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Fluid Phase Equilibria 264 (2008) 259263

Measurement and correlation of vaporliquid equilibria for the system carbon dioxidediisopropyl ether
Caifeng Zhu, Xianghong Wu, Danxing Zheng , Wei He, Shuhong Jing
College of Chemical Engineering, Beijing University of Chemical Technology, Beijing 100029, China Received 30 May 2007; received in revised form 14 November 2007; accepted 15 November 2007 Available online 22 November 2007

Abstract A view cell with on-line sampling of the vapor and the liquid phase has been built for measuring vaporliquid equilibria data under high pressure. The samples are analyzed by gas chromatography. VLE data for the system carbon dioxidediisopropyl ether has been measured at 265.15333.15 K and 0.52.5 MPa. The isothermal data were correlated using the PengRobinson equation. The correlated results agree well with the experimental results. The experiments conrm that diisopropyl ether is an excellent absorbent of carbon dioxide. 2007 Elsevier B.V. All rights reserved.
Keywords: Vaporliquid equilibria; Carbon dioxide absorbent; Diisopropyl ether; Thermodynamic correlation

1. Introduction The emission of carbon dioxide (CO2 ) has been identied as the main contributor to global warming and climate change. The challenge for modern industry is to nd cost-effective solutions that will reduce the release of CO2 into the atmosphere. Reduction of CO2 emissions can be achieved by a variety of means [1]. A physical absorption process is one of the most important possibilities. The advantage of this method is that it requires relatively little energy. Diisopropyl ether, an excellent solvent, is expected to absorb CO2 [2,3]. So the vaporliquid equilibrium (VLE) data of the system carbon dioxidediisopropyl ether is very important for understanding this absorption process. Earlier studies on the solubility and the VLE of the carbon dioxidediisopropyl ether system are only made Zhang et al. [2] at experimental temperatures of 299.15 K, 308.65 K and 318.15 K, and pressure ranging from 0.82 MPa to 8.32 MPa. The determination of the solubility of carbon dioxide in diisopropyl ether is the rst step in the design of a diisopropyl ether-based carbon dioxide absorption process and was considered as the main objective of this paper. The VLE behavior of the carbon dioxidediisopropyl ether binary system was studied by a set

of VLE device [4,5] which was established on a serial VLE experimental methods [611] for references. 2. Experimental 2.1. Chemicals Carbon dioxide with purity greater than 99.9 mass% was purchased from Zhaoge Gas Co. Diisopropyl ether was purchased from Tianjin Jinke Fine Chemical Co.; the purity was greater than 99 mass%. These chemicals were used without further purication. 2.2. Apparatus The phase equilibrium apparatus used in this study is shown in Fig. 1. It is a static type apparatus and its design was similar to that used by Baba et al. [12]. There are three main sections: one for the high-pressure equilibrium cell, another for the input of the sample and the last one for on-line gas chromatography (GC) analysis of the composition of the equilibrium phases. The stainless steel equilibrium cell has an internal volume of 120 mL. The maximum operation pressure is 6 MPa. In the side of the equilibrium cell is a glass window for visual observation of the phase behavior. The equilibrium cell is shown in Fig. 2. It was xed inside a thermostat bath lled with water. An electric heater, connected

Corresponding author. E-mail address: dxzh@mail.buct.edu.cn (D. Zheng).

0378-3812/$ see front matter 2007 Elsevier B.V. All rights reserved. doi:10.1016/j.uid.2007.11.010

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C. Zhu et al. / Fluid Phase Equilibria 264 (2008) 259263

Fig. 1. Schematic diagram of the experiment apparatus: (1) gas cylinder; (2) gas storage tank; (3) liquid injector; (4) stirrer; (5) constant temperature water bath; (6) equilibrium cell; (7) magnetic mixer; (8) cooling unit; (9) temperature controller; (10) cushion tank; (11) gas chromatography; (12) vacuum pump; (13) computer.

to a PID thermal regulator (Model WD-D90) that was supplied by Wideplus Precision Instruments Co., was immersed in water. The temperature stability of the bath was <0.1 K. The temperature of the phase equilibrium was measured by a Pt100 resistance thermometer, which was supplied by Sailing Technology Co. The temperature uncertainty of this was <0.1 K. The thermometer was inserted into the liquid phase in the cell as an input signal for the temperature controller. Thus, the PID thermal regulator could adjust the temperature to the experimental condition automatically. Also side, a spiral coil connected to a cooling unit (Churchill Instrument Co.) was immersed in water. When the experimental temperature is below ambient temperature (273.15 K), the cooling unit decreased the temperature of the thermostat bath to the desired temperature. The pressure was measured by a pressure transducer (Realwill Technology Co.) with a full scale of 6 MPa and an uncertainty of 0.006 MPa. On-line analyses of the equilibrium compositions were carried out using a gas chromatograph produced by Shimaden Co. (Model GC-9A) with an estimated uncertainty of 0.001 in mole fraction. The GC) was equipped with a thermal conductivity detector (TCD) and a GDX-104 column 2 m in length and 3 mm in diameter. The carrier gas was hydrogen, with a ow rate of 60 mL min1 . The injection temperature was 160 C, the TCD temperature was 160 C and the column of the GC was 150 C. The current of the TCD was 120 mA. The sample size of vapor phases is no more than 10 L, and the sample size of liquid phases is no more than 1 L, respectively.

