Article pubs.acs.

org/jced

PressureDensityTemperature Measurements of Binary Mixtures Rich in CO2 for Pipeline Transportation in the CCS Process
Michela Mazzoccoli,* Barbara Bosio, and Elisabetta Arato
Department of Civil, Chemical and Environmental Engineering, University of Genoa, via Opera Pia 15, 16145 Genoa, Italy ABSTRACT: Often, power plants and industrial production plants large point sources of CO2are situated at long distances from storage locations; thus the transportation of the resulting CO2-rich streams, containing small amounts of impurities, is required from the point of capture to the storage site, making it very important to understand the thermodynamic properties of CO2-rich mixtures. The range of conditions studied in this work are of great interest for carbon capture and storage applications, in particular for pipeline transportation of CO2-mixtures. Pressuredensitytemperature measurements were taken for binary mixtures of carbon dioxide with nitrogen, oxygen, or argon. Density was measured for all of the binary systems for temperatures between 273.15 K and 293.15 K and pressures between 1 MPa and 20 MPa, using a vibrating tube densimeter, Anton Paar DMA 512-HPM. The molar CO2 concentration was greater than 85 % for all mixtures tested.

INTRODUCTION Today, reducing the emissions of greenhouse gases has become one of the most important challenges to be faced. CO2 emissions must be reduced by 50 % to 80 % by 2050 (in comparison with 1990 levels).1 Increasing energy eciency and renewable energy levels may oer the most sustainable solutions for guaranteeing energy supplies; however the benets will most probably be obtained only in the long term. Therefore, for the short to medium term, fossil fuels will continue to be a primary energy resource, and the issue has become how these fossil fuels can be used in a more environmentally friendly way. An answer could be the carbon capture and storage (CCS) processa good option in a portfolio of technologies with the potential to cut the CO2 emissions that consents the continued use of fossil fuels.1 Transportation is a crucial issue in CCS technology, as power and industrial production plants where CO2 is captured are usually located at long distances from the storage locations, requiring the transportation of CO2 from the point of capture to the storage site. For the purposes of transportation, the CO2-mixture must have high density and purity levels. Furthermore, for nal safe storage, a CO2 molar concentration of over 95 % is required.2 Therefore the requirement for transportation may also inuence the type of capture technology chosen. One of the main transport solutions is via pipeline. CO2-rich streams will most likely be transported in the dense stage (above critical pressure, Pc, and under critical temperature, Tc, in Figure 1), so that the volumes to be transported are not large, in contrast with the gas phase when the density is very low. It is extremely important to know the thermodynamic properties of the dierent CO2-mixtures to be transported under these conditions. The type and quantity of impurities contained in CO2-mixtures depend on the fuels and on the type of capture technology used. If the CO2 is captured from power plants using
2012 American Chemical Society

Figure 1. PT diagram for pure CO2.

postcombustion capture, N2, O2, H2O, NH3, SOx, and NOx may be present. In the case of oxy-combustion capture, normally N2, O2, SO2, H2S, and Ar are present, while for precombustion capture, H2, CO2, N2, H2S, and CH4 may be found.3 Even so, volumetric experimental data for the CO2-mixtures of interest in the CCS process to date are limited. To our knowledge there are no published data on the volume of CO2 O2, CO2CO, and CO2NH3. The volumetric experimental data of mixtures containing Ar, H2, and H2S cover a small range of temperature and pressure,3 while a higher number of experimental data on volume have been published for CO2N2 and CO2CH4 mixtures.37 A preliminary comparison between pT experimental data found in literature of CO2N2 and CO2CH4 binary mixtures
Received: June 14, 2012 Accepted: September 6, 2012 Published: September 19, 2012
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Figure 2. Schematic diagram of experimental apparatus. Reprinted with permission from Paolo Chiesa of LEAP.

and dierent equations of state have been made by authors.8 However more volumetric experimental data on CO2-mixtures in pipeline transport conditions are needed; thus an experimental campaign was realized at LEAP (Energy and Environmental Laboratory of Piacenza). Volumetric experimental data of CO2N2, CO2O2, and COAr systems in supercritical conditions obtained at LEAP using a vibrating tube densimeter have been published by Mantovani et al.9 This paper reports new experimental results for pT measurements of CO2N2, CO2O2 and CO2Ar mixtures in the liquid and vapor stages at dierent temperatures (273.15 K, 283.15 K, and 293.15 K) and for the pressure range 1 MPa to 20 MPa.

