Proceedings of the ASME 2022 14th International Pipeline Conference

IPC2022
September 26-30, 2022, Calgary, Alberta, Canada

IPC2022-88861
Experimental Study of Natural Gas Hydrate Formation Kinetics and Inhibition in Brine
and Water

Farzan Maziyar Mahmoodi Edison Sripal Majid A. Abdi

Sahari Moghaddam Memorial University of Memorial University of M. A. Procense Inc. and
Memorial University Newfoundland Newfoundland Memorial University of
of Newfoundland St John’s, Canada St John’s, Canada Newfoundland (Adjunct
St John’s, Canada Professor)
St John’s, Canada

Lesley James
Memorial University
of Newfoundland
St John’s, Canada

ABSTRACT A novel macro scale isothermal approach was applied

Hydrates formed under high pressure and low-
temperature pipeline conditions are a serious flow assurance
challenge. Furthermore, there are uncertainties with respect to
the performance of different hydrate inhibitors based on their
type, hydrocarbon and brine compositions, and operating
conditions. Considering the inhibiting effect of salt ions in the
brine composition can benefit hydrate chemical management
strategies by reducing the high quantities of inhibitors.
This study experimentally evaluates the performance of
kinetic and thermodynamic inhibitors and investigates the
growth of hydrate under subsea pipeline pressure and
temperature conditions. The effect of hydrate inhibitors was
studied through a novel isothermal approach using varied brine
compositions. Few studies such as Kakati et al. (2015) have
focused on the inhibiting effect of multivalent ionic brine
composition. Our study considers several multivalent ionic salts
in formation brine and seawater including NaCl concentrations
of 9.7 wt% and 2.4 wt%, compared to previous isochoric and
isothermal studies relying only on one salt type. The influence of
high and low salinity levels, including multivalent ionic salts,
were evaluated, as they have been shown to be able to reduce the
quantity of inhibitors used in hydrate chemical management
strategies. The results were benchmarked against experiments
using de-ionized (DI) water to capture the individual effect of the
inhibitors and brine in inhibiting hydrate formation. Growth
detection was also captured through image analysis to improve
the understanding of hydrate kinetics in water and brine. The
experimental results were evaluated according to hydrate
equilibrium curves simulated using Calsep PVTsim Nova.
in PVT Cell to investigate natural hydrate formation and growth
in DI water and brine systems. The ability of i) a kinetic hydrate
inhibitor (KHI) and ii) methanol as a thermodynamic hydrate
inhibitor (THI) to inhibit hydrate formation was studied. A
sudden drop in the pressure (indirect measurement) confirmed
through visual observations (direct measurement) is applied to
identify the hydrate formation point.
Nine isothermal hydrate tests were conducted, with and
without inhibitors, in DI water and brine systems. Results
indicate that the KHI was best able to inhibit hydrate formation.
KHI inhibited hydrate formation for more than 20 hours in the
presence of formation brine at 4.8°C and 97 bar (>1400 psi). In
the absence of an inhibitor, hydrate formation in water occurred
during the pressurization step, at a pressure below 35 bar (500
psi). The hydrate mixture resulted in a sudden shift to darker
colours upon formation, further grew, and agglomerated.
Keywords: DI Water, Formation Brine, Seawater, Hydrate
Formation, Inhibitor, KHI, Methanol
NOMENCLATURE
AA Anti Agglomerant
DCS Differential Scanning Calorimetry
DI De-ionized
EOR Enhanced Oil Recovery
GC Gas Chromatography
GOM Gulf of Mexico
IOR Improved Oil Recovery

