Journal of Petroleum Science and Engineering 38 (2003) 57 77 www.elsevier.

com/locate/jpetscieng

An empirical model for estimating the saturation pressures of crude oils

Adel M. Elsharkawy *
College of Engineering and Petroleum, Kuwait University, P.O. Box 5969, Safat 13060, Kuwait Received 20 March 2002; accepted 17 January 2003

Abstract Recently, there has been an increasing interest in enhanced oil recovery (EOR) calculations of saturation pressures when various gases contact crude oils. Equations of state are usually used for calculations of saturation pressure at initial condition of discovery or later during EOR design. However, the equations of state results are not reliable unless they are properly tuned using some experimental data of reservoir fluid. The availability of extended analysis of reservoir fluids, characterization of heavy fraction, and number of components are influencing the saturation pressure estimated by equations of state. A simple empirical model to calculate the saturation pressures of crude oil systems was developed. Experimentally measured compositions and saturation pressures of 60 crude oil samples from the Middle East were used to develop the model. Compositions and saturation pressures of 75 crude oil samples from the literature were used to test the accuracy and validity of the model against measured data and simulations by equations of state. The results indicate that the model is accurate, valid, reliable, and eliminates the splitting and characterizing of the heavy fraction, which is necessary for the equations of state. The model is useful for estimating the saturation pressure where experimental data is not available. For EOR processes, the model can be used to calculate the saturation pressure during single contact by hydrocarbon gases. D 2003 Elsevier Science B.V. All rights reserved.
Keywords: PVT; Equations of state; Correlations; Hydrocarbons; Reservoir fluids; Saturation pressure

1. Introduction Recently, there has been increasing interest in enhanced oil recovery (EOR) calculations of saturation pressure when crude oil is contacted by various
Abbreviations: BIN, binary interaction number; EOR, enhanced oil recovery; EOS, equation of state; GOR, gas oil ratio; PAN, paraffinic naphthenic aromatic; PR, Peng-Robinson; PVT, pressure volume temperature; SRK, Soave Redlich-Kwong; VPO, vapor pressure osmometer. * Fax: +965-4849558. E-mail address: asharkawy@kuc01.kuniv.edu.kw (A.M. Elsharkawy).

gases (Whitson, 1984). A pressure volume temperature (PVT) property such as saturation pressure is required for reservoir studies. It is frequently measured in PVT cell using bottom-hole sample or surface recombined sample. Occasionally, the saturation pressure may not be available because representative sample is not available. For such cases, PVT correlations or equation of states (EOSs) are used to predict saturation pressures. PVT correlations use production data such as producing GOR, oil gravity, gas gravity, and reservoir temperature to calculate the saturation pressure. These PVT correlations have several limitations. They have limited accuracy. PVT correlations

0920-4105/03/$ - see front matter D 2003 Elsevier Science B.V. All rights reserved. doi:10.1016/S0920-4105(03)00035-4

58

A.M. Elsharkawy / Journal of Petroleum Science and Engineering 38 (2003) 5777

developed from local or regional crudes cannot be used for oils other than those used in deriving their correlations. Cubic equations of state are widely used for calculations of saturation pressures and representing the phase behavior of petroleum reservoir fluids (Pedersen, 1988a). The EOSs are also used to check accuracy of sampling and consistency between geological reservoir continuity. There have been many comparative studies concerning accuracy of equations of state and PVT correlations ability to predict PVT properties of reservoir fluids (Ahmed, 1986; Danesh et al., 1991; Wu and Rosenegger, 2000). The general conclusion is that none of the available EOSs can be singled out as the most superior one to predict all properties for reservoir fluids at all conditions. The accuracy of EOSs calculations depends on the procedures that have been used to regress the EOS parameters (Wu and Rosenegger, 2000). It also depends on characterizations of the hydrocarbon fraction (Whitson, 1983, 1984), extended analyses of the hydrocarbon fraction (Coats and Smart, 1986), and the inclusion of the proper binary interaction numbers (Pedersen et al., 1985). In the first procedure, EOS constants (ra and rb) are obtained by regression such that the EOS is forced to predict the measured saturation pressure or phase behavior of reservoir fluid. In the second, the EOS is characterized by adjusting the critical pressure, critical temperature, and the acentric factor to match some experimental data (Whitson, 1983, 1984; Agarwal et al., 1990) or adjusting the molecular weight of the plus-fraction (Zaitsev et al., 1996; Christensen, 1999; Rosenegger and Wu, 1999). Oil mixtures contain more heavy components than do gas condensate mixtures. It could therefore be anticipated that phase behavior or saturation pressure of oil mixture would be difficult to predict from EOS than that of gas condensate; however, the phase behavior of oil mixture is mainly controlled by the contribution of lighter fractions. At the saturation pressure, the newly formed gas phase is totally dominated by lighter components for which accurate analytical data are available. Therefore, the details of the heavy fraction (C7 +) are not important. The analytical data of the heavy hydrocarbon fraction obtained from gas chromatograph measurements are less accurate than those obtained from true boiling point experiments (Li et al., 1985). The measured and real average molecular

weight of the plus-fraction may deviate as much as 10% (Pedersen, 1988a). For these reasons, the molecular weight of the plus-fraction is used as a tuning parameter of the EOS. In the third procedure, the heavy hydrocarbon fraction is split into several subfractions using gamma distribution model (Whitson et al., 1990), continuous distribution model (Cotterman and Prausnltz, 1985), semicontinuous distribution model (Behrens and Sandler, 1988), logarithmic distribution (Pedersen et al., 1984), or a more general one (Ahmed, 1986). Because insufficient description of the heavier components of the hydrocarbon mixture reduced EOS accuracy to predict saturation pressure, the heavy fraction is commonly extended to C20 + or C30 +. Volatile oil and gas condensate volumetric phase behavior is particularly sensitive to composition and properties of the heaviest hydrocarbon plus-faction. It is difficult to make objective conclusions about which of the C7 + characterization schemes are the best or possible alternate such that measured values of molecular weight and specific gravity of the plus-fraction are forced-fit by EOS (Whitson, 1984). In the fourth, the binary interaction number (BIN) of one or several components is adjusted for the EOS to match the experimental data (Katz and Firoozabadi, 1978; Kikani and Ratulowski, 1996). Several EOS studies have considered using a given constant value of the binary interaction for each EOS independent of temperature, pressure, and composition (Danesh, 1998; Whitson and Brule, 2000). Others have indicated BIN dependency on temperature (Kato et al., 1981), pressure (Voros and Tassios, 1985), and composition (Varotsis, 1986; Bjorlykke and Firoozabadi, 1992). The predictive capabilities of the EOSs are often questioned, and parameter estimation procedures (tuning) are commonly used to improve agreement between measured and calculated phase equilibrium results (Pedersen, 1988b; Coats and Smart, 1986). The tuned parameters provide satisfactory estimation at condition of measured data. At conditions different from these, the tuned EOS might lead to highly uncertain prediction (Pedersen, 1988b). Another limitation of the EOS is that properly tuned EOS to described phase behavior of one fluid may not describe another fluid even from the same basen or source. Furthermore, the EOS has difficulty converging to the right solution near critical point (Baker and Luks, 1980).

A.M. Elsharkawy / Journal of Petroleum Science and Engineering 38 (2003) 5777

59

Therefore, the objective of this study is to develop a simple, accurate, and reliable empirical model for estimating the saturation pressures for black oils. Two groups of data are used. The first group is experimentally measured saturation pressures and compositions of 60 crude oil samples either collected from bottom-hole of producing formation or collected at the well head from surface separator and recombined knowing the producing gas oil ratio (GOR). The second group of data that is collected from literature is used to test the accuracy and validity of the proposed model against Soave Redlich-Kwong (SRK) and Peng-Robinson (PR) equations of states.

