OTC-27621-MS

Gas Hydrate Management Strategies Using Anti-Agglomerants: Continuous

& Transient Large-Scale Flowloop Studies

J. A. Dapena, A. A. Majid, V. Srivastava, and Y. Wang, Colorado School of Mines; T. B. Charlton, The University
of Western Australia; A. A. Gardner, Monterrey Institute of Technology and Higher Education; E. D. Sloan, L. E.
Zerpa, D. T. Wu, and C. A. Koh, Colorado School of Mines

Copyright 2017, Offshore Technology Conference

This paper was prepared for presentation at the Offshore Technology Conference held in Houston, Texas, USA, 1–4 May 2017.

This paper was selected for presentation by an OTC program committee following review of information contained in an abstract submitted by the author(s). Contents of
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Abstract
Subsea oil and gas flowlines can provide favorable conditions for gas hydrate formation, which can lead
to flow assurance issues as hydrate particles agglomerate and accumulate in the flowline. Shut-in and
restart operations are particularly critical for hydrate plug formation. Traditional strategies to mitigate
hydrate plugging use total hydrate avoidance with thermodynamic inhibitors; however, thermodynamic
inhibition can become cost-prohibitive as oil production moves towards harsher environments associated
with deeper drilling. Hydrate management strategies using low dosage hydrate inhibitors (LDHI), such
as anti-agglomerants (AA), are an attractive alternative to reduce operational and capital expenditures in
offshore oil and gas production. In order to successfully deploy anti-agglomerants to mitigate hydrate
plugging, a comprehensive understanding of the variables affecting the performance of these additives,
such as oil composition and mixture velocity, is needed. Industrial-scale flowloop studies are valuable to
investigate the influence of these variables on hydrate particle transportability when using AAs. These
experimental setups could be also useful to assess AA performance during transient operations (i.e. shut-in
and restart); however, large-scale flowloop data at these conditions is limited.
High pressure industrial-scale flowloop tests were conducted using a non-dispersing oil at 50 vol. % water
content and 70 vol. % liquid loading. The aqueous phase is a 3.5 wt. % NaCl solution and the gas phase
comprises a natural gas favoring the formation of sII gas hydrates. The AA used in these tests is a quaternary
ammonium salt. Both baseline (without AA injection) and AA dosed (2 vol. % AA) tests were conducted
in order to compare the influence of mixture velocity on hydrate transportability using AAs with respect
to systems without AA injection. Three different mixture velocities (2.3, 3.7 and 5.8 ft s‐1) were employed.
The experimental procedure included shut-in and restart operations. A combination of different data, such
as temperature and pressure drop profiles, mass flow rate and droplet/particle size evolution was used to
analyze the effects of AA injection at the different studied velocities. Additionally, water/oil dispersion tests
were carried out in order to investigate the influence of the AA on the properties of the dispersion.
Both hydrate growth rate and droplet/particle size were influenced by mixture velocity in baseline
tests; however, experiments with 2 vol. % AA showed similar hydrate growth rates and droplet/particle
sizes regardless of the mixture velocity. In addition, despite AAs reducing hydrate bedding at all mixture
2 OTC-27621-MS

velocities with respect to baseline experiments, a certain velocity was needed to completely suppress any
indication of hydrate bedding in these systems. Moreover, AA injection successfully inhibited hydrate
particle size increase (agglomeration) under static conditions (shut-in), allowing solid material flow after
restarting the system. Finally, dispersion tests showed that this particular AA formulation modifies the
surface chemistry properties of the system and favors water-continuous dispersions at room conditions with
respect to systems without addition of AA.

