Chemical Engineering Science 56 (2001) 68836895

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Hydrate phase diagrams for methane + ethane + propane mixtures

A. L. Ballard, E. D. Sloan Jr.
Center for Hydrate Research, Department of Chemical Engineering, Colorado School of Mines, Golden, CO 80401-1887, USA

Abstract In this work, we present the hydrate phase behavior of methane, ethane, propane, and water systems. Phase diagrams for the ternary and each binary hydrocarbon mixture with excess water have been generated at 277:6 K ( deep sea oor temperature) using a Gibbs free energy minimization ash routine. Each pseudo-binary phase diagram (excluding water) is related to the pseudo-ternary. The main focus is the phase behavior of the pseudo-ternary hydrocarbon mixture around the incipient hydrate formation pressures at 277:6 K. Phase diagrams at this temperature are presented for pressures ranging from 10 to 45 atm. Unexpected phenomena such as the coexistence of hydrate structures, solid melting on pressure increases, and several four phase regions (Lw sIsIIV and Lw sIsIILhc ) were encountered. Similar phenomena may exist when a real natural gas contacts water. ? 2001 Elsevier Science Ltd. All rights reserved.
Keywords: Hydrate; Methane; Ethane; Propane; Phase diagrams; Phase equilibria

1. Introduction Natural gas hydrates are crystalline compounds comprised of water and gas molecules. The hydrate lattice is formed by hydrogen bonding of water molecules to form cages, which are stabilized due to the inclusion of small guest molecules such as methane, ethane, and propane. Hydrates are unusual in that the enclathrated gas molecules are not chemically bonded to the water lattice. Two di erent hydrate structures commonly exist in the presence of small guest molecules; structure I (sI) and structure II (sII). The type of hydrate formed depends on the size of the gas molecules included in the hydrate. In general, small molecules such as methane or ethane form sI hydrates as single guests while larger molecules such as propane form sII hydrates. When sI and sII hydrate formers are in a mixture, it is not easy to generalize which hydrate structure will be present. The type of hydrate that forms will depend on the composition, temperature, and pressure of the system. Natural gas mixtures typically contain greater than 97 mol% methane, ethane, and propane combined. Therefore,
Corresponding author. Tel.: +1-303-273-3723; fax: +1-303273-3730. E-mail address: esloan@gashydrate.mines.edu (E. D. Sloan Jr).

the hydrate phase behavior of a natural gas mixture in contact with water will likely be approximated by that of a simple mixture of methane, ethane, and propane in contact with water. For this reason, we generated phase diagrams with all possible combinations of methane, ethane, and propane at one isotherm, 277:6 K. The phase equilibria of the pure gases in contact with water have been fairly well mapped out both experimentally and computationally. However, binary gas mixtures of methane, ethane, or propane have been studied to a lesser extent. Recently, the phase equilibria of the methane + ethane + water system was investigated (Subramanian, Kini, Dec, & Sloan, 2000a, Subramanian, Ballard, Kini, Dec, & Sloan, 2000b; Ballard & Sloan, 2000a) suggesting unusual behavior such as hydrate structural (sI sII) transitions. The ethane + propane + water system was previously measured by Holder and Hand (1982). Recently, Ballard et al. (2001) suggested hydrate melting with pressure increase for the ethane + propane + water system. These studies show that even simple binary gas mixtures (with excess water) exhibit complex phase equilibria. A ternary gas mixture with excess water may have further complexities. This paper relates the phase equilibria of pure and binary gas mixtures of methane, ethane, and propane in contact with water to the phase equilibria of the ternary

0009-2509/01/$ - see front matter ? 2001 Elsevier Science Ltd. All rights reserved. PII: S 0 0 0 9 - 2 5 0 9 ( 0 1 ) 0 0 3 2 4 - 4

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gas mixture in contact with water at 277:6 K, the most common temperature a natural gas will encounter in a pipeline on the ocean oor at water depths beyond 600 m. The hydrate components of the phase diagrams presented are calculated using the ideal solid solution theory of van der Waals and Platteeuw (1959). However, experimental evidence for the unexpected pseudo-binary behavior has been obtained.