2. Experimental Measurements of saturation pressures and compositional analyses of 60 crude oil samples from Middle East were determined in the PVT-lab. The details of these measurements are listed in Table 1 and are used to develop the proposed empirical model. 2.1. Measurements of saturation pressures of crude oils The bottom-hole sample of reservoir fluids is charged into 250 cm3 volume PVT cell (Fig. 1). The cell is fitted with two-glass windows, which permit observation of the hydrocarbon system inside the cell. The PVT cell is installed inside an air bath for temperature control ( F 0.1 jF, jF=(jC 32)/1.8)). The temperature measurements were made with thermocouples embedded in the PVT cell. The volume of the cell can be controlled by injecting mineral oil with a piston located at the bottom of the PVT cell. A calibrated Bourden gauge and a pressure transducer can measure the pressure inside the cell to 5-psia accuracy (1 psia = 6.894757e 3 mPa). Agitation of the sample to ensure equilibrium can be obtained by rocking the entire PVT cell. Before running any phase behavior measurement, integrity of the sample is checked to ensure against leakage. The saturation pressure is measured at room temperature for a quality check of the bottom-hole sample. Later, the sample is left for some time to reach thermal equilibrium at the desired temperature. Afterwards, the PVT cell is subjected to constant mass expansion by changing

the cell volume at constant temperature. The total volume of the hydrocarbon mixture is determined at each pressure point with a pressure gauge mounted at the pump and checked by the pressure transducer connected to the PVT cell. The hydrocarbon system inside the PVT cell can be inspected through the windows and the last bubble of gas going into solution can be detected. The pressure at which the last bubble disappears is the saturation pressure (bubble point pressure). The change from two phases to one phase can be clearly seen, for black oils, as a discontinuity in the pressure versus volume plot. The agreement between visual observation and PV plot is close to F 20 psia (137.995e 3 mPa). For volatile oil, the change from two phases to a single phase and vice versa is gradual, and the agreement between visual observation and PV plot is within F 50 psia (344.7375e 3 mPa). The procedure used to measure the bubble point pressure was to increase the pressure isothermally in small increments until gas bubbles disappear. The process is repeated by decreasing the pressure if visual observation does not agree with PV plot. 2.2. Measurements of composition, molecular weight, and density of heptane plus-fraction The molar composition of reservoir fluids is obtained from analysis of the gas and oil samples. These samples are obtained from reservoir fluid bottom-hole sample or from gas and oil samples taken from wellhead separator. In either case, the samples are flushed to standard condition before composition analysis is made. Afterwards, the reservoir fluid composition is obtained by combining the gas and liquid phase compositions using the measured gas oil ratio. The compositional analyses of the gas phase and oil phase are carried out with packed and capillary column gas chromatograph [N2, CO2, H2S, and C1 C10]. Standard gas samples were used to calibrate the GC, which enable identification of hydrocarbons C1 C10. The packed columns were molecular sieve 13 , Porapak R. The capillary columns were 50 m of Chrompack Sil 5 (fused silica). The hydrocarbons were analyzed by split injection using capillary column and temperature programming at 30 jC. The permanent gases were analyzed isothermally at 50 jC using packed column.

60

A.M. Elsharkawy / Journal of Petroleum Science and Engineering 38 (2003) 5777

Table 1 Experimentally measured compositions and saturation pressures for Middle East crude oils No. N2 1 2 4 5 6 7 8 9 10 11 12 13 14 15 16 18 19 20 21 22 23 24 25 26 27 28 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 0.36 0.29 0.33 0.35 0.12 0.16 0.21 0.11 0.79 0.036 0 0.45 0.56 0.03 0.06 0 0.48 0.15 0.5 0.68 0.22 0.19 0.18 0.2 0.44 0.14 0.15 0.26 0.2 0 0.54 0.41 0.2 0.1 0.2 0.15 0.49 0.15 0.45 0.23 0.19 0.21 0.08 0.13 0 0 0 0.05 0.06 0.04 0.01 0.06 CO2 H2S 0.17 0.48 0.22 0.47 0.51 0.3 0.15 0.28 0.1 0.17 0.17 0.08 0.07 0.3 0.81 0.15 0.41 0.19 0.87 1.02 1.37 2.51 2.46 1.23 0.83 0.54 0.39 1.26 0.8 1.3 0.5 0.65 1.19 1.16 0.49 0.48 0.47 0.65 0.51 1.06 0.12 0.72 1.37 1.45 1.12 1.25 0.68 0.85 0.94 0.78 0.89 0.85 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0.04 0 0 0 0.01 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0.01 0 0 0.69 0.75 0.21 0 0 0 0 0 0.3 0 C1 27.23 28.36 25.56 26.52 28.81 24.66 27.77 27.53 24.79 31.22 28.56 29.35 29.9 27.8 31.34 19.5 33.25 31.15 29.85 25.49 27.92 31.89 30.26 26.54 27.75 29.44 27.55 28.27 31.42 34.53 27.79 30.21 32.26 32.93 29.46 28.51 31.55 30.48 30.56 24.75 28.62 33.12 35.97 36.02 26.95 33.35 48.79 41.05 44.44 40.91 39.68 40.7 C2 8.93 8.29 6.87 7.71 7.91 7.51 7.68 6.9 6.84 6.5 8.63 7.85 7.84 8.26 7.42 8.17 7.55 8.92 7.33 6.37 6.51 7.51 7.3 6.64 7.54 7.96 7.86 6 7.6 7.24 6.89 6.89 7.57 7.78 8.51 8.17 8.66 7.27 7.25 6.78 8.66 7.44 8.67 8.83 10.76 9.24 10.57 11.07 10.76 10.72 10.37 10.54 C3 8.6 7.38 6.39 6.05 6.46 6.92 6.19 5.87 6.5 4.75 7.43 7.28 6.98 6.73 5.68 8.43 6.21 7.38 5.98 6.53 5.16 6.59 6.36 5.54 6.9 6.19 6.3 4.85 7.23 5.31 6.34 6.6 5.97 6.06 6.63 6.36 7.92 5.15 7.28 6.8 6.52 6.07 5.94 6.13 9.23 6.07 6.21 7.07 6.18 6.64 7.18 6.55 C4 6.07 5.06 5.61 4.03 3.17 4.76 3.41 4.42 5.37 2.53 3.81 6.03 6.05 3.72 2.82 6 4.11 4.07 3.48 5.15 2.52 4.77 4.61 4.15 4.61 3.96 3.59 3.6 4.88 2.79 4.45 5.88 3.85 3.73 3.97 4.15 5.48 2.04 5.24 6.01 4.78 3.22 2.97 4.1 4.97 2.4 3.46 4.82 4.04 4.44 4.47 4.41 C5 3.71 3.42 4.68 4.08 2.07 2.65 1.81 2.47 4.09 1.71 2.61 4.81 2.84 4.08 1.63 2.92 2.2 3.48 1.96 4.88 1.58 3.51 3.54 3.14 3.1 3.25 2.58 4 1.97 1.91 3.29 4.62 3.17 2.92 3.37 3.73 3.47 1.96 3.76 4.35 2.71 1.79 1.5 2.8 2.62 1.62 4.56 2.89 2.63 2.62 3.09 2.72 C6 2.55 4.41 4.33 4.22 3.25 3.43 2.84 3.52 3.67 2.64 4.11 4.53 2.66 4.2 2.64 3.61 2.88 4.34 4.28 3.81 2.59 3.29 3.22 3.34 3.11 3.84 3.68 4.26 0.99 3.48 3.5 4.27 3.63 3.7 3.79 3.87 4.45 2.76 3.85 3.89 3.62 3.05 3.1 2.49 3.33 2.78 2.8 3.19 2.57 2.51 2.75 2.81 C7 + 42.38 42.31 46.01 46.57 47.7 49.61 49.94 48.9 47.85 50.45 44.68 39.62 43.1 44.88 47.6 51.22 42.91 40.32 46.2 46.03 52.13 39.74 42.08 49.22 45.72 44.68 47.9 47.5 44.91 43.44 46.7 40.47 42.16 41.62 43.59 44.59 37.51 49.54 41.1 46.12 44.78 44.38 39.71 37.3 40.81 43.29 24.8 29.01 28.38 31.34 31.53 31.36 GR.C7 + MWC7 + Temp. Ps (jF) (psi) 0.879 0.880 0.878 0.892 0.876 0.875 0.863 0.879 0.884 0.889 0.862 0.863 0.877 0.880 0.892 0.849 0.880 0.848 0.882 0.902 0.893 0.920 0.914 0.910 0.902 0.901 0.896 0.908 0.889 0.892 0.887 0.875 0.879 0.879 0.900 0.897 0.904 0.866 0.892 0.905 0.925 0.900 0.898 0.896 0.876 0.851 0.847 0.848 0.846 0.845 0.932 0.847 271 252 222 253 250 239 228 245 227 264 249 227 242 254 270 225 236 221 271 264 255 324 299 290 272 290 152 274 251 132 214 247 134 279 145.8 141.9 289 239 268 256 274 271 274 230.1 249 252 218 198 195 202 197 195 130 133 133 135 134 134 134 135 134 135 134 134 133 134 132 132 136 135 134 134 135 134 134 132 133 134 132 134 132 1920 133 135 133 133 135 135 133 130 135 134 135 140 168 166 208 230 230 241 240 241 243 243 1365 1632 1595 1500 1615 1400 1590 1540 1399 1690 1548 1705 1653 1645 1751 1025 1640 1650 1634 1533 1548 1825 1825 1597 1565 1580 1380 1680 1738 1655 1880 1788 1805 1500 1500 1715 1670 1735 1530 1766 1730 2505 2873 1877 2110 2730 3335 3630 3120 3061 3180 Ps-model Ps-SRK Ps-PR 1429 1544 1442 1427 1574 1348 1545 1585 1399 1793 1476 1651 1770 1427 1787 962 1985 1681 1693 1450 1659 1934 1849 1523 1558 1597 1582 1648 1890 2029 1614 1792 2020 1899 1718 1675 1720 1709 1737 1444 1566 1942 2247 2324 1781 2424 3427 3061 3319 3066 2947 3073 1602 1672 1441 1613 1665 1372 1532 1561 1509 1873 1551 1649 1808 1583 1943 964 2101 1683 1830 1645 1728 2331 2102 1628 1799 1860 1742 1808 1979 2209 1705 1776 2047 1998 1933 1831 2139 1707 1937 1529 1984 2232 2710 2667 1939 2313 3622 2991 3283 3347 3727 2938 1431 1477 1252 1380 1476 1214 1377 1371 1289 1606 1429 1494 1590 1400 1657 899 1816 1567 1614 1380 1462 1863 1714 1381 1505 1572 1268 1491 1684 1891 1422 1586 1487 1785 1386 1313 1792 1531 1668 1274 1552 1865 2318 2236 1794 2278 3529 2841 3110 3196 2873 2779

