equilibria is an important aspect of supercritical fluids behavior. Many researchers have estimated, using analytical methods, the equilibrium phases composition at high pressure and supercritical state to

______________________________ Tcnico Laboratrio de Termodinmica e Cintica Aplicada, Escola de Qumica, Universidade Federal do Rio de Janeiro (LATCA-EQ-UFRJ) 2 Ph.D, Pesquisador Laboratrio de Termodinmica e Cintica Aplicada, Escola de Qumica, Universidade Federal do Rio de Janeiro (LATCA-EQ-UFRJ) 3 Ph.D, Professor Titular Laboratrio de Termodinmica e Cintica Aplicada, Escola de Qumica, Universidade Federal do Rio de Janeiro (LATCA-EQ-UFRJ)

Rio Oil & Gas Expo and Conference 2012 complex mixtures, but few experimental data are available for the evaluation of multicomponent mixtures involving carbon dioxide (CO2), especially at high concentrations and/or with heavy compounds. It is therefore necessary to study experimentally the behavior and the thermodynamic properties of these mixtures. In this work we evaluated vapour-liquid equilibrium experimental data of a standard synthetic mixture of cyclohexane, n-hexadecane and CO2, the latter at high concentrations, measured in a temperature range of 303.15 to 333.15 K and pressure range from 10 to 600 Bar, conditions similar to pre-salt reservoirs off the Brazilian coast. Petroleum fluids can present a complex phase behaviour in the presence of CO2, where two-phase (VLE and LLE) and three phase regions (VLLE) might occur within ranges of supercritical conditions of temperature and pressure. The objective of this study is to assess the effectiveness of the procedure used to develop a methodology capable of producing experimental VLE data (vapour-liquid equilibrium) and the thermodynamic properties of Pressure-Volume-Temperature (PVT) systems in supercritical state and close that state.

2. Experimental Method
2.1. Experimental Apparatus For this work we used PVT equipment developed by Schlumberger. The experiments were carried out in a variable-volume vapor-liquid equilibrium cell consisting of a Pyrex cylinder closed at each end by stainless valves. The cell had an internal capacity of about 112 cm3. This cell is presented in Figure 1. To maintain the system pressure, a highpressure positive displacement pump developed by Schlumberger is employed. This pump is built and tested to perform reliably, smoothly and safely with a high precision in pumped volumes to a maximum working pressure of up to 1400 Bar. The phase compositions were determined with GC chromatographic analysis.

Figure 1. Schematic Diagram of Equilibrium Cell

2.2. Simulation Procedure One of the first steps in the simulation process is the choice of thermodynamic property package. In general the first criteria considered is the choice in type of property package is governed by the use of Kays rule: If the reduced temperature Tr of any of the components in the mixture (Tr = T/Tci, where Tci is the critical temperature), under investigation is greater than 0.75 then the type of property package should be an equation of state, EOS, (Walas , 1985). The reduced temperature for CO2 at 303.15 K is 1. Therefore the property package type should be limited to EOS. The Peng Robinson (PR) is the property package recommended for systems covering a large range of conditions and rigorously describes the larger part of monophasic, biphasic and triphasic systems with a high degree of efficiency and accuracy. The methods based on state of equations used in this work were: Peng- Robinson (PR) (Peng and Robinson, 1976), Soave-Redlich-Kwong (SRK) (Soave, 1972), Sour PR (Rajagopal et al., 2009), Sour SRK (Erbar et al., 1980), Peng-Robinson-Stryjek-Vera (PRSV) (Stryjek and Vera, 1986), Zudkevitch Joffee (ZJ) (Zudkevitch and Joffee, 2

Rio Oil & Gas Expo and Conference 2012 1970). These equations of state are available in the process simulation program, UniSim Design 370 R1, used in this work. 2.3 Experimental Procedure Phase equilibria of mixtures were determined using a synthetic mixture composed of cyclohexane, n-hexadecane and CO2. Before the PVT cell was filled with the mixture, the cell and the tubing were evacuated for at least 40 minutes. After that a mixture of known composition of cyclohexane (TEDIA, USA, above to 99%) and n-hexadecane (TEDIA, USA, above to 99%) is injected in the cell. By weighing the syringe before and after the injection, the amount of liquid injected in the PVT cell can be determined. Then, a known amount of pure CO2 is added in the mixture. The amount of CO2 added was determined with a precision of 0.011g. For this work three different ternary mixtures of cyclohexane (1), n-hexadecane (2) and CO2 (3) were studied. Table 1 shows the experimental compositions employed for this study. Table 1. The Molar Compositions of the Mixtures Mixture Cyclohexane n-C16 CO2 M [1] 0.18 0.08 0.75 M [2] Mole Fraction 0.28 0.12 0.60 0.19 0.42 0.40 M [3]