1 © 2022 by ASME
 KHI Kinetic Hydrate Inhibitor
MEG Mono Ethanol Glycol
LDHI Low Dosage Hydrate Inhibitor
PVT Pressure Volume Temperature
ROI Region of Interest
THI Thermodynamic Hydrate Inhibitor
1. INTRODUCTION
The formation of hydrate is a nuisance for oil
and gas production activities under high-pressure and low-
temperature conditions [1-2]. If adequate hydrate management
steps are not implemented, hydrate can grow and lead to pipeline
blockage, resulting in economic and safety consequences [2].
The situation could significantly exacerbate and deeply affect
pipeline integrity when integrated with the impact of corrosion
resulting from hydrate [3]. Hence, managing hydrate formation
is critical to ensure the success of subsea production facilities
(e.g., pipelines).
Hydrates receive a lot of attention in other research
areas beyond flow assurance, including i) the potential of
methane gas production from hydrate sediments [4-7]. ii)
desalination [8] iii) storage of gas [9], and iv) CO2 capture [10].
The presence of hydrocarbon and non-hydrocarbon gas
molecules, such as methane and carbon dioxide, with water can
form cage structures known as hydrate. Three dominant
structures of I, II, H can be formed [1]. SII is the common hydrate
structure formed from natural gas under pressure and
temperature conditions of oil and gas operations [2]. However,
parameters such as the amount of subcooling and the dominancy
of methane in gas composition can cause SI to form instead of
SII under severe pressure and temperature conditions of a
pipeline. The type of the guest molecule and its diameter, which
range from 4.2 to 9 Ȧ , are the determining parameters
responsible for hydrate type. Further information about hydrate
structure and the effect of guest molecules can be found
elsewhere [1, 3].
Three governing mechanisms of i) intrinsic kinetics, ii)
mass, and iii) heat transfer limitations impact the process of
hydrate nucleation and growth [1]. Experimentally, based on
purposeful high stirring rates and adequate cooling supplied to
the system (e.g., high pressure cell), both restrictions of mass and
heat transfer can be neglected. Hence the determining factor in
hydrate formation and growth is the intrinsic kinetics of the
system [11-12]. However, hydrate formation due to the
occasional deactivation of the stirred mass transfer restriction
also plays an important role in hydrate growth [13]. High rates
of stirring created in experiments promoted a significantly high
mass transfer rate [14].
There are different approaches to hydrate formation and
equilibrium detection points, each with advantages and
disadvantages. In an isochoric approach, although both pressure
and temperature can be studied for hydrate formation, many
experiments fulfill their pressurization by increasing the supply
of gas [12].
Hydrate formation can take place in any part of the fluid
system; however, the gas-liquid interface is the most likely
nucleation location; primarily due to significant gas saturation at
the interface [11]. Hydrate formation is stochastic and might not
occur instantly after the formation pressure and temperature
conditions are fulfilled. The time span between the state of
hydrate equilibrium and the detection of initial hydrate is known
as the induction time, which is the parameter used to evaluate the
performance of hydrate inhibitors [15]. The primary driving
force in reducing the induction time and increasing the chance of
hydrate formation is fugacity variations between equilibrium and
experimental conditions [16]. Subcooling as the temperature
difference between equilibrium and experimental status of the
fluid system can significantly affect the fugacity differences.
The application of common thermodynamic hydrate
inhibitors (e.g., methanol) in the industry is being replaced by
low dosage hydrate inhibitors (e.g., KHIs) to reduce the
significant quantities of inhibitor used [17]. Thermodynamic
hydrate inhibitors (THIs) influence the formation condition of
hydrate, whereas the main functionality of kinetic hydrate
inhibitors (KHIs) is to influence the hydrate kinetics by causing
a disturbance in the hydrate nucleation process followed by
growth [17]. Salt components are mostly considered THI since
they influence the formation temperature and pressure of hydrate
and are not involved in hydrate nucleation kinetics [18].
Modelling shows that monovalent salt had less tendency to
inhibit hydrate formation than divalent salt, and the size of salt
molecules and valence number are the determining factors in
their efficiency [19].
Field application of low dosage hydrate inhibitors has
been successful in the Gulf of Mexico (GOM). This is due to the
reduced use of THIs (e.g., methanol), which offers noticeable
advantages in terms of economic and environmental
considerations (i.e., as a result of decreased inhibitor usage) [20].
The application of KHIs with major polymeric nature
includes extending the induction time or inhibiting hydrate from
the formation. Moreover, it has been suggested that KHIs may
also impact hydrate growth [16]. A variety of apparatus such as
flow loops [21], differential scanning calorimetry [22], PVT Cell
[23], rocking cell [24] and experimental approaches have been
used to investigate the hydrate inhibition and growth in the
presence and absence of inhibitors.
1.1 The effect of salinity on hydrate formation -
experimental studies
Woo et al. (2019) studied the influence of NaCl and
MgCl2 on hydrate formation and equilibrium under isochoric
conditions in a high-pressure cell. The results indicated that
although salt ions did not take part in hydrate structure, the
presence of ions considerably influences the kinetics of hydrate
nucleation and growth. When salt concentration is increased (to
10 wt%), formation rate was reduced, and formation pressure
increased [12]. Aminnaji et al. (2021) experimentally assessed
the structural changes and existence in natural gas-water system
with differential scanning calorimetry and confirmed through
simulations with Hydrafact. Although the main notion about
2 © 2022 by ASME
natural gas hydrate structure is the existence of SII, both SI and
SII structures exist in the natural gas hydrate structure. When the
fluid system enters into the hydrate formation region, the SII
hydrate structure is formed with the highest phase stability
through the consumption of natural gas propane fraction.
However, with increased subcooling and resulting higher
fraction of methane and ethane, SI is the major structure formed
from natural gas [13]. Chen et al. (2010) investigated the
performance of three KHIs for inhibiting natural gas hydrate in