Introduction
Natural gas hydrates are solid inclusion compounds comprised of small hydrocarbon molecules within a
crystalline network of water molecules, which form at high pressure and low temperature. Subsea oil and gas
flowlines operating under hydrate formation conditions require additional measures, such as thermodynamic
hydrate inhibitor injection, in order to assure oil and gas fluid flow (Sloan and Koh, 2007).
Traditional oil and gas production strategy has relied on hydrate avoidance strategies using
thermodynamic hydrate inhibitors (THIs) (e.g. methanol, mono-ethylene glycol) to shift the hydrate
equilibrium conditions of the system to higher pressure and lower temperatures. However, as oil and
gas production moves to deeper water developments with environments of higher pressures and lower
temperatures, in addition to longer tiebacks and higher water content as the field matures, the required THI
dosage increases considerably given THI injection is based upon the water content and this can become
cost-prohibitive. Low dosage hydrate inhibitors (LDHIs), such as anti-agglomerants (AAs), constitute an
attractive alternative to minimize injection of THIs and to reduce costs by moving from traditional avoidance
to management strategies. Using AAs could represent significant savings both in operational expenditure
(OPEX) and in capital expenditure (CAPEX), as well as extend the field lifetime (Kelland, 2006).
Shut-in and cold restart operations are major flow assurance concerns in subsea oil and gas production.
Restart operations are critical for hydrate formation due to decreasing temperature in the system during the
shut-in period (Chen, 2010). AAs can be considered to prevent hydrate plugging in restart operations, while
minimizing injection of THIs (Mehta et al., 2002). In order to deploy hydrate management strategies, such
as AAs, comprehensive understanding of the mechanisms leading to successful hydrate particle transport
is needed, as well as recognizing the influence that different operational parameters can have on the
performance of these additives. These parameters include the properties of the organic phase, fluid velocity,
or the type of chemical used.
Flowloop facilities offer the closest laboratory conditions to subsea flowlines in order to study hydrate
particle transportability before deploying new technologies in oil production fields. Data such as particle
size evolution can be utilized to determine whether AAs can prevent hydrate particle agglomeration under
static conditions (i.e. shut-in period). Various properties can be used to evaluate hydrate transportability
in flowloop studies: pressure drop and temperature profiles, mass flowrate, and visual video observations.
Droplet/particle chord length distribution (CLD) analysis and particle video imaging methods are
particularly useful to evaluate hydrate growth and hydrate particle agglomeration, both with and without
AA injection (Leba et al., 2010). These two latter methods can provide insights into the mechanisms leading
to hydrate particle accumulation and plugging in different systems. In addition, these tools allow exploring
the effects of shut-in conditions on hydrate particle morphology and size distribution. This information,
coupled with pressure drop and temperature profiles, is valuable to assess AA performance during transient
operations.
The analysis of results obtained from high pressure industrial-scale flowloop tests are presented in this
work. A non-dispersing oil was used to evaluate the effect of mixture velocity on hydrate formation kinetics
and hydrate particle size evolution in a system dosed with an AA. These tests allow quantification and
comparison of the influence of mixture velocity with respect to baseline experiments without AA injection.
OTC-27621-MS 3

Experimental Procedure
High Pressure Industrial-Scale Flowloop Tests
Hydrate transportability studies under continuous pumping (CP) and transient conditions were conducted
using a high pressure industrial-scale flowloop. The experimental setup consists of a 295 ft. (~ 90 m) long
and 3.8 inches (~ 9.7 cm) internal diameter pipe connected to a custom-made multiphase sliding vane pump
(positive displacement pump). The system is located in a temperature-controlled room with a temperature
range from 20 °F (~ -7 °C) to 90 °F (~ 32 °C). A gas-filled piston accumulator is connected to a HPU
(hydraulic pressure unit) to control the pressure in the flowloop (Turner and Talley, 2008).
Multiple data acquisition tools are available in this flowloop facility. Pressure and temperature are
recorded at several locations in the loop, including fluids and surface temperatures. Mass flowrate is
measured with a multiphase flow meter (Coriolis type). Video imaging and chord length distribution
measurements are used to track droplet/particle size evolution during the experiments. Finally, regular video
recording of the fluids inside the loop is possible through the viewing ports. Figure 1 provides a schematic
representation of the experimental setup.

Figure 1—Schematic of the high pressure industrial-scale flowloop used in these studies (adapted from (Boxall, 2009))

Flowloop tests were conducted at 70 vol. % liquid loading and 50 vol. % water content. The oil phase is
a mineral oil with a specific gravity of 865 kg m‐3and a viscosity of 59.1 cP (at 104 ºF (40 ºC)). The aqueous
phase is a brine solution (3.5 wt. % NaCl) with a density of 1023 kg m‐3. The gas phase was a natural gas
composition, which forms a hydrate structure II (sII). The experimental matrix included both baseline tests
and experiments with 2 vol. % AA injection. The AA (a quaternary ammonium salt) was dosed with respect
to the volume of the aqueous phase of the system. Three different mixture velocities were studied (2.3, 3.7
and 5.8 ft s‐1) for both baseline and AA tests.
The flowloop experimental procedure starts by charging the system with fluids, followed by
pressurization to 1000 psig at 85 º F (chamber temperature). The fluids were mixed for about an hour at the
experimental mixture velocity. After mixing, the room temperature set point was changed to 38 °F (~ 3.3
°C), initiating a cooling stage at a rate of ~ 25 °F hr‐1 (~ 14 °C hr‐1), and eventually leading to hydrate onset.
An experiment continues until either hydrate formation ceases and pressure drop stabilizes, or the system
was considered to be plugged (i.e. the safety threshold for the pump power output was reached). Flowloop
4 OTC-27621-MS

temperature and pressure, together with the gas accumulator volume, were used to calculate the amount of
hydrates formed throughout the experiment. In the case that the system had not plugged, a shut-in period
was allowed for a given amount of time (i.e. mixture velocity was set to zero), while keeping the temperature
and pressure set points constant. The shut-in time for experiments with AA was set to six hours in order to
maximize shut-in time within the experimental framework. After the shut-in period, the pump was restarted
(i.e. cold restart test) to verify whether an AA was able to prevent hydrate particle agglomeration under
static conditions, and also to recover the flow conditions and hydrate particle size distribution observed
before the shut-in stage. Finally, a dissociation stage was conducted by increasing the fluids temperature
above the hydrate equilibrium conditions. Figure 2 illustrates the experimental procedure for flowloop tests.