EXPERIMENTAL SECTION Experimental Apparatus. A schematic diagram of the experimental apparatus is provided in Figure 2. The apparatus provides simultaneous density, pressure, and temperature measurements for a single phase uid of known composition during an isothermal transformation. The allowed temperature range is from 263 K to 388 K, and the allowed pressure range from vacuum conditions to 20 MPa. The apparatus consists of a pressurization circuit, a mixture vessel, a measurement circuit, a data acquisition system, and a vacuum circuit. The vessel containing the mixture is a cylindrical titanium vessel, 20 mm in diameter and 100 mm in length. A sliding piston is housed inside the vessel, separating the two chambers: the low chamber (LC) contains the sample uid; the pressure chamber (PC) contains the pressurization gas (normally nitrogen). The pressure level of the pressurization circuit can be controlled by means of the hand pump (HP), and it cannot exceed 30 MPa: when this value is reached, the rupture disk (RD) breaks and depressurizes the whole circuit to maintain its structural integrity. To prevent the disk rupture, a dierential manometer (MA) is introduced in the pressurization line. It can work from 0.1 MPa up to 40 MPa, and it is produced by Nuova Fima.
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The measurement circuit is composed of the measurement devices: the vibrating tube densimeter (VTD) and pressure and temperature meters. The vibrating tube densimeter is a DMA 512-HPM model produced by Anton Paar. The uncertainty associated with the vibrating period10 is 108 s. Temperature is controlled by means of a thermostatic bath (T1) supplied by Huber, model CC3-K12, with a temperature range from 253 K to 473 K and a stability of 0.02 K. The temperature is maintained by an electric resistance (EH2). Temperature measurements are supplied by two Pt100 platinum probes (PP1 and PP2), calibrated in the Milan Polytechnic laboratory. The temperature measurement accuracy is 0.05 K. Pressure measurements are taken by dierent pressure transmitters supplied by GE Druck of the series PTX611. Three sensors (VPT group) are high temperature transmitters and one sensor (LPT) a lower temperature transmitter. The VPT group is maintained at 288 K by an electric resistance (EH1). The pressure limits of the three sensors are 0.6 MPa, 6 MPa, and 25 MPa, respectively. The LPT transmitter is maintained at 258 K by a thermostatic bath (T2) produced by Huber, model CC1-K6, with a temperature range from 253 K to 423 K with a stability of 0.02 K; its pressure limit is 25 MPa. The pressure sensors are calibrated using a hydraulic balance produced by Scandura which, in turn, was calibrated at the Scandura Calibration center for the pressure ranges 1 MPa to 6 MPa and 6 MPa to 20 MPa. Corrections for the actual temperature, local gravity, and transmitter positions have all been applied. The estimated accuracy achieved for pressure measurements is 0.03 %. The temperature is maintained at the desired value inside the measurement circuit, where valves V6, V6R, V7, V8, V9, and V9R are located, by a thermostatic bath (TB) containing a heat exchanger (HE). The thermostatic bath was produced by Huber, model CC1 Variostat CC, with a temperature range from 253 K to 423 K and a stability of 0.02 K.
dx.doi.org/10.1021/je300590v | J. Chem. Eng. Data 2012, 57, 27742783

Journal of Chemical & Engineering Data The data acquisition system consists of an Aglient datalogger, model 34970A (DL1), for sampling the pressure and temperature signals, and of an Anton Paar device, model mPDS 2000 V3 (DL2), for sampling density/period signals. The two instruments are connected to a personal computer that, using an acquisition system developed in Labview, processes and stores the values measured. The vacuum circuit is connected to the measurement circuit and is needed to prevent gas residues inside from contaminating the sample mixture. It is possible to use two vacuum circuits: one is composed of the vacuum pump (VP), Pirani gauge 1 (PG1), and valve V5, the other one is composed of the same vacuum pump, Pirani gauge 2 (PG2), and valve V11. Using the vacuum pump, a pressure under 10 Pa can be obtained inside the measurement circuit. The values of the pressure are registered by a data logger for the vacuum sensors (DL3). For the tests, high purity carbon dioxide (99.998 %) and high purity nitrogen, argon, and oxygen (99.999 %) were supplied by Rivoira S.p.A. Table 1. Molar Fraction x of the Binary Mixtures Investigateda
N2a xCO2 xN2 xO2 xAr
a

Article

N2b 0.8785 0.1215

O2a 0.9558 0.0442

O2b 0.8512 0.1488

Ara 0.9605

Arb 0.9276

0.9873 0.0127

0.0395

0.0724

Standard uncertainty u(x) = 0.0002.

Figure 3. Vessel loading circuit. Reprinted with permission from Paolo Chiesa of LEAP.

Experimental Procedure. The vibrating tube densimeter is able to measure the density of only a single phase uid; therefore dierent testing procedures are used in the case of a mixture that is a subcooled liquid or a superheated vapor. In the vapor phase tests, as suggested by refs 11 to 13, the pressure transducers (VPT group) and the thermostatic bath TB must be set at a temperature higher than that of the chosen isothermal line, to avoid condensation of the uid and formation of two phases in a device other than the vibrating tube densimeter. In this case, in fact, the two uid phases have a dierent composition to the overall mixture, and the vibrating tube densimeter measures the density of a uid with an unknown composition. The temperature of the vibrating tube densimeter must be set at the temperature of the chosen isothermal line. Before starting the experiment, the measurement circuit must be made to work under vacuum. The vacuum pump must be started with the V4 valve closed to conserve the sample mixture, and the V10B valve closed to insulate the measurement circuit from the external environment. All of the other valves must be left open to allow the uid contained inside the measurement circuit to be completely extracted. When a pressure level under 10 Pa is reached inside the measurement circuit, the V10A valve must be closed and the vacuum pump stopped. This operation ensures that the eects of contaminant substances on the tested mixture are negligible. To obtain the pT measurements for the vapor phase, the V8 and V9 valves must be closed and the V7 valve opened. The V4 valve must be opened fully to allow the mixture to ow inside the measurement circuit, and the V6/V6R valves regulated to obtain the lling speed required. The latter must be lower than 0.005 MPas1 as suggested by refs 1113. Pressure, temperature, and density are measured every second starting from 1 MPa. During the test, the three dierent pressure transducers composing the VPT group must be used in sequence to obtain more precise pressure measurements. Furthermore, as the transducers approach their upper pressure limit, they must be isolated from the measurement circuit to guarantee that their integrity is preserved. When the dew point is reached, a two-phase uid forms inside the vibrating tube densimeter, and the density values cannot be eectively measured, thus ending the test. In the case of the liquid phase test, as suggested by Bouchot and Richon,11 the pressure transducers (LPT) and the thermostatic bath TB must be set at a temperature lower than that of the chosen isothermal line such as the rst vapor bubble forms inside the vibrating tube densimeter.

