Fluid Phase Equilibria 540 (2021) 113034

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Fluid Phase Equilibria

journal homepage: www.elsevier.com/locate/fluid

A robust and highly efficient phase boundary method for determining

the thermodynamic equilibrium conditions of bulk gas hydrate
systems
Ye Zhang, Gaurav Bhattacharjee, Praveen Linga∗
Department of Chemical and Biomolecular Engineering, National University of Singapore, Singapore 117 585, Singapore

a r t i c l e i n f o a b s t r a c t

Article history: The phase equilibrium conditions of gas hydrate systems play a fundamental and essential role in es-
Received 8 January 2021 tablishing the feasibility of the various hydrate based technological applications. Although the classical
Revised 25 March 2021
isochoric and isothermal pressure search methods can provide accurate and reliable gas hydrate phase
Accepted 30 March 2021
equilibrium data, these methods require researchers to devote tremendous time towards achieving each
Available online 6 April 2021
data point. Herein, we extend the phase boundary (PB) method for bulk hydrate systems and demon-
Keywords: strate it to be robust and highly efficient. The PB method involves a controlled pressure drop of the
Gas hydrates hydrate system to initiate the automatic trace of the pressure and temperature region upon dissocia-
Bulk system tion of the hydrates. Three-phase equilibrium data for four different gas hydrate systems, namely pure
Thermodynamics methane (CH4 ), mixed CH4 /1,3-dioxolane (DIOX), mixed hydrogen (H2 )/DIOX, and mixed carbon dioxide
Phase equilibrium (CO2 )/DIOX, have been obtained using the PB method. Independent measurements made using the iso-
Mixed hydrate
choric pressure search method have been obtained to validate the accuracy and reliability of the data
obtained using the PB method.
© 2021 Elsevier B.V. All rights reserved.

1. Introduction search method (hydrate dissociation via continuous or stepwise

Gas or clathrate hydrates are ice-like solid composites, formed
at suitable pressure and temperature conditions by the enclathra-
tion of guest molecules inside cages formed by the hydrogen bond-
ing of host water molecules [1,2]. Common hydrate guests in-
clude gases such as CH4 , CO2 , etc, as well as hydrocarbons such as
tetrahydrofuran (THF) and cyclopentane (CP) [1,3]. In nature, the
spontaneous formation of natural gas hydrates over millions and
millions of years has resulted in the creation of a vast reserve of
yet untapped natural gas [4–6]. Gas hydrates may also be synthe-
sized as a possible pathway for a number of technological applica-
tions such as hydrate-based gas separation [7–13], natural gas stor-
age [14–18], hydrogen storage [19–22], desalination [23–26], and
CO2 storage/sequestration [11,27–29].
The starting point for all technological applications of gas hy-
drates are their fundamental thermodynamic properties and as
such, an investigation into the phase equilibrium conditions of
a particular system is the desired starting point for any gas hy-
drate related research. The commonly used methods to measure
the phase equilibrium of gas hydrates are the isochoric pressure
∗
Corresponding author.
E-mail addresses: praveen.linga@nus.edu.sg, praveen.linga@nus.edu.sg (P. Linga).
heating) [30–33], and the isothermal pressure search method (hy-
drate dissociation via pressure decrease in tiny steps coupled with
visual observation), having proven to be relevant and reliable [34–
40]. However, one common disadvantage of these classic methods
is the requirement of tremendous amounts of time devoted to de-
termining the three-phase (hydrate, liquid, gas) equilibrium curves
for each investigated gas hydrate system.
In the past, researchers have suggested innovative and faster
methods that can cut down on the time required to establish
three-phase boundaries for gas hydrate systems. As a modification
to the isochoric pressure search method, the phase boundary dis-
sociation method has been suggested to reduce the time require-
ment where the phase equilibrium condition is obtained at ev-
ery increased temperature step during hydrate dissociation rather
than only the one hydrate dissociation point which is obtained at
the intersection of the cooling curve and heating curve [41,42].
Another innovative approach proposed recently is the dissociation
along the phase boundary (PB) method wherein the three-phase
equilibrium boundary of the gas hydrate system is directly ob-
tained through a slow depressurization process to dissociate the
formed hydrates. The PB method offers a significant advantage over
conventional gas hydrate phase equilibrium methods as employing
this technique, the entire system three-phase boundary can pos-