Figure 2—Schematic of the experimental procedure used for the flowloop tests.

Water/Oil Dispersion Tests

Hydrate growth mechanisms can vary depending on the continuous phase of the system before hydrate
onset (Zerpa, 2013; Zerpa et al., 2012; Zerpa et al., 2010). In order to obtain better understanding of the
properties of the water/oil systems, particularly in the presence of anti-agglomerants, dispersion tests were
conducted at ambient temperature and pressure conditions using a simple in-house setup. The experimental
equipment consists of a 600 mL beaker and a mechanical mixer equipped with a propeller-type impeller.
The continuous phase of the dispersion was inferred from conductivity measurements using a multimeter to
record voltage in an electrical loop that includes the dispersion as a conducting medium. These experiments
allow analyzing the influence of the AAs on the water/oil dispersions.
The experimental procedure consisted of initially loading the system with a pure liquid phase, either an
aqueous or an organic phase. Mixing was started at a given constant velocity (e.g. 500 RPM) and at ambient
temperature and pressure. The water content in the system was systematically increased or decreased by
5 vol. % with the addition of a given volume of dispersed phase (i.e. an aqueous phase was added to
increase water content and an organic phase was added to decrease water content). After each addition of
the dispersed phase, the system was allowed to stabilize for 30 min before measuring voltage. In the case of
using an AA, this was dosed based on the water content in the system (i.e. if water content was increased,
more AA was directly dosed to the dispersion), yielding a constant concentration of AA with respect to the
aqueous phase throughout the experiment. Independent tests were run either by increasing or decreasing
water content in the system in order to determine the phase inversion point from a water-in-oil to oil-in
water dispersion, and vice versa.
OTC-27621-MS 5

Results and Discussion

Experiments were designed and conducted using a non-dispersing mineral oil at 50 vol. % water content (3.5
wt. % NaCl) with 70 vol. % liquid loading, and natural gas. Mineral oil (MO) was selected as the oil phase
for several reasons. The transparent color allows good visualization of droplets and hydrate particles both for
video recording in the visual port. Rheological studies using mineral oils have shown similar trends to those
with non-dispersing oils, such as kerosene (Karanjkar et al., 2016). Mineral oils provide a surfactant-free
organic phase suitable to better understand the effects of AAs on water/oil and water/oil/hydrate dispersions.
Temperature, pressure and gas reservoir volume data were used to calculate gas consumption during
hydrate formation. The hydrate volume fraction (HVF) is defined as the volume of hydrate particles with
respect to the total volume of liquids and solids in the slurry according to Equation 1.

(1)

The pressure drop evolution after hydrate formation is analyzed in terms of the relative pressure drop at
a given time with respect to the pressure drop measured at hydrate onset according to Equation 2.

(2)

Mixture Velocity Effects on Hydrate Particle Transportability Using AAs

Experiments at three different mixture velocities (2.3, 3.7 and 5.8 ft s‐1) were conducted both with and
without injection of 2 vol. % AA. Dispersion tests suggest that the mineral oil system selected for these
experiments at 50 vol. % water content and 3.5 wt. % NaCl is within the transition region making it difficult
to determine the continuous phase of the dispersion before hydrate onset (i.e. relative time < 0). Measured
data, such as pressure drop and droplet/particle CLDs were used to infer the type of dispersion present in
the system before hydrate onset.
Relative pressure drop profiles as a function of hydrate volume fraction at the three studied velocities
with and without AA (Figure 3) show that this particular AA does not help reduce the relative pressure
drop of the system with respect to baseline tests. However, as discussed in the next section, hydrate bedding
is observed in baseline experiments reducing the amount of hydrate particles transported in the flowing
slurry. Lower solids concentration in the flowing liquids could reduce the overall slurry viscosity and lower
the relative pressure drop across the pump. Also, relative pressure drop fluctuations are minimized by the
injection of AA, particularly at the lower velocity (2.3 ft s‐1), suggesting a more homogeneous material flow
in the pipe with respect to baseline tests. In addition, experiments dosed with AA show a sudden increase
in relative pressure drop at HVF ~ 0.03 at the three mixture velocities studied, suggesting a sudden change
in the hydrate slurry properties (e.g. phase inversion from a water- to an oil-continuous dispersion).
6 OTC-27621-MS

Figure 3—Relative pressure drop behavior during hydrate formation in mineral oil systems at
50 vol. % water content with and without injection of 2 vol. % AA. Three different velocities are
studied (2.3, 3.7 and 5.8 ft s‐1). Hydrate bedding is detected in baseline tests at all mixture velocities
for hydrate volume fractions > 0.2. AA injection minimized bedding, even at the lower velocities.