A.M. Elsharkawy / Journal of Petroleum Science and Engineering 38 (2003) 5777 Table 1 (continued ) No. N2 56 57 58 59 0.03 0.06 0.03 0.02 CO2 H2S 0.97 1.1 1.04 0.99 0 0 0.03 0.04 C1 41.64 43.13 41.88 38.79 C2 10.82 10.46 10.6 10.07 C3 7.52 7.24 7.01 6.86 C4 4.5 4.57 4.29 4.18 C5 3 2.82 3.16 2.92 C6 2.43 2.34 2.89 2.77 C7 + 29.08 28.29 29.07 33.38 GR.C7 + MWC7 + Temp. Ps (psi) (jF) 0.850 0.884 0.848 0.849 208 214 200 210 241 241 235 240 3069 3218 3234 3019

61

Ps-model Ps-SRK Ps-PR 3080 3218 3077 2895 3109 3646 3047 2793 2979 3242 2894 2477

Molecular weights of the plus-fraction or residue were determined by vapor pressure osmometer (VPO). In this study, VPO is used to measure the molecular weight of the plus-fraction because freezing point depression has a high degree of uncertainty. The VPO was calibrated with benzyl using chloroform as a solvent. Density of the heptane plus-fraction or residue was determined using a density meter.

2.3. Experimental and literature data The 60 measurements of saturation pressures and compositional analyses of crude oil samples were used to develop a simple yet accurate and physically sound empirical model for estimating the saturation pressures of crude oils in case laboratory measurements are not available. The accuracy of the proposed model should

Fig. 1. Schematic of the phase behavior cell.

62

Table 2 Compositions and saturation pressures for crude oils collected from literature Ref. Coats-86 Coats-86 Coats-86 Coats-86 Measured Measured Measured Dansh-92 Dansh-92 Dansh-92 Dansh-92 Ahmed-89 Ahmed-89 Ahmed-89 Pedersen Pedersen Pedersen Pedersen Pedersen Pedersen Pedersen Pedersen Pedersen Hofman-83 Coats-86 Coats-86 Coats-86 Coats-86 Moharam-96 Moharam-96 Moharam-96 Moharam-96 Moharam-96 Moharam-96 Moharam-96 Rosenegger-99 Rosenegger-99 No. 62 64 66 67 71 72 73 81 83 84 85 91 92 93 101 102 103 104 105 106 107 108 109 111 112 113 114 115 121 122 123 124 125 126 127 131 132 N2 0.30 0.11 0.55 1.64 0.24 0.06 0.10 0.16 0.90 0.00 0.56 1.64 0.45 0.00 0.56 0.40 0.67 0.34 0.44 0.90 0.36 0.33 0.41 0.00 0.45 0.11 0.55 1.64 0.25 0.24 0.17 0.32 0.43 0.21 0.77 0.21 0.88 CO2 0.90 2.35 1.03 0.08 0.39 5.01 1.32 0.91 1.49 0.00 3.55 0.08 0.44 0.00 3.55 1.00 2.11 0.84 0.38 0.16 1.06 0.19 0.44 0.00 0.44 2.35 1.03 0.08 2.19 1.53 0.65 3.69 3.47 0.34 1.99 0.75 1.34 H2S 0.00 0.00 0.00 0.00 0.00 2.67 0.34 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 1.16 0.60 1.93 0.68 3.68 0.00 1.40 0.51 0.00 C1 53.47 35.21 36.47 28.40 5.82 23.03 8.86 36.47 51.54 57.53 45.34 28.40 35.05 42.00 45.34 45.40 34.93 49.23 49.10 47.12 50.50 35.42 40.48 52.00 35.05 35.21 36.47 28.40 16.33 13.16 12.59 21.55 19.49 20.04 17.38 6.05 5.63 C2 11.46 6.72 9.33 7.16 0.84 8.49 4.13 9.67 6.57 10.16 5.48 7.16 4.64 8.00 5.48 4.20 7.00 6.32 7.60 5.97 4.54 3.36 7.74 3.81 4.64 6.72 9.93 7.16 6.29 6.38 6.05 8.60 8.28 7.93 6.42 2.59 2.51 C3 8.79 6.24 8.85 10.48 0.43 8.26 5.41 6.95 4.83 5.83 3.70 10.48 2.46 6.00 3.70 0.89 7.82 4.46 6.13 4.62 0.90 0.90 8.20 2.37 2.46 6.24 8.85 10.48 7.48 7.62 6.51 7.66 6.85 8.00 7.62 5.83 4.60 C4 4.56 5.07 6.00 8.40 1.14 5.39 3.91 5.37 3.07 3.28 2.35 8.40 7.66 2.00 2.35 1.08 5.48 3.04 3.84 3.49 1.15 0.95 5.45 1.72 1.66 5.07 6.00 8.40 6.09 6.77 4.26 6.40 4.30 6.60 5.62 7.69 7.31 C5 2.09 5.23 3.78 3.82 3.01 4.38 3.45 2.85 2.38 2.71 1.60 3.82 1.60 1.00 1.60 0.94 3.80 2.26 2.52 2.55 0.89 0.40 3.64 1.20 1.60 5.23 3.78 3.82 4.36 5.65 4.52 5.07 4.18 5.87 4.53 6.14 5.99 C6 1.51 4.10 3.56 4.05 4.92 3.89 3.81 4.33 2.17 1.40 1.33 4.05 5.46 4.00 1.33 1.01 3.04 2.06 2.00 2.19 1.60 0.72 2.83 2.06 5.46 4.10 3.56 4.05 3.58 6.37 1.14 2.62 2.42 5.08 5.14 5.42 4.71 C7 + 12.69 34.97 30.43 35.97 83.20 38.82 68.67 33.29 27.05 19.11 36.12 35.97 48.24 37.00 36.12 45.08 35.15 31.45 28.00 33.00 39.00 57.73 31.42 36.84 48.24 34.97 30.43 35.97 52.27 51.68 62.18 43.41 46.90 45.93 49.13 64.81 67.03 GR.C7 + 0.864 0.841 0.837 0.843 0.942 0.877 0.934 0.852 0.833 0.81 0.836 0.843 0.836 0.823 0.817 0.888 0.855 0.865 0.836 0.85 0.901 0.917 0.845 0.841 0.9 0.841 0.837 0.843 0.88 0.876 0.877 0.869 0.876 0.861 0.891 0.857 0.855 MWC7 + 143 213 200 252 304 254 243 218 265 203 253 252 225 255 255 250 230 230 231 217 291 255 210 199 225 213 200 252 249 275 230 243 246 230 267 231 224 Temp. (jF) 176 250 234 131 160 198 178 220 195 212 199 131 180 155 199 160 238 200 199 166 156 159 208 200 180 250 234 131 215 190 239 239 230 235 234 148 128 Ps (psi) 4460 2547 2746 1694 313 1731 677 2620 4566 5065 3885 1708 2520 3250 3885 3466 2724 3981 3739 3394 3690 2307 2886 3839 2520 2547 2746 1694 1261 1140 1490 1591 993 900 1190 352 376 Ps-model 3608 2884 2730 1615 313 1614 607 2664 3663 3991 3494 1615 2732 2508 3491 3184 2779 3528 3418 3188 3461 2447 2851 3772 2408 2884 2714 1615 1290 849 977 1913 1387 1531 1348 347 376 Ps-SRK 4472 2412 2539 1674 377 1742 652 2533 3930 4105 3262 1674 1877 2394 3064 3437 2593 3837 3522 3274 4372 2598 2729 3523 2503 2412 2537 1674 1185 882 922 1695 1593 1353 1426 345 392 Ps-PR 3791 2378 2473 1618 291 1621 518 2426 4057 4255 3300 1618 1828 2459 3254 2905 2509 3525 3507 3037 3579 2019 2612 3286 2062 2378 2472 1618 1092 823 849 1615 1489 1290 1303 321 358 A.M. Elsharkawy / Journal of Petroleum Science and Engineering 38 (2003) 5777