Table 2. FPCM Model Parameters: the Youngs Modulus E, the Standard Temperature T1, the Linear Dilatation Coecient , the Poissons Ratio , the Internal Radius, ri00, and the External Radius, re00, of the Vibrating Tube under Vacuum
parameter E(T)/MPa value

1 1 E(T ) = E(T1) + 1.174105 1298.51/ T1 1298.51/ T exp 1 1 exp

2.07105 298.15 1.14105 0.307 1.073 1.588
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E(T1)/MPa T1/K /K1 ri00/mm re00/mm

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Table 3. Experimental Values of Density with Standard Uncertainty u() at Temperature T and Pressure p for Pure CO2a
p/MPa 1.001 2.001 3.001 3.300 3.500 4.001 5.001 6.000 7.000 8.003 9.001 10.002 11.003 12.000 13.004 14.002 15.001 16.002 17.000 18.001 19.001 20.000
a

/kgm3 T = 273.15 K 21.2 45.7 77.3 89.9 928.1 932.4 940.7 948.2 955.3 961.9 968.1 974.1 979.7 985.1 990.1 995.0 999.7 1004.3 1008.6 1012.8 1017.0 1020.8

u()/kgm3 0.1 0.1 0.1 0.1 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3

p/MPa 1.000 2.001 3.001 4.000 4.400 5.001 6.003 7.000 8.001 9.001 10.001 11.001 12.000 13.001 14.001 15.000 16.001 17.001 18.002 19.001 20.000

/kgm3 T = 283.15 K 20.4 43.1 70.9 108.4 130.1 869.1 882.2 893.3 903.0 912.2 920.4 928.2 935.5 942.2 948.3 954.3 960.1 965.5 970.8 975.7 980.4

u()/kgm3 0.1 0.1 0.1 0.1 0.1 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3

p/MPa 1.011 2.001 3.001 4.000 5.000 5.600 5.800 6.001 7.003 8.001 9.002 10.001 11.001 12.000 13.000 14.000 15.003 16.003 17.001 18.002 19.002 20.000

/kgm3 T = 293.15 K 19.8 41.0 66.2 97.3 140.4 182.2 774.1 783.3 809.1 827.5 843.2 856.1 867.7 877.9 887.3 895.9 904.0 911.5 918.6 925.0 931.2 937.1

u()/kgm3 0.1 0.1 0.1 0.1 0.1 0.1 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3

Standard uncertainty u(T) = 0.05 K and relative standard uncertainty ur() = 0.03 %.

Table 4. FPCM Model Optimized Parameters: The Mass, M0, and the Length, L00, of the Vibrating Tube under Vacuum and the Isothermal Linear Expansion Coecient T at Dierent Temperatures T
vapor phase T/K 273.15 283.15 293.15 M0/L00/kgm1 5.6710 5.60102 5.60102
2