https://doi.org/10.1016/j.fluid.2021.113034
0378-3812/© 2021 Elsevier B.V. All rights reserved.
Y. Zhang, G. Bhattacharjee and P. Linga
sibly be obtained in a single experiment. So far, however, the PB
method has only been applied to determine the phase equilibrium
of methane hydrates in the presence of porous media [43]. The ap-
plicability and accuracy of this potentially time-saving and robust
method for phase equilibrium measurement of bulk hydrate sys-
tems is therefore an aspect that is yet to be addressed.
1,3-dioxolane (DIOX) forms sII hydrates on its own and is com-
monly used to function as a thermodynamic promoter [44–46].
DIOX is fast gaining popularity in gas hydrate research owing to
its ability to moderate the formation conditions of gas hydrates as
well as promote the kinetics of hydrate formation [47]. However,
phase equilibrium data for CH4 , CO2 , and H2 hydrates in the pres-
ence of stoichiometric concentration of DIOX is fairly scarce in the
literature, a gap that needs to be addressed quickly. In this paper,
we apply the dissociation along the phase boundary (PB) method
to bulk hydrate systems. Four such systems were investigated -
phase equilibrium conditions of the classical methane (CH4 ) hy-
drate system, as well as mixed CH4 /1,3-dioxolane (DIOX) hydrate
system, mixed hydrogen (H2 )/DIOX hydrate system, and mixed car-
bon dioxide (CO2 )/DIOX hydrate system, have been obtained using
the PB method. The reliability and accuracy of the PB method have
been independently validated using the classical isochoric pressure
search method.
2. Experimental
2.1. Materials
1,3-dioxolane (anhydrous, contains ~75 ppm BHT as inhibitor,
99.8% purity (GC assay)) and reagent grade L-tryptophan (≥ 98%
purity (HPLC assay)) were purchased from Sigma Aldrich. Methane
gas (99.995% mol% purity), hydrogen gas (99.9995% mol% purity),
and carbon dioxide (99.8% mol% purity) were procured from Air
liquid Singapore Private Limited. Deionized water was used for all
the experiments, obtained using an Elga micromega (Merck Milli-
pore Direct-Q® 3 UV) deionization apparatus.
3. Methods
3.1. Apparatus used for hydrate phase equilibrium measurements
The schematic illustration of the setup used is shown in Fig. 1.
A customized stainless-steel crystallizer (CR) equipped with acrylic
viewing windows at the front and back (to allow visual obser-
vation) was used to conduct all the experiments in the present
study. The CR was placed in a water bath and an external refriger-
ator (Polyscience) was used to maintain the temperature of the CR.
The CR pressure was measured using a Pressure Transmitter Rose-
mount 3051 (PT) supplied by Emerson Process Management with
an uncertainty of 0.1% within the pressure range of 0–20 MPa. An
analog pressure gauge (PG) supplied by WIKA was further used to
monitor CR pressure. The CR temperature was measured using a
copper-constantan T-type thermocouple, supplied by Omega Engi-
neering that has an uncertainty of 0.1 K. The thermocouple was
positioned about 1 cm below the gas-liquid interface so that it
can be enclosed within the formed hydrates, thus providing the
most accurate reading of the hydrate temperature. To mix the CR
contents a magnetic stirrer bar was placed inside the CR and was
controlled using a ‘2mag MIXdrive1’ submersible magnetic stir-
rer. Both the pressure transmitter (PT) and the thermocouple were
connected to a Data Acquisition (DAQ) system supplied by National
Instruments, which was further connected to a computer (PC). The
DAQ system measured temperature and pressure data within the
CR at 1 second intervals, which were simultaneously viewed in the
PC, using “LabVIEW” software provided by National Instruments.
2
Fluid Phase Equilibria 540 (2021) 113034
3.2. Experimental procedure used for the dissociation along the phase
boundary (PB) method
The masses of 48.85 g and 11.82 g of water and 1,3-dioxolane
(DIOX), respectively, were weighed and added to the reactor. This
gives a total solution volume of 60 ml and the initial volume ratio
of the aqueous solution to the gas is about 0.47. In the experiments
involving L-tryptophan (300 ppm or 500 ppm), it was weighed rel-
ative to the total weight of liquid and added to the reactor. The
CR was cooled to the desired experimental temperature (-2.8 °C,
0 °C, 7 °C, and 10 °C for mixed H2 /DIOX hydrates, pure methane
(CH4 ) hydrates, mixed CO2 /DIOX hydrates, and mixed CH4 /DIOX
hydrates respectively) using the external chiller. The CR then was
purged with the hydrate forming gas (methane, hydrogen, or car-
bon dioxide based on the particular experiment being carried out)
to remove air present in the CR, followed by pressurization with
the same experimental gas up to the desired experimental value
(~2.4 MPa for CO2 /DIOX hydrates; ~7.2 MPa for mixed CH4 /DIOX
hydrates; ~8 MPa for methane hydrates; and ~10 MPa for mixed
H2 /DIOX hydrates, respectively.). The mass of gas present initially
inside the reactor can be calculated by first obtaining the number
of moles of gas present in the system at the start of the experi-
ment based on the initial system pressure, experimental tempera-
ture, and volume of gas phase available (a modified ideal gas equa-
tion capable of representing a real gas was used for this purpose,
with the compressibility factor (z) calculated using the Pitzer’s cor-
relation), and then multiplying the number of moles of gas ob-
tained by the molecular weight of the particular gas being used.
For the sake of brevity, the equations used to calculate the mass
of gas present initially inside the reactor have not been included
in the manuscript but can be found elsewhere in the literature
[12,47]. Hydrate nucleation was indicated by an abrupt rise in the
system temperature, coupled with a simultaneous sudden pressure
drop, and hydrates formation continued until the pressure drop ob-
served over 1 h was less than 0.01 MPa. Once hydrate formation