3. Predictions 3.1. Pure gases Experimental data for hydrates of pure gases in contact with water are the most abundant, comprising of nearly 50% of all equilibrium hydrate related data. Of the entire available pure gas hydrate data, the majority are for methane, ethane, and propane hydrates; driven by applications in the energy industry. Although a typical natural gas is mainly comprised of these components, the phase equilibria of each of the rst three normal para ns with water will be quite di erent from that of a natural gas with water. Therefore, the evaluation of phase equilibria of a pure gas hydrate is for fundamental understanding. The hydrate phase equilibria of pure gases with water form the basis for understanding the phase equilibria of water with binary and ternary mixtures of gases. Fig. 1 is the pressure vs. temperature phase diagram for the methane + water system. Note that excess water is present so that, as hydrates form, all gas is incorporated into the hydrate phase. The phase equilibria of methane hydrates are well predicted as can be seen by a comparison of the prediction and data in Fig. 1. It is important to note for later discussions that the predicted hydrate formation pressure for methane hydrates at 277:6 K is 40:06 atm. Fig. 2 is the pressure vs. temperature phase diagram for the ethane + water system. Again, the predictions represent the data well, especially along the Lw sIV

2. Model A multiphase ash routine based on the Gibbs energy minimization method developed by Bishnoi and co-workers (Gupta, 1990; Gupta, Bishnoi, & Kalogerakis, 1991) was used in this work. The method is similar to that of Michelsen (1994) and Avlonitis (1992) in that it stems from the Gibbs energy tangent plane criterion, which enables identication of the phases present at equilibrium without a priori knowledge of the system. This prediction method has been generally used for determining phase amounts and compositions with increases in pressure and temperature (Bishnoi, Gupta, Englezos, & Kalogerakis, 1989). In this work, however, we have extended the use of the predictive method to generate thermodynamic hydrate phase diagrams for mixtures of methane, ethane, propane, and water. Ballard and Sloan (2000b) give a detailed discussion of the method and equations.

1000 Prediction (this work) Roberts et al (1940) Jhaveri and Robinson (1965) Galloway (1970) Deaton and Frost (1946) McLeod and Campbell (1961)

Lw-sI

Pressure (atm)

Verma (1974) de Roo et al (1983) 100 Thakore and Holder (1987) Adisasmito et al (1991)

-V L w-sI

Lw-V

10 273 275 277 279 281 283 285 287 289 291

Temperature (K)
Fig. 1. Pressure vs. temperature diagram for methane + water system.

A. L. Ballard, E. D. Sloan Jr. / Chemical Engineering Science 56 (2001) 68836895

1000 Prediction (this work) Roberts et al (1940) Deaton and Frost (1946) Reamer et al (1952) Galloway et al (1970) 100 Holder and Grigoriou (1980) Holder and Hand (1982) Ng and Robinson (1985) Avlonitis (1988)
c -L h -sI L w L -L w hc

6885

Pressure (atm)

Lw-sI

Lw-V-Lhc
L w-sI-V

10

Lw-V

1 273 275 277 279 281 283 285 287 289 291

Temperature (K)
Fig. 2. Pressure vs. temperature diagram for ethane + water system.