Rosenegger-99 Rosenegger-99 Rosenegger-99 Rosenegger-99 Rosenegger-99 Rosenegger-99 Rosenegger-99 Rosenegger-99 Rosenegger-99 Rosenegger-99 Rosenegger-99 Rosenegger-99 Rosenegger-99 Rosenegger-99 Rosenegger-99 Rosenegger-99 Coats-86 Li-85 Vogel-80 William-80 Drohm-80 Hoffman-53 Danesh 91 and 92 Danesh 91 and 92 Danesh 91 and 92 Danesh 91 and 92 Hong-82 Hong-82 Agarwal-90 Riemens-88 Jhaveri-88 Jhaveri-88 Pedersen-88 Rosenegger-99 Rosenegger-99 Rosenegger-99 Rosenegger-99 Jacopy-58

133 134 135 136 137 138 140 141 142 143 144 145 146 147 148 149 151 152 153 155 156 157 158 159 160 161 162 163 164 165 166 167 168 169 170 171 172 173

0.30 0.35 0.31 0.29 0.33 0.41 0.53 0.78 0.60 1.13 0.37 0.54 1.39 0.68 0.39 1.02 0.30 1.67 0.65 0.25 0.24 0.00 0.00 0.00 0.00 0.00 0.00 1.02 0.33 0.71 0.00 0.00 0.31 0.03 0.52 0.34 0.38 1.67

0.01 0.56 0.28 0.46 0.35 0.26 0.12 0.10 0.12 0.13 0.02 0.18 0.28 0.16 0.14 0.12 0.90 1.38 0.02 0.24 0.27 0.00 0.00 0.00 0.00 0.00 0.01 0.40 3.03 3.84 0.00 9.11 0.69 8.39 6.47 7.10 7.03 2.18

0.00 1.41 0.02 0.49 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 1.17 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00

7.14 9.99 6.80 10.75 6.72 6.14 22.80 20.64 23.71 25.45 17.28 21.62 21.32 22.84 21.40 19.76 53.47 26.68 45.02 40.91 66.83 52.00 46.78 36.15 74.18 73.36 31.00 54.62 41.33 59.49 60.88 45.58 47.69 47.43 39.58 48.43 48.73 60.51

1.54 1.45 1.98 1.11 2.19 2.38 6.45 5.80 7.18 6.99 6.11 6.03 6.21 6.28 6.40 5.52 11.46 9.25 12.45 10.38 8.28 3.81 8.77 12.17 5.32 5.35 10.41 11.47 8.89 5.55 7.38 5.11 6.64 10.29 10.68 9.24 8.93 7.52

3.71 1.87 4.01 1.58 4.04 4.71 8.51 7.05 8.71 9.60 8.23 8.39 8.11 7.83 7.43 6.89 8.79 10.18 8.93 9.01 5.15 2.37 7.44 8.05 4.67 4.71 11.87 7.33 5.95 4.06 5.03 3.03 4.59 6.12 7.27 5.84 5.48 4.74

7.31 3.64 6.62 3.68 5.54 6.27 6.60 6.90 6.85 7.87 5.47 7.10 6.37 6.24 5.06 4.87 4.56 6.40 6.03 5.13 3.31 1.72 4.01 5.81 2.58 2.62 7.32 4.01 4.12 3.06 2.78 2.18 2.59 4.20 5.28 4.39 4.05 4.12

6.65 4.47 6.57 4.03 5.30 5.64 4.71 5.95 5.17 5.93 3.76 4.75 3.84 4.63 4.34 4.49 2.09 4.03 3.02 3.28 2.04 1.20 2.56 4.79 0.97 1.00 4.41 1.96 2.66 1.58 1.96 1.92 1.16 2.89 3.65 3.21 3.00 2.97

6.19 5.23 6.65 4.75 4.47 4.68 4.24 5.11 2.85 1.88 3.96 3.85 5.45 3.44 4.45 2.67 1.51 0.00 1.44 2.21 1.85 2.01 4.02 5.24 1.56 1.62 2.55 1.42 0.00 1.27 1.84 1.54 1.69 2.05 2.90 2.28 2.14 0.00

67.15 71.03 66.76 72.86 71.06 69.51 46.04 47.67 44.81 41.02 54.80 47.54 47.03 47.90 50.39 54.66 16.92 40.41 22.44 28.58 12.03 36.84 26.40 27.79 10.72 11.18 32.43 17.77 33.69 19.27 20.13 31.53 34.64 18.61 23.67 19.17 20.26 16.29

0.86 0.872 0.858 0.861 0.858 0.86 0.864 0.857 0.868 0.851 0.851 0.863 0.87 0.864 0.842 0.85 0.836 0.855 0.81 0.8 0.8 0.841 0.766 0.772 0.766 0.767 0.743 0.808 0.848 0.78 0.836 0.894 0.869 0.830 0.858 0.805 0.805 0.789

233 258 237 261 225 225 242 237 238 237 242 236 257 226 245 247 173 217 184 182 182 199 158 191 159 161 199 218 200 297 191 270 234 180 176 183 181 181

140 148 144 145 138 134 156 157 156 157 156 156 156 156 149 160.5 176 210 140 300 215 201 212 212 212 212 130 164 200 158 190 190 232 295 310 314 309 246

374 506 374 519 360 346 1325 1209 1386 1446 537 1257 1220 1407 1124 1152 4460 1954 3002 3043 4810 3828 2941 2238 4753 4742 1620 3900 3200 6880 5000 3840 3800 4000 3627 4082 4156 4823

431 506 374 653 361 291 1325 1241 1401 1567 914 1306 1245 1382 1149 1173 3554 1993 2742 3300 4778 3779 3248 2409 5339 5280 1622 3535 3164 4153 4192 3892 3573 4460 3830 4566 4568 4794

361 531 360 524 358 344 1323 1189 1426 1550 938 1246 1389 1349 1118 1164 3815 2060 2624 2729 4867 3526 2550 1981 4737 4705 1273 3892 3013 4167 4586 4183 3855 3933 3418 3743 3740 4513

331 481 333 486 326 312 1222 1110 1300 1470 888 1148 1247 1228 1080 1110 3473 1938 2548 2819 5007 3289 2594 2117 4883 4862 1407 4114 2812 5053 4302 3433 3568 3879 3198 3902 3871 4738

A.M. Elsharkawy / Journal of Petroleum Science and Engineering 38 (2003) 5777 63

64

A.M. Elsharkawy / Journal of Petroleum Science and Engineering 38 (2003) 5777

be comparable to EOSs but eliminate the splitting and characterization of the plus-fraction, which is necessary for the EOSs. These measurements cover a pressure range of 800 5000 psia (5.516 34.474 mPa) and temperature of 130 250 jF (54.4 121 jC) for a variety of black oils. In these measurements, black oils are defined as crude oils having heptane plus-fraction of 30% or more, oil formation-volume factor of 1.0 2.0 m3/m3, and solution gas oil ratio of 0 2000 (350 m3/m3). Most of these oil samples are sweet crude with low content of non-hydrocarbons (less than 10%). The second group of data were collected from the literature (Hoffmann et al., 1953; Jacopy and Berry, 1958; Baker and Luks, 1980; Williams and Zana, 1980; Drohm and Goldthrope, 1988; Vogel and Yarborough, 1980; Hong, 1982; Li et al., 1985; Coats and Smart, 1986; Varotsis et al., 1986; Slot-Petersen and Olie-Og, 1987; Riemens et al., 1988; Jhaveri and Youngren, 1988; Pedersen et al., 1988a,b; Ahmed, 1989; Danesh et al., 1990, 1991, 1992; Danesh, 1998; Agarwal et al., 1990; Joergensen and Stenby, 1995; Rosenegger and Wu, 1999). These include 75 measurements of saturation pressures and compositions of a variety of crude oils from the Middle East, North Sea, and North America, Table 2. This group was used to test the accuracy and reliability of the proposed model against EOSs.

high content of paraffinic and naphthenic content. Extending the plus-fraction into C10 + might increase the accuracy of the proposed model. However, it would reduce its simplicity. No distinction is made between iso-paraffins and normal paraffins for two reasons: first, concentrations of these hydrocarbons are usually very small when compared with methane and heptane plus-fraction, and second, EOSs simulations have indicated minor change in the estimated saturation pressure when iso and normal are lumped as single component. s f N2 ; CO2 ; H2 S; C1 First; define p C6 ; C7 ; MW7 ; c7 ; T 1

where p s is the calculated saturation pressure of crude oil sample. The objective is to find f that minimizes the average relative deviation (ARD) between measured ( ps) and estimated saturation pressure (p s) for all the experimentally measured samples in this study. The average relative deviation is defined as X s ps =ps g=n ARD fp 2 Multiple regression and minimization resulted in the empirical model s A1 N2 A2 CO2 A3 H2 S A4 C1 A5 C2 p

3. Estimation of saturation pressures 3.1. Empirical model The molecular weight and specific gravity of the heptane plus-fraction are used as input variable distinguishing the plus-fraction. The density and molecular weight of the total plus-fraction is important in the proposed model because it reflect the paraffinic naphthenic aromatic (PAN) content of the plus-fraction. A large density indicates a high content of aromatic compounds and a low density indicates a The constants A1 through A13 are A1 17:065 A6 50:255 A11 3:836 A2 74:494 A7 53:966 A12 1:044 A3 92:275 A8 29:063 A13 5:410

A6 C3 A7 C4 A8 C5 A9 C6 A10 C7 A11 c7 A12 MW7 A13 T 3

where p s is the saturation pressure in psia, T is the reservoir temperature in jF, composition analysis of [N2, CO2, H2S, C1 C6, C7 +,] is expressed as mole percent, MW7 + is the molecular weight of the heptane plus and c7 + is the specific gravity of the heptane plusfraction. It is important that the summation of mole percentages of all components forming the hydrocarbon equal 100%.