brine systems within a high-pressure cell under isochoric
method. The best performance, with 1 wt% concentration, was
noticed up to approximately 10.6 K of subcooling. Increased
subcooling resulted in the reduction of onset hydrate formation
time, whereas an increase in the concentration of KHIs had the
opposite effect. The inhibiting impact of each KHI on hydrate
growth varied significantly based on its nature and the
subcooling of the system [25]. Zheng et al. (2020)
experimentally evaluated the effect of brine (NaCl 3.5 and 5
wt%) in inhibiting hydrate from methane-carbon dioxide gas
with an isochoric method in a PVT cell. Based on the effect of
salt ions over water activity, the dissociation pressure of hydrate
was noticed to reduce with enhanced NaCl concentration in
brine. After hydrate formation, the roughness of the hydrate layer
reduces upon hydrate layer growth [14].
Kakati et al. (2015) experimentally assessed the performance of
NaCl (2-3 wt%), CaCl2 (2-3 wt%), and seawater in displacing
gas hydrate (CH4+CO2+N2) equilibrium curve and in inhibiting
hydrate formation. To detect the formation and dissociation
points, an autoclave cell with a maximum stirring rate of 1,000
rpm was utilized in a temperature search method. The inhibiting
performance of brine was enhanced with an increased salt
concentration (induction time increased from 93 min to 185 min
3 wt% NaCl). However, CaCl2 performed more poorly (i.e.,
resulted in lower induction time) compared to NaCl at the same
concentration. Also, hydrate formation was reduced in the
presence of salt components. Kakati et al. (2015) compared the
inhibiting influence of NaCl and CaCl2. The equilibrium
temperature for NaCl was found to be almost 1 K greater than
that of CaCl2 at the same concentration. They found that hydrate
growth slows considerably after the initial hydrate nucleation
and less hydrate growth was noticed in brine compared to water.
Growth was further slowed as salt concentration increased [26].
The synergic effect of KHIs and THIs, such as methanol with
brine, was not investigated. This can significantly add to the
hydrate inhibiting effect of the system and might even impact
hydrate growth after formation. The author evaluated hydrate
growth based normalized rate calculations from moles of gas
consumption and volume of water used for the study. However,
hydrate morphological variations based on growth was not
studied through image analysis.
Kang et al. (2014) used an isothermal approach to
experimentally evaluate the performance of KHIs (PVP and
PVCaP) with concentration ranges of 0.1-2 wt% in de-ionized
(DI) water within a high-pressure cell. Various levels of
subcooling from 4.72 to 14.72 K were tested to evaluate natural
gas hydrate formation. In comparison with experiments without
KHIs, induction time significantly extended up to longer than
1500 min for 1 wt% PVCap under 9.72 K of subcooling. The
increased induction time was noticed up to 470 times more than
the case of DI water with only 20 min. However, under
subcooling of 14.72°C, PVCap performed better than PVP,
which did not have the inhibiting characteristic [16]. Jensen et
al. (2011) used various approaches in a high-pressure cell to
investigate formation of natural gas hydrate in the presence of
salt (3.5 wt% NaCl) and KHI (PVCaP). Due to the slower
kinetics of SII compared to SI, KHI's most efficient performance
was to delay SII structure of hydrate. The inclusion of salt
unexpectedly enhanced the rate of hydrate formation despite its
inhibiting nature in delaying hydrate formation at higher
pressure and lower temperature conditions [27]. Alef and
Barifcani (2018) investigated Mono Ethanol Glycol (MEG)
inhibiting efficiency in brine (NaCl 1.75 wt% and KCl 0.55 wt%)
and methane gas. They conducted an experiment in a high-
pressure PVT cell under an isochoric approach. They found that
thermal oxidation resulted in MEG degradation in brine in the
regeneration process, which impacted hydrate formation
performance despite the additional hydrate inhibition cause by
the presence of salt ions [28].
Sahari Moghaddam et al. (2022) conducted isothermal
experiments with a PVT cell to study the equilibrium and
formation of natural gas hydrate in brine (NaCl 3.5 wt%). Two
different KHIs with concentrations of 0.5 wt% and 1 wt%, and
low dosage methanol (5 and 10 wt%) were used. The highest
performance of KHIs (1 wt%) to inhibit hydrate formation was
up to 10°C of subcooling, and the best performance of methanol
(10 wt%) was at 7.49°C of subcooling. KHI-B was shown to
most effectively inhibit hydrate formation under the same gas
composition up to 10°C. In the study, the influence of KHIs and
THIs was investigated in brine having only NaCl. This cannot
fully replicate the effect of multivalent ion brine naturally
present in oil and gas reservoirs and offshore operations where
seawater is injected for pressure support or in
enhanced/improved oil recovery (EOR/IOR) techniques. Also,
we previously only considered hydrate growth in DI water as
opposed to brine [23].
1.2 Objectives
Although various studies investigated the effect of
inhibitors in the presence of salt ions, few experiments have
focused on hydrate formation in the presence of multivalent salt
composition, such as the study done by Kakati et al. (2015) [26].
Salt components other than NaCl (a major salt component in
brine) can also affect hydrate formation. In addition, few studies
have investigated hydrate formation and growth morphology in
both the presence and absence of multivalent salt compositions.
In this study, we assessed the influence of KHI and THI in the
absence and presence of two different multivalent salt
compositions (i.e., formation brine and seawater). Furthermore,
we evaluate the growth of hydrate in DI water and the formation
brine having multivalent ions. The study contributes toward
improving the understanding of hydrate inhibition in various
systems and hydrate morphological behavior in the presence and
3 © 2022 by ASME
absence of brine during growth. The inhibiting effect of
multivalent ion salts are considered in this study such as few
other hydrate kinetic studies (e.g., Kakati et al. (2015)) in
multivalent ions brine compositions [26]. However, we also
investigate the influence of KHI and methanol inhibitors in
different multivalent ionic brine compositions. This work further
studies the performance of inhibitors used by Sahari
Moghaddam et al. (2022) under various brine compositions. It
also sheds more light onto hydrate growth detection by image
processing under saline condition of the system.