1000 Prediction (this work) Miller and Strong (1946) Wilcox et al (1941) Deaton and Frost (1946) Reamer et al (1952) Robinson and Mehta (1971) Verma (1974) Kubota et al (1972) Thakore and Holder (1987) Patil (1987) Holder and Hand (1982)

Lw-sII-Lhc
Lw-sII

100

Lw-Lhc

Pressure (atm)
10

Lw-V-Lhc
Lw-sII-V
1 273 274 275 276 277 278 279 280

Lw-V

Temperature (K)
Fig. 3. Pressure vs. temperature diagram for propane + water system.

three-phase equilibrium line. Note that the Lw sIV line intersects the Lw VLhc line at 288:1 K and 34:9 atm. Due to di erences in the volume and enthalpy of the vapor and liquid hydrocarbon, the three-phase hydrate formation line changes from Lw sIV to Lw sILhc . Mathematically, this change in the three-phase hydrate formation line can be reconsidered by applying the Clapeyron equation to the phase change (Jager & Sloan,

2001). Note that the hydrate formation pressure for ethane hydrates at 277:6 K is predicted to be 8 atm. Fig. 3 is the pressure vs. temperature phase diagram for the propane + water system. Again, the predictions represent the data well along the Lw sIIV equilibrium line. However, note that the data are quite scattered along the Lw sIILhc line due to di culties in measuring hydrate equilibria with three relatively

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Fig. 4. Pseudo-P-x diagram for methane + propane + water system at 277:6 K.

Lw-sI-V Lw-sI-sII

Deaton and Frost (1946) 41 36 31 Jhaveri and Robinson (1965)

Lw-sII Lw-sI-sII Lw-sI Lw-sII-V

Pressure (atm)

26 21 16

Lw-sI-V
11 6 1 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1

Lw-V

Mole Fraction Methane

Fig. 5. Pseudo-P-x diagram for methane + ethane + water system at 277:6 K.

incompressible phases. As with the ethane + water system in Fig. 2, the slope of the three-phase hydrate formation line changes drastically when the Lw sIIV line intersects the Lw VLhc line. In fact, the Lw sII Lhc line is nearly vertical but comes back to lower temperature at high pressure. The predictions suggest pseudo-retrograde phenomena for the propane hydrates in which the sII hydrate is predicted to dissociate

by pressurization at a constant temperature. For example, at 278:2 K, hydrates form at a pressure of 5 atm and dissociate upon pressurization at 600 atm. A more detailed explanation of the pseudo-retrograde hydrate phenomena can be found in Ballard et al. (2001). Note that the hydrate formation pressure of propane hydrates along the Lw sIIV line at 277:6 K is predicted to be 4:4 atm.

Lw-sI

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19 Holder and Hand (1982)

Lw-sII-Lhc
15 13

Lw-Lhc

17

Lw-sI-Lhc

Lw-sII

Pressure (atm)

Lw-V-Lhc Lw-sI-V Lw-sII-V

11 9 7 5 3 1 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8

Lw-V

0.9

Mole Fraction Ethane

Fig. 6. Pseudo-P-x diagram for ethane + propane + water system at 277:6 K.

3.2. Binary gas mixtures To evaluate the phase equilibria of binary gas mixtures in contact with water, we have computed pseudo-binary pressure vs. water-free composition phase diagrams. Although a binary gas mixture with water is a ternary system, a pseudo-binary phase diagram displays the phase equilibria of the mixture on a water-free basis. That is, water is present in excess throughout the phase diagrams, as detailed by Ballard and Sloan (2000b). Fig. 4 is the pseudo-binary pressure vs. water-free composition diagram for the methane + propane + water system at a temperature of 277:6 K. At 277:6 K the hydrate formation pressures are 4:4 and 40:06 atm for pure propane (sII) and pure methane (sI) hydrates, respectively, as shown at the water-free composition extremes in Fig. 4. As methane is added to pure propane, there will be a composition at which the incipient hydrate structure changes from sII to sI. As seen in the inset of Fig. 4, this composition is predicted to be 0.9995 mole fraction methane in the vapor. In other words, a very small amount of propane added to pure methane gas with water will form sII hydrates. At pressures above incipient hydrate formation conditions, sII hydrates are predicted to be present throughout the entire composition range. Of the possible binary mixture combinations of methane, ethane, and propane, the methane + propane + water system (Fig. 4) is the simplest. Fig. 5 is the pseudo-binary pressure vs. water-free composition diagram for the methane + ethane +