The phase equilibrium has been studied at the temperatures of 303.15, 313.15, 323.15 and 333.15 K. The phase transition resulting from pressure variations were studied by visualization through an optical device specially configured for this purpose. For each temperature, phase equilibrium measurements were made from the operating pressure of the liquidvapor biphasic system, of about 47.57 Bar, until the monophasic equilibrium pressure. After reaching the equilibrium phase, the system is depressurized slowly to determine the bubble point pressure at each equilibrium temperature. An aliquot of gas and liquid phase of about 3 cm3 is removed and collected in a pycnometer for chromatographic analysis. The analysis of the gas aliquot is performed by transferring it to an Agilent gas chromatograph, model 7890A, equipped with a capillary and a packing columns fitted with FID and TCD detectors, specially configured for the CO2 and hydrocarbons analysis. The liquid phase analysis is carried out in other Agilent chromatograph, model 7890A with a capillary column and FID detector.

3. Experimental and Simulation Results

The compatibility between the simulated and the experimental data for this asymmetric ternary mixture was evaluated for the mixtures M [1], M [2] and M [3] under pressures high enough to obtain monophasic conditions at temperatures between 303.15 and 333.15 K. These conditions are more appropriate for an experimental pilot study and will help in the exploration of the super-critical conditions of this ternary mixture close to the operating temperature of the PVT equipment. The simulated data were obtained using the experimental temperature and composition with each of the property packages. Bubble point pressure was measured for all mixtures at each of the four temperatures. The values for the bubble point pressures are reported in Table 2 where it can be seen that the pressure of the bubble point increased in function of the temperature for each composition. Table 2. Bubble Point Pressure at Different Temperatures for Mixtures M [1], M [2], M [3] Bubble Point Pressure, Bar M [1] 58.95 70.33 85.49 96.53 M [2] 52.54 55.85 72.19 88.25 M [3] 50.68 66.88 67.22 86.24

Temperature, K 303.15 313.15 323.15 333.15

Rio Oil & Gas Expo and Conference 2012 Chromatographic analysis of the gas phase produced after the determination of the bubble point at a pressure of 41.37 Bar (initial pressure of the experiment) showed that the gas phase is formed of cyclohexane and CO2 and that the composition is mainly CO2, around 90%. The composition of the gas phase did not change with temperature. The absolute average percentage deviation (AAD %) between the experimental and calculated bubble points is shown in Table 3. Table 3. Absolute Average Deviation between Experimental and Simulated Bubble Point Pressures Property Package Peng Robinson (PR) Soave-Redlich-Kwong (SRK) Sour PR Sour SRK Peng Robinson Stryjek Vera (PRSV) Zudkevitch-Joffee (ZJ) AAD % 6.96 8.48 7.10 8.48 21.51 10.00

Even though the Peng - Robinson Equation of State (PR EOS) presented the smallest deviation of the property packages examined it did not achieve accuracy within experimental error, which is 1.72 Bar. Figure 2 shows the experimental and simulated bubble point pressures using the PR and SRK property packages for M [1]. The PR and Sour PR property packages estimated bubble point pressure values close to the experimental values for the temperature range studied. It can be seen, in Figure 2 that the SRK bubble point pressure values increasingly deviate with increasing temperature for the mixture M [1] with a high CO2 mole fraction content of 0.75. 140 120 Pressure, Bar 100 80 60 40 20 0 300 310 320 Temperature, K Figure 2. Experimental and Simulated Bubble Points pressures for M [1] The simulation of the experimental bubble point pressures using the PR EOS was reliable using the conditions of the experiment throughout the temperature range in these sub-critical conditions. 330 340 Experimental SRK PR

4. Conclusions
Experimental data of the VLE of the synthetic mixture of cyclohexane + hexadecane + CO2 were obtained for different temperatures and pressures, and compared with estimated values using several EOS in order to choose an appropriate equation suitable for the study of complex mixtures such as reservoir fluids. Three different compositions were evaluated experimentally and the results were compared with simulated values using EOS methods. The simulated bubble points were found to be close to the values obtained experimentally using the Peng Robinson property package, although the difference between them were larger than the experimental error.

Rio Oil & Gas Expo and Conference 2012 The consistency of the results confirms the reliability of the apparatus, the technique employed and simulation method used in this work for determining and predicting VLE. It would thus be possible to study the supercritical region, using a process simulation program to calculate the composition of this complex ternary mixture, in the PVT apparatus. The experimental data for higher compositions of CO2 will be useful for a complete study of the application of these equations of state

5. Acknowledgments
The authors acknowledge the financial support PETROBRAS/CENPES e UFRJ.

6. References
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