Article

Cite This: J. Chem. Eng. Data XXXX, XXX, XXX−XXX pubs.acs.org/jced

Hydrate Phase Equilibria of Methane + Mixed (TBAB + THF) in the

Presence and Absence of NaCl and/or MgCl2 Aqueous Solutions
Hassan Pahlavanzadeh,*,† Mohammad Pourranjbar,† Ali Askari Zadeh Mahani,‡
and Amir H. Mohammadi§
†
Faculty of Chemical Engineering, Tarbiat Modares Unversity, Tehran 14115-114, Iran
‡
Department of Chemical Engineering, Faculty of Engineering, University of Qom, Qom 3716146611, Iran
§
Discipline of Chemical Engineering, School of Engineering, University of KwaZulu-Natal, Howard College Campus, King George
V, Avenue, Durban, South Africa
See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.

ABSTRACT: Available water for the formation of natural gas hydrate at

the industrial scale is normally saline water in which the dissolved salts
Downloaded via UNIV TWENTE on December 24, 2019 at 05:39:23 (UTC).

inhibit the hydrate formation. To overcome this challenge, thermody-

namic promoters can be used. In the present work, hydrate phase
equilibria of methane + mixed promoters of tetrahydrofuran (THF) and
tetra-n-butyl ammonium bromide (TBAB) were investigated in the
absence and presence of NaCl, MgCl2, and NaCl + MgCl2 aqueous
solutions. The phase equilibrium data, which were generated using an
isochoric pressure-search method with a step heating technique, are
reported in the pressure and temperature ranges of 1.09−5.16 MPa and
286.0−299.0 K, respectively. Equilibrium data show that an aqueous
mixture of THF + TBAB (0.15 + 0.05 mass fractions) in the presence of
NaCl systems is a more effective promoter compared to a single
promoter TBAB or THF even at a high concentration of about 0.2 mass
fraction.

1. INTRODUCTION
Clathrate hydrates, or gas hydrates, are ice-like crystalline
compounds formed by entrapping some specific molecules
such as methane and carbon dioxide (called guest molecules)
in the cages made of water molecules (called host molecules).1
Hydrates are typically formed at low temperatures and high
pressures. Gas hydrates at first appeared as an annoying
problem in the petroleum industry because of pipeline
plugging.1 After some years, gas hydrates were introduced as
a potential source of gas production from natural gas hydrate
reservoirs.1,2 Also, gas hydrate formation can be used as a
method for separation of gases, water desalination, storage and
transportation of natural gas, and so forth.3,4 However,
industry hinders the use of hydrates as a transportation
method because of the slow formation process, low storage
capacity, relatively high pressure, and stability.5,6 Many
researchers have worked on methane hydrate formation
conditions from kinetic and thermodynamic points of view
in order to accelerate hydrate formation by using kinetic
promoters6−10 and moderate the thermodynamic stability
conditions by using thermodynamic promoters.11 Water is the
main part of hydrate and for using gas hydrate at an industrial
scale, a large amount of water is needed. This is not a problem
because large amounts of water of the sea and ocean are
normally reachable. However, the problem arises when it is
revealed that many dissolved components in water such as salts
(NaCl, MgCl 2 , CaCl2 , etc.) inhibit the formation of
hydrate.12−15 It means that the dissolved salts shift the hydrate
phase equilibrium curve to the lower temperature and/or
higher pressures. In fact, dissolved salts lower the activity of
water in the aqueous phase and subsequently inhibit the
formation of hydrate.16 For overcoming this issue, thermody-
namic promoters can be used to shift the hydrate phase
equilibrium curve to the mild conditions.17 Tetrahydrofuran
(THF) was introduced as a potential thermodynamic hydrate
promoter that forms hydrate with methane at comparatively
much higher temperatures (up to 21 K depending on
concentration) and lower pressure conditions ideal for
industrial applications.18
Also, recently tetra-n-butyl ammonium halides (fluoride,
TBAF; chloride, TBAC; bromide, TBAB) as thermodynamic
hydrate promoters have been proposed.17 These additives form
semiclathrate structures at a much lower pressures and higher
temperatures. Many researchers have been working on the
hydrate phase equilibrium conditions in the presence of THF,
TBAB, and so forth.
Recently, researchers have reported hydrate phase equili-
brium conditions from synthetic saline water in the presence of
promotors. Mech et al.18 investigated the effect of NaCl,
methanol, and ethylene glycol on the hydrate phase equilibria
Received: September 15, 2019
Accepted: December 10, 2019