water system at a temperature of 277:6 K. Ballard & Sloan (2000b) supplement the brief review given here. In the diagram, pure ethane and pure methane both form sI hydrates in the presence of water at pressures of 8 and 40:06 atm, respectively. However, it is interesting to note that between the compositions of 0.74 and 0.994 mole fraction methane, sII hydrates form at the incipient formation pressure. These predictions have been conrmed via Raman and NMR spectroscopy (Subramanian et al., 2000a, b). Similar to the methane + propane + water system, only a small amount of ethane added to pure methane will form sII hydrates. At pressures well above the incipient formation pressure, sII hydrates are predicted to be present in the composition range of 0.39 and 0.96 mole fraction methane. Fig. 6 is the pseudo-binary pressure vs. water-free composition diagram for the nal pseudo-binary the ethane (sI) + propane (sII) + water system at a temperature of 277:6 K. Similar to the methane + propane + water system, as ethane is added to pure propane on a water-free basis, the incipient hydrate structure changes from sII to sI for this system at a vapor composition of 0.62 mole fraction ethane. However, a discontinuity in the transition from sII to sI hydrates is encountered. That is, at 0.62 mole percent ethane, the incipient sII hydrate forms at a pressure of 11:3 atm while incipient sI hydrate forms at 12:4 atm. This results in a pressure window of 1 atm in which sII hydrates are predicted to dissociate with pressurization (between 0.32 and 0.62 mole fraction ethane) at constant temperature. This is unusual because, as a general rule-of-thumb, as pressure is

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propane
0 1

0.1

0.9

0.2

0.8

0.3

0.7

0.4

L w -sII

0.6

0.5

0.5

0.6

0.4

0.7

0.3

0.8

L w -sII-V

0.2

0.9

0.1

L w -sI-V
ethane
0 0.1 0.2 0.3
1

L w -V
methane
0.4 0.5 0.6 0.7 0.8 0.9 1
0

Fig. 7. Pseudo-ternary diagram for methane + ethane + propane + water system at 277:6 K and 10 atm.

increased, more hydrate forms. This pseudo-retrograde hydrate phenomenon has been conrmed via experiment and is discussed by Ballard et al. (2001). 3.3. Ternary gas mixture With the phase equilibria of water in contact with the pure and binary gases, the next step is to consider phase equilibria of the ternary gas mixture with water. Pseudo-ternary phase diagrams were created at a temperature of 277:6 K and pressures ranging from 10 to 45 atm. The pseudo-ternary phase diagrams are similar to true ternary phase diagrams except that water is in excess and therefore all compositions are given on a water-free basis. The pseudo-ternary phase diagrams are composites of the phase diagrams discussed earlier: PT diagrams for the pure gases and pseudo-binary diagrams for the binary gas mixtures. That is, the corners represent the intersection of an isotherm and isobar in the pure gas PT diagrams while the edges represent an isobar in the pseudo-binary phase diagrams at 277:6 K. Fig. 7 is a pseudo-ternary phase diagram for the methane + ethane + propane + water system at a temperature and pressure of 277:6 K and 10 atm, respectively. An example of how this diagram is related to the previous diagrams is given. The ethanepropane edge of

the phase diagram in Fig. 7 can be directly compared to the pseudo-binary phase diagram for the ethane + propane + water system in Fig. 6 at a pressure of 10 atm. At 10 atm in Fig. 6, the composition range for the Lw sII phase region is between 0 and 0.16 mole fraction ethane. This is the same composition range for the Lw sII phase region on the ethanepropane edge of Fig. 7. Similar comparisons can be made with each edge of the pseudo-ternary phase diagram and the corresponding pseudo-binary phase diagram. However, the interior of the phase diagram in Fig. 7 cannot be determined by a simple analysis of the pseudo-binary phase diagrams. An example of the procedure to determine the phase equilibria of a given water-free composition of the gas mixture is given. Suppose the water-free composition of the gas mixture is 0.3333 mole fraction for each of the three components. At a temperature and pressure of 277:6 K and 10 atm (Fig. 7), respectively, the overall composition is in the center of the diagram, in the three-phase region (Lw sII V). The tie line (dashed line) in Fig. 7, passing through the overall composition, gives the water-free composition (CH4 , C2 H6 , C3 H8 ) of the sII hydrate (0.39, 0.19, 0.42) and vapor (0.25, 0.58, 0.17) phases. Note that, because this is a pseudo-ternary phase diagram with excess water throughout, as is the case of the other diagrams, the composition of water in any of the phases cannot be determined.