2. METHODOLOGY
In this work, we used natural gas (composition presented in Table
1) and PVT sapphire cell (shown in Figure 1). DI water with a
purity of >99% was used for the blank (i.e., no inhibitor)
experiments, and for brine solution preparation. a KHI type
known as KHI-B and methanol as the THI with concentrations
of 1 wt% and 10 wt%, respectively, were used as the inhibitors
FIGURE 1: SCHEMATIC OF PVT SAPPHIRE CELL USED FOR
in the experiments [23]. KHI-B with 50% active content and PH HYDRATE FORMATION TESTS [23]
value of approximately 8, which was also studied by Sahari
Moghaddam et al. (2022), had the best ability to inhibit hydrate TABLE 2: BRINE COMPOSITION USED IN EXPERIMENTS
formation compared to the other inhibitors studied.
Concentration- Concentration-
Two different brines, a high salinity multivalent Component Formation Seawater
formation brine (NaCl 9.7 wt%) and a lower salinity multivalent Brine (wt%) (wt%)
ion seawater (NaCl 2.4 wt%), were prepared in the Hibernia
NaCl 9.70 2.44
EOR Laboratory according to the composition shown in Table 2.
CaCl22H2O 1.42 0.15
MgCl26H2O 0.30 1.10
TABLE 1: NATURAL GAS COMPOSITION FROM GC RESULTS
COMPARED TO SUPPLIER REPORT [23] KCl 0.05 0.08
Na2SO4 0.04 0.41
Concentration NaHCO3 N /A 0.02
Deviation
Component (mol %) After preparing the brine with the required salt
(%)
GC* Supplier concentrations, the PVT Cell was cleaned with DI water,
CH4 89.97025 90.23 0.2887 followed by injection of nitrogen and vacuuming. This process
CO2 2.16625 1.98 8.5978 was repeated five times to ensure the readiness of the
C2H6 5.86175 5.33 9.0715 experimental apparatus to conduct the tests. In the next step, the
C3H8 2.002 1.45 27.5724 liquid mixture was loaded into the cell with a stainless-steel
N2 NA 1.01 NA syringe, then the valve for liquid entry was closed, and the gas
Total 100 100 was loaded to the cell up to pressure below the dissociation of
* Average of 4 runs hydrate. Hydrate curves simulated in Calsep PVTsim Nova used
as the basis of the experiments are shown in Figure 2. After
loading the fluids (i.e., liquid and gas) and setting the
temperature to a predefined value, the stirrer was turned on to
2500 rpm. Afterward, the cell was pressurized by the piston
pump up to the required pressure for the experiment and
maintained at that pressure for at least 20 hrs. During the
experiment, the hydrate formation was detected based on a
sudden drop in the pressure profile or visual observation.