A4 63:633 A9 25:869

A5 26:962 A10 5:350

A.M. Elsharkawy / Journal of Petroleum Science and Engineering 38 (2003) 5777

65

3.1.1. Lumping the extended analysis of the hydrocarbon mixture Petroleum fluids consist of thousands of different hydrocarbon constituents. The diversity of the chemical structure of the individual components increases with carbon number; it is therefore impractical to analyze for all the C7 + components. A standard composition analysis characterization most often used is to stop at C7 +, C10 + or rarely C20 +. The extended analysis of the plus-fraction was lumped into single component plus-fraction. This single component plusfraction was used as the input parameter of the empirical equation. This lumping, or grouping, was carried such that the mole fraction of the individual carbon number fraction of the extended analysis sum to the total mole fraction of the plus-fraction. The average molecular weight of the individual components of the extended analysis is equal to plus-fraction. Similarly, the density of the individual fractions or components is equal the density of the total plusfraction. The density of the total plus-fraction is important in the model because it reflect the PAN content of the plus-fraction. A large density indicates a high content of aromatic compounds and a low density indicates a high paraffinic and naphthenic content. The lumping is carried as follows: X X C7 Xi ; i 7; 8; n 4 MWC7 X Xi MWi =X C7 ; i 7; 8; n 5

3.2.1. Soave Redlich-Kwong equation of state Soave (1972) Redlich-Kwong (SRK-EOS) developed the following equation: P RT =V b aa=V V b 7

where P is the pressure, V is the molar volume, T is the absolute temperature, and R is the universal gas constant. The parameter a is a dimensionless factor, which becomes the unity at critical pressure. At the bubble point pressure, the composition of the liquid phase (xi) equals the overall composition (zi) of the reservoir fluids. This leads to the following expression: X z i ki 1 8

where ki is the equilibrium ratio for the component calculated from the equation of state. Thus, the saturation pressure ( Ps) is calculated from the above equations using the following expression: Ps X fiL =uV i 9

L where uV i is the vapor fugacity coefficient and fi is the liquid fugacity of the ith component, which is calculated from the equation of state.

cC7 X C7 MWC7 =Xi MWi =ci ; i 7; 8; n 6 3.2. Equation of state Two cubic equations of state, Soave RedlichKwong (SRK-EOS) and Peng-Robinson (PR-EOS), are considered in this paper because they are commonly used by the petroleum industry for predicting phase behavior and volumetric properties of hydrocarbon reservoir fluid mixtures. These equations predict the saturation pressure and vapor/liquid equilibrium conditions with reasonable accuracy if the heptane plus-fraction of the hydrocarbon fluids is properly characterized (Jhaveri and Youngren, 1988).

3.2.2. Peng-Robinson equation of state Peng and Robinson (1976) evaluated the performance of SRK-EOS for predicting the behavior of petroleum reservoir fluids. They showed that SRKEOS needs to be improved to predict phase properties near the critical point. Therefore, Peng-Robinson proposed the following EOS: P RT =V b aa=V V b bV b 10 The difference between SRK-EOS and PR-EOS lies in calculation of the parameters a, b, and a. This difference results in that the calculated fugacity, fugacity coefficient, and compressibility factor from each of the equations of state are quite different. Therefore, the results from calculations bubble point pressures using SRK-EOS and PR-EOS are not the same.

66

A.M. Elsharkawy / Journal of Petroleum Science and Engineering 38 (2003) 5777

3.3. Equations of state characterization of the plusfraction 3.3.1. Splitting the plus-fraction Reservoir fluid is a complex mixture formed of several components, the properties of which depend significantly upon he interaction of various components. Because each fluid has its own unique composition, the interaction among various components varies from one fluid to another. It is impossible to describe every component in the EOS. The reservoir fluid compositional analysis is usually carried out by defining the pure hydrocarbon components (C1 C6), non-hydrocarbons (N2, H2S, CO2), and grouping components heavier than heptane or decane into one components or limited number of pseudo-components. Because EOS accuracy depends on number and characterization of the plus-fraction, the heptane plusfraction is divided into 12 subfractions. It might be reasoned that accuracy of EOS prediction increases with the number of pseudo-component used to describe reservoir fluid. Recent simulation studies of crude oils and gas condensates have shown that 10 12 subfractions are sufficient enough to describe phase behavior of hydrocarbon systems (Pedersen, 1984; Joergensen and Stenby, 1995; Elsharkawy, 2002). In this work, Pedersen et al. correlation was used to split the plus-fraction into 12 subfractions. This was done because extensive compositional analysis comprising very many reservoir fluids from all over the world have shown that natural logarithm of the mole fraction of a given C7 + fraction is approximately a linear function of carbon number (Pedersen et al., 1992; Zuo and Zhang, 2000). This logarithmic distribution is given by lnXi A BMWi 11

The density of the distribution (qi) versus the molecular weight is calculated from the following equation: qi C DlnCNi 13

where C and D are constants determined from measured or densities of the plus-fraction and that of the last defined fraction. Once the mole fraction and the molecular weight and gravity of each subfraction are determined, critical property and acentric factor are calculated. 3.3.2. Properties of the subfraction To use the EOS, it is required to characterize the subfractions by estimating their critical properties, boiling point, and acentric factor. The Pedersen et al. (1989) correlation is used to calculate critical properties and acentric factor for the pseudo-fractions forming the heptane plus using the molecular weight (Mw) and density (q) of the subfraction as follows: Tc 1:6312e2 q 8:6052e1 lnMW 4:3475e 1 MW 1:8774e 3=MW 14 lnPc 1:3408e 1 2:5019 q 2:0846e2=MW 3:9872e3=MW2 15

The acentric factor is calculated from the following equations: m 0:48 1:574x 0:176x2 where m 7:4310e 1 4:8122e 3 MW 9:6707e 3 q 3:7184e 6 MW2 17 16

The constants A and B are determined from the measured mole fraction and molecular weight of the plus-fraction, and Mwi are the mole fraction and molecular weight of the subfraction, respectively. The molecular weight distribution versus the carbon number (CNi) is estimated from the following equations: MWi 14CNi 4 12

In Eqs. (14) (17), Tc is in K, Pc in atm, MW is in g/ mol, and q is in g/cm3. 3.4. Binary interaction numbers To use the SRK or PR equations of state to predict saturation pressure of complex hydrocarbon mixture, it is necessary to correct for the binary interaction (Ki,j) between different components by means of empirically derived interaction numbers. The use of

A.M. Elsharkawy / Journal of Petroleum Science and Engineering 38 (2003) 5777

67

BIN in equations of state calculations is controversial. Some researchers neglected BIN for hydrocarbon to hydrocarbon components, used standard values for EOS (Whitson and Brule, 2000), and others used BIN, which are function of temperature (Varotsis et al., 1986), pressure (Voros and Tassios, 1985), or compositions (Bjorlykke and Firoozabadi, 1992). In this study, the objective is not to find the optimum BIN that leads to accurate prediction of the saturation pressure. Therefore, the interaction between hydrocarbons is set to zero. For interaction between nonhydrocarbon and hydrocarbon, constant values for SRK and PR reported by Pedersen et al. (1989) are used. In naturally occurring oil gas mixtures, the content of non-hydrocarbon mainly (N2, CO2, H2S) are often less than 7%. For such hydrocarbon mixture, even using Ki,j = 0 for all interaction parameters has virtually no effect on the calculated results by EOS (Pedersen et al., 1985).

of the model under conditions that were not used in the development process. 4.1. Accuracy of the empirical model The accuracy of the new empirical model with respect of the SRK and PR equations of state for estimating the saturation pressures of various crude oils is given in Table 3. This table reports the average relative deviation (ARD), average absolute deviation (AAD), and relative mean square error (RMSE) for the 60 crude oil samples that were used to derive the model and the 75 crude oil samples that were used to test the model. The proposed model has the smallest errors for the measured saturation pressures of the Middle East crudes that were used to develop the model. Table 3 also shows that the new model has comparable accuracy to the SRK and PR equations of state for the crude oils that was used to test the model. The current model has the advantage of being simple and accurate, eliminate the need for splitting the heptane plus-fraction and characterization of the subfractions. Avaullee (2002) studied the performance of the model against a database including 42 experimental bubble points of reservoir oil. The database were measured and verified in PVT laboratory of TOTALFINAELF. The oils come from Middle East, Africa, and North Sea. Avaullee found that the model calculate bubble point pressure for the database with AAD of 15.5% and RMSE of 21%. Saturation pressure calculations by SRK-EOS and PR-EOS for the 42 crude oils were not reported for comparison with the model. Results reported in Table 3 as well as by Avaullee indicate that the accuracy of the model depends on the database, composition of reservoir oils, and geographic location.