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propane
0 1

6889

0.1

0.9

0.2

0.8

0.3

0.7

0.4

0.6

L w -sII
0.5 0.5

0.6

0.4

0.7

0.3

L w-V
0.8

L w -sII-V

0.2

0.9

L w -sI-V L w -V

0.1

ethane
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1

methane

Fig. 8. Pseudo-ternary diagram for methane + ethane + propane + water system at 277:6 K and 10:9 atm.

The predicted phase diagram in Fig. 7 indicates that sII hydrate is the predominate hydrate that forms. Propane clearly stabilizes the hydrate over a wide composition range. In Fig. 7 four major phase regions appear from the top to the bottom of the diagram: Lw sII, Lw sII V, Lw V, and Lw sIV. Three of the four phase regions contain hydrates and encompass approximately 80% of the overall phase diagram. In other words at a temperature and pressure of 277:6 K and 10 atm, respectively, the likelihood of hydrate formation is large given all possible mixture compositions. As pressure is increased, the likelihood of hydrate formation will be greater. Fig. 8 is the pseudo-ternary phase diagram for the methane + ethane + propane + water system at 277:6 K and 10:9 atm. There are still the same four phase regions present as in Fig. 7. However, the Lw sIIV and Lw sIV phase regions have expanded in size and are nearly intersecting. As pressure is increased further to 11 atm (Fig. 9), the two three-phase regions intersect. The intersection of the two three-phase regions results in two four-phase regions (Lw sIsIIV) and a new three-phase region (Lw sIsII) in which all vapor is consumed by hydrate. Note that the four-phase regions have no tie lines. As explained by Gibbs phase rule, there are two degrees-of-freedom in the system (4 components and 4 phases), which are used by setting the temperature and

pressure. Therefore, if the overall mixture composition puts the system in a four-phase region, the composition of the four phases is the same anywhere within that region. For example, if the overall water-free composition (CH4 , C2 H6 , C3 H8 ) of the feed is (0.25, 0.65, 0.10), the system is in the lower four-phase region of Fig. 9. The water-free composition of the vapor phase is (0.30, 0.59, 0.11), the sI phase is (0.17, 0.83, 0.00), and the sII phase is (0.42, 0.24, 0.34). If the overall water-free composition puts the system anywhere within this four-phase region, the composition of each of the phases will be the same, however the amounts of each phase will change accordingly. The pseudo-retrograde hydrate phenomenon observed in the ethane + propane + water system in Fig. 6 occurs on the pseudo-ternary phase diagram at a pressure of 11:3 atm in Fig. 10. The Lw sIIV and Lw sIV phase regions have grown in size relative to these at 11 atm in Fig. 9 and thus increased the size of the resulting fourand three-phase regions. Of greater interest, however, is the e ect of the pseudo-retrograde phenomenon on the ethanepropane edge. The pseudo-retrograde binary phenomenon disappears when methane is added to ethane + propane + water. The reason for the pseudo-retrograde hydrate phenomenon in the ethane + propane + water system, as described by Ballard et al. (2001), is the intersection of the Lw sIIV and Lw VLhc phase envelopes; creating