4 © 2022 by ASME

FIGURE 2: SIMULATED HYDRATE CURVES IN FORMATION
BRINE, SEAWATER, AND DI WATER
Figure 3 presents the workflow to analyze the
experiment images [23, 29]. After storing the images in a
database, the region of interest (ROI) is defined for all the studied
images. The intensity scale is extracted from the ROI of each
image, and the related histogram is generated for each ROI. Both
the mean value and standard deviation (SD) of the histograms
are compared to investigate the behavior of hydrate formation
and growth.
In the isothermal hydrate formation experiment with
natural gas-DI water-KHI-B conducted at 4.8°C, hydrate did not
form for 21 hrs at a stabilized pressure of 50.7 bar (equivalent to
subcooling of 9.7°C). In contrast, methanol (MeOH) as the THI
was tested in DI water and failed to completely inhibit hydrate
formation. Hydrate formation occurred after 14 hrs of induction
time, under 7.6°C of subcooling. The results correspond with our
previous study, where hydrate formation occurred at a
subcooling of 7.3°C in 3.5% brine [23]. However, in that study,
the induction time was 7.8 hrs for methanol concentration of 5
wt% compared to 14 hrs induction time in this study with
methanol concentration of 10 wt%. This can be explained by
higher methanol concentration of 10 wt% in this study compared
to 5 wt% methanol concentration in previous study. Table 3
summarizes the natural gas hydrate formation experiments in DI
water with different subcooling and the resulting induction
times. A summary of the experiments according to the hydrate
curve is presented in Figure 5. The amount of subcooling shown
in Figure 5 (two-way blue arrow) is the temperature difference
between hydrate nucleation and simulated hydrate equilibrium
temperatures. As the amount of subcooling increases in a system,
the potential for hydrate formation increases, which is associated
with more stringent hydrate management strategies.

TABLE 3: HYDRATE FORMATION IN DI WATER UNDER

VARIOUS CONDITIONS

Concentration

Temperature
Composition

Subcooling
Induction
FIGURE 3: IMAGE PROCESSING WORKFLOW [23, 29] Inhibitor

Pressure

Pressure
(wt%)

(Bar)
Time

(psi)
(°C)

(°C)
(hr)
3. RESULTS AND DISCUSSION
3.1. Hydrate Formation in DI Water
Three experiments were conducted to investigate DI water
and natural gas (NG) hydrate in the presence and absence of the NG-DI N/ 33.0
N/A No 4.7 478 6.5
inhibitors (KHI-B 1 wt% and methanol 10 wt%). As expected, Water A
hydrate formed in the pressurizing step under subcooling of NG-DI
KHI-B 1 21 4.8 50.7 736 9.7
6.5°C at pressure and temperature conditions of 33 bar and 4.7°C, Water
respectively. The rapid hydrate formation with no induction time NG-DI
MeOH 10 14 4.8 38.4 557 7.6
is due to the absence of inhibitors and salt. Upon formation, there Water
is a sudden drop in the pressure profile (presented in Figure 4)
due to the sudden consumption of the gas. However, such a
pressure drop is not always seen in hydrate formation; hence
visual observations should also be considered.

