Measurement of H–LW–V and Dissociation Enthalpy of Carbon

Article pubs.acs.org/jced

Measurement of H−LW−V and Dissociation Enthalpy of Carbon Dioxide Rich Synthetic Natural Gas Mixtures Khalik M. Sabil,*,†,§ Qazi Nasir,‡ Bezhad Partoon,‡,§ and Akbar A. Seman∥ †

Institute of Petroleum Engineering, Heriot-Watt University Malaysia, No. 1, Jalan Venna P5/2, Precinct 5, 62200 Putrajaya, Malaysia Department of Chemical Engineering, Universiti Teknologi PETRONAS Bandar Seri Iskandar, 31750, Perak, Malaysia § Phase Separation Laboratory, Research Center for CO2 Capture (RCCO2C), Universiti Teknologi PETRONAS, Bandar Seri Iskandar, 31750, Perak, Malaysia ∥ CO2M R&D, PETRONAS Research Sdn Bhd (PRSB), Bangi, 43000, Kajang, Selangor, Malaysia ‡

S Supporting Information *

ABSTRACT: In this work, hydrate−liquid water−vapor (H−LW−V) equilibrium data for methane (CH4), carbon dioxide (CO2), and four synthetic carbon dioxide (CO2) rich natural gas mixtures are measured. The measured pressure and temperature are in the range of (1.10 to 15.29) MPa and (272.15 to 290.15) K, respectively. In addition, a thermodynamic model based on Peng−Robinson (PR) EoS coupled with van der Waals−Platteeuw and modified Krichevsky and Kasarnovsky (KK) equation has been used for prediction of the equilibrium condition. The comparison between experimental measurements and model prediction shows excellent agreement obtained with an absolute average error of temperature (AAE) as low as 0.09. Additionally, the enthalpy of dissociation for simple and mixed gas hydrates is estimated using the measured equilibrium data by applying the Clausius−Clapeyron equation.

1. INTRODUCTION As the market price of natural gas increases and its resources are limited, efforts are placed to produce natural gas from carbon dioxide (CO2) rich gas reservoirs. These types of gas reservoir exist throughout the globe. The biggest reservoirs among them are located in Europe,1,2 South America,1 North America,3 and Asia.1,2,4 For example, the El Trapial Field in Argentina produces gas that contains as much as 0.75 in mole fraction of CO21,5 whereas the Changshen gas reservoir in China has CO2 content that varies between (5 to 98) %.3 Among Southeast Asia regions, Indonesia, Malaysia, and Thailand are known to have reservoirs with CO2 content more than 0.50 in mole fraction. The Tugu Barat Field in West Java and the Natuna Field, Indonesia, produce gas contains (0.71 to 0.76) in mole fraction of CO2.6 The northwestern part of the Erawan Field in Thailand produces gas that contains up to 0.60 in mole fraction of CO2.7 In Malaysia, the K5 Field, located offshore of Sarawak shows evidence to contain gas reserves of more than 0.70 in mole fraction CO2. The gas produced from CO2 rich reservoirs is neither marketable nor suitable to be used as feed for an LNG plant and needs to be treated to reduce the CO2 content. One of the main concerns for the production of natural gas from CO2 rich gas is the susceptibility of the gas to form gas hydrate. Gas hydrate is an ice like inclusion compound formed when molecules of low molecular weight gas or volatile liquid are trapped by cavities formed by water molecules at © XXXX American Chemical Society

appropriate pressure and temperature conditions. Light components typically found in natural gas such as methane (CH4), ethane (C2H6), propane (C3H8), isobutene (i-C4H10), carbon dioxide (CO2), and nitrogen (N2) can form gas hydrate when temperature and pressure conditions favor its formation. For deep water operation, the temperature and pressure conditions that favor the formation of gas hydrate may be encountered in a portion of the gas pipeline8 or at the separation facilities. It is well-known that CO2 is more favorable to form gas hydrate compared to CH4 since at any given pressure, the equilibrium temperature of CO2 hydrate is higher than that of CH4. With the increase of CO2 concentration to as high as 0.70 in mole fraction, the pipeline and separation process of the CO2 rich natural gas are more vulnerable for gas hydrate formation. One of the best prevention methods to avoid the formation of gas hydrate is to ensure that the operating conditions of the pipeline and top facilities are set above the gas hydrate forming region. For this purpose, the precise data for gas hydrate equilibria are crucial. In literature, a wide range of reported data is available for synthetic natural gas mixtures of binary component such as CH4−CO2 with various concentrations,9−15 and for ternary component of CH4−CO2−X where the Received: May 22, 2014 Accepted: September 8, 2014