liquid phase M0/L00/kgm1 5.7110 5.72102 5.73102

2

T/MPa1 2.1210 8.84106 8.65106

5

T/MPa1 7.38106 8.01106 9.17106

The uid pressure is raised to 20 MPa by means of the pressurization circuit. Once the pressure required is reached, the valves V4 and V6 are closed. The pT values for the liquid phase are obtained by an emptying transitory. In this case, the LPT pressure transducer is used as it can work at low temperatures; thus valve V8 must be opened, whereas valve V7 must be closed. Valves V9/V9R are regulated to obtain the required emptying speed (<0.005 MPas1), and the V10B valve opened to allow the mixture to ow externally. When the bubble point is reached, a two-phase uid forms inside the vibrating tube densimeter, and the density values cannot be eectively measured, thus ending the test. Sample Preparation. Preparation of the mixture requires the pure species composing the mixture to be introduced into the vessel consecutively. First, the vessel is connected to the supply line and to the vacuum pump (VP), as represented in Figure 3. Vacuum conditions are created keeping valves V11, V14, and V4 open. When a pressure below 10 Pa is measured, valve V4 must be closed to insulate the volume of the vessel from the external environment, and the vacuum pump stopped. The vessel is then weighed to determine its own weight using a balance produced by Orma (model bc), having a sensitivity of 103 g.
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The uid can then be introduced into the vessel. If possible, it should be introduced in the liquid phase to maximize the mass supplied. The pure carbon dioxide can be introduced as a liquid as its critical temperature is suciently high and a simple cooling circuit is sucient. During the lling operation, valves V11 and V14 must be closed, while valves V4 and V15 must be opened. The amount of carbon dioxide introduced is calculated as the dierence between the current weight and the one measured during the previous step. If a further chemical species is to be introduced, the procedure is the same as that described above for introducing carbon dioxide. The only dierence is that, in this case, no cooling circuit is needed because the other components (N2, O2, and Ar) are introduced in the gaseous phase, due to their complex condensation conditions. This procedure does not allow a mixture of a denite composition to be produced so, in general, a number of lling attempts are necessary to achieve a satisfactory composition that is close enough to the one desired. For each contaminant species, two dierent CO2-rich mixtures are investigated, their molar composition reported in Table 1. The uncertainty factor for the molar fraction9 calculated is 2104. Densimeter Calibration. A vibrating tube densimeter, generally speaking, consists of a hollow U-shaped tube. The two ends of the tube are locked onto an isolating block. Two magnets are mounted on the free section of the tube, and two coils are wound around the magnets. The drive coil is connected to a current source, while the frequency counter induces a current with a frequency equal to that of the vibrating tube. The resonant frequency of the tube is measured by analyzing the signal from the pick up coil. When the density of the uid contained inside the tube changes, the resonant frequency of the tube changes as a consequence of the variation in the tube mass. This is the reason why the density value can be calculated from the vibrating period when a suitable model is used.
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Table 5. Experimental Values of Density with Standard Uncertainty u() at Temperature T and Pressure p for the Ara Mixturea
p/MPa 1.000 2.000 3.000 3.500 4.901 5.001 6.001 7.000 8.001 9.002 10.002 11.002 12.000 13.000 14.000 15.001 16.001 17.002 18.001 19.003 20.001
a

/kgm3 T = 273.15 K 22.5 46.1 75.5 96.9 893.5 894.8 905.7 915.5 924.0 932.1 939.5 946.4 952.9 959.1 965.0 970.6 975.9 981.0 986.0 990.8 995.3

u()/kgm3 0.1 0.1 0.1 0.1 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3

p/MPa 1.001 2.000 3.001 4.000 4.600 6.000 7.001 8.001 9.001 10.001 11.001 12.001 13.000 14.001 15.003 16.001 17.000 18.000 19.002 20.003

/kgm3 T = 283.15 K 20.9 43.1 69.6 104.2 133.2 827.6 844.5 859.1 871.9 883.2 893.1 902.4 910.9 918.7 926.0 932.8 939.4 945.6 951.6 957.3

u()/kgm3 0.1 0.1 0.1 0.1 0.1 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3

p/MPa 1.001 2.000 3.001 4.001 5.001 6.000 7.151 8.002 9.001 10.001 11.001 12.000 13.000 14.001 15.001 16.002 17.002 18.001 19.001 20.001

/kgm3 T = 293.15 K 20.4 41.0 65.0 94.2 132.6 198.0 728.4 765.2 790.8 811.1 827.5 841.6 853.5 864.3 874.3 883.4 891.9 899.7 906.9 913.8

u()/kgm3 0.1 0.1 0.1 0.1 0.1 0.1 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3

Standard uncertainty u(T) = 0.05 K and relative standard uncertainty ur() = 0.03 %.

Table 6. Experimental Values of Density with Standard Uncertainty u() at Temperature T and Pressure p for the Arb Mixturea
p/MPa 1.001 2.001 3.001 3.800 5.900 6.000 7.001 8.001 9.001 10.001 11.001 12.000 13.000 14.002 15.000 16.001 17.000 18.001 19.001 20.000
a

/kgm3 T = 273.15 K 21.2 44.2 72.9 104.5 881.4 880.2 886.5 898.0 907.8 917.3 925.5 933.4 940.6 947.4 953.8 959.9 965.7 971.2 976.5 981.5

u()/kgm3 0.1 0.1 0.1 0.1 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3

p/MPa 1.001 2.000 3.001 4.001 5.000 7.301 8.001 9.001 10.001 11.001 12.001 13.002 14.000 15.001 16.001 17.001 18.000 19.001 20.001

/kgm3 T = 283.15 K 20.1 42.2 68.4 101.2 151.6 801.8 816.3 833.9 848.6 861.6 873.0 883.5 892.6 901.4 909.4 916.9 924.1 930.8 937.2

u()/kgm3 0.1 0.1 0.1 0.1 0.1 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3

p/MPa 2.001 3.000 4.000 5.000 6.001 6.500 8.201 9.001 10.001 11.001 12.002 13.003 14.002 15.000 16.001 17.002 18.000 19.001 20.001

/kgm3 T = 293.15 K 40.6 64.4 92.6 128.2 179.0 220.5 680.3 726.1 760.3 785.0 804.5 820.2 834.1 846.1 857.1 867.1 876.3 884.9 892.9

u()/kgm3 0.1 0.1 0.1 0.1 0.1 0.1 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3

Standard uncertainty u(T) = 0.05 K and relative standard uncertainty ur() = 0.03 %.