had been completed, stepwise changes were made to the pres-
sure and temperature of the system to move them towards the
desired values at which the hydrate dissociation was to be initi-
ated. For mixed systems, such as CH4 /DIOX and CO2 /DIOX which
are expected to form sII hydrates [47,48] as opposed to the sI type
formed by pure CH4 and pure CO2 systems [1], the stepwise pres-
sure and temperature change was carried out making sure that at
no point did the system’s thermodynamic conditions cross into sI
hydrate stability zone.
A schematic illustration of the hydrate dissociation process for
the phase boundary method is shown in Fig. 2. When the system
pressure and temperature had stabilized at the desired experimen-
tal values (point A) (here the system pressure is higher than the
equilibrium pressure of the hydrate at the system temperature in-
dicating that hydrates would remain stable), the CR pressure was
slowly released by partially opening the vent valve and the disso-
ciation process was allowed to commence. During the entire hy-
drate dissociation period, the CR contents (gas, aqueous solution,
and hydrates) remained in a quiescent (unstirred) state. Once the
CR pressure is reduced to point B, the hydrates started to dissoci-
ate, and thereafter, the real phase boundary of the hydrates was
traced automatically until point C, during which the heat resis-
tance between the thermocouple and hydrates is negligible with
a large number of hydrates directly enclosing the thermocouple.
After point C the real phase boundary could not be obtained any-
more possibly because of the increased heat resistance between
the thermocouple and hydrates, with the thermocouple now being
exposed to the aqueous solution or gas phase as a result of some
of the hydrates enclosing the thermocouple having already disso-
ciated. Finally, complete hydrate dissociation was accomplishead at
point D. For each system, at least three individual hydrate dissocia-
Y. Zhang, G. Bhattacharjee and P. Linga
Fig. 1. Schematic illustration of the experimental setup.
Fig. 2. The schematic illustration of hydrate dissociation process for the phase
boundary (PB) method.
tion runs were carried out at various starting pressures so that the
entire three-phase equilibrium boundary of the system within the
interested thermodynamic range, may be covered. After the phase
boundary curve is obtained, the hydrate phase equilibrium data are
extracted at suitable pressure or temperature intervals.
3.3. The experimental procedure used for the isochoric
pressure-search method
The isochoric pressure-search method was employed in this
study to independently validate the accuracy of the PB method.
The experimental procedure for the isochoric pressure search
method is described in detail in the literature [30,31,33,49–52].
Briefly, a 60 mL solution sample was introduced into the CR,
with the solution volume being chosen so as to maintain the gas-
liquid interface at an appropriate height for visualization of the
CR contents through the viewing windows present. Prior to start-
3
Fluid Phase Equilibria 540 (2021) 113034
ing the experiment, the CR was purged with the hydrate forming
gas (methane, hydrogen, or carbon dioxide) via rapid pressuriza-
tion (~ 0.3 MPa) and depressurization cycles to remove any air
that may have been present internally. Next, the CR was pressur-
ized to a predetermined initial value with the hydrate forming gas,
and the system temperature was slowly lowered to form hydrates.
Abrupt pressure drop and temperature increase were simultane-
ous markers for the onset of hydrate formation. The reaction con-
tinued until a point when the pressure drop observed was less
than 0.01 MPa over 1 h. Once hydrate formation was complete,
the system temperature was gradually increased until the hydrates
started to dissociate. When this point had been reached, the tem-
perature was elevated in small steps (0.1 K per 6~12 h), until a
steady equilibrium state had been achieved at each temperature
(no pressure increase). After the hydrate crystals had dissociated
completely, the pressure increase was only due to the gas expan-
sion. Consequently, a pressure-temperature (P-T) profile was ob-
tained for each experimental run and the point at which the slope
of the P-T curve changed sharply was considered as the hydrate or
three-phase equilibrium point. With the initial pressure value var-
ied, the procedure was repeated to obtain other points along the
three-phase equilibrium trace.
4. Results and discussion
A typical pressure versus temperature (P-T) curve obtained
during the hydrate dissociation process, for a representative PB
method based phase equilibrium measurement experiment, as em-
ployed in the present study is shown in Fig. 3a. Point A in Fig. 3a
indicates the start of depressurization and it can be observed from
the figure, that even as the system pressure decreases, the system
temperature remains largely stable up until a particular point B
where a marked deflection in the P-T curve appears. The slight
temperature decrease from point A to point B is simply due to
the depressurization (pressure release). As the rate of depressur-
ization is slow, the temperature decrease is also very small. Once
the initial deflection at point B occurs, the temperature is then
observed to be decreasing along with the evolution of pressure.
This implies, a) point B is the exact instant in the depressuriza-
Y. Zhang, G. Bhattacharjee and P. Linga
Fig. 3. (a) A typical pressure versus temperature curve obtained for an experi-
mental run of the dissociation along the phase boundary (PB) method for a pure
methane hydrate system (b) Images of the morphology of the CR contents corre-
sponding to the particular points during the depressurization process (to effect hy-
drate dissociation) marked in Figure (a).
tion process when hydrate dissociation begins and b) the absorp-