A

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wire thermometer probe (Pt-25 Ω, a Tinsley precision instrument) according to 1990 International Temperature Scale (ITS-90) standard. Pressure, temperature, and volume are measured and recorded continuously in 2 s interval with an accuracy of ± 0.1 K, ± 0.01 MPa, and ± 0.001 cm3, respectively. The equilibrium cell in immersed in thermostatic bath. Ethanol is used as refrigerant liquid, and the temperature is controlled using Lauda + DLK45 thermostats. A magnetic torque stirrer is placed inside the equilibrium cell to achieve proper mixing of sample. The stirrer can be operated up to 2000 rpm. The gas sample in the mixed tank is transferred to the equilibrium cell using Haskel AG-303 air driven booster compressor with maximum outlet pressure of 31 MPa. Liquid water is injected into the equilibrium cell using a variable volume displacement manual pump. Furthermore, a video recorder with image enlargement options is used to visually monitor any changes to the sample placed in the equilibrium cell. 2.3. Experimental Method. A T-cycle method with isochoric step heating technique is employed in this work.31 Before the experiment begins, the sapphire cell is thoroughly washed with deionized water, dried, and vacuumed. The equilibrium cell is immersed into thermostatic bath, where the temperature of thermostatic bath is controlled by circulating ethanol as a refrigerant liquid. The cell is charged with 25 cm3 of deionized water followed by the selected gas sample and pressurized to the required pressure setting. The overall gas composition of the system is fixed as the system is a closed system. Once the system is stabilized, the stirrer is set at 600 rpm, and the mixture is stirred to ensure proper mixing. Then, the temperature of the system is reduced stepwise until gas hydrate is formed. During the formation process, the rapid pressure drops indicates the consumption of gas during formation is confirmed with the visual observation obtained. Once the hydrate is fully formed and pressure stabilized, the cell is heated up by increasing the temperature of the system with a stepwise method of 0.5 K/step. The length of each step varies between (2 to 4) hours maximum based on the stability of pressure and temperature. Finally the P−T diagram for hydrate formation and dissociation is plotted. The hydrate equilibrium point is taken at the first point where the heating curve meets with the cooling curve. Since the equilibrium point is taken at the point when the last particle of hydrate is completely dissociated, the overall composition of the individual gas component is also used to fix the degree of freedom of the system together with pressure and temperature when necessary.

concentration of CO2 varies with combination of the X component.16−18 However, most of these data are limited to CO2 concentration of less than 20 %.19−26 Among the reported data, only Wilcox et al.,27 Ng and Robinson,28 and Adisasmito et al.29 reported data for synthetic natural gas with concentration of CO2 ranging more than 25 %. Although these data are adequate to be used to evaluate gas produced from conventional reservoirs, they are insufficient for the gas produced from CO2 rich reservoirs. Therefore, there is an urgent demand for gas hydrate equilibrium data for CO2 rich natural gas. In this work, phase equilibrium measurements have been performed on four different synthetic CO2 rich natural gas mixtures as well as CH4 and CO2 systems. The gas mixtures are binary, ternary, and multicomponent with CO2, CH4, and alkane up to n-butane. The hydrate equilibrium conditions are measured in a temperature and pressure range of (272.15 to 290.15) K and (1.10 to 15.29) MPa, respectively. A thermodynamic model based on PR-EoS coupled with van der Waals−Platteeuw is used to model the H−LW−V equilibrium line. The solubility of CO2 in water is calculated by using the modified Krichevsky and Kasarnovsky (KK) equation proposed by Nasrifar and Moshfeghian.30 In addition, the dissociation enthalpy of each system is calculated by employing the indirect method.