In general, a vibrating tube densimeter can be modeled as a linear system in terms of internal volume V(T,p), stiness K(p,T), and mass M(T,p). The latter is composed of two terms represented in eq 1:10
M = M 0 + ( T , p ) V ( T , p)
(1)

M 0 + V 1 = +B K A

(2)

where M0 is the mass of the vibrating tube itself under vacuum and is the density of the inner uid. According to the mechanical vibration theory, the resonant vibrating period can be expressed as follows:
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where both coecients A and B are temperature- and pressuredependent due to the stiness and volume variables. To obtain the density measurements, coecients A and B must be calculated for every pressure and temperature. Dierent methods to calculate the density from the vibrating period have been developed. In this work, the continuous method called forced path mechanical calibration (FPMC) proposed by Bouchot and Richon10 was used.
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Table 7. Experimental Values of Density with Standard Uncertainty u() at Temperature T and Pressure p for the N2a Mixturea
p/MPa 1.001 2.001 3.001 3.470 3.902 4.000 5.001 6.000 7.000 8.001 9.000 10.000 11.001 12.000 13.002 14.001 15.001 16.000 17.002 18.012 19.011 20.001
a

/kgm3 T = 273.15 K 21.9 46.0 76.9 96.4 911.4 911.6 922.2 930.9 938.7 946.0 952.8 959.2 965.2 970.8 976.3 981.5 986.6 991.4 996.1 1000.6 1004.8 1008.7

u()/kgm3 0.1 0.1 0.1 0.1 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3

p/MPa 1.000 2.000 3.000 4.000 4.500 5.101 6.001 7.000 8.000 9.001 10.001 11.001 12.001 13.000 14.000 15.001 16.001 17.001 18.003 19.002 20.001

/kgm3 T = 283.15 K 20.1 42.5 69.8 106.2 131.6 841.4 857.5 870.7 882.2 892.5 901.7 910.2 918.0 925.4 932.2 938.7 944.9 950.9 956.5 961.9 967.0

u()/kgm3 0.1 0.1 0.1 0.1 0.1 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3

p/MPa 1.000 2.000 3.001 4.001 5.000 5.700 6.300 7.000 8.001 9.000 10.000 11.002 12.001 13.000 14.000 15.001 16.002 17.001 18.001 19.001 20.001

/kgm3 T = 293.15 K 18.4 39.5 64.3 94.5 135.5 180.8 750.2 775.0 799.6 818.4 833.7 846.8 858.3 868.3 877.6 886.2 894.2 901.7 908.6 915.2 921.4

u()/kgm3 0.1 0.1 0.1 0.1 0.1 0.1 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3

Standard uncertainty u(T) = 0.05 K and relative standard uncertainty ur() = 0.03 %.

The frame of the FPMC model is represented by eq 3:

= M 0 K (p , T ) 2(p , T ) 1 V (p , T ) K 0(T )02(T )

In the second term of eq 7, the relative quadratic moment of inertia, I/I0, appears, and if the U-shaped thick-walled tube has its two branches in the same vertical plane, it is represented by eq 8:
(3)
4 r 4 rint I = 4ext 4 I0 rext0 rint 0

The tube is considered as a thick-walled cylinder and is submitted to stress and strain. The overall expressions for stress and strain in this kind of vibrating tube conguration are reported in ref 12. The internal volume of the vibrating tube is represented by the expression given in eq 4:
2 V = rint L00L

(8)

where rext is the external radius of the tube at the current temperature and pressure conditions, rext0 and rint0 are, respectively, the external and internal radius of the tube under vacuum conditions. The relative inverse cubic length in eq 7 is represented by eq 9:
L 0 3 = exp( 3 p) T L

(4)

where rint is the internal radius of the tube, and the length of the vibrating tube is represented by eq 5:
L = L00 exp(

(9)

(T )dT +

T dp) = L00L

The values of rint0 and rext0 can be calculated by means of eqs 10 and 11:
rint 0(T ) = rint 00 exp( rext0(T ) = rext00exp(

(5)

where L00 is the length of the vibrating tube under vacuum and at a reference temperature corresponding to 273.15 K, (T) is the linear dilatation coecient, and T is the isothermal linear expansion coecient in one direction of the tube at the temperature T represented by eq 6:

273.15K (T )dT )
T

(10)

273.15K (T )dT )

(11)

1 L T = L p

(6)

where rint00 and rext00 are the radius values at the reference temperature and under vacuum conditions. The radius value under the action of an internal pressure can be calculated as the positive root of eq 12:
2 2 1 print 0 prext0 2 1 rk rint 0rk 2 2 E rext0 rint 0

The ratio between the actual stiness, K, and the stiness at the same temperature but under vacuum, K0, can be represented by eq 7:
3 K I L = 0 K0 I0 L

(7)
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1 + pr 2 r 2 int 0 ext0 =0 2 2 E r ext0 rint 0

(12)