tion of thermal energy by the system due to the characteristically
endothermic nature of hydrate dissociation far surpasses the rate
of energy transfer from the external chiller to the CR, which orig-
inally maintains the temperature of the system [43]. Most impor-
tantly, point B to point C in Fig. 3a represents the period where
hydrates dissociate along the phase boundary, and it is this pe-
riod that is relevant for the determination of the hydrate phase
equilibrium conditions. Images of the morphology of the CR con-
tents, corresponding to the particular points during the depressur-
ization process marked in Fig. 3a, have been presented as Fig. 3b.
As seen in the figure, at points A and B, where depressurization
and hydrate dissociation commence respectively, the CR is com-
pletely filled with solid hydrates. However, at point C, it can be
noticed that a substantial amount of hydrate mass has already dis-
sociated, including some that was previously enveloping the ther-
mocouple. The further that hydrate dissociation continues beyond
this point, means the further that the thermocouple directly gets
exposed to the dissociated liquid solution or gas phase. Moreover,
an increase in the heat transfer resistance with the presence of liq-
uid solution or gas phase means that beyond point C, the temper-
ature of the system starts to revert towards the original experi-
mental temperature that is being constantly maintained by the ex-
ternal chiller. As a result, the P-T curve deviates from the phase
4
Fluid Phase Equilibria 540 (2021) 113034
boundary beyond point C, which we term as the second deflec-
tion point. Hydrate dissociation continues beyond point C up until
point D marked in Fig. 3a. The same can be corroborated using the
morphology images for the system presented in Fig. 3b; in the im-
age corresponding to point D, a clear solution can be observed in-
side the CR, signifying that complete hydrate dissociation has taken
place. Finally, the external chiller gradually regulates the system
temperature back to the original experimental value by point E.
The results obtained in the present work strongly suggest that for
all the bulk hydrate systems studied, the instantaneous equilibrium
temperature of hydrates have a one-to-one correspondence to the
instantaneous equilibrium pressure during the particular hydrate
dissociation stage (point B to point C for the representative exper-
iment showcased in Fig. 3a).
One critical parameter for this innovative method is the depres-
surization rate at which the dissociation process progress. Fig. 4
represents the instantaneous pressure change in the system with
the evolution of time during the entire dissociation process for
the representative experiment as showcased in Fig. 3. It should
be noted that the system pressure is released by partially open-
ing the vent valve to initiate the dissociation process. However,
this method has been proven to be robust although the intrinsic
limitation of pressure releasing methods. An example to character-
ize the depressurization rate is shown in the inset of Fig. 4 where
the initial depressurization rate was calculated by fitting the ini-
tial pressure range to give an R-square value great than 0.996. A
relatively large range of initial depressurization rate (~1-4 kPa/s)
adopted in this work has been determined to be effective in pro-
ducing accurate and reliable phase equilibrium conditions of gas
hydrates. Details of the various experimental parameters for each
individual run conducted have been provided in Table 1.
The PB method was first applied to determine the phase equi-
librium conditions of bulk pure methane (CH4 ) hydrates. Being one
of the most commonly studied gas hydrate systems, starting with
pure methane hydrates would give a fair estimation of the ac-
curacy and applicability of the PB method for bulk hydrate sys-
tems, and whether this approach may be further adopted to de-
termine the phase equilibrium conditions of more novel hydrate
systems. Fig. 5 shows the obtained phase equilibrium boundary
for bulk pure methane hydrates using the PB method. As shown
in Table 1 methane hydrate formation was carried out with and
without the presence of 500 ppm of the amino acid L-tryptophan.
The phase boundary curves obtained with and without the pres-
ence of 500 ppm L-tryptophan agree with each other perfectly, in-
dicating that the presence of 500 ppm L-tryptophan did not affect
the applicability of the PB method as well as the phase equilib-
rium conditions of methane hydrates. Furthermore, the length of
phase boundary curves obtained with the presence of 500 ppm L-
tryptophan in a single experiment is more than twice the length
of that obtained without the presence of 500 ppm L-tryptophan. L-
tryptophan is a well-known kinetic promoter, enhancing both the
hydrate formation rate and the final gas uptake due to hydrate for-
mation; exhaustive investigations on the kinetic promotion effect
of L-tryptophan on methane hydrate formation can be found in
the literature [53]. The use of the kinetic promoter is important
to increase the quantity of hydrate formed within a short time:
the more the quantity of hydrate present in the system prior to
dissociation, the more extensive the three-phase boundary curve
obtained in a single experiment. Three-phase equilibrium data for
pure methane hydrates, obtained from the literature has also been
shown in Fig. 5 for comparison [54]. An excellent match can be
observed in Fig. 5 between the literature data and the three-phase
equilibrium boundary obtained in this work, which validates the
reliability and accuracy of the PB method for bulk methane hydrate
system, and also underlines its potential application in determining
the three-phase equilibrium boundaries for other novel gas hydrate
Y. Zhang, G. Bhattacharjee and P. Linga Fluid Phase Equilibria 540 (2021) 113034