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propane
0 1

0.1

0.9

0.2

0.8

0.3

0.7

0.4

0.6

L w-sII 0.5 0.5

L w-sII-V
0.6 0.4

0.7

L w-sII-V
0.3

L w-V
0.8 0.2

0.9

L w-sI-V L w-sI-V

L w-sI-sII-V

L w-sII-V
0.1

ethane
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9

L w-V 1

methane

Fig. 9. Pseudo-ternary diagram for methane + ethane + propane + water system at 277:6 K and 11 atm.
propane
0 1

0.1

0.9

L w -sII-L hc 0.2 L w -L hc 0.3 L w -sII-V-L hc 0.4 L w -V-L hc L w -sII-V

0.5

0.8

0.7

L w -sII
0.6

0.5

0.6

0.4

0.7 Lw-V 0.8

0.3

L w -sI-sII
0.2

I -V

L w -sI-sII-V L w -sII-V
0.1

0.9

w -s

ethane
0 0.1 0.2 0.3 0.4

Lw-sI-V

L w -V
0.5 0.6 0.7 0.8 0.9 1

methane

Fig. 10. Pseudo-ternary diagram for methane + ethane + propane + water system at 277:6 K and 11:3 atm.

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propane
0 1

6891

0.1

0.9

0.2

0.8

L w -sII-L hc
0.3 0.7

L w -L hc
0.4 0.6

L w -sII
0.5 0.5

L w -sI-sII-L hc
0.6 0.4

L w -sI-L hc
0.8

0.7

0.3

L w -sI-sII L w -sI-V
0.2

0.9

L w -sII-V L w -sI-sII-V

L w -V

ethane
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1

methane

Fig. 11. Pseudo-ternary diagram for methane + ethane + propane + water system at 277:6 K and 15 atm.

a four-phase pressure. Gibbs phase rule dictates that this four-phase pressure is unique. Therefore, as pressure is increased, the sII hydrate phase must disappear. Using this explanation as a starting point, we can describe why the pseudo-retrograde hydrate phenomenon does not occur in the quaternary system, methane + ethane + propane + water. Note that the four-phase region Lw sIIVLhc results from the intersection of the Lw sIIV and Lw VLhc phase regions. Since there are four components in this mixture, Gibbs phase rule indicates that there are two degrees-of-freedom (4 components and 4 phases), as opposed to only one degree-of-freedom in the pseudo-binary mixture (ethane + propane + water). Therefore, the four-phase region can exist at multiple pressures. At 15 atm in the pseudo-binary phase diagram for the ethane + propane + water system (Fig. 6), hydrates are present throughout the composition range of 0.0 1.0 mole fraction ethane except for the small region in which only liquid water and liquid hydrocarbon are present. The pseudo-ternary phase diagram at this pressure is shown in Fig. 11. Two four-phase regions are seen at this pressure: Lw sIsIIV and Lw sIsII Lhc . The Lw sIsIIV phase region is the result of the Lw sIV and Lw sIIV phase regions intersecting, while the Lw sIsIILhc phase region is due to the intersection of the Lw sILhc and Lw sIILhc phase regions. Note that the Lw Lhc phase region seen in Fig. 6 does not extend into the pseudo-ternary

phase diagram in Fig. 11. Hence, as methane is added to the ethane + propane + water mixture, sII hydrates form. In fact, at 277:6 K and 15 atm, sII hydrates are predicted to form at nearly any methaneethanepropane mixture composition. However, for compositions rich in ethane ( 40 mol%), sI hydrates are predicted to coexist in equilibrium with sII. Note that the pseudo-binary phase diagram for the methane + ethane + water system shown in Fig. 5 does not show sI and sII hydrates coexisting at 277:6 K and 15 atm. Hence, as small amounts of propane are added to the methane + ethane + water mixture, sII hydrates form resulting in the large Lw sI sII phase region shown in Fig. 11. As discussed, the reason for the four-phase region, Lw sIsIIV, in Fig. 11 is due to the intersection of the two three-phase regions, Lw sIV and Lw sIIV. The Lw sIV phase region extends into the pseudo-ternary phase diagram from the pseudo-binary methaneethane edge. At 15 atm, the pseudo-binary in Fig. 5 clearly shows a Lw sIV region. However, as pressure is increased to 16:5 atm, the Lw sIV phase region is replaced with Lw sIsII and Lw sIIV phase regions. Fig. 12 shows the impact of the pseudo-binary phase diagram on the pseudo-ternary diagram. Near the methaneethane edge, the four-phase region, Lw sIsIIV, is no longer present. Note that the remainder of the phase diagram is essentially identical to that in Fig. 10. In fact, all phase regions without a vapor phase present will not change