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Table 8. Experimental Values of Density with Standard Uncertainty u() at Temperature T and Pressure p for the N2b Mixturea
p/MPa 1.001 2.000 3.001 4.001 4.100 8.401 9.001 10.001 11.003 12.000 13.001 14.000 15.002 16.001 17.000 18.000 19.001 20.000 /kgm3 T = 273.15 K 22.5 43.7 69.6 104.0 108.6 805.0 811.5 824.0 836.0 847.0 856.6 865.1 873.4 880.8 887.8 894.6 900.7 906.6 u()/kgm3 0.1 0.1 0.1 0.1 0.1 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 p/MPa 1.004 2.001 3.000 4.001 5.001 5.500 9.001 10.002 11.001 12.000 13.002 14.001 15.002 16.001 17.000 18.000 19.001 20.001 /kgm3 T = 283.15 K 19.4 40.3 64.6 93.7 131.6 157.6 708.8 736.1 757.6 775.3 790.5 803.8 815.4 825.4 835.0 843.9 852.1 859.6 u()/kgm3 0.1 0.1 0.1 0.1 0.1 0.1 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 p/MPa 1.001 2.000 3.000 4.001 5.000 6.000 7.002 7.601 9.401 10.001 11.001 12.002 13.000 14.001 15.001 16.001 17.000 18.000 19.001 20.000 /kgm3 T = 293.15 K 18.8 38.4 60.8 86.7 117.2 156.7 213.8 271.4 526.3 579.5 633.1 669.7 696.3 718.1 736.4 752.3 766.2 778.4 789.6 799.8 u()/kgm3 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3

Standard uncertainty u(T) = 0.05 K and relative standard uncertainty ur() = 0.03 %.

Table 9. Experimental Values of Density with Standard Uncertainty u() at Temperature T and Pressure p for the O2a Mixturea
p/MPa 2.001 3.001 3.600 5.101 6.000 7.001 8.001 9.001 10.001 11.001 12.001 13.001 14.000 15.002 16.001 17.000 18.001 19.001 20.001
a

/kgm3 T = 273.15 K 44.5 74.2 97.6 895.0 902.5 911.9 920.4 928.6 936.0 943.1 949.6 955.8 961.5 967.1 972.4 977.6 982.4 987.2 991.7

u()/kgm3 0.1 0.1 0.1 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3

p/MPa 2.000 3.001 4.000 4.600 6.200 7.000 8.001 9.001 10.001 11.004 12.000 13.000 14.002 15.000 16.001 17.000 18.001 19.001 20.003

/kgm3 T = 283.15 K 43.2 69.8 103.9 132.1 819.0 835.3 849.8 862.8 873.8 884.1 893.2 901.9 909.9 917.3 924.2 930.8 937.0 943.0 948.7

u()/kgm3 0.1 0.1 0.1 0.1 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3

p/MPa 2.002 3.001 4.001 5.000 6.001 7.402 8.002 9.001 10.001 11.002 12.002 13.000 14.000 15.001 16.001 17.000 18.000 19.001 20.000

/kgm3 T = 293.15 K 42.6 66.2 95.2 132.4 190.2 718.0 747.0 775.6 797.4 813.9 828.6 841.3 852.2 862.4 871.6 880.2 888.3 895.9 902.8

u()/kgm3 0.1 0.1 0.1 0.1 0.1 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3

Standard uncertainty u(T) = 0.05 K and relative standard uncertainty ur() = 0.03 %.

where E is the Youngs modulus, is the Poissons ratio, and if k = int the expression applies to the internal radius, while if k = ext the expression applies to the external radius. Thus, the complete FPMC model becomes:
r 4(T , p) M 1 = 0 2 4 L00 ri (T , p)L(T , p) r0 (T ) 2(T , p) 1 exp( 3TP) 2 0 (T )

The relations between the FPCM model and the parameters A and B in eq 2 are represented by eqs 14 and 15:
M 0 1 K (p , T ) A= V (p , T ) 02(T ) K 0(T )
K (p , T ) B = 02(T ) 0 K (T )

(14)

(15)

(13)
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Most of the parameters in eq 13 are derived from a study by Sanmamed et al.14 and are reported in Table 2.
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Table 10. Experimental Values of Density with Standard Uncertainty u() at Temperature T and Pressure p for the O2b Mixturea
p/MPa 1.001 2.001 3.000 4.001 4.400 9.013 10.003 11.001 12.001 13.001 14.000 15.002 16.000 17.003 18.000 19.039 /kgm3 T = 273.15 K 20.0 41.9 68.0 101.0 121.1 798.3 811.5 825.1 837.4 848.5 858.7 868.2 877.0 885.4 892.9 898.3 u()/kgm3 0.1 0.1 0.1 0.1 0.1 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 p/MPa 1.002 2.001 3.000 4.001 5.000 6.001 9.610 10.001 11.001 12.001 13.000 14.001 15.000 16.001 17.001 /kgm3 T = 283.15 K 19.2 39.7 63.3 91.1 125.7 175.6 686.6 699.4 728.8 751.4 770.5 786.6 800.0 812.4 823.5 u()/kgm3 0.1 0.1 0.1 0.1 0.1 0.1 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 p/MPa 1.001 2.000 3.001 4.001 5.003 6.002 7.000 8.001 8.600 9.801 10.001 11.001 12.001 13.002 14.001 15.001 16.001 17.002 /kgm3 T = 293.15 K 18.7 38.1 59.8 84.6 113.5 148.8 194.6 260.9 316.0 460.3 481.5 564.7 617.8 657.7 686.2 710.2 730.8 747.7 u()/kgm3 0.1 0.1 0.1 0.1 0.1 0.3 0.1 0.1 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3

Standard uncertainty u(T) = 0.05 K and relative standard uncertainty ur(p) = 0.03 %.