Figure 4 (A-F) shows the time evolution of the relative pressure drop, the mean droplet/particle size
(derived from the measured square-weighted chord lengths) and the mass flow rate at the lowest and highest
mixture velocities used during these tests (2.3 and 5.8 ft s‐1), both with and without 2 vol. % AA. Particle size
data is not available at the intermediate velocity (3.7 ft s‐1), and therefore comparisons are not possible. Some
general features can be appreciated, such as considerably greater mean droplet/particle sizes in baseline
experiments after hydrate onset (relative time > 0) compared to AA tests, indicating the presence of large
aggregates (Figure 4 C, D). Moreover, the mean droplet size before hydrate onset (relative time < 0) is lower
in tests with AA injection than in baseline experiments. AAs, containing surface active components, can
lower the interfacial tension between aqueous and organic phases, thereby promoting droplet dispersion.
As discussed above, mineral oil is a surfactant free organic phase, leading to highly unstable water/oil
dispersions with large droplets and fast coalescence. Additionally, a gradual decrease in mean droplet size
is observed in baseline tests at 2.3 and 5.8 ft s‐1 before hydrate onset, coinciding with the cooling down
period. This could be related to higher viscosity of the fluids as temperature decreases, increasing shear
in the system and promoting droplet break up. Hydrate bedding signals are observed in the mean droplet/
particle size (Figure 4 C, D) and in the mass flow rate (Figure 4 E, F) from both baseline experiments (i.e.
0 vol. % AA).
OTC-27621-MS 7

Figure 4—Time evolution of relative pressure drop across the pump (A, B), Mean particle/droplet size (C, D),
and mass flow rate using a Coriolis multiphase flow meter (E, F) during hydrate formation at 2.3 ft s‐1 (Left) and
5.8 ft s‐1 (Right) for mineral oil systems at 50 vol. % water content, 3.5 wt. % NaCl, with and without 2 vol. % AA.

The baseline test at 2.3 ft s‐1 (Figure 4, left column) shows a sharp decrease in the mean droplet/particle
size approximately 90 minutes after hydrate onset (Figure 4 C), probably corresponding to settling of large
hydrate aggregates. Simultaneously, the mass flow rate decreases sharply (Figure 4 E). The hydrate volume
fraction is ~ 0.15 at this point (i.e. at hydrate bedding onset). Significant fluctuations are observed in
relative pressure drop (Figure 4 A), particle size (Figure 4 C) and mass flow rate (Figure 4 E) after this
point that could be related to intermittent movement of the hydrate beds. In this case, both the relative
pressure drop (Figure 4 A) and the mass flow rate (Figure 4 E) drop to values close to zero during
8 OTC-27621-MS