10000
7400
Pressure
Fitted line
7200

Pressure (kPa)
8000
A 7000
Pressure (kPa)

6800

6000 B
6600
Initial pressrue range: 7268 kPa - 6521 kPa
Initial depressurization rate = 1.7 kPa/s
6400
0 100 200 300 400
Time (s)
4000
C
D

2000
E
0 5000 10000 15000 20000 25000 30000
Time (s)
Fig. 4. Typical pressure drop obtained with the evolution of time for the experiments showcased in Fig. 3. The inset of the figure shows the initial depressurization rate
obtained for this representative experimental run with the R-squared value of the fitted line is 0.998.

Table 1
Details of the experiments conducted in the present work using the PB method.

System Exp. No Initial depressurization rate (kPa/s) R-Square Initial pressure range (MPa)

CH4 /H2 O + 500 ppm M1 2.9 0.998 7.27 ~ 6.54

L-tryptophan M2 3.1 0.997 6.11 ~ 5.21
M3 2.3 0.996 10.32 ~ 9.72
CH4 /H2 O M4 0.8 0.998 9.52 ~ 9.00
M5 1.6 0.998 7.725 ~ 7.203
CH4 /DIOX/H2 O+ 300 ppm M/D-1 1.8 0.998 5.99 ~ 5.37
L-tryptophan M/D-2 1.0 0.998 4.67 ~ 4.05
M/D-3 1.1 0.997 5.13 ~ 4.09
M/D-4 1.5 0.997 8.20 ~ 7.14
CH4 /DIOX/H2 O M/D-5 2.6 0.998 5.85 ~ 3.58
M/D-6 2.1 0.998 4.11 ~ 3.58
H2 /DIOX/H2 O H/D-1 1.8 0.997 7.20 ~ 6.16
H/D-2 2.5 0.997 6.89 ~ 5.90
H/D-3 1.2 0.997 9.89 ~ 8.76
H/D-4 0.9 0.997 3.52 ~ 2.97
H/D-5 1.3 0.997 11.72 ~10.43
H/D-6 2.7 0.998 5.003 ~ 4.522
CO2 /DIOX/H2 O + 500 ppm C/D-1 4 0.998 2.298 ~ 1.978
L-tryptophan C/D-2 1.3 0.997 1.196 ~ 1.092
C/D-3 0.8 0.998 1.519 ~ 1.414
C/D-4 1.7 0.998 2.016 ~ 1.736