Figure 4. Experimental pT data of pure carbon dioxide and the Ara mixture: , Ara at 293.15 K; , CO2 at 293.15 K; , Ara at 283.15 K; , CO2 at 283.15 K; , Ara at 273.15 K; , CO2 at 273.15 K.

Figure 5. Experimental pT data of pure carbon dioxide and the Arb mixture: , Arb at 293.15 K; , CO2 at 293.15 K; , Arb at 283.15 K; , CO2 at 283.15 K; , Arb at 273.15 K; , CO2 at 273.15 K.

M0/L00 and T are the two unknown parameters that have to be determined by a nonlinear t of eq 13. As all mixtures investigated consist mainly of carbon dioxide, the latter was chosen as the reference uid. Its density values, experimentally determined by the vibrating tube densimeter, are reported in Table 3. The M0/L00 and T have been found by the least-squares minimization in eq 16.
N

The uncertainty in density calculated using a propagation of error formula10 is 0.1 kgm3 for the vapor density and 0.3 kgm3 for the liquid density.

(FPMC S&W )2
i=1

(16)

where N is the number of experimental data for each isotherm, FPCM is the density value calculated by the FPCM model, and S&W is the density calculated by the Span and Wagner model15 which to date is the most precise EOS available for pure CO2.16 The values of the M0/L00 and T parameters are reported in Table 4 for the dierent temperatures and phases investigated.
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RESULTS AND DISCUSSION The binary mixtures reported in Table 1 have been tested at temperatures of 273.15 K, 283.15 K, and 293.15 K and at pressures of 1 MPa to 20 MPa, except for the O2a and O2b mixtures for unpredicted technical reasons. In Tables 5 to 10 the experimental results are shown. The density values have been calculated by means of the FPCM model using the parameters reported in Tables 2 and 4. The isothermal lines measured are represented in Figures 4 to 9 as pressure against density for each of the mixtures tested. Also represented in these gures is a comparison between the density values of pure carbon dioxide and the dierent binary mixtures. For all mixtures, it is evident that the introduction of a lighter element causes a reduction in density at the same
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Figure 6. Experimental pT data of pure carbon dioxide and the N2a mixture: , N2a at 293.15 K; , CO2 at 293.15 K; , N2a at 283.15 K; , CO2 at 283.15 K; , N2a at 273.15 K; , CO2 at 273.15 K.

Figure 8. Experimental pT data of pure carbon dioxide and the O2a mixture: , O2a at 293.15 K; , CO2 at 293.15 K; , O2a at 283.15 K; , CO2 at 283.15 K; , O2a at 273.15 K; , CO2 at 273.15 K.

Figure 7. Experimental pT data of pure carbon dioxide and the N2b mixture: , N2b at 293.15 K; , CO2 at 293.15 K; , N2b at 283.15 K; , CO2 at 283.15 K; , N2b at 273.15 K; , CO2 at 273.15 K.

Figure 9. Experimental pT data of pure carbon dioxide and O2b mixture: , O2b at 293.15 K; , CO2 at 293.15 K; , O2b at 283.15 K; , CO2 at 283.15 K; , O2b at 273.15 K; , CO2 at 273.15 K.

temperature and pressure values with respect to the pure carbon dioxide case. In particular, if the impurity concentration is high (> 10 %), the isothermal line at 293.15 K shows a trend similar to that of a mixture in a supercritical phase (Figures 7 and 9); thus the critical temperature (Tcm) of the mixture may be considered to decrease as the concentration of these contaminant species increases. In fact, the Tc of pure CO2 is 303.15 K, while for CO2N2 mixtures (xCO2 87 %) and for CO2O2 mixtures (xCO2 85 %), the Tcm is probably nearer to 293.15 K. To prove the reliability of the results showed in this work, a comparison with other literature experimental data, where possible, has been done. As already said, no volumetric experimental data of CO2O2 mixtures in subcritical conditions have been published, and very few data are available for CO2Ar mixtures; therefore only a comparison for CO2N2 binary mixture was possible, even if the volumetric data in the same conditions of temperature, pressure, and composition of our experimental results are few. The results of this work resulted in consistence with the available experimental data reported by Brugge et al.,6 con2782

sidering volumetric data at the same temperature ( 283 K) and dierent pressures and compositions, and reported by Ely et al.,7 considering experimental data at the same pressure values (9 MPa, 12 MPa, and 16 MPa) and dierent temperatures and compositions. Some dierences were noticed in the comparison with the data reported by Arai et al.;4 however some of latter results are also not consistent with other experimental works.6

CONCLUSIONS New pT experimental data are presented for six binary mixtures rich in carbon dioxide under working conditions similar to those applying for CO2 pipeline transportation. The mixtures contain carbon dioxide and gases, such as oxygen, argon, and nitrogen, that are noncondensable under such conditions and are among the main contaminants in ue gases treated by CCS processes. In scientic literature where, to date, so little volumetric data on carbon dioxide-based mixtures are available, this study could be seen as providing an important contribution in promoting the further study of pipeline transportation of CO2-rich streams from the capture plant through to the storage site.
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Journal of Chemical & Engineering Data Moreover the comparison made, where possible, between the results and the experimental data found in literature proved the reliability of the volumetric data showed in this work. As the knowledge of the thermodynamic properties of CO2rich mixtures containing small amounts of impurities becomes very important in the CCS process and a suitable equation of state (EOS) under the appropriate conditions for pipeline transport, in particular with a high CO2 concentration, has not been clearly dened yet, a comparison between the new experimental data here presented and the results of dierent EOS could be fundamental. A further development of this work, regarding a comparison with both cubic and nonanalytical EOS to evaluate the accuracy of them for density prediction, is going to be published by the authors.