© XXXX American Chemical Society A DOI: 10.1021/acs.jced.9b00886

J. Chem. Eng. Data XXXX, XXX, XXX−XXX
Journal of Chemical & Engineering Data
of methane + aqueous solutions of tetrahydrofuran (THF) and
tetra-n-butyl ammonium bromide (TBAB). TBAB was used in
the presence of 0.03 and 0.1 NaCl mass fractions, and the
hydrate inhibition effect of NaCl was investigated.
Mech and Sangwai reported hydrate phase equilibrium
conditions of methane with low THF mass fractions of 0.005
and 0.010 in the presence of NaCl aqueous solutions with mass
fractions of 0.03, 0.05, and 0.10 over a pressure range of 2.17−
6.43 MPa.19 They concluded that despite the inhibition
provided by NaCl, the effect of adding THF shifts the phase
equilibrium to milder conditions, as compared to methane
hydrate phase equilibrium conditions. In another study, they
investigated the effect of mixed promoters THF + TBAB on
the phase equilibrium of methane hydrate in the presence of
aqueous solutions of some inhibitors such as NaCl.17
Sangwai and Oellrich16 conducted experiments to obtain
hydrate equilibrium conditions of methane + TBAB (0.05 and
0.2 mass fractions) aqueous solutions in the absence and
presence of NaCl (0.03 and 0.1 mass fractions). They reported
a peculiar trend for the effect of NaCl on the hydrate
equilibrium conditions of the methane + TBAB + water
system. In the presence of the 0.03 mass fraction of NaCl and
0.05 mass fraction of TBAB, the promotion effect was observed
as compared to the 0.05 mass fraction of TBAB. It appears that
NaCl acts as a promoter than an inhibitor. However, with two
concentrations of TBAB + NaCl (0.2 + 0.03 and 0.2 + 0.1
mass fractions), the inhibition effect of NaCl was reported.16
Lv et al.20 studied the effect of seawater ions (cation of K+,
Na+, Mg2+, and Ca2+ and anions of Cl− and SO42−) in the
presence of cyclopentane and methane. Cyclopentane was
used as a promoter for methane hydrate. The inhibition effect
of these ions was quantified and sorted.
Kumar et al. gathered hydrate equilibrium data of methane +
THF + water in the presence and absence of NaCl.21 From the
point of view of the environment and health issues, TBAB is
environmentally friendly as compared to THF but THF is
normally a more effective promoter which reduces the
equilibrium pressures drastically.16,17 Therefore, by using
mixtures of these two promoters, the advantages of each one
can be addressed.
Because two major salts existing in the seawater are NaCl
and MgCl2, investigation of their effects on methane hydrate is
necessary. In the present work, aqueous solutions of THF +
TBAB were used in the presence and absence of NaCl and
MgCl2, and hydrate phase equilibrium data for four systems of
methane + THF + TBAB + MgCl2 + water, methane + THF +
TBAB + NaCl + water, methane + THF + TBAB + MgCl2 +
NaCl + and water and methane + THF + TBAB + water were
generated. To the best of our knowledge, hydrate phase
equilibrium data for the methane + THF + TBAB + MgCl2 +
water and methane + THF + TBAB + NaCl + MgCl2 + water
systems have not been reported in the open literature.
2. EXPERIMENTS
2.1. Materials. Table 1 shows the materials used in this