systems. Table 2 shows the three-phase equilibrium data for the
bulk methane hydrate system extracted from the phase boundary
for the same obtained using the PB method.
The PB method was further extended to various other hydrate
systems, with scant three-phase equilibrium data available in the
literature, to demonstrate its versatility. Fig. 6 below shows the
three-phase equilibrium boundary of mixed methane (CH4 )/1,3-
dioxolane (DIOX) hydrates measured using the PB method with
DIOX used in stoichiometric concentration (5.56 mol%). As shown
in Table 1, experiments M/D-1 to M/D-4 were conducted in the
presence of 300 ppm L-tryptophan as a kinetic promoter and
experiments M/D-5 and M/D-6 were conducted without any L-
tryptophan present in the system. A recent study establishes L-
tryptophan as an excellent kinetic promoter for the CH4 /DIOX
system and affirms that its presence does not alter the hydrate
structure being formed [47]. Phase equilibrium data for mixed
CH4 /DIOX hydrates without the pressure of L-tryptophan was sep-
arately obtained using the isochoric pressure search method and

5
Y. Zhang, G. Bhattacharjee and P. Linga Fluid Phase Equilibria 540 (2021) 113034

9
Isochoric method
8 M/D-1
M/D-2
7 M/D-3
M/D-4
6 M/D-5

Pressure (MPa)
M/D-6
5

0
282 284 286 288 290 292 294 296
Temperature (K)
Fig. 5. The phase equilibrium boundary for CH4 hydrates (the initial mass ratio of
gas to water is ~0.15:1) obtained using the PB method along with relevant data Fig. 6. Three-phase equilibrium boundary for mixed CH4 /DIOX hydrates (5.56 mol%
points from the literature, shown for comparison [54]. DIOX solution before mixing with the CH4 gas; the initial mass ratio of gas to
aqueous solution is ~0.12:1) obtained using the PB method. Three-phase equilib-
rium data points for the same system obtained using the isochoric pressure search
Table 2 method have been included for comparison.
Three-phase equilibrium data for CH4 hydrates (the initial mass ratio of gas to water
is ~0.15:1) obtained using the PB method.α Table 3
Three-phase (liquid, hydrate, and gas) equilibrium data for mixed CH4 /DIOX hy-
T/K P/MPa T/K P/MPa
drates (5.56 mol% DIOX solution before mixing with the CH4 gas; the initial mass
284.80 8.60 280.50 5.40 ratio of gas to aqueous solution is ~0.12:1) obtained using the PB method.α
284.61 8.40 280.16 5.20
T/K P/MPa T/K P/MPa
284.43 8.20 279.76 5.00
284.18 8.00 279.38 4.80 294.26 6.40 290.25 3.50
283.99 7.80 278.98 4.60 294.11 6.30 290.09 3.40
283.71 7.60 278.57 4.40 294.04 6.20 289.13 3.00
283.52 7.40 278.14 4.20 293.98 6.10 288.88 2.90
283.31 7.20 277.73 4.00 293.86 6.00 288.69 2.80
283.03 7.00 276.89 3.80 293.73 5.90 288.44 2.70
282.78 6.80 276.40 3.60 293.67 5.80 288.22 2.60
282.53 6.60 275.90 3.40 293.55 5.70 287.94 2.50
281.34 6.00 275.27 3.20 293.39 5.60 287.66 2.40
281.10 5.80 274.71 3.00 293.33 5.50 287.45 2.31
280.85 5.60 293.17 5.40 287.1 2.20
α Uncertainties u are u(T)= ± 0.10 K, and u(P)= ± 0.02 MPa. 293.01 (±0.06)∗ 5.30 286.79 2.10
292.93 (±0.05)∗ 5.20 286.48 2.00
292.80 (±0.04)∗ 5.10 286.26 1.91
292.70 (±0.02)∗ 5.00 285.45 1.70
292.52 4.90 285.27 1.65
the same has also been included in Fig. 6, for the sake of com- 292.38 (±0.03)∗ 4.80 285.11 1.60
parison. As expected, the presence of L-tryptophan does not af- 292.26 (±0.02)∗ 4.70 284.86 1.55
fect the phase equilibrium of mixed CH4 /DIOX hydrates confirming 292.07 (±0.06)∗ 4.60 284.68 1.50
that this additive only serves as a kinetic promoter. The applicabil- 291.93 (±0.08)∗ 4.50 284.49 1.45
291.80 (±0.04)∗ 4.40 284.05 1.40
ity and reliability of the PB method for the mixed CH4 /DIOX sys-
291.67 (±0.02)∗ 4.30 283.87 1.35
tem are confirmed by the excellent agreement of the phase equi- 291.52 4.20 283.65 1.30
librium data obtained using the two different methods. It is well 291.46 4.10 283.43 1.25
accepted that it may take even an experienced experimentalist 291.24 4.00 283.21 1.20
291.09 3.90 283.03 1.15
as much as three days to obtain a single three-phase equilibrium
290.78 3.80 282.78 1.10
point using the classical isothermal or isochoric pressure searching 290.68 3.70 282.56 1.05
methods. However, using the PB method, the entire three-phase 290.43 3.60 282.43 1.02
boundary curve can possibly be obtained in a single experiment, α Uncertainties u are u(T)= ± 0.10 K, and u(P)= ± 0.02 MPa.
and within about 3 h of initiating the depressurization process to ∗
Standard deviations in brackets have been calculated for the overlapping areas
the end of effective hydrate dissociation (point A to Point C show- of the phase equilibrium boundary between different runs.
cased in Fig. 3). More realistically, on average it might take up
to three to four experimental runs to obtain the entire system’s
three-phase boundary in the interested thermodynamic range. This Next, the PB method was employed to determine the three-
still affords an attractive improvement with regards to the time phase equilibrium conditions for the mixed hydrogen (H2 )/1,3-
saved to obtain the necessary data, as compared to the classical gas dioxolane (DIOX) system, with DIOX used in stoichiometric concen-
hydrate phase equilibrium measurement methods. The extracted tration (5.56 mol%). Separately, phase equilibrium points for this
three-phase equilibrium points for the mixed CH4 /DIOX hydrate system were also measured using the isochoric pressure search
system are listed in Table 3 given below. method. Fig. 7 shows the phase equilibrium boundary and a to-