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propane
0 1

0.1

0.9

L w -sII-L hc L w -L hc L w -sI-sII-L hc
0.4 0.3

0.2

0.8

0.7

0.6

0.5

L w -sII

0.5

0.6

0.4

L w -sI-L hc 0.7
0.8

0.3

L w -sI-sII

0.2

0.9

L w -sII-V

L w -V
0

ethane
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1

methane

Fig. 12. Pseudo-ternary diagram for methane + ethane + propane + water system at 277:6 K and 16:5 atm.

signicantly with pressure. Each phase present in these regions (Lw , sI, sII, Lhc ) are essentially incompressible and therefore change very little with pressure. The vertical lines in the pseudo-binary phase diagrams are representative of this. The only phase regions in Fig. 12 that have compressible phases (i.e. vapor) are near the pure methane corner. Therefore, as pressure is increased, the only signicant change in the pseudo-ternary phase diagram will be near that corner. Fig. 13 is the pseudo-ternary phase diagram at 38:5 atm. As expected, the incompressible phase regions remain the same while the Lw sIIV phase region is smaller. Evaluation of Figs. 4 and 5 near the pure methane axis give evidence of this as well. As the pressure is increased beyond 38:6 atm, which is the pressure at which a Lw sIV phase region appears in the pseudo-binary phase diagram for the methane + ethane + water system, another four-phase region, Lw sI sIIV, appears in Fig. 14 (P = 39 atm). This four-phase region appears as the result of the Lw sIV and Lw sIIV phase regions intersecting. Since only a small fraction of the phase diagram is di erent from Fig. 13, only the phase regions near high methane concentrations are shown in Fig. 14. Note the small region near the pure methane corner in which only liquid water and vapor are present. This diagram indicates that, at 277:6 K and 39 atm, if pure methane in contact with water is contaminated with any mixture of ethane and propane by as little as 0.005 mole fraction in the vapor, hydrates will form.

The highest pressure in which a Lw sIV phase region is present is 40:09 atm and it last occurs in the methane + propane + water pseudo-binary phase diagram in Fig. 4. Therefore at pressures higher than 40:09 atm, there will no longer be a Lw sIsIIV four-phase region. Fig. 15 is the pseudo-ternary phase diagram at 277:6 K and 45 atm. Hydrates are predicted to be present throughout the entire composition range except along the ethane + propane + water edge. sII hydrates are present in over 90% of the diagram while sI hydrates in over 60% of the diagram. Since all phase regions present in this gure are incompressible, the phase diagrams at higher pressures do not change signicantly. 4. Implications The methane + ethane + propane + water system is the simplest approximation of a natural gas mixture. As shown in Figs. 715, the phase equilibria of such a simple mixture is quite complicated at pressures above incipient hydrate formation conditions. The two most interesting phenomena found are the coexistence of sI and sII hydrates and the lack of the pseudo-retrograde phenomenon in the interior of the pseudo-ternary phase diagrams. These two phenomena could have industrial implications as indicated in the below paragraphs.