study along with their supplier names and purities. All
chemicals were used as received from the manufacturer.
Deionized water was used for preparing all aqueous solution
samples.
2.2. Experimental Apparatus. The schematic diagram of
the experimental setup used in this work is shown in Figure 1.
The hydrate cell (reactor) is a stainless steel cylindrical vessel,
with a 390 cm3 inner volume and 12 MPa design pressure. For
B DOI: 10.1021/acs.jced.9b00886
Article
Table 1. Purities and Supplier Names of the Chemicals
Used in This Study
chemical supplier purity
TBAB Merck 99.99 (wt %)
THF Merck 99.5 (wt %)
NaCl Merck 99.5 (wt %)
MgCl2 Merck 98 (wt %)
CH4 Technical gas services 99.9995 (mol %)
Figure 1. Schematic diagram of the experimental setup.
mixing the contents inside the reactor, a stainless steel stirrer
coupled with an electromotor is used. The temperature of the
cell is controlled by using a programmable circulator
connected to the jacket of the cell. A pressure transducer
(type 26-600G) and a platinum resistance thermometer
(Pt100) are mounted in the cell. The uncertainty of the
temperature sensor is below 0.1 K as a result of calibration
against a 25× reference platinum resistance thermometer. Also,
the pressure sensor has less than 5 kPa uncertainty because of
calibration against a dead weight gauge (Desgranges and Huot,
model 520). The thermometer and pressure sensors are
connected to a data acquisition system, and temperature and
pressure during the experiments are recorded every 20 s.
2.3. Experimental Procedure. In the present work, the
isochoric pressure-search method with a step heating
technique was utilized to obtain the equilibrium data for the
three-phase hydrate−liquid water−gas system. The step
heating technique is based on increasing the temperature in
steps and keeping it constant to reach the equilibrium state.
First, the vessel was washed and evacuated to ensure no water
and gases. Then, the prepared aqueous solution (up to 25% by
volume of the vessel) was injected into the cell. After that, the
cell was pressurized by methane gas up to the desired pressure.
Subsequently, by turning on the circulator, the cell temperature
was decreased to the lower temperatures with a cooling rate of
5 K/h in order to form the hydrate. The hydrate formation was
detected by sudden reduction in pressure and increase in
temperature. Finally, the temperature of the cell increased in a
stepwise manner by increasing 0.5 K in 30 min and then
keeping the temperature constant for enough time to ensure
that the system reached the equilibrium state. By using the
recorded pressure and temperature data, cooling line and
heating curve were plotted. The intersection of the cooling line
and the heating curve was defined as the dissociation point for
this experiment.
Before starting the hydrate formation experiments in the
presence of additives, phase equilibrium data of methane
hydrate in pure water were determined to verify the reliability
of the experimental technique and reported data in the present
work. The experimental data for hydrate dissociation of the
J. Chem. Eng. Data XXXX, XXX, XXX−XXX
Journal of Chemical & Engineering Data Article