6
Y. Zhang, G. Bhattacharjee and P. Linga Fluid Phase Equilibria 540 (2021) 113034

12 1.6
Isochoric method
H/D-1 Isochoric method
C/D-1
10 H/D-2 1.4
C/D-2
H/D-3
C/D-3
H/D-4 C/D-4
H/D-5 1.2
8
H/D-6
Pressure (MPa)

Pressure (MPa)
1.0
6

0.8

4
0.6

2
0.4

0
0.2
271.0 271.5 272.0 272.5 273.0 273.5 274.0 274.5
274 275 276 277 278 279 280 281
Temperature (K) Temperature (K)

Fig. 7. The phase equilibrium boundary for mixed H2 /DIOX hydrates (5.56 mol%
DIOX solution before mixing with the H2 gas; the initial mass ratio of gas to
aqueous solution is ~0.02:1) obtained using the PB method. Three-phase equilib-
rium data points for the same system obtained using the isochoric pressure search
method have been included for comparison.
Fig. 8. The phase equilibrium boundary for mixed CO2 /DIOX hydrates (5.56 mol%
DIOX solution before mixing with the CO2 gas; the initial mass ratio of gas to
aqueous solution is ~0.11:1) obtained using the PB method. Three-phase equilib-
rium data points for the same system obtained using the isochoric pressure search
method have been included for comparison.

Table 4 Table 5
Three-phase (liquid, hydrate, and gas) equilibrium data for mixed H2 /DIOX hydrates Three-phase (liquid, hydrate, and gas) equilibrium data for mixed CO2 /DIOX hy-
(5.56 mol% DIOX solution before mixing with the H2 gas; the initial mass ratio of drates (5.56 mol% DIOX solution before mixing with the CO2 gas; the initial mass
gas to aqueous solution is ~0.02:1) obtained using the PB method.α ratio of gas to aqueous solution is ~0.11:1) obtained using the PB method.α