4. Results and discussion First, the accuracy of the empirical model is compared with accuracy of SRK and PR equations of state to estimate saturation pressures for the experimentally measured samples as well as those collected from the literature. When comparing the model and equations of state predictions of saturation pressures, it is important to remember that the empirical model uses a single fraction for the heptane plus, and EOSs use 12 pseudo-components to describe the plus-fraction. Second, the validity of the model is checked against equations of state by studying the sensitivity of the proposed model to the most important input variables. Finally, some single contact experiments from the literature are used to show the performance
Table 3 Error analysis of various methods for calculation of saturation pressures

60 samples from Middle East used to develop the model Model ARD AAD RMSE 0.58 6.36 8.38 SRK 7.98 10.91 13.72 PR 6.71 9.23 10.95

75 samples from the literature used to test the model Model 0.59 10.40 17.01 SRK 1.79 10.39 17.14 PR 7.10 12.20 16.65

ARD: average relative deviation. AAD: average absolute deviation. RMSE: relative mean square error.

68

A.M. Elsharkawy / Journal of Petroleum Science and Engineering 38 (2003) 5777

Fig. 2. Error distribution for samples used to derive the model.

Fig. 2 shows the average absolute deviation (AAD) for all the 60 samples used to derive the proposed model. This figure indicates that model successfully estimated the saturation pressures for a total of 40 samples of out the 60 samples with AAD of 5% versus 15% by EOSs and only 4 samples have AAD exceeding 15%. For these four samples, both the model and the EOSs show high AAD. The extremely

high errors are a result of the uncertainty in experimental data. Fig. 3 shows the error distribution for the 75 crude oil samples collected from literature. The new model as well as the EOSs has AAD of less than 10% for 50 samples out of the 75. Only four samples have errors in their estimated saturation pressures exceeding 30%. These four samples (125, 126, 144, and 165) have

Fig. 3. Error distribution for testing samples.

A.M. Elsharkawy / Journal of Petroleum Science and Engineering 38 (2003) 5777 Table 4 Range of input variable used for developing and testing the empirical model Data used to develop the model Min. Ave. Max. Data used to test the model Min. Ave. Max.

69

N2 0.00 0.21 0.79 0.00 0.45 1.67 0.07 0.75 2.51 0.00 1.34 9.11 CO2 H2S 0.00 0.04 0.75 0.00 0.21 3.68 C1 19.50 31.57 48.79 5.63 33.97 74.18 C2 6.00 8.23 11.07 0.84 6.73 12.45 4.75 6.57 9.23 0.43 6.16 11.87 C3 C4 2.04 4.28 6.07 0.95 4.77 8.40 C5 1.50 3.01 4.88 0.40 3.45 6.65 0.99 3.34 4.53 0.00 3.13 6.65 C6 C7 + 24.80 42.06 52.13 10.72 39.82 83.20 GR.C7 + 0.85 0.88 0.93 0.74 0.85 0.94 MWC7 + 134 239 324 143 225 303 Temp. 130 156 243 66 191 314 (jF) Pb (psi) 1025 1946 3630 313 2505 6880

experimental uncertainty. Examining the range of input variables given in Table 2 for samples 121 127 (from Moharam, 1995) reveals that they are from the same formation as they have close values for methane, heptane plus-fraction, and formation temperature. The measured saturation pressures for all the samples vary from 1140 to 1490 psi (7.8 10.27 mPa) except for sample nos. 125 and 126 (900 993 psi or

6.2 6.84 mPa, respectively). Because the model as well as EOSs had unusually high errors for those two samples, the reported saturation pressures believe to be incorrect. Sample nos. 140 149 are from Rosenegger and Wu (1999). These samples are from the same reservoir as they have the same temperature, low non-hydrocarbon content, methane, and heptane plusfraction. The reported saturation pressure for all the samples range from 1124 to 1446 psi (7.77 10.0 mPa), except sample no. 144, which has a reported saturation pressure of 537 psi (3.71 mPa). The empirical model, SRK, and PR equations of state predicted the saturation pressure to be 913, 938, and 890-psi (6.31, 6.48, and 6.15 mPa), respectively. This indicates that the reported saturation pressure is incorrect. Finally sample no. 165 is from Riemens et al. (1988). The reported saturation pressure is 6880 psi (47.5 mPa) at 158 jF (70 jC) for very light oil having 19% heptane plus and molecular weight of plus-fraction of 297. The proposed model and SRK equation of state predicted the saturation pressure in the order of 4153 and 4167 psi (28.63 and 28.73 mPa), respectively. The compositional analysis or the saturation pressure for this sample might have some error. These examples illustrate that the model can be used to check uncertainty of the measured saturation pressure. Table 4 shows the range of input variables that have been used to develop and test the empirical model presented in this study. Comparing this range

Fig. 4. Saturation point for sample no. 72.

70

A.M. Elsharkawy / Journal of Petroleum Science and Engineering 38 (2003) 5777

Fig. 5. Saturation point for sample no. 113.

of variables clearly demonstrates that the model has been tested in wider methane content (6 75%), heptane plus-fraction (10 83%), temperature (66 314 jF, 18.8 157 jC), and pressure range (313 6880 psia, 2.15 47.43 mPa) than the range of input variables to derive the model. The high methane content (74%), low heptane content (11%), or the higher temperature represents very light crudes (volatile oils). It is important to note that the experimentally meas-

ured data represents black crude oils, which are mostly sweet having very low content of nitrogen, carbon dioxide, and hydrogen sulfide. The model has also been tested for crude oils having as high as 9% carbon dioxide and 4% hydrogen sulfide. Thus, the model can be extended to estimate saturation pressures for volatile, heavy, and sour crudes. The errors in the saturation pressures calculated by the model are checked against all input variables. No correlation was

Fig. 6. Sensitivity of various methods to MWC7 +, sample no. 6 at 134 jF.

A.M. Elsharkawy / Journal of Petroleum Science and Engineering 38 (2003) 5777

71

Fig. 7. Sensitivity of various models to g7+, sample no. 6 at 134 jF.

found between the errors and any of the input variables. 4.2. Validity of the empirical model To make sure that the proposed empirical model is physically correct, it is important to check its validity. Therefore, the model response to most important variables is studied and compared to that of SRK and PR equations of state. The most important input variables for black oils are reservoir

temperature, methane content, heptane contents, and properties of heptanes (molecular weight and density). The intermediate hydrocarbon and nonhydrocarbons are the least important input variable as their concentration is very low. Figs. 4 and 5 show comparison between model response to a change in temperature as compared with SRK and PR-EOSs. Fig. 4 illustrates that the model captured the trend of increasing the saturation pressure as a function of increasing the temperature. It also shows that accuracy

Fig. 8. Sensitivity of models to C1/C7 +, sample no. 2 at 133 jF.

72

A.M. Elsharkawy / Journal of Petroleum Science and Engineering 38 (2003) 5777

of the model is close to PR-EOS. It is important to note that the measured saturation pressures at different temperatures for this sample (no. 72) were not used in deriving the model. Saturation pressure versus temperature for crude oil sample (no. 113) reported by Coats and Smart (1986) also has been used to check validity of the model (Fig. 5). This figure depicts that the model successfully predict the measured saturation pressures at low temperatures better than SRK, PR, and better than EOS calculations reported by Coats and Smart (1986). The sensitivity of the model to molecular weight and density of heptane plus-fraction are also studied (Figs. 6 and 7). Because the change of saturation pressure as a function of changing the molecular weight of the heptane plus-fraction has neither measured nor reported, the saturation pressure is calculated

at different molecular weights of heptane plus and plotted in Fig. 6. As expected, both SRK and the proposed model show little decline in calculated saturation pressure as a function of increasing the molecular weight of heptane plus. The slight sensitivity of both SRK and the model to change in molecular weight of heptane plus is an advantage as the molecular weight of heptane plus is the most uncertain parameter among all the input variables. PR-EOS, however, predicts the saturation pressure to increase as a function of increasing the molecular weight of the heptane plus-fraction. Fig. 7 shows the model response to a change in density of the heptane plus-fraction as compared to SRK and PR equations of state. This figure indicates that PR-EOS is highly sensitive to density of heptane plus-factions than the other methods. The proposed model and SRK predict