FIGURE 5 NATURAL GAS HYDRATE FORMATION

FIGURE 4: PRESSURE PROFILE NATURAL GAS - DI WATER EXPERIMENTS WITH AND WITHOUT INHIBITORS.
HYDRATE FORMATION

5 © 2022 by ASME
 Figure 6 shows the image histograms (pixels versus hydrate at the point of formation in the formation brine.
intensity) of the natural gas DI water hydrate formation However, 5 hrs after the formation, hydrate agglomerates in
experiments. Lower numbers for mean and SD represent darker formation brine are smaller compared to the agglomerates in DI
colours. From the intensity profiles of the experiment images water, as shown in Figure 8. The values for the mean and SD
(i.e., from start to 5 hrs after the formation), both mean and SD increase to 50.8 and 30.2, which indicates the mixture color is
of the histograms suddenly drop from 87.5 and 53.4 to 52.5 and becoming lighter, although it is darker than the hydrate
29.9 (shown in Table 4). Hence, the color of the mixture is darker agglomerate in DI water system.
after hydrate formation (i.e., intensity reduces) compared to the
start of the experiment. Upon formation, hydrate starts to grow
and the values for mean and SD are further reduced to 51.2 and
28 as the mixture turns darker. As the hydrate starts to
agglomerate and create a lump with lighter color, the mean and
SD values increase to 76.5 and 51.6 (5 hrs after the formation).

FIGURE 7: IMAGE HISTOGRAMS FOR NATURAL GAS-

FORMATION BRINE HYDRATE FORMATION EXPERIMENT

TABLE 4: MEAN AND SD VALUES FOR IMAGE HISTOGRAMS

OF HYDRATE FORMATION EXPERIMENTS FROM START UP TO
5 HRS AFTER THE FORMATION
FIGURE 6: IMAGE HISTOGRAMS FOR NATURAL GAS-DI
Mean and SD Values
WATER HYDRATE FORMATION EXPERIMENT
Experiments Start Formation After 1 hr After 5 hr
87.5 52.5 51.2 76.5
3.2. Hydrate Formation in Formation Brine NG+DI water
±53.4 ±29.9 ±28 ±51.6
The second phase of experiments were conducted with NG+
65.4 4.4 30.8 50.8
and without the presence of inhibitors (KHI-B and methanol) in Formation
±39.2 ±0.86 ±17.9 ±30.2
formation brine. Natural gas hydrate formation occurred in Brine
formation brine after 16 hrs of induction time. Hydrate formed
without inhibitors at a temperature of 4.8°C and pressure of 68.1
DI
bar (7.3°C subcooling). The long induction time under 7.3°C
Water
subcooling indicates the effect of high multivalent salinity in the
brine and the stochastic nature of hydrate. Brine
After hydrate formation, the pressure and temperature
were maintained up to 5 hrs to study hydrate growth and
agglomeration. As shown in the image histograms in Figure 7, FIGURE 8: IMAGES OF HYDRATE AFTER 5 HR OF
hydrate formation in formation brine is much darker (i.e., lower FORMATION IN DI WATER (TOP) AND FORMATION BRINE
(BOTTOM). ROI IS WITHIN GREEN FRAME.
intensity) than the formation in DI water (i.e., higher intensity).
From the intensity profiles of natural gas hydrate in formation To further investigate the effect of KHI-B and methanol, a series
brine, both the mean and SD values decreased from 65.4 and 39.2 of experiments was conducted. As expected, the mixture of
to 4.4 and 0.86 The results indicate an almost complete black formation brine-KHI-B withstands the hydrate formation for 21
mixture at the time of formation. One hour after formation, the
hr under temperature and pressure of 4.8°C and 96.7 bar (9.4°C
mean and SD values rise to 30.8 and 17.9, respectively, upon
subcooling). Due to synergic effect of brine with methanol 10
hydrate growth and agglomeration. Hence, the mixture color
wt% concentration, hydrate did not form under temperature and
moves toward lighter color ranges (i.e., intensity enhances). This
pressure of 4.7°C and 68.1 bar (7.45°C subcooling). The
is in contrast with the color of the hydrate mixture in the DI water
after 1 hr, which became darker. This difference in the behavior
of hydrate formation can be attributed to a greater amount of

6 © 2022 by ASME
summary of the results is presented in Figure 9 and Table 5.