2. EXPERIMENTAL SECTION 2.1. Materials. In this work, methane (≥ 99.9 % pure), carbon dioxide (≥ 99.9 % pure), and four carbon dioxide rich synthetic natural gas mixtures are purchased from gas walkers SDN BHD. The composition of these gases in molar basis is given in Table 1. All gases are used without further purification. Table 1. Composition of Gas Mixture (Mole Fraction) Used in This Work component

Mix-A

Mix-B

kMix-C

Mix-D

CO2 N2 CH4 C2H6 C3H8 i-C4H10 n-C4H10 average molecular weight gas gravity

0.72490 0.27510

0.70350 0.03096 0.26550

0.69220 0.03090 0.26460 0.00943 0.00288

36.32 1.25

35.68 1.23

35.59 1.23

0.69103 0.03100 0.26197 0.00900 0.00300 0.00200 0.00200 35.67 1.23

Deionized water is used in all experiments. The overall global composition of system contains gases + water is used in each experimental run (Supporting Information). 2.2. Apparatus. Equilibrium cell, a mercury-free PVT apparatus, specifically designed to study gas hydrate equilibrium conditions, is employed in this work. The schematic diagram of experimental equipment used in this study is shown in Figure 1. The setup consists of a sapphire cell with an internal volume of 60 cm3. The apparatus can be operated up to 20 MPa in a temperature range of (253.15 to 338.15) K. The pressure inside the equilibrium cell is measured with pressure transducer (model PAA-33X/80794) and calibrated according to the secondary standard provided by the CTP Armines-Mines Paristech Research Centre. The temperature inside the equilibrium cell is measured by platinum resistance (Pt-100 Ω) thermometer probes and calibrated against a reference four

3. THERMODYNAMIC MODEL The modified model of Holder et al.32 based on classical model of van der Waals and Platteeuw is used in this work to model the hydrate −liquid water−vapor (H−LW−V) equilibrium line. In addition, the Peng−Robinson equation of state (PR-EoS) with combination of classical mixing rules is used to calculate the fugacity of the gas phase,33 whereas the binary interaction between hydrocarbon and nonhydrocarbon are taken from Aspen Plus (Supporting Information). The three Kihara parameters used to describe the gas−water interaction including the molecular distance σ, depth of binary potential well with unit of energy ε, and the gas molecules core radius, α, are optimized. In this work, “fminsearch” minimization method of MATLAB is utilized to obtain the Kihara parameter of guest molecules. The parameters are fitted to all measured data of B

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Figure 1. Schematic diagram of experimental apparatus.

CO2 in water is relatively high as compared to other components. Therefore, the solubility of CO2 is corrected by using a modified form of KK equation as proposed by Nasrifar and Moshfeghian.30

single and multicomponent hydrate phase behavior using the following objective function: AADT =

1 NP

NP

∑ Dev (1)

i=1

4. RESULTS AND DISCUSSION 4.1. Hydrate−Liquid Water−Vapor (H−LW−V) Equilibrium Data. 4.1.1. Simple Methane (CH4) and Carbon Dioxide (CO2) Hydrates. To verify the accuracy of the experimental apparatus and procedures adapted in this work, the H−LW−V equilibrium lines of simple CH4 and CO2 hydrate systems are measured and compared with literature data.14,34−38 The H−LW−V for CH4 is measured with temperature and pressure ranges of (280.15 to 288.65) K and (5.55 to 15.29) MPa, while for CO2 are (272.65 to 281.45) K and (1.10 to 3.38) MPa, respectively. These data are presented in Table 3 and illustrated together with the predictions based on the developed model in Figure 2 and Figure 3, respectively. As depicted in these figures, the data measured in this work agree very well with earlier reported data in the whole region where a comparison could be made. It should be emphasized that the reproducibility of the hydrate equilibrium conditions reported in this work is very good. Satisfactory predictions are made using the developed model for H−LW−V of CH4 and CO2 systems with AAE of 0.72 and 0.09, respectively. The results also show that the correction on solubility of CO2 in water using the modified KK equation significantly improves the accuracy of the prediction for CO2 hydrate system.

where Dev = 100·

Tcal − Texp Texp

(2)

and NP is the number of experimental data points. The values of the optimized parameter used in this work are presented in Table 2. The gas mixtures used in this work contain relatively high carbon dioxide (CO2) content, which means the solubility of Table 2. Optimized Kihara Parameters (Radius of Spherical Core a, Core Distance σ, and Maximum Attractive Potential ϵ·κ−1) Used in This Work comp

a/nm

σ/nm

ϵ·κ−1/K

CH4 C2H6 C3H8 i-C4H10 n-C4H10 N2 CO2

0.030 0.040 0.068 0.080 0.094 0.035 0.072

0.324 0.329 0.330 0.312 0.313 0.322 0.301

153.2 175.0 201.0 220.5 177.9 128.0 171.9 C

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Table 3. Hydrate−Liquid Water−Vapor (H−LW−V) and Enthalpy (ΔH) of Methane (CH4) and Carbon Dioxide (CO2) Systems at Pressure P, Temperature T, and Compressibility Factor za simple CH4 hydrate P/MPa