2.3. Experimental procedure The experimental procedure [13] to obtain a complete set of data consists of nine steps. (1) Leakage must be completely prevented during the experiment. Thus, check carefully for any leakage from the connections and valves. (2) Evacuate the whole apparatus with a vacuum pump. (3) Fill the equilibrium cell with a specied quantity of pure diisopropyl ether from a liquid injector. (4) Introduce carbon dioxide gas from the carbon dioxide gas cylinder into the gas storage cell. (5) Equilibrium is reached after the equilibrium cell pressure remains at a constant value for more than 30 min; at this point, record the nal pressure of the equilibrium cell. (6) Control the needle valves, and sample the microscale vapor and liquid sample to the on-line GC. (7) Close the sampling valve and evacuate the pipeline. (8) Change the experimental pressure to the next designated pressure state and repeat steps (4)(7) to obtain a complete set of isothermal px-y data. (9) Change the designated temperature and repeat steps (1)(8) to obtain another set of isothermal experiment data. 3. Results and discussion In this work, the p-T-x-y data for the carbon dioxidediisopropyl ether binary system were measured at ve temperatures (265.15 K, 273.15 K, 293.15 K, 313.15 K and 333.15 K) and ve pressures (0.5 MPa, 1.0 MPa, 1.5 MPa, 2.0 MPa and 2.5 MPa). The measured equilibrium compositions at various temperature and pressure states for this binary mixture are shown in Table 1. All the experimental results were correlated with the PengRobinson (PR) equation [1416]. The PR equation has been widely used and is regarded to be a good tool to analyze systems at high pressure. The PR equation of state [17] is given below: p= with a = 0.45725 R2 Tc2 pc (2) (3) RT a 2 Vm b V m + 2bVm b2 (1)

Fig. 2. Schematic diagram of equilibrium cell: (1) ange; (2) glass window; (3) vapor sampling tube; (4) pressure transducer; (5) temperature transducer; (6) liquid sampling tube; (7) magnetic rotor.

b = 0.0778

RTc pc

C. Zhu et al. / Fluid Phase Equilibria 264 (2008) 259263 Table 1 Vaporliquid equilibrium pressures and compositions for the system carbon dioxide (1)diisopropyl ether (2) system pexp (MPa) T = 265.15 K 0.682 1.049 1.505 2.021 2.478 T = 273.15 K 0.547 0.983 1.471 2.031 2.526 T = 293.15 K 0.56 1.185 1.537 2.051 2.551 T = 313.15 K 0.661 1.116 1.542 2.135 2.490 T = 333.15 K 0.741 1.104 1.672 2.181 2.554 x1
exp

261

y1

exp

cal x1

cal y1

x 0.0030 0.0055 0.0032 0.0000 0.0010 0.0004 0.0009 0.0003 0.0082 0.0018 0.0003 0.0002 0.0004 0.0004 0.0004 0.0002 0.0008 0.0004 0.0013 0.0007 0.0003 0.0009 0.0022 0.0037 0.0039

x% 1.07 1.45 0.63 0.01 0.13 0.21 0.28 0.08 1.42 0.28 0.27 0.10 0.12 0.09 0.08 0.15 0.39 0.14 0.35 0.17 0.29 0.50 0.82 1.06 1.02

y 0.0009 0.0006 0.0003 0.0001 0.0002 0.0046 0.0018 0.0000 0.0014 0.0013 0.0073 0.0006 0.0001 0.0016 0.0022 0.0105 0.0036 0.0013 0.0035 0.0026 0.0105 0.0047 0.0029 0.0037 0.0011

y% 0.09 0.06 0.03 0.01 0.02 0.46 0.18 0.00 0.14 0.13 0.76 0.06 0.016 0.17 0.22 1.12 0.37 0.13 0.36 0.26 1.13 0.50 0.30 0.39 0.11

0.2795 0.3754 0.5112 0.6565 0.7589 0.1831 0.3091 0.4361 0.5756 0.6450 0.1127 0.2281 0.2961 0.4015 0.4907 0.1235 0.1946 0.2728 0.3666 0.4024 0.1154 0.1728 0.2668 0.3447 0.3828

0.9968 0.9976 0.9986 0.9995 0.9998 0.9805 0.9876 0.9903 0.9918 0.9927 0.9653 0.9771 0.9811 0.9833 0.9845 0.9419 0.9572 0.9649 0.9705 0.9729 0.9269 0.9456 0.9562 0.9631 0.9683