FIGURE 10: INHIBITORS PERFORMANCE IN SEAWATER

UNDER HIGH SUBCOOLING

TABLE 5: HYDRATE FORMATION IN FORMATION AND

FIGURE 9: HYDRATE FORMATION POINT OF NG IN SEAWATER UNDER VARIOUS CONDITIONS.

Concentration
FORMATION BRINE WITH AND WITHOUT INHIBITORS

Temperature

Subcooling
Induction
Time (hr)
Inhibitor

Pressure

Pressure
Brine

(Bar)

(psi)
(°C)

(°C)
(%)
3.3. Hydrate Formation in Seawater

In the last experimental phase, we used multivalent

seawater composition since seawater injection is used in offshore Formation N/A N/A 16 4.8 68.1 987 7.3
Newfoundland and Labrador (NL) for reservoir pressure
maintenance. After simulating the hydrate curve according to the
Brine KHI-B 1 21 4.8 67.9 985 7.3
NaCl concentration shown in Figure 2, we imposed a high level KHI-B 1 21 4.8 96.7 1402 9.4
of subcooling to the system according to the simulated curve. MeOH 10 >20 4.7 68.1 988 7.5
The results show that under high subcooling of 15.2°C, the KHI- KHI-B 1 4.7 3.6 116.7 1693 15.2
Seawater

B failed, and hydrate formed after 4.7 hr of induction time.

However, in the other experiment with lower subcooling of
13.1°C, the induction time significantly increased to 12 hr.
Although hydrate formation is a stochastic process, the results
show the significant impact of subcooling on induction time. In
the last experiment with seawater, the results showed that 10
wt% methanol inhibited hydrate formation for more than 20 hr
in the presence of multivalent ions. The synergic effect of salt
and THI could potentially influence the inhibition of hydrate
formation under a high subcooling of 10°C. In our previous study
with 3.5% NaCl brine, methanol failed to inhibit hydrate
formation at 7.6°C [23]. Although the low dosage methanol
inhibition of hydrate formation in seawater can be attributed to
hydrate stochastic nature, in the formation brine experiments
also, hydrate did not form under 7.5°C of subcooling. Figure 10
summarizes the experiments according to the hydrate curve.
Table 5 also summarizes hydrate formation in both formation
brine and seawater under various subcooling levels and
operating conditions.
KHI-B 1 12 4.6 96.0 1392 13.1
MeOH 10 >20 3.6 55.2 800 10.5
By considering the effect of salt ions, hydrate was inhibited up
to 10.5°C subcooling with MeOH in seawater compared to
MeOH-DI water system that hydrate was inhibited at 7.6°C.
Also, the image analysis revealed noticeably slower growth of
hydrate in brine, which can considerably reduce the MeOH
concentration (e.g., 20-50%) used in offshore oil and gas
operations [16]. This is based on the conservative approach of
fully inhibiting hydrate and not considering the effect of salt ions
to impact the formation and growth of hydrate.
3. CONCLUSIONS
From our study with natural gas DI water, formation brine and
seawater the following conclusions are drawn:
• KHI-B succeeded in inhibiting hydrate formation up to 9.7
°C subcooling, which is in agreement with the literature.
• In seawater under 15°C, hydrate formed but with 4.7 hr
induction time. Also, under 13°C subcooling, the induction
time significantly increased from 0.4 to 12.2 hrs.
• The synergic effect of multivalent ion seawater and 10 wt%
methanol inhibited hydrate formation up to 10.5°C of
subcooling.

7 © 2022 by ASME
 • Hydrate formation in both DI water and formation brine
grew and agglomerated; however, the agglomeration in DI
water was faster and denser.
ACKNOWLEDGEMENTS
The authors would like to thank the Hibernia Management and
Development Company (HMDC), Chevron Canada Ltd, Energy
Research and Innovation Newfoundland and Labrador (ERINL),
the Natural Sciences and Engineering Research Council of
Canada (NSERC), the Province of Newfoundland and Labrador,
and Mitacs for financial support. We also thank our colleague
Norah Hyndman in the Hibernia EOR Research Group.
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