methane + water system are shown in Figure 2 and satisfactory

agreement with data reported in the literature16,22 can be seen.

Figure 3. Hydrate phase equilibrium data for the methane + THF +

Figure 2. Hydrate phase equilibrium data of the methane + water TBAB + water system: (+) pure water;22 (■) TBAB (0.2 mass
system: (Δ) Gayet et al.;22 (+) Sangwai and Oellrich;16 (⧫) Present fraction);23 (⧫) TBAB (0.3 mass fraction);23 (○) THF (0.1741 mass
work. fraction);24 (▲) THF (0.191 mass fraction);25 (□) THF (0.3672
mass fraction);24 and (−) THF + TBAB (0.15 + 0.05 mass fractions
− present work).
3. RESULTS AND DISCUSSION evident from Figure 3, an aqueous mixture of promoters THF
The concentration of salts and promoters and the equilibrium + TBAB (0.15 + 0.05 mass fraction) promotes hydrate
temperatures and pressures are reported in Table 2. equilibrium conditions of the methane system containing THF
Figure 3 illustrates the hydrate phase equilibrium data for aqueous solutions with 0.1741, 0.191, and 0.3672 mass
methane + water and methane + THF + TBAB (0.15 and 0.05 fractions. It seems that TBAB does not improve the hydrate
mass fractions) + water systems. The temperature promotion equilibrium conditions. Also, comparison of the methane +
as compared to the methane + water system at the same THF + TBAB + water system with the methane + TBAB +
pressure is about 18 K averagely. Also, comparisons with high water system reveals that an aqueous mixture of the 0.15 +
concentrations of THF and TBAB can be observed. As it is 0.05 mass fraction of THF + TBAB promotes the hydrate
equilibrium conditions better as compared to the system of
Table 2. Hydrate Phase Equilibrium Data of the Methane + TBAB + water with mass fractions of 0.2 and 0.3.
THF + TBAB + Water System in the Presence and Absence Hydrate phase equilibrium data for methane + THF +
of NaCl and MgCl2 TBAB + NaCl + water are plotted in Figure 4. It is evident that
aqueous solution system equilibrium dataa
mass mass
mass fraction fraction fraction
salt (salt) (THF) (TBAB) T (K) P (MPa)
0.15 0.05 289.7 1.24
294.5 2.58
296.0 3.29
297.9 4.35
299.0 5.16
NaCl 0.05 0.15 0.05 287.5 1.26
291.4 2.31
293.6 3.27
295.0 4.15
296.2 4.92
MgCl2 0.05 0.15 0.05 287.0 1.09
291.6 2.16
Figure 4. Hydrate phase equilibrium data for the methane + THF +
TBAB + NaCl + water system: (▲) Pure water;22 (●) NaCl (0.05
294.1 3.19
mass fraction);14 (■) NaCl (0.05 mass fraction);26 and (⧫) THF +
296.0 4.28 TBAB + NaCl (0.15 + 0.05 + 0.05 mass fractions-present work).
297.0 4.88
NaCl + MgCl2 0.05 + 0.05 0.15 0.05 286.0 1.29
289.5 2.38 NaCl inhibits the hydrate formation of methane from pure
291.7 3.40 water and shifts the hydrate phase equilibrium curve to higher
292.6 4.25 pressures and lower temperatures. Comparison with the NaCl-
293.8 5.09 containing system shows that the aqueous mixture of TBAB +
THF promotes methane hydrate stability conditions in saline
a
Temperatures and pressures were determined with maximum water drastically. As can be seen in Figure 4, the hydrate phase
uncertainties of UC(T) = ± 0.2 K and UC(P) = ± 0.05 MPa, equilibrium curve is shifted about 20 K to the right. Hence, the
respectively. temperature required for the methane hydrate stability in the
C DOI: 10.1021/acs.jced.9b00886
J. Chem. Eng. Data XXXX, XXX, XXX−XXX
Journal of Chemical & Engineering Data Article

presence of TBAB + THF + NaCl + water is much higher as

compared to the methane hydrate system in the presence of
saline water. Also, the formed hydrate from the mixture of
methane + THF + TBAB + NaCl + water at the low
temperature, for example, 274.1 K (at 5.0 MPa), is more stable
than the formed hydrate system containing NaCl + water.
Figure 5 shows other hydrate phase equilibrium data for the
methane + THF + TBAB + NaCl + water system. Equilibrium

Figure 6. Hydrate phase equilibrium data for the methane + THF +

TBAB + MgCl2 + water system: (▲) MgCl2 (0.05 mass fraction);15
(■) MgCl2 (0.05 mass fraction);27 and (●) THF + TBAB + MgCl2
(0.15 + 0.05 + 0.05 mass fractions-present work).