these fluctuations, indicating that solid/liquid flow is limited after hydrate bedding at this low velocity. In
contrast, experiments with injection of AA show minimal fluctuations, suggesting homogeneous slurry flow
throughout the experiment. The mean droplet/particle sizes remain relatively small during the experiment
(note the logarithmic scale on the ordinate for mean droplet/particle size), with only a mild decrease in mass
flow rate after ~ 270 minutes, suggesting minimal particle settling (Figure 4 C). The mass flow rate starts
decreasing at HVF ~ 0.27, compared with ~ 0.15 for the baseline test (Figure 4 E).
The baseline test at a higher velocity (5.8 ft s‐1) also shows signals of hydrate bedding occurring in the
system (Figure 4, right column). Both the mean droplet/particle size (Figure 4 D) and the mass flow rate
(Figure 4 F) decrease about 70 min after hydrate onset, coinciding again with fluctuations in the relative
pressure drop (Figure 4 B). This behavior indicates settling of larger hydrate aggregates, reducing the mean
droplet/particle size in the flowing slurry. The mean droplet/particle size starts decreasing before hydrate
bedding onset, but at a much lower rate than at 2.3 ft s‐1(Figure 4 D). However, the decreasing trend in the
mean droplet/particle size is magnified 70 minutes after hydrate onset, coinciding with a HVF of ~ 0.16. In
contrast, with injection of 2 vol. % AA, both the mean droplet/particle size (Figure 4 D) and the mass flow
rate (Figure 4 F) remain fairly constant throughout the test, indicating efficient hydrate transport without
accumulation during the entire experiment.
Although the mean droplet/particle size remains fairly constant in tests dosed with AA, a sudden increase
is observed about 30 minutes after hydrate onset (Figure 4 C, D), coinciding with the sharp increase in
relative pressure drop taking place at HVF of ~ 0.03 (Figure 3, left and right plots). Simultaneously, the
mass flow rate sharply decreases at this point (Figure 4 E, F). The oil phase, having a higher viscosity than
the aqueous phase, would cause a sudden increase in the relative pressure drop when a dispersion phase
transition takes place, i.e., from a water-continuous to oil-continuous slurry. Moreover, this particular AA
was found to favor water-continuous dispersions according to dispersion tests using 2 vol. % AA and the
same mineral oil used in the flowloop tests. Figure 5 shows the transition from an oil-continuous dispersion
to a water-continuous dispersion occurs at ~ 55 vol. % water content in systems both with and without
injection of AA (Figure 5 A, B). Similarly, the transition from a water-continuous to an oil-continuous
dispersion takes place at ~ 25 vol. % water content in baseline experiments (i.e. without injection of AA)
(Figure 5 A). However, dosing with 2 vol. % AA in these flowloop studies is sufficient to prevent a transition
from a water-continuous to an oil-continuous dispersion at water contents up to 15 vol. % (Figure 5 B).
Therefore, hysteresis in the dispersion phase inversion augments as the stability of a water-continuous
dispersion increases. Water-continuous dispersions in the presence of this AA are significantly more stable
to phase separation than systems without addition of AA. Dispersions of mineral oil and water without AA
show phase separation almost instantly after mixing is halted; whereas, dispersions in the presence of 2 vol.
% of this particular AA remain homogenous (i.e. no phase separation is observed) for more than six hours
without mixing. Additional dispersion tests are required to better quantify the stability of mineral oil/water
dispersions in the presence of this AA. These results further suggest that flowloop tests with injection of 2
vol. % AA might involve a water-continuous dispersion before hydrate onset.
The relative conductivity in Figure 5 is calculated with respect to the conductivity of a pure mineral oil
phase according to Equation 3:

(3)

where σRel is the relative conductivity, V is the measured voltage using a dispersion with a given water content
as conducting medium and V0 is the measured voltage using a pure mineral oil phase as conducting medium.
OTC-27621-MS 9

Figure 5—Water/oil dispersion tests for mineral oil systems without AA injection (Figure A) and with injection
of 2 vol. % AA (Figure B). Hollow markers correspond to tests with decreasing water content (i.e. oil is added
to the system) and solid markers correspond to tests with increasing water content (i.e. water is added
to the system). Low relative conductivity is related to oil-continuous dispersions. Transition from an oil-
continuous to a water-continuous dispersion occurs at a different water content than transition from a water-
continuous to an oil-continuous dispersion, leading to hysteresis in the phase inversion point of the system

Figure 6 (B) provides further insights on the effects of mixture velocity in these studies. For baseline
tests (50 vol. % water content and 0 vol. % AA), the mean droplet sizes before hydrate onset decrease as
the mixture velocity increase, in agreement with Boxall's droplet size model (Boxall et al., 2012) for both
inertial and viscous sub-regimes. Similarly, the mean droplet/particle sizes after hydrate onset are greater
at lower velocities, suggesting that larger hydrate aggregates are present in the system as a consequence of
lower shear forces (as suggested by the force balance proposed in the Camargo and Palermo viscosity model
(Camargo and Palermo, 2002)). Conversely, the mean droplet sizes before hydrate onset in tests with AA at
both mixture velocities (2.3 and 5.8 ft s‐1) are roughly the same (i.e. 19 and 21 μm, respectively). It should
be noted that the flowloop test at 5.8 ft s‐1 mixture velocity was conducted first, leading to the mean droplet
size observed in Figure 6 (B), followed by the test at 2.3 ft s‐1 mixture velocity. As discussed above, the AA
used in these studies promotes and stabilizes dispersions of oil droplets in water; hence, the AA could be
slowing down the expected recombination process of droplets after the mixture velocity was reduced to 2.3
ft s‐1, maintaining a similar droplet size to that in the test at 5.8 ft s‐1. This could be considered as a kinetic
effect on droplet size caused by addition of this particular AA to the system.
10 OTC-27621-MS