T/K P/MPa T/K P/MPa T/K P/MPa T/K P/MPa

273.94 9.20 272.57 4.80 280.35 1.40 277.95 0.80

273.81 8.80 272.47 4.40 280.19 1.35 277.67 0.75
273.75 8.40 272.37 (±0.06)∗ 4.00 280.01 1.30 277.30 0.70
273.61 (±0.07)∗ 8.00 272.19 3.60 279.82 1.25 276.99 0.65
273.5 7.60 272.06(±0.02)∗ 3.20 279.63 1.20 276.68 0.60
273.38 7.20 271.82(±0.04)∗ 2.80 279.48 1.15 276.33 (±0.04)∗ 0.55
273.28 6.80 271.68(±0.02)∗ 2.40 279.29 1.10 275.93 0.50
273.16 6.40 271.51 2.00 279.09 (±0.02)∗ 1.05 275.59 0.45
273.03 (±0.09)∗ 6.00 271.32 1.60 278.79 1.00 275.18 0.40
272.85 5.60 271.17 1.20 278.57 0.95 274.75 0.35
272.71 (±0.02)∗ 5.20 278.33 0.90 274.43 0.30
278.14 0.85
α Uncertainties u are u(T)= ± 0.10 K, and u(P)= ± 0.02 MPa.
∗
α Uncertainties u are u(T)= ± 0.10 K, and u(P)= ± 0.02 MPa.
Standard deviations in brackets have been calculated for the overlapping areas
∗
of the phase equilibrium boundary between different runs. Standard deviations in brackets have been calculated for the overlapping areas
of the phase equilibrium boundary between different runs.

tal of six, phase equilibrium points for the mixed H2 /DIOX sys-
tem obtained using the PB method and the classical isochoric pres-
sure search method, respectively. The two sets exhibit a perfect
match with the phase equilibrium points obtained using the iso-
choric pressure search method serving as an independent verifi-
cation tool for the accuracy and reliability of the PB method. The
three-phase equilibrium points for mixed H2 /DIOX hydrates have
been extracted based on the obtained phase equilibrium bound-
ary at a fixed increasing pressure step of 0.4 MPa and the same is
shown in Table 4.
The final bulk hydrate system investigated in the present work
is the mixed carbon dioxide (CO2 )/1,3-dioxolane (DIOX) system
with DIOX used in stoichiometric concentration (5.56 mol%), and
500 ppm L-tryptophan added to the system as a kinetic promoter.
The PB method was used to obtain the three-phase equilibrium
boundary for mixed CO2 /DIOX hydrates, while separately the iso-
choric pressure searching method was used to obtain two hydrate
dissociation points for the same system, albeit without the pres-
ence of L-tryptophan. The latter would serve as validation for the
accuracy of the PB method for the bulk CO2 /DIOX hydrate sys-
tem. Fig. 8 shows the obtained phase equilibrium boundary for
CO2 /DIOX hydrates using the PB method as well as the two sep-
arate phase equilibrium points obtained for the same system using
the isochoric pressure search method. Similar to what has already
been observed and discussed for a couple of the other systems in-
vestigated in the present study, L-tryptophan functions purely as a
kinetic promoter without affecting the phase equilibrium of mixed
CO2 /DIOX hydrates. Excellent agreement between the two sets of
data represented in Fig. 8 verifies the applicability and reliability
of the PB method for the mixed CO2 /DIOX hydrate system. The ex-
tracted three-phase equilibrium data for the system based on the
obtained three-phase boundary using the PB method is provided
in Table 5.
5. Conclusion
The innovative dissociation along the phase boundary (PB)
method has been applied for bulk hydrate systems. Specifically, the
applicability of the PB method has been investigated for four dif-
ferent systems: the most commonly studied pure CH4 hydrate sys-
tem, and the more unconventional mixed CH4 /DIOX hydrate, mixed
H2 /DIOX hydrate, and mixed CO2 /DIOX hydrate systems, with scant

7
Y. Zhang, G. Bhattacharjee and P. Linga
three-phase data available in the literature. The accuracy of the
PB method for the aforementioned systems has been validated by
comparing with relevant data obtained from the literature or using
data measured independently in this study employing the classi-
cal isochoric pressure search method. The innovative and robust PB
method presents a pathway for highly efficient and rapid gas hy-
drate phase equilibrium measurement that can accurately be em-
ployed for bulk hydrate systems. However, the technique is still
very much in its infancy and further studies are needed to extend
it to other hydrate systems, promoters with non-stoichiometric
concentration, and its suitability to be employed for binary gas
mixtures and beyond needs to be investigated.
Credit Author Statement
PL supervised the project. PL, YZ, and GB conceptualized the
work and designed the experiments. YZ carried out the experi-
ments. YZ and GB analyzed the data. YZ and GB wrote the original
manuscript draft. PL edited the manuscript and contributed to the
final version. All authors read the final manuscript and consented
to the submission.
Declaration of Competing Interest
There are no conflicts to declare.
Acknowledgments
The authors acknowledge the funding support from MoE AcRF
Tier 1 (R-279-0 0 0-542-114) and the National University of Singa-
pore.
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