Table 5 Comparison between the accuracy of different methods for estimating saturation pressure for some crudes from literature (A) Black oils from Moharam (1995) Sample C7 + AD%-model AD%-SRK AD%-PR (B) Volatile oils Ref. Sample C7 + AD%-model AD%-SRK AD%-PR Exp. 62 12.69 19.1 0.3 15.0 Danesh 84 19.11 21.2 19.0 16.0 Coats 151 16.92 20.3 14.5 22.1 Vogel 153 22.44 8.7 12.6 15.1 Drohm 156 12.03 0.7 1.2 4.1 Rosenegger 170 23.67 5.59 5.76 11.83 Rosenegger 171 19.17 11.87 8.30 4.41 Rosenegger 172 20.26 9.92 10.01 6.86 Jacopy 173 16.29 0.78 6.68 2.03 AAD% 121 52.27 2.3 6.0 13.4 122 51.68 25.5 22.6 27.8 123 62.18 34.5 38.1 43.0 124 43.41 20.2 6.5 1.5 125 46.9 39.6 60.4 49.9 126 45.93 70.1 50.3 43.3 127 49.13 13.3 19.8 9.5 AAD% 29 29 27

9 9 11

(C) Heavy oils from Rosenegger and Wu (1999) Sample C7 + AD%-model AD%-SRK AD%-PR 131 64.81 1.46 1.99 8.81 132 67.03 0.00 4.26 4.79 133 67.15 15.35 3.48 11.50 134 71.03 0.01 4.94 4.94 135 66.76 0.00 3.74 10.96 136 72.86 25.75 0.96 6.36 137 71.06 0.34 0.56 9.44 138 69.51 15.91 0.58 9.83 AAD% 7 3 8

(D) Synthetic oil from Danesh et al. (1992) Sample C7 + AD%-model AD%-SRK AD%-PR 158 26.4 10.43 13.29 11.80 159 27.79 7.62 11.48 5.41 160 10.72 12.32 0.34 2.74 161 11.18 11.34 0.78 2.53 AAD% 10 7 6

AD: absolute deviation. AAD: average absolute deviation.

A.M. Elsharkawy / Journal of Petroleum Science and Engineering 38 (2003) 5777

73

Fig. 9. Pressure composition for oil/methane.

the saturation pressure to slightly increase as a function of increasing density of the heptane plus. Because no experimental data was available to study the effect of methane/heptane ratio on saturation pressure, the model response to a change in methane/heptane is compared against that of equations of state (Fig. 8). As expected, this figure shows that all the three methods predict an increase in the saturation pressure as a function of increasing the methane/heptane ratio. Fig. 8 also indicates good agreement between calculated saturation pressures by the proposed model and PR-EOS. These examples indicate that the model is accurate and physically correct. Table 5 reports comparison between accuracy of different methods for estimating saturation pressure for

four groups of crudes from literature. The first group is black oils from Moharam (1996) represented by sample nos. 121 127. For such group, the model has 29% AAD, SRK, and PR have 29 and 27, respectively. The second group is volatile, oils from various sources. Both the model and SRK have the same AAD (9%) and they are more accurate than PR (AAD of 11%). The third group contains heavy crude oils from Rosenegger and Wu (1999). The model, SRK, and PR have AAD of 7%, 3%, and 8%, respectively. The last group is synthetic hydrocarbon mixtures from Danesh (1991, 1992). The prediction of saturation pressures for the first two samples (black oils) is comparable with SRK and PR. The model did not perform as good as the EOSs for the last two synthetic mixtures. Note that

Fig. 10. Pressure composition diagram for light oil/CO2 mixture.

74

A.M. Elsharkawy / Journal of Petroleum Science and Engineering 38 (2003) 5777

Fig. 11. Comparison between model and EOSs prediction of saturation pressure. Single contact experiment of black oil and rich gas at 212 jF.

these synthetic mixtures are light hydrocarbons having low content of heptane plus-fraction. 4.3. Single contact experiments The ability of the empirical model to predict saturation pressure during single contact experiments by methane, rich gas, carbon dioxide, and hydrogen sulfide is examined. Fig. 9 shows comparison of saturation pressures predicted by different methods when crude oil sample (no. 71) was contacted by

various amounts of methane. This sample was chosen from the testing data because it represents very heavy oil, which initially contains low amount of methane (5.8%) and high amount of heptane plus (83.2%). Three points can be concluded from Fig. 9. First, the proposed model predicted the measured saturation pressure (313 psia, 2.15 mPa) at 160 jF (71 jC) better than SRK and PR equations of state. Second, the model captured the correct physical trend of increasing saturation pressure as a function of increasing the amount of injected methane. Third, the empir-

Fig. 12. Comparison of saturation prediction by different models for Hoffman Oil contacted by H2S.

A.M. Elsharkawy / Journal of Petroleum Science and Engineering 38 (2003) 5777

75

ical model matched the saturation pressure predicted by SRK-EOS. The second example is a single-contacted experiment of light oil by CO2 reported by Agarwal et al. (1990). Fig. 10 shows a pressure composition diagram of swelling experiment for light oil/CO2 mixture. This figure indicates that the predicted saturation pressure by the model at low concentration of CO2 (0 20%) is better than SRK and PR equations of state. The model predicts extremely high saturation pressures at CO2 concentration exceeding 20% due to the fact that it was derived from crude oil having low CO2 concentration. The third example is a single contact experiment of black oil and rich gas reported by Danesh et al. (1991). Comparison between the empirical model and EOSs predictions of saturation pressures is shown in Fig. 11. It is clear from this figure that the unadjusted EOSs could not predict the measured saturation pressures. The model, however, is much closer to the experimental data than PR and SRK equations of state. The fourth example is a simulated single contact experiment of H2S with crude oil from Hoffmann et al. (1953) (Fig. 12). This oil was chosen from the testing data, as it initially contains no hydrogen sulfide. The model captured the physical trend of declining the saturation pressure as a function of increasing the amount of H2S. However, saturation pressure predictions by the model did not match values predicted by EOSs.

(2) Examples have been presented where the models as well as PR and SRK equations of state are used to check for uncertainty in the measured saturation pressure. (3) Although the proposed model was derived from experimental data of black oils from Middle East, it was tested using other black oils, volatile oils, heavy oils, and synthetic mixtures. (4) Validity of the model was examined against equations of state for the most important input variables such as temperature, methane/heptane ratio, and properties of heptane plus. It indicated that the model successfully captured the physical trend of changing the saturation pressure as a function of changing the input variable and matched the simulated behavior predicted by SRK and PR equations of state. (5) Furthermore, four examples of single contact experiments for methane, rich gas, CO2, and H2S were simulated using the model and EOS(s). These examples indicate that the model successfully matched the experimentally measured saturation pressure when the injected gases are hydrocarbon gases. Nomenclature a constant for EOS AAD average absolute deviation = AabsA{(p s ps) /ps}A/N x acentric factor ARD average relative deviation = A{(p s ps)/ps}N b constant for EOS COR coefficient of correlation q 1 R p s ps 2 =R p s p 2 f fugacity k equilibrium ratio for the component m constant (Eq. (17)) MWC7+ molecular weight of C7 + N number of data points P mean value of measured saturation pressure (psia) Pc critical pressure (atm) (Eq. (15)) Ps experimentally measured saturation pressure (psia) R universal gas constant RMSE q relative mean square error
1 N

5. Conclusions (1) An empirical model has been presented to estimate the saturation pressures of crude oils. Input variables are compositional analysis and reservoir temperature. Accuracy of the model was compared to that of SRK and PR equations of state using experimentally measured data for 60 crude oil samples and 75 crude oil samples collected from the literature. The proposed model has better overall accuracy than EOSs for all the data considered in this study. The empirical model uses a single fraction for the heptane plus and EOSs use 12 pseudo-components to describe the plus-fraction. Thus, the model has several advantages over equations of state. It is simple, accurate, and eliminates the need for splitting and characterizing the heptane plus-fraction.