Figure 6—(A) Hydrate growth at different velocities, (B) Mean

droplet/particle size during hydrate formation at different velocities

The hydrate growth (Figure 6 (A)) in baseline experiments (i.e. 50 vol. % water content and 0 vol. %
AA) was also affected by mixture velocity, with a higher initial gas consumption rate at a higher velocity
(i.e. gas consumption rate is ~ 1.3 times higher at 5.8 ft s‐1 compared to 2.3 ft s‐1). The mean droplet sizes at
hydrate onset are ~ 48 and ~ 38 μm at 2.3 and 5.8 ft s‐1, respectively, leading to a ratio of inverse diameters
of ~1.3. This is in agreement with the kinetic model for hydrate growth in water-in-oil emulsions we have
developed and incorporated in a multiphase flow simulator (Zerpa et al., 2012), which suggests that the
initial rate of gas consumption for hydrate growth is linearly dependent on the surface area of water droplets,
as given in Equation 4:

(4)

where ngasis moles of gas consumed for hydrate formation, k1and k2are the intrinsic rate constants, ASis
the surface area between the water and the hydrocarbon phases, Wgis the average molecular weight of the
hydrate forming components, Tsysis the system temperature, ∆Tsubis the subcooling or thermal driving force
for hydrate formation (∆Tsub=Thyd_eq-Tsys). Thyd_eqis the hydrate equilibrium temperature at a given system
pressure and composition. Finally, uis a scaling factor accounting for mass and heat transfer resistances
that are not present in the original intrinsic hydrate growth kinetic model. Theoretical gas consumption
rates for the baseline tests were calculated using the droplet size data from Figure 6 (B), the temperature
of the system and the experimental subcooling at hydrate onset. The theoretical gas consumption rate at
the onset of hydrate formation was approximately three orders of magnitude higher than the experimental
gas consumption rate. It is worth noting that the droplet size used in these calculations corresponds to
the mean square-weighted chord length that may not correspond to the actual droplet size in the system
(Boxall et al., 2012). This analysis also assumes that all available water is fully dispersed in the oil phase
as droplets. However, previous studies showed that the water phase could be partially dispersed in the oil
phase at low mixture velocities, with the remaining water as a separated aqueous phase reducing the water/
oil interfacial area (Vijayamohan, 2015). Extent of water dispersion cannot be verified in these studies.
Additionally, both surface area and subcooling are considered constant throughout hydrate formation.
However, salt concentration in the aqueous phase would increase as water is consumed to form hydrates,
lowering the hydrate equilibrium temperature and, therefore, decreasing subcooling. The available surface
OTC-27621-MS 11

area for hydrate formation could also vary due to water consumption following hydrate formation and
subsequent changes in the flow regime.
The effect of mixture velocity on the mean droplet size at hydrate onset in experiments with 2 vol. % AA
is masked by the increased stability of the dispersion with these surfactants, which help maintain the low
mean droplet size obtained in the initial tests at the higher mixture velocity. Hence, similar surface area is
available for hydrate growth at the different mixture velocities and the initial gas consumption rate is similar
for experiments with AA both at 2.3 and 5.8 ft s‐1mixture velocity. Moreover, the initial gas consumption
rate in experiments dosed with this particular AA is lower when compared with baseline tests, despite
offering more surface area for hydrate growth. This result suggests possible hydrate kinetic inhibition effects
associated with this AA. Gas consumption rates in baseline tests at 2.3 and 5.8 ft s‐1 mixture velocity are
~ 1.6 and ~ 2 times higher, respectively, when compared with gas consumption rates from corresponding
tests with 2 vol. % AA.

AA Performance During Shut-in and Restart Operations

Stagnant conditions during shut-in can lead to hydrate particle agglomeration due to negligible shear
forces in the system, therefore, increasing overall hydrate particle size and making solid material transport
throughout the system difficult. Injection of AAs could reduce hydrate cohesive forces, favoring re-
dispersion of hydrate particles once fluid flow restarts.
Simulating a shut-in period after hydrates stop forming in flowloop tests allows assessment of the
potential of AAs to prevent hydrate particle agglomeration in stagnant conditions, and to recover hydrate
transportability after restart. Flowloop experiments with injection of 2 vol. % AA were shut in for six hours
and restarted. Tests initially conducted at 2.3 and 3.7 ft s‐1 were restarted at the same velocity used for
hydrate formation under continuous pumping. The test with hydrate formation at higher velocity (5.8 ft s‐1)
was restarted at a low velocity (2.3 ft s‐1) in order to evaluate the consequences of restarting the system at
a lower velocity than that at which hydrates were formed. Moreover, the baseline experiment with hydrate
formation at 5.8 ft s‐1 was also shut-in for a period of two hours and restarted at 5.8 ft s‐1 again. Baseline
tests at lower velocities were not shut-in due to time limitations. Relative pressure drop and mass flow rate
data were used to determine whether flowing conditions observed before shut-in can be recovered after
restarting the system. Particle/droplet size measurements provide information about the evolution of the
hydrate particle size during shut-in.
Figure 7 shows relative pressure drop (A) and mass flowrate (B) from experiments with 2 vol. % AA
injection, two hours before shut-in and after restart. Results from experiments at two different mixture
velocities (2.3 and 3.7 ft s‐1) are included. Both relative pressure drop and mass flowrate are almost identical
before shut-in and after restart at 3.7 ft s‐1, suggesting that the properties of the flowing slurry are unaffected
during the shut-in period. Similar results are observed at lower velocity (2.3 ft s‐1); however, relative pressure
drop is slightly lower after restart with respect to relative pressure drop values before shut-in. This reduction
in the relative pressure drop could be attributed to some hydrate particles deposited at the bottom of the
pipe, which cannot be lifted at this low velocity. Deposited hydrate particles might reduce viscosity in the
slurry due to lower solids concentration, causing the slight decrease in viscosity observed in Figure 7 (A).
In this figure, the relative time is defined with respect to the time at which the system is shut-in.
12 OTC-27621-MS