0.2765 0.3809 0.5144 0.6565 0.7599 0.1827 0.3100 0.4364 0.5674 0.6468 0.1124 0.2283 0.2964 0.4012 0.4911 0.1233 0.1954 0.2724 0.3653 0.4031 0.1157 0.1737 0.2646 0.3410 0.3867

0.9977 0.9982 0.9989 0.9994 0.9996 0.9759 0.9858 0.9903 0.9932 0.9940 0.9580 0.9766 0.9810 0.9849 0.9866 0.9314 0.9536 0.9662 0.9740 0.9755 0.9164 0.9409 0.9591 0.9668 0.9694

= [1 + (0.37464 + 1.54226 0.269922 ) (1 Tr0.5 )] (4) The mixing rule is: a =

i j

Table 2 Pure component properties used in this work [18] Component Tc (K) 304.10 500.32 pc (MPa) 7.38 2.85 0.239 0.331

yi yj (a)ij yi bi
i

(5) (6)

Carbon dioxide Diisopropyl ether

b=

(a)ij = (1 kij ) kij = kji kii = 0

(a)i (a)j

(7) (8) (9)

where kij indicates the binary interaction parameters for obtaining better agreement in mixture EOS calculations. This parameter is obtained by tting the EOS to VLE data. It was estimated by minimizing the sum of squared relative deviations of bubble point pressures and the sum of squared deviations in mole fraction of phase equilibrium compositions. Tc and pc are the critical temperature and pressure, and denotes the acentric factor. These parameters [18] of the two pure components are shown in Table 2. The experimental and calculated data at different temperatures are illustrated in Figs. 3 and 4. The measured data in the

Fig. 3. VLE for the system carbon dioxide + diisopropyl ether: mole function CO2 in the liquid phase at ve temperatures: ( ) 265.15 K; () 273.15 K; ( ) 293.15 K; ( ) 313.15 K; ( ) 333.15 K. -: PR correlation.

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C. Zhu et al. / Fluid Phase Equilibria 264 (2008) 259263 Table 3 Parameters of the PR equation for the carbon dioxidediisopropyl ether system T (K) 265.15 273.15 293.15 313.15 333.15 kij 0.06197 0.04081 0.08942 0.03274 0.02353

the calculation data agree well with the experimental results. So the PR equation is able describe the VLE data of the system carbon dioxide + diisopropyl. 4. Conclusion The VLE data are presented for the system carbon dioxide + diisopropyl ether at temperatures of 265.15 K, 273.15 K, 293.15 K, 313.15 K and 333.15 K and pressures of 0.5 MPa, 1.0 MPa, 1.5 MPa, 2.0 MPa and 2.5 MPa. The VLE data were correlated with the PR equation of state. The measured data in the study agrees well with the calculated data and the reliability of the apparatus in the study was conrmed. It was proven that diisopropyl ether is an excellent absorbent of carbon dioxide. Therefore, diisopropyl ether, which has considerable potential as a new carbon dioxide absorbent, is worthy of further research. List of symbols a energy parameter of the PR equation (Pa m6 kmol2 ) b co-volume parameter of the PR equation (m3 kmol1 ) k binary interaction parameter of the PR equation p pressure (MPa) R gas constant (8314.5 m3 Pa kmol1 K1 ) T temperature (K) V molar volume (m3 kmol1 ) x liquid phase molar fraction y vapor phase molar fraction Greece letters parameter of the PR equation difference operator acentric factor Subscripts c critical property i, j component i or j m molar property r reduced property
Fig. 5. VLE for the system carbon dioxide + diisopropyl ether: vapor phase composition deviations of the experimental data from the calculated results at ve temperatures: ( ) 265.15 K; () 273.15 K; ( ) 293.15 K; ( ) 313.15 K; ( ) 333.15 K.

Fig. 4. VLE for the system carbon dioxide + diisopropyl ether: mole function CO2 in the vapor phase at ve temperatures: ( ) 265.15 K; () 273.15 K; ( ) 293.15 K; ( ) 313.15 K; ( ) 333.15 K. -: PR correlation.

study agrees well with the calculated data and the reliability of the apparatus is conrmed. The results in Fig. 3 demonstrate that the liquid mole fraction of carbon dioxide in diisopropyl ether increases with increasing pressure but decreases with increasing temperature. In the experimental temperature range, the liquid mole fraction of carbon dioxide changes strongly, especially at low temperatures. For example, the liquid mole fraction of carbon dioxide is 0.7589 at a temperature of 265.15 K and pressure of 2.478 MPa. This conrms that diisopropyl ether is an excellent absorbent for carbon dioxide. In the PR equation, the interaction parameter kij can be obtained from experimental data. This parameter could be used to predict the equilibrium data of the carbon dioxidediisopropyl ether system. The calculated results from the experimental data show in Table 3. The deviations of the calculated results by PR equation from the experimental data were shown in Fig. 5. It can be seen that

Superscripts cal calculated property exp experimental property

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Acknowledgements The support provided by the National Key Project (Nos.: 90210032, 50576001) for the completion of the present work is gratefully acknowledged. References
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