expected to inhibit the hydrate stability conditions. Hydrate

phase equilibrium data for the methane + THF + TBAB +
NaCl + MgCl2 + water system and its comparison with the
system of methane + THF + TBAB + water are shown in
Figure 7. Mixed salts of NaCl + MgCl2 inhibit the hydrate
Figure 5. Hydrate phase equilibrium data for the methane + THF +
TBAB + NaCl + water system: (⧫) THF + NaCl (0.197 + 0.023 mass
fractions);21 (■) TBAB + NaCl (0.2 + 0.03 mass fractions);16 and
(▲) THF + TBAB + NaCl (0.15 + 0.05 + 0.05 mass fractions-present
work).

data of the THF + NaCl (0.197 + 0.023 mass fraction)

aqueous solution-containing system are near to the data of the
THF + TBAB + NaCl (0.15 + 0.05 + 0.05 mass fraction)
aqueous solution-containing system. Also, the hydrate stability
conditions of the methane + THF + TBAB + NaCl (0.15 +
0.05 + 0.05 mass fraction) + water system are more moderate
than the hydrate stability conditions of the methane + TBAB +
NaCl (0.2 + 0.03 mass fraction) + water system. Although the
concentration of NaCl (0.05 mass fraction), as an inhibitor, in Figure 7. Hydrate phase equilibrium data for the methane + THF +
TBAB + NaCl + MgCl2 + water system: (▲) THF + TBAB (0.15 +
the system of methane + THF + TBAB + NaCl + water is two 0.05 mass fractions) and (■) THF + TBAB + NaCl + MgCl2 (0.15 +
times higher than its concentration (0.023 mass fraction) in 0.05 + 0.05 + 0.05 mass fractions).
the methane + THF + NaCl + water system, the hydrate phase
equilibrium curves almost overlap and have the same
promotion effects. In other words, the aqueous mixture of
THF + TBAB (0.15 + 0.05 mass fractions) shows a higher stability conditions in the presence of THF + TBAB and
promotion effect than single promoters THF (0.197 mass suppress the temperature about 5 K compared to the system of
fraction) and TBAB (0.2 mass fraction) do. methane + THF + TBAB aqueous solution.
From data of Figure 5, it is concluded that the aqueous
mixture of THF + TBAB could have synergism and it can have
an advantage over using the single promoter for methane 4. CONCLUSIONS
hydrate formation in the presence of NaCl. In this work, hydrate phase equilibrium data for the methane +
Hydrate phase equilibrium data for the methane + THF + THF + TBAB + water system are reported in the absence and
TBAB + MgCl2 + water system is presented in Figure 6. presence of NaCl, MgCl2, and NaCl + MgCl2 (Table 2). NaCl
Hydrate equilibrium conditions in the presence of 0.05 mass inhibits the hydrate stability conditions more than MgCl2. It
fraction of MgCl2 and mixture of THF + TBAB + MgCl2 (0.15 was observed that the mixed promoter THF + TBAB can act as
+ 0.05 + 0.05 mass fractions) in aqueous solutions are plotted.
a better promoter than even a high concentration of the single
The THF + TBAB + MgCl2 + water system shifts the hydrate
phase equilibrium curve in the presence of MgCl2 aqueous promoter THF or TBAB. Results show that THF + TBAB
solution to the right and promotes the hydrate stability promotes the methane hydrate stability conditions of about 20
temperature about 19 K. THF + TBAB overcomes the and 19 K in the presence of the 0.05 mass fraction of NaCl and
inhibition effect of MgCl2, and hydrate can form at moderate MgCl2, respectively. In conclusion, the mixed promoter THF +
conditions. TBAB seems to be a reliable thermodynamic promoter to
As mentioned earlier, NaCl and MgCl2 act as thermody- moderate the temperature and pressure conditions for
namic inhibitors; therefore, the mixture of NaCl + MgCl2 is methane hydrate stability in saline water.
D DOI: 10.1021/acs.jced.9b00886
J. Chem. Eng. Data XXXX, XXX, XXX−XXX
Journal of Chemical & Engineering Data