T/K

z

5.55 6.41 7.27 8.07 10.61 10.90 11.70 12.28 15.29

280.15 281.25 282.55 283.45 285.95 286.45 287.05 287.45 288.65

0.86 0.85 0.83 0.82 0.79 0.79 0.79 0.78 0.77

average a

simple CO2 hydrate −1

ΔH/kJ·mol 58.46 56.95 55.39 54.30 51.68 51.27 50.79 50.51 50.27

P/MPa

T/K

z

ΔH/kJ·mol−1

1.10 1.22 1.64 1.75 2.01 2.41 2.56 2.60 2.84 3.06 3.38

272.65 273.45 275.75 276.25 277.35 278.75 279.25 279.35 280.05 280.65 281.45

0.90 0.90 0.88 0.87 0.86 0.83 0.81 0.81 0.79 0.77 0.74

67.8 69.6 68.9 67.7 65.6 64.1 69.2 70.1 68.1 63.8 59.7 66.8

53.29

Standard uncertainties u are ur(P) = 0.01 MPa and ur(T) = 0.1 K.

4.1.2. Mixed Hydrates. For the synthetic CO2 rich natural gas mixtures, the measured equilibrium data are presented in Table 4. For Mix-A, the equilibrium data are collected within temperature and pressure ranges of (280.35 to 287.95) K and (2.76 to 11.28) MPa, respectively. Similarly, Mix-B data are collected within temperature and pressure ranges of (280.65 to 289.86) K and (2.71 to 12.10) MPa, while those for Mix-C data are collected within temperature and pressure ranges of (281.55 to 289.80) K and (2.84 to 10.30) MPa. Lastly, the data for MixD are measured within temperature and pressure ranges of (283.45 to 290.15) K and (3.76 to 12.50) MPa. The data together with the predictions of the developed model are illustrated in Figure 4, respectively. As depicted in Figure 4, an excellent agreement between measured and developed model prediction is achieved in the pressure and temperature range. The average absolute errors (AAE) between the measured and predicted data are tabulated in Table 5, and the values are calculated by using the following equation:

Figure 2. Experimental and predicted hydrate−liquid water−vapor (H−LW−V) condition of methane (CH4): ●, this work; ⧫, Hachikubo et al.,14 ∗, Nakmura et al.,34 □, Kharrat et al.;35 ▲, Mohammadi et al.,36 and , prediction.

*AAE =

1 NP

NP

∑ |Texp − Tcal| i=1

NP = number of data points

(3)

To further demonstrate the applicability of the developed model, the model predictions have been compared with some literature data for relatively high CO2 gas mixtures.10,29,39,40 The AAE is calculated and presented in Table 6. As shown in Table 6, the prediction of the developed model agrees well with the experimental data with AAE ranges from (0.02 to 0.48) K for systems of CO2 + CH4 and CO2 + CH4 + C2H6 + N239 with CO2 concentration ranges from (0 to 1) in mole fraction. Similarly, for the system of CO2 + CH4 + C2H6 + C3H8 + iC4H10 + n-C4H1029 with five different compositions, the prediction of developed model agrees well with the experimental data with a combined AAE of 0.22 K. 4.2. Enthalpies of Dissociation of Simple and Mixed Hydrates. In this work, te Clausius−Clapeyron equation is used to calculate the enthalpy of dissociation (ΔH) of gas hydrate. In order to take into account on the gas compressibility, the compressibility factor, z, is calculated for each equilibrium data point. The results for ΔH and z for CO2 and CH4 systems are tabulated in Table 3. Analysis of the data

Figure 3. Experimental and predicted hydrate−liquid water−vapor (H−LW−V) condition of carbon dioxide (CO2): ●, this work; ×, Hachikubo et al.;14 ▲, Robinson et al.;37 ○, Mohammadi et al.;36 ∗, Sabil et al.38 and , prediction.