Figure 7—(A) Relative pressure drop two hours before shut-in and two hours after restart in mineral oil systems at 50
vol. % water content dosed with 2 vol. % AA. (B) Mass flowrate two hours before shut in and two hours after restart in
mineral oil systems at 50 vol. % water content dosed with 2 vol. % AA. Results correspond to hydrate tests conducted
at two different mixture velocities (2.3 and 3.7 ft s‐1). Inset plots show relative pressure drop (A) and mass flow rate (B)
throughout the full experiment. Relative time in these plots is defined with respect to the time at which the system is shut-in.

Another interesting aspect in shut-in operations is the evolution of the hydrate particle size. Figure 8
shows mean particle/droplet sizes before shut-in and after restart from mineral oil systems dosed with 2
vol. % AA. Mean droplet/particle sizes from 2.3 and 5.8 ft s‐1 tests are included. As discussed in Figure 4,
mixture velocity has a minor influence on hydrate particle size when sufficient AA is dosed to the system.
This suggests that once hydrate particles are broken by shear forces, the recombination process of such
particles can be slowed down by the AA. This could lead to a stable dispersion of fine hydrate particles,
similar to the droplet behavior in a surfactant-stabilized emulsion. After restarting the system at 2.3 ft s‐1,
a sudden increase in mean droplet/particle size is observed. Such an increase could be related to hydrate
particles that have come together during shut-in forming weakly bonded agglomerates and that are initially
detected after restarting flow in the system. However, as the cohesive forces between hydrate particles are
reduced by the AA, such hydrate clumps could break easily, eventually leading to the same mean droplet/
particle sizes obtained before shut-in, regardless of the velocity at which hydrate particles were formed.
OTC-27621-MS 13

Figure 8—Mean droplet/particle size an hour before shut-in and an hour after restart in mineral oil systems at 50 vol.
% water content dosed with 2 vol. % AA. Hydrate particles are formed at two different mixture velocities (2.3 and 5.8
ft s‐1). Restart is conducted at 2.3 ft s‐1 in both cases. Insets shows mean droplet/particle size evolution throughout
the full experiment. Relative time in this plot is defined with respect to the time at which the system is shut-in.

Finally, it is worth comparing the evolution of particle size during the shut-in period in systems with and
without AA injection. Figure 9 shows different droplet/particle size data from tests conducted at 5.8 ft s‐1
with and without 2 vol. % AA dosed to the system. Results include mean droplet/particle sizes before and
after the hydrate onset, including the shut-in stage, as well as the chord length count from different size
ranges of droplet/particles. Chord length counts are divided in small droplets/particles (d < 50 μm), medium
droplets/particles (50 < d < 150 μm) and large droplets/particles (150 < d < 300 μm).
14 OTC-27621-MS

Figure 9—Droplet/particle size evolution throughout hydrate formation in tests at 5.8 ft s‐1 with and
without AA injection, including mean droplet/particle size (A and E), small droplet/particle counts
(B and F), medium droplet/particle counts (C and G) and large droplet/particle counts (D and H)
OTC-27621-MS 15