■
Article

AUTHOR INFORMATION bromide (TBAB) and TBAB−NaCl. Fluid Phase Equilib. 2014, 367,
95−102.
Corresponding Author (17) Mech, D.; Sangwai, J. S. Phase Equilibrium of the Methane
*E-mail: pahlavzh@modares.ac.ir. Phone: +98 2182883312. Hydrate System in the Presence of Mixed Promoters (THF + TBAB)
Fax: +98 2182883381. and the Effect of Inhibitors (NaCl, Methanol, and Ethylene Glycol). J.
Chem. Eng. Data 2016, 61, 3607−3617.
ORCID (18) Mech, D.; Pandey, G.; Sangwai, J. S. Effect of NaCl, methanol
Hassan Pahlavanzadeh: 0000-0001-5203-3566 and ethylene glycol on the phase equilibrium of methane hydrate in
Notes aqueous solutions of tetrahydrofuran (THF) and tetra-n-butyl
ammonium bromide (TBAB). Fluid Phase Equilib. 2015, 402, 9−17.
The authors declare no competing financial interest. (19) Mech, D.; Sangwai, J. S. Phase Stability of Hydrates of Methane

■ REFERENCES
(1) Sloan, E. D.; Koh, C. A. Clathrate Hydrates of Natural Gases;
in Tetrahydrofuran Aqueous Solution and the Effect of Salt. J. Chem.
Eng. Data 2014, 59, 3932−3937.
(20) Lv, Q.; Zang, X.; Li, X.; Li, G. Effect of seawater ions on
cyclopentane-methane hydrate phase equilibrium. Fluid Phase Equilib.
CRC Press, 2008. 2018, 458, 272−277.
(2) Li, F.; Yuan, Q.; Li, T.; Li, Z.; Sun, C.; Chen, G. A review: (21) Kumar, A.; Vedula, S. S.; Kumar, R.; Linga, P. Hydrate phase
Enhanced recovery of natural gas hydrate reservoirs. Chin. J. Chem. equilibrium data of mixed methane-tetrahydrofuran hydrates in saline
Eng. 2018, 27, 2062. water. J. Chem. Thermodyn. 2018, 117, 2−8.
(3) Eslamimanesh, A.; Mohammadi, A. H.; Richon, D.; Naidoo, P.; (22) Gayet, P.; Dicharry, C.; Marion, G.; Graciaa, A.; Lachaise, J.;
Ramjugernath, D. Application of gas hydrate formation in separation Nesterov, A. Experimental determination of methane hydrate
processes: A review of experimental studies. J. Chem. Thermodyn. dissociation curve up to 55 MPa by using a small amount of
2012, 46, 62−71. surfactant as hydrate promoter. Chem. Eng. Sci. 2005, 60, 5751−5758.
(4) Khan, M. N.; Peters, C. J.; Koh, C. A. Desalination using gas (23) Arjmandi, M.; Chapoy, A.; Tohidi, B. Equilibrium Data of
hydrates: The role of crystal nucleation, growth and separation. Hydrogen, Methane, Nitrogen, Carbon Dioxide, and Natural Gas in
Desalination 2019, 468, 114049. Semi-Clathrate Hydrates of Tetrabutyl Ammonium Bromide. J. Chem.
(5) Chatti, I.; Delahaye, A.; Fournaison, L.; Petitet, J.-P. Eng. Data 2007, 52, 2153−2158.
Review:Benefits and drawbacks of clathrate hydrates: a review of (24) de Deugd, R. M.; Jager, M. D.; de Swaan Arons, J. Mixed
their areas of interest. Energy Convers. Manage. 2005, 46, 1333−1343. hydrates of methane and water-soluble hydrocarbons modeling of
(6) Ganji, H.; Manteghian, M.; Rahimi Mofrad, H. Effect of mixed empirical results. AIChE J. 2001, 47, 693−704.
compounds on methane hydrate formation and dissociation rates and (25) Lee, Y.-J.; Kawamura, T.; Yamamoto, Y.; Yoon, J.-H. Phase