Rp s ps =ps 2

76

A.M. Elsharkawy / Journal of Petroleum Science and Engineering 38 (2003) 5777

T Tc Z p s u a q cC7+ ra rb

temperature (jF) critical pressure (K) (Eq. (14)) overall composition predicted saturation pressure (psia) fugacity coefficient dimensionless factor for the EOS density (g/cm3) (Eq. (14)) specific gravity of the C7+ equation of state constant equation of state constant

References
Agarwal, R.K., Li, Y.K., Nghiem, L., 1990. A regression technique with dynamic parameter selection for phase behavior matching. SPE Reserv. Eng. February, 115 120. Ahmed, T., 1986. Comparative study of eight equations of state for predicting hydrocarbon volumetric phase behavior. SPE 15673, 61st Ann. Tech. Conf., Oct. 5 8, New Orleans, LA. Ahmed, T., 1989. Hydrocarbon Phase Behavior. Gulf Publishing, Houston. Avaullee, L., 2002. Personal communication. Baker, L.E., Luks, K.D., 1980. Critical point and saturation pressure calculations for multipoint systems. Soc. Pet. Eng. J. Feb., 15 24. Behrens, R.A., Sandler, S.I., 1988. The use of semicontinuous description to model the C7+ fraction in equation of state calculations. SPE Reserv. Eng. Aug., 1041 1047. Bjorlykke, O.P., Firoozabadi, A., 1992. Measurement and computation of near-critical phase behavior of a C1/nC24 binary mixture. SPE Reserv. Eng., 271 281. Christensen, P.L., 1999. Regression to experimental PVT data. J. Can. Pet. Technol., Spec. Ed. 38 (13) (Paper 96-10-15). Coats, K.H., Smart, G.T., 1986. Application of a regression-base EOS PVT program to laboratory data. SPE Reserv. Eng. May, 277 299. Cotterman, R.L., Prausnltz, J.M., 1985. Flash calculations for continuous or semicontinuous mixtures using an equation of state. Ind. Eng. Chem. Process Des. Dev. 24, 434 443. Danesh, A., 1998. PVT and Phase Behavior of Petroleum Reservoir Fluids. Elsevier, Amsterdam. Danesh, A., Xu, D.H., Todd, A.C., 1990. An evaluation of cubic equations of state for phase behavior calculations near miscibility conditions. SPE 20267, 7th Symp. on Enhanced Oil Recovery, April 20 25, Tulsa, OK. Danesh, A., Xu, D.H., Todd, A.C., 1991. Comparative study of cubic equations of state for predicting phase behavior and volumetric properties of injection gas-reservoir oil systems. Fluid phase Equilib. 63, 259 278. Danesh, A., Xu, D.H., Todd, A.C., 1992. A grouping method to optimize oil description for compositional simulation of gasinjection processes. SPE Reserv. Eng. Aug., 343 348. Drohm, J.K., Goldthorpe, W.H., 1988. Enhancing the evaluation of

PVT data. OSEA paper 88174 presented at the 7th Offshore South East Asia Conf., February 2 5, Singapore. Elsharkawy, A.M., 2002. Predicting the dew point pressure for gas condensate reservoirs: empirical models and equations of state. Fluid phase Equilib. 193 (1 2), 147 166. Hoffmann, J.S., Crump, J.S., Hocott, C.R., 1953. Equilibrium constants for a gas-condensate system. Pet. AIME 198, 1 10. Hong, K.C., 1982. Lumped-component characterization of crude oils for compositional simulation. SPE paper 10691 3rd joint Symp. on Enhanced Oil Recovery, April 7 17, Tulsa, OK. Jacopy, R.H., Berry, V.J., 1958. A method for predicting pressure maintenance for reservoirs producing volatile oil. Petrol. Trans. AIME 213, 59 65. Jhaveri, B.S., Youngren, G.K., 1988. Three-parameter modification of the Peng-Robinson equation of state to improve volumetric predictions. SPE Reserv. Eng. Aug., 1033 1039. Joergensen, M., Stenby, E.H., 1995. Optimization of pseudo-component selection for compositional studies of reservoir fluids. SPE 30789, 70th Annu. Tech. Conf., Oct. 22 25, Dallas, TX. Kato, K., Nagahama, K., Hirata, M., 1981. Generalized interaction parameters for the Peng-Robinson equation of state: carbon dioxide-n-paraffin binary systems. Fluid phase Equilib. 7, 219 231. Katz, D.L., Firoozabadi, A., 1978. Predicting phase behavior of condensate/crude-oil system using methane interaction coefficients. J. Pet. Technol. Nov., 1649 1655. Kikani, J., Ratulowski, J., 1996. Consistency check and reconciliation of PVT data from samples obtained with formation tester using EOS models. SPE 36743, SPE Ann. Tech. Conf., Oct. 6 9, Denver, CO. Li, Y.K., Nghiem, L.X., Siu, A., 1985. Phase behavior computations for reservoir fluids: effect of pseudo-components on the phase diagrams and simulation results. J. Can. Pet. Technol. Nov. Dec., 29 36. Moharam, H.M., 1995. Prediction of viscosity of heavy petroleum fractions and crude oil using a corresponding states method. Ind. Eng. Chem. Res. 34, 4140 4144. Pedersen, K.S., Thomassen, P., Fredenslund, Aa., 1984. Thermodynamic of petroleum mixtures containing heavy hydrocarbons: 1. Phase envelope calculations by the use of the Soave RedlichKwong equation of state. Ind. Eng. Chem. Process Des. Dev. 23, 163 170. Pedersen, K.S., Thomassen, P., Fredenslund, Aa., 1985. Thermodynamic of petroleum mixtures containing heavy hydrocarbons: 3. Efficient flash calculations procedures using the SRK equation of state. Ind. Eng. Chem. Process Des. Dev. 24, 948 954. Pedersen, K.S., Thomassen, P., Fredenslund, Aa., 1988a. Characterization of gas condensate mixtures. AIChE Spring National Meeting, March 6 10, New Orleans, LA. Pedersen, K.S., Thomassen, P., Fredenslund, Aa., 1988b. On the danger of tuning equation of state parameters. Chem. Eng. Sci. 43, 269 278. Pedersen, K.S., Fredenslund, Aa., Thomassen, P., 1989. Properties of Oil and Natural Gases. Gulf Publishing, Houston. Pedersen, K.S., Blilie, A.L., Meisingest, K.K., 1992. PVT calculations on petroleum reservoir fluids using measured and esti-

A.M. Elsharkawy / Journal of Petroleum Science and Engineering 38 (2003) 5777 mated compositional data for the plus fraction. IEC Res. 1, 1378 1384. Peng, D.Y., Robinson, D.B., 1976. A new two-constant equation of state. Ind. Eng. Chem. Fundam. 15, 59 63. Riemens, W.G., Schutle, A.M., Jong, L.N.J., 1988. Birba field PVT variations along the hydrocarbon column and confirmatory field tests. J. Pet. Technol. Jan., 83 88. Rosenegger, L., Wu, R., 1999. Integrated oil PVT data characterization-lessons from four case histories. J. Can. Pet. Technol., Spec. Ed. 38 (13) (Paper 97-05). Slot-Petersen, Olie-Og, D., 1987. A systematic and consistent approach to determine binary interaction coefficients for the PengRobinson equation of state. SPE16941, SPE 62nd Ann. Tech. Conf., Sept. 27 30, Dallas, TX. Soave, G., 1972. Equilibrium constants from a modified RedlichKwong equation of state. Chem. Eng. Sci. 27, 1197 1203. Varotsis, N., Stewart, G., Todd, A.C., Clancy, M., 1986. Phase behavior of system comprising North Sea reservoir fluids and injection gases. J. Pet. Technol. Nov., 1221 1233. Vogel, J.L., Yarborough, L., 1980. The effect of nitrogen on the phase behavior and physical properties of reservoir fluids. SPE 8815, SPE/DOE on Enhanced Oil Recovery, April 20 23, Tulsa, OK. Voros, N.G., Tassios, D.P., 1985. Vapour-liquid equilibria in nonpolar/weakly polar systems with different types of mixing rules. Fluid phase Equilib. 91, 1 29.

77

Whitson, C.H., 1983. Characterizing the hydrocarbon plus fraction. Soc. Pet. Eng. J. Aug., 683 694. Whitson, C.H., 1984. Effect of C7+ properties on equation-of-state predictions. Soc. Pet. Eng. J. Dec., 685 694. Whitson, C.H., Brule, M.R., 2000. Phase behavior. SPE Monograph, vol. 20. Richardson, Texas. Whitson, C.H., Anderson, T.F., Soreide, I., 1990. Application of the gamma distribution model to molecular weight and boiling point data for petroleum fractions. Chem. Eng. Commun. 96, 259 278. Williams, C.A., Zana, E.N., 1980. Use of the Peng-Robinson equation of state to predict hydrocarbon phase behavior and miscibility for fluid displacement. SPE 8817, SPE/DOE on Enhanced Oil Recovery, April 20 23, Tulsa, OK. Wu, R., Rosenegger, L., 2000. Comparison of PVT properties from equation of state analysis and PVT correlations for reservoir studies. J. Can. Pet. Technol. 39, 45 51. Zaitsev, I.Y., Dmitrievsky, S.D., Norvik, H., Yhfin, P.A., Bolotnik, D.N., Sarkisov, G.G., Schepkina, N.E., 1996. Compositional modeling and PVT analysis of pressure maintenance effect in gas condensate field: comparative study. SPE 36923, SPE European Petroleum Conference, Oct. 22 24, Milan, Italy. Zuo, J., Zhang, D., 2000. Plus fraction characterization and PVT data regression for reservoir fluids near critical conditions. SPE 64520, the Asia Pacific Oil and Gas Conf., Oct. 16 18, Brisbane, Australia.