Useful information on the effects of an AA on hydrate particle size evolution can be extracted at different
stages of the experiment. First, at hydrate onset (relative time ~ 0), a sudden increase in mean droplet
particle size was observed in tests both with and without AA (Figure 9 (A) and (E)); however, this increase
was more significant for the experiment without AA. Increasing droplet/particle size around the hydrate
onset could be related to a decrease in the counts of small particles in both systems (Figure 9 (B) and (F)).
Decreasing counts of small chord length at hydrate onset has been associated with systems that are water-
continuous before hydrate onset, according to previous studies using chord length counts to analyze hydrate
growth and agglomeration (Melchuna et al., 2016). Furthermore, counts of both medium and large droplets/
particles (Figure 9 (C) and (D)) increase by one and two orders of magnitude respectively at hydrate onset
in the system without AA. On the other hand, in systems with AA injection, medium and large droplet/
particle counts (Figure 9 (G) and (H)) remain roughly the same throughout the experiment, despite a sudden
dip in medium particle counts and slight appearance of large particles (which are close to zero for most
of the test) around the onset. According to this, the increase in mean droplet/particle size (Figure 9 (A))
around hydrate onset in systems without AA might be controlled by the appearance of medium and large
hydrate agglomerates (Figure 9 (C) and (D)). Conversely, increasing droplet/particle size in systems with
AA injection (Figure 9 (E)) could be related to decreasing counts of small particles (Figure 9 (F)). Such a
decrease in small particle counts could be caused by changes in the reflective properties of water/oil droplets
turning into hydrate particles (Turner, 2006). As time progresses in the test, medium and large droplet/
particle counts decrease, particularly in the experiment without AA injection, suggesting bedding of larger
hydrate particles in the system and causing a decrease in mean droplet/particle sizes.
Høiland (Høiland et al., 2005) showed that hydrate formation could have different effects on the surface
chemistry of a system depending on the composition of the oil phase. Crude oils with low plugging tendency
tend to form oil-wet hydrate particles, favoring oil-continuous dispersions after hydrates start to form in the
system. Effective hydrate AAs have been associated with formation of oil-wet hydrate particles (Kelland,
2006). This provides further support to a possible transition from a water-continuous to an oil-continuous
dispersion occurring after hydrate onset in the system dosed with 2 vol. % AA.
Finally, after a shut-in period of six hours and a restart at 2.3 ft s‐1, all droplet/particle counts (small,
medium and large) recover to similar values observed before shut in (Figure 9 (F), (G) and (H)). Increasing
counts of medium and large droplets/particles are noticed right after restart; however, such increasing counts
disappeared within 30 minutes after the restart. These medium and large droplet/particle counts could be
related to clumps of hydrate particles moving together, which are weakly interacting due to reduced cohesive
forces between hydrates in the presence of AAs. Such hydrate clumps might be easily re-dispersed into fine
hydrate particles under shear forces leading to the same particle size distribution observed before shut-in.
On the other hand, an appreciable increase in the mean droplet/particle size during shut-in (Figure 9 (A))
was observed for the test without AA injection. Medium and large droplet/particle counts increased during
shut-in leading to greater mean droplet/particle size (Figure 9 (C) and (D)). This could be related to large
hydrate aggregates formed under static conditions during shut-in. Medium and large droplet/particle counts
further increased as time progresses after the restart, suggesting that large aggregates, which cannot be
broken up by shear forces, might be incorporated into the slurry. These results indicate that hydrate particle
agglomeration during shut-in may be prevented using an AA in a system with a non-dispersing oil phase.

Conclusions
High pressure industrial-scale flowloop tests using a non-dispersing oil were conducted in order to compare
the influence of mixture velocity on hydrate particle transportability studies utilizing an AA compared to
systems without AA injection. Experiments included shut-in and restart operations, which are important
in flow assurance. Mixture velocity effects are observed in baseline tests both in the hydrate growth rate
(directly proportional) and the mean droplet/particle size (inversely proportional); however, such effects
16 OTC-27621-MS

were masked with injection of this particular AA formulation leading to similar hydrate growth and particle
size evolution regardless of the mixture velocity. Moreover, dispersion tests showed that this AA formulation
also modifies the surface chemistry of water/oil dispersions favoring water-continuous systems.
AA injection helps reduce hydrate particle bedding at all studied velocities; however, certain flow
conditions were required to fully prevent hydrate particle bedding. Additionally, this particular AA
formulation successfully inhibited hydrate particle size increase (agglomeration) under static conditions
(shut-in), allowing full recovery of solid material flow after restarting the system. In this sense, the droplet/
particle CLD measurements yielded useful information to understand the influence of an AA on both water/
oil and water/oil/hydrate dispersions through analysis of the evolution of the droplet/particle size throughout
the experiments.

Acknowledgements
The authors acknowledge the significant contributions to this work by Brendon Keinath, Doug Turner,
Geetha Mahadevan, Todd Lagus, Giovanny Grasso, Tabish Maqbool, Glenn Cobb, Roy Livingston and
all staffs from ExxonMobil Upstream Research Company (Houston, TX 77098, USA) for access to the
flowloop facilities and guidance during the experimental investigation and analyses of this work. The
authors would also like to thank the CSM Hydrate Consortium members for funding and support.

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