storage capacity. Fuel Process. Technol. 2007, 88, 891−895. Equilibrium Studies of Tetrahydrofuran (THF) + CH4, THF + CO2,
(7) Ganji, H.; Manteghian, M.; Sadaghiani zadeh, K.; Omidkhah, M. CH4 + CO2, and THF + CO2 + CH4 Hydrates. J. Chem. Eng. Data
R.; Rahimi Mofrad, H. Effect of different surfactants on methane 2012, 57, 3543−3548.
hydrate formation rate, stability and storage capacity. Fuel 2007, 86, (26) Du, J.; Wang, X.; Liu, H.; Guo, P.; Wang, Z.; Fan, S.
434−441. Experiments and prediction of phase equilibrium conditions for
(8) Govindaraj, V.; Mech, D.; Pandey, G.; Nagarajan, R.; Sangwai, J. methane hydrate formation in the NaCl, CaCl2, MgCl2 electrolyte
S. Kinetics of methane hydrate formation in the presence of activated solutions. Fluid Phase Equilib. 2019, 479, 1−8.
carbon and nano-silica suspensions in pure water. J. Nat. Gas Sci. Eng. (27) Atik, Z.; Windmeier, C.; Oellrich, L. R. Experimental Gas
2015, 26, 810−818. Hydrate Dissociation Pressures for Pure Methane in Aqueous
(9) Lin, W.; Chen, G.-J.; Sun, C.-Y.; Guo, X.-Q.; Wu, Z.-K.; Liang, Solutions of MgCl2 and CaCl2 and for a (Methane + Ethane) Gas
M.-Y.; Chen, L.-T.; Yang, L.-Y. Effect of surfactant on the formation Mixture in an Aqueous Solution of (NaCl + MgCl2). J. Chem. Eng.
and dissociation kinetic behavior of methane hydrate. Chem. Eng. Sci. Data 2006, 51, 1862−1867.
2004, 59, 4449−4455.
(10) Najibi, H.; Mirzaee Shayegan, M.; Heidary, H. Experimental
investigation of methane hydrate formation in the presence of copper
oxide nanoparticles and SDS. J. Nat. Gas Sci. Eng. 2015, 23, 315−323.
(11) Pourranjbar, M.; Pahlavanzadeh, H.; Mohammadi, A.
Experimental Measurements and Thermodynamic Modeling of
Hydrate Dissociation Conditions for Methane + TBAB + NaCl,
MgCl2 or NaCl-MgCl2 + Water Systems. Ind. Eng. Chem. Res. 2019,
DOI: 10.1021/acs.iecr.9b04844.
(12) Hu, Y.; Lee, B. R.; Sum, A. K. Phase equilibrium data of
methane hydrates in mixed brine solutions. J. Nat. Gas Sci. Eng. 2017,
46, 750−755.
(13) Kang, S.-P.; Chun, M.-K.; Lee, H. Phase equilibria of methane
and carbon dioxide hydrates in the aqueous MgCl2 solutions. Fluid
Phase Equilib. 1998, 147, 229−238.
(14) Mohammadi, A. H.; Afzal, W.; Richon, D. Gas hydrates of
methane, ethane, propane, and carbon dioxide in the presence of
single NaCl, KCl, and CaCl2 aqueous solutions: Experimental
measurements and predictions of dissociation conditions. J. Chem.
Thermodyn. 2008, 40, 1693−1697.
(15) Mohammadi, A. H.; Kraouti, I.; Richon, D. Methane hydrate
phase equilibrium in the presence of NaBr, KBr, CaBr2, K2CO3, and
MgCl2 aqueous solutions: Experimental measurements and predic-
tions of dissociation conditions. J. Chem. Thermodyn. 2009, 41, 779−
782.
(16) Sangwai, J. S.; Oellrich, L. Phase equilibrium of semiclathrate
hydrates of methane in aqueous solutions of tetra-n-butyl ammonium

E DOI: 10.1021/acs.jced.9b00886
J. Chem. Eng. Data XXXX, XXX, XXX−XXX