D

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z

68.60 65.50 68.80 69.10 67.60 63.50 59.20 55.50 53.20 49.60 68.60 60.41 0.79 0.73 0.84 0.82 0.76 0.68 0.60 0.51 0.46 0.38 0.37 280.95 281.85 283.45 284.35 285.55 286.35 287.55 288.35 288.76 289.35 290.15 2.75 3.12 3.76 4.30 4.80 5.46 6.64 7.80 8.47 9.87 12.5 63.98

68.80 68.40 65.10 62.60 60.80 58.20 0.84 0.77 0.66 0.55 0.46 0.38 281.55 284.25 287.15 288.35 289.00 289.80

Table 5. Absolute Average Error (AAE) Obtained for Pure and Multicomponent Mixtures at Pressure P system

2.84 4.10 5.90 7.40 8.60 10.30

CH4 CO2 Mix-A Mix-B Mix-C Mix-D

60.69

69.80 69.90 67.80 63.60 56.40 50.50 46.80

65.24

Standard uncertainties u are ur(P) = 0.01 MPa and ur(T) = 0.1 K.

average

a

72.3 71.2 68.2 61.3 53.2 280.35 283.15 284.75 286.35 287.95 2.76 3.92 5.12 7.56 11.28

0.84 0.77 0.70 0.50 0.34

ΔH/kJ·mol z T/K P/MPa

P/MPa (5.55 (1.34 (2.76 (2.71 (2.84 (2.75

to to to to to to

15.29) 4.03) 11.28) 12.10) 10.30) 12.50)

data points

*AAE/K

9 11 5 7 6 11

0.72 0.09 0.36 0.17 0.14 0.15

shows that ΔH is strongly related to z where both ΔH and z change with same order of magnitude. The observation is supported by Skovborg and Rasmussen,41 who stated that for a slope of ln P vs 1/T to be constant, these values must display the same order of magnitude. For comparison, the calculated enthalpy of dissociation for simple CH4 and CO2 hydrates are compared with those reported in literature42−52 and tabulated in Table 7. The calculated value of ΔH for CH4 and CO2 agrees very well with reported data. The Clausius−Clapeyron equation is further utilized to calculate the hydrate enthalpy of dissociation of the gas mixtures. By imposing a hypothetical condition of no water/gas or gas/gas interaction in the hydrate crystals and assuming an ideal solution, the enthalpy of dissociation of mixed gas can be calculated using the method adopted from Sarshar et al.53 Through superimposed of the H−LW−V equilibrium data of pure components and the gas mixtures, the enthalpy of dissociation can be estimated by plotting ln P vs 1/T as adopted previously for simple hydrates. Since gas mixtures used in this study contain ethane, propane, n-butane, iso-butane, and nitrogen, the three-phase H−LW−V equilibrium data of these pure components are obtained from literature.54,55 The calculated enthalpy of dissociation and compressibility factor for Mix-A, Mix-B, Mix-C, and Mix-D is tabulated in Table 4. The average value of enthalpy of dissociation for Mix-A, Mix-B, Mix-C, and Mix-D are (65.24, 60.69, 63.98, and 60.41) kJ· mol−1, respectively. By comparing the values to that of listed in Table 7, the enthalpy of dissociation of these mixed hydrates is

0.85 0.79 0.73 0.66 0.48 0.38 0.37 280.65 283.05 284.95 286.65 288.35 289.35 289.86 2.71 3.80 4.85 5.98 8.45 10.50 12.10

P/MPa

T/K

Mix-B

z

ΔH/kJ·mol

−1

P/MPa

T/K

Mix-C

z

ΔH/kJ·mol

−1

P/MPa

T/K

Mix-D

Article

Figure 4. Experimental and predicted hydrate−liquid water−vapor (H−LW−V) of the synthetic natural gas mixtures: ●, measured data and , prediction.

−1

Mix-A

Table 4. Hydrate−Liquid Water−Vapor (H−LW−V) and Enthalpy (ΔH) for the Gas Mixtures at Pressure P, Temperature T, and Compressibility Factor za

ΔH/kJ·mol−1

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Table 6. Comparison of Average Absolute Error (AAE) of Hydrate Equilibrium Dissociation Conditions at Pressure P and Temperature T Using the Developed Model system CH4 + CO2

CO2 + CH4 + C2H6 + N2 CO2 + CH4 + C2H6 + C3H8 + i-C4H10 + n-C4H10

dissociation condition P and T

NP

CO2 mole fraction

AAE/K

reference

(273.70 to 287.60) K (2.52 to 10.95) MPa (273.50 to 282.30) K (1.10 to 4.80) MPa (273.56 to 283.26) K (1.50 to 5.00) MPa (272.8 to 279.3) K (1.16 to 2.77) MPa (273.70 to 282.00) K (0.50 to 3.51) MPa