Article

AUTHOR INFORMATION

lHydrogen e Sulfure, Mesures par Densimet rie a Tube Vibrant et Model isation. Ph.D. thesis, Paris School of Mines, France, 2005. (13) Khalil, W. Dev eloppement dun Appareil Automatise de Mesure Simultanee dEquilibres de Phases et de Proprieta Volumetriques. Exploitation des Donnee s Volumetriques pour le Calcul Pred ictif de Grandeurs Thermodynamiques Der ivee s. Ph.D. thesis, Paris School of Mines, France, 2006. (14) Sanmamed, Y.; Dopazo-Paz, A.; Gonzalez-Salgado, D.; Troncoso, J.; Romani, L. An accurate calibration method for high pressure vibrating tube densimeters in the density interval (700 to 1600) kgm3. J. Chem. Thermodyn. 2009, 41, 10601068. (15) Span, R.; Wagner, W. A New Equation of State for Carbon Dioxide covering the fluid region from the triple point temperature to 1100 K at pressures up to 800 MPa. J. Phys. Chem. Ref. Data 1996, 25, 15091596. (16) Mazzoccoli, M. Carbon Capture, Storage and Transportation (CCS&T) process: general aspects and focus on CO2 pipeline modeling. Ph.D. thesis, University of Genoa, Italy, 2011.

Corresponding Author

*Tel.: +39 010 353 2588, fax: +39 010 353 2589, e-mail address: michela.mazzoccoli@gmail.com.
Notes

The authors declare no competing nancial interest.

ACKNOWLEDGMENTS The experimental campaign presented in this work was performed at LEAP laboratory. The authors would like to thank sincerely all of the LEAP sta. REFERENCES

(1) Special report on carbon dioxide capture and storage. IPCC: Geneva, 2005. (2) De Visser, E.; Hendriks, C.; Barrio, M.; Mlnvik, M. J.; De Koeijer, G.; Liljemark, S.; Le Gallo, Y. Dynamis CO2 quality recommendations. Int. J. Greenhouse Gas Control 2008, 2, 478484. (3) Li, H.; Jacobsen, J. P.; Wilhelmsen, .; Yan, J. PVTxy properties of CO2 mixtures relevant for CO2 capture, transport and storage: Review of available experimental data and theoretical models. Appl. Energy 2011, 88, 35673579. (4) Arai, Y.; Kaminishi, G.; Saito, S. The experimental determination of the P-V-T-x relations for the carbon dioxide-nitrogen and the carbon dioxide-methane systems. J. Chem. Eng. Jpn. 1971, 4, 113112. (5) Magee, J. W.; Ely, J. F. Isochoric (p,v,T) measurements on CO2 and (0.98 CO2 + 0.02 CH4) from 225 to 400 K and pressures to 35 MPa. Int. J. Thermophys. 1988, 9, 547557. (6) Brugge, H. B.; Holste, J. C.; Hall, K. R.; Gammon, B. E.; Marsh, K. N. Densities of Carbon Dioxide + Nitrogen from 225 to 450 K at pressures up to 70 MPa. J. Chem. Eng. Data 1997, 42, 903907. (7) Ely, J. F.; Haines, W. M.; Bain, B. C. Isochoric (p, Vm, T) measurements on CO2 and on (0.0982 CO2 + 0.018 N2) from 250 to 330 K at pressures to 35 MPa. J. Chem. Thermodyn. 1989, 21, 879894. (8) Mazzoccoli, M.; Bosio, B.; Arato, E. Analysis and comparison of Equations-of-State with pT experimental data for CO2 and CO2mixture pipeline transport. Energy Procedia, 2012, 23, 274283. (9) Mantovani, M.; Chiesa, P.; Valenti, G.; Gatti, M.; Consonni, S. Supercritical pressure-density-temperature measurements on CO2-N2, CO2-O2 and CO2-Ar binary mixtures. J. Supercrit. Fluids 2012, 61, 3443. (10) Bouchot, C.; Richon, D. An enhanced method to calibrate vibrating tube densimeters. Fluid Phase Equilib. 2001, 191, 189208. (11) Bouchot, C.; Richon, D. Direct Pressure-Volume-Temperature and Vapor-Liquid Equilibrium Measurements with a Single Equipment Using a Vibrating Tube Densimeter up to 393 K and 40 MPa: Description of the Original Apparatus and New Data. Ind. Eng. Chem. Res. 1998, 37, 32953304. (12) Rivollet, F. Etude des Propriet es Volumet riques (PVT) dHydrocarbures Leg ers (C1-C4), du Dioxyde de Carbone et de
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