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propane
0 1

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L w -sII-L hc L w -L hc L w -sI-sII-L hc 0.4

0.3 0.7

0.6

0.5

0.5

0.6

0.4

L w -sII
0.7 0.3

0.8

L w -sI-sII

0.2

L w -sI-L hc
0.9

L w -V L w -sII-V

ethane
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1

methane

Fig. 13. Pseudo-ternary diagram for methane + ethane + propane + water system at 277:6 K and 38:5 atm.
propane
0.08

0.05

L w -sII

L w -sII-V L w -sI-V L w -V L w -sI-sII

ethane
0.9 0.95 1

Lw -sI-sIIV

methane

Fig. 14. Pseudo-ternary diagram for methane + ethane + propane + water system at 277:6 K and 39 atm (note the expanded scale).

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A. L. Ballard, E. D. Sloan Jr. / Chemical Engineering Science 56 (2001) 68836895

propane
0 1

0.1

0.9

L w -sII-L hc L w -L hc L w -sI-sII-L hc
0.4 0.3

0.2

0.8

0.7

0.6

0.5

0.5

0.6

L w -sII

0.4

0.7

0.3

0.8

L w -sI-sII

0.2

L w -sI-L hc
0.9 0.1

L w -sI-sII
ethane
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
1

methane

Fig. 15. Pseudo-ternary diagram for methane + ethane + propane + water system at 277:6 K and 45 atm.

Hydrates in the permafrost and beneath the sea oor are formed from nearly pure methane and are therefore assumed to be sI hydrates. Calculations of the amount of methane gas trapped in these in situ hydrates are based on this assumption. At low pressures, as little as a 0.005 mole fraction contamination of ethane and propane could force the stable hydrate to be sII. At higher pressures, any contamination of ethane and=or propane ( 0:005) will force the sII hydrates to be in equilibrium with sI hydrates. The amount of methane trapped in sI hydrates vs. sII hydrates is di erent (Subramanian et al., 2000b) and the incorrect assumed structure could signicantly a ect the calculations for the amount of methane trapped in natural hydrates. Chemicals such as kinetic inhibitors or anti-agglomerates are added to natural gas pipelines to prevent hydrate plugs. Kinetic inhibitors are designed to slow hydrate formation kinetics while anti-agglomerates are designed to prevent hydrate particles from agglomerating. Typical natural gas hydrates are assumed to be sII and therefore these chemicals are designed to prevent sII hydrates from plugging a pipeline. Fig. 15 suggests that if a natural gas mixture is rich in methane or fairly rich in ethane, sI and sII hydrates will coexist. Therefore, a kinetic inhibitor or anti-agglomerate may prevent the sII hydrates from plugging the pipeline but not the sI hydrates. Since most natural gases are rich in methane, it is not likely that the pseudo-retrograde hydrate phenomena

will occur in a natural gas pipeline. However, in a gas mixture with very little methane, such as the bottoms product of a demethanizer, the pseudo-retrograde hydrate phenomenon could be possible. This suggests that a demethanizer bottoms product pipeline could be operated at pressures above the incipient hydrate formation pressure without hydrate formation. Similarly, if a hydrate plug formed in such a pipeline, the hydrates might be dissociated by pressurization of the pipeline, whereas, hydrates are normally dissociated via pipeline depressurization.

5. Conclusions Pure, pseudo-binary, and pseudo-ternary hydrate phase diagrams have been generated using a Gibbs energy minimization method, and links between them have been made. It is likely that the pseudo-ternary phase diagrams give an approximation of the phase equilibria of a real natural gas. Coexistence of sI and sII hydrates over a wide composition range is predicted and could have importance in both natural hydrates and natural gas pipelines. It is also predicted that the pseudo-retrograde hydrate phenomena found in the ethane + propane + water system will not occur in a natural gas containing signicant amounts of methane.

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Acknowledgements This work was funded by a consortium of oil companies; ARCO, Chevron, Department of Energy, Halliburton, Mobil, Petrobras, Phillips, Shell, and Texaco. The authors would like to thank Dr. Bishnoi of the University of Calgary and Dr. Luks of the University of Tulsa for their valuable advice.
References
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