42

0.08 to 0.85

0.09

10

9

0.97

0.48

39

16

0.00 to 1.00

0.02

40

5

0.89

0.06

39

20

0.00 to 0.90

0.22

29

Table 7. Reported Values of the Enthalpies of Dissociation (ΔH) for Simple Methane (CH4) and Carbon Dioxide (CO2) Hydrate at Temperature T simple CH4 hydrate reference 42

ΔH/kJ·mol−1

T/K

simple CO2 hydrate method

54.19

273.15

calorimeter

45

53.81

273.15

Rueff et al.46

54.67

285.00

Clausius−Clapeyron equation calorimeter

Lievois et al.47 Kang et al.43

57.65

278.15

56.84

Anderson49 this work

Handa

Yoon et al.

reference

T/K

method

Delahaye et al.44 Sabil et al.52

65.22

280.30

DSC

67.42

273.15 to 282.06

Yoon et al.45

57.66

Q1

calorimeter

Kang et al.43

65.22

273.65

Clausius−Clapeyron equation Clausius−Clapeyron equation Calorimeter

274.15

microcalorimeter

Long51

73.00

53.5

273.15

Clapeyron equation

Kamath50

80.10

53.29

280.15 to 288.65

Clausius−Clapeyron equation

Anderson49

58.20 to 62.50

282.15 to 274.15

Clausius−Clapeyron equation Clausius−Clapeyron equation Clapeyron equation

this work

66.8

272.65 to 281.45

■

in the range of that of simple CO2 hydrate. Since these gases contain more than 0.69 in mole fraction of CO2, it is highly possible that the mixed hydrate formed from these gases is mainly consisting of CO2.

Clausius−Clapeyron equation

AUTHOR INFORMATION

Corresponding Author

*Phone: +603 88810918. Fax: +60388810194. E-mail: k. [email protected]. Funding

5. CONCLUSION

The authors are grateful for PETRONAS for the financial assistance through YUTP and PRF research grants.

In this work new experimental hydrate equilibrium H−LW−V data for pure CH4, pure CO2, and synthetic CO2-rich natural gas mixture have been reported. A thermodynamic model has been developed to predict the equilibrium condition. A good agreement is obtained between the measured and the predicted data for all systems studied. In addition, the enthalpy of dissociation for the gas hydrates is calculated by using the Clausius−Clapeyron equation. For simple CH4 and CO2 hydrates, the results are in agreement with reported literature data. For the high CO2 gas mixtures, the calculated enthalpy of dissociation indicates mainly CO2 is present in the gas hydrates.

■

ΔH/kJ·mol−1

Notes

The authors declare no competing financial interest.

■

REFERENCES

(1) Riedel, M.; Bahk, J. J.; Kim, H. S.; Scholz, N. A.; Yoo, D. G.; Kim, W. S.; Ryu, B. J.; Lee, S. R. Seismic Facies Analyses as Aid in Regional Gas Hydrate Assessments Part-II: Prediction of Reservoir Properties, Gas Hydrate Petroleum System Analysis, and Monte Carlo Simulation. Mar. Pet. Geol. 2013, 47, 269−290. (2) Eslamimanesha, A.; Mohammadia, H. A.; Richona, D.; Naidoob, P.; Ramjugernath, D. Application of Gas Hydrate Formation in Separation Processes: A Review of Experimental Studies. J. Chem. Thermodyn. 2012, 46, 62−71. (3) Boswell, R.; Collett, T. S.; Frye, M.; Shedd, W.; McConnell, D. R.; Shelander, D. Subsurface Gas Hydrates in the Northern Gulf of Mexico. Mar. Pet. Geol 2012, 34, 4−30. (4) Klauda, J. B.; Sandler, S. I. A Fugacity Model for Gas Hydrate Phase Equilibria. Ind. Eng. Chem. Res. 2000, 39, 3377−3386. (5) Burgers, W.; Northrop, P.; Kheshgi, H.; Valencia, J. Worldwide Development Potential for Sour Gas. Energy Proc. 2011, 4, 2178− 2184.

ASSOCIATED CONTENT

S Supporting Information *

Detailed description of the binary interaction parameters and global feed composition used in this work tabulated in Table S1 and Table S2. This material is available free of charge via the Internet at http://pubs.acs.org. F

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