OTC-30710-MS

Managing Hydrate Formation in Subsea Production

Eric F. May, Peter J. Metaxas, Vincent W. S. Lim, Kwanghee Jeong, Bruce W. Norris, Temiloluwa O. Kuteyi, Paul L.
Stanwix, Michael L. Johns, and Zachary M. Aman, University of Western Australia

Copyright 2020, Offshore Technology Conference

This paper was prepared for presentation at the Offshore Technology Conference originally scheduled to be held in Houston, TX, USA, 4-7 May 2020. Due to COVID-19
the physical event was not held. The official proceedings were published online on 4 May 2020.

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Abstract
Quantitative prediction of gas hydrate formation risk is critical for the successful implementation of risk-
based approaches to hydrate management in subsea production. Here we use a high pressure, stirred,
automated lag-time apparatus and a high pressure acoustic levitator to experimentally obtain smooth
probability distributions describing stochastic hydrate formation. Robust, repeatable hydrate nucleation and
growth rate probability distributions as a function of induction time and subcooling are measured for various
gases, shear rates and inhibitor dosages in systems with interfacial areas ranging from (0.1 to 60) cm2. The
results reveal that new engineering models can be used to reliably predict hydrate formation probability.
Importantly these new models have solid theoretical foundations which enables them to be generalized with
confidence to industrial systems.

Introduction
The ability to quantitatively predict gas hydrate formation risk would significantly advance many areas
of offshore oil and gas production. For example, conservative margins for methanol or MEG injection
rates could be reduced and/or the required dosage of kinetic hydrate inhibitors needed to lower formation
risk could be optimized. More broadly, such an ability will be critical for the implementation of risk-
based approaches to flow assurance. A first step towards quantifying hydrate formation risk is however the
characterization of hydrate formation probability. Hydrate formation onset arises due to hydrate nucleation,
an intrinsically stochastic process which can be rigorously characterized only using large datasets wherein
multiple, independent hydrate formation events have been measured. Conventional laboratory apparatus are
typically not conducive to achieving such measurements over practical timeframes (e.g. [1] and references
therein). However, these measurements are critical for the collection of high quality datasets which can be
used to rigorously validate theories that can then be generalized with confidence to industrially-applicable
engineering models. Here, high-pressure, stirred automated lag-time apparatus, sapphire autoclaves, and a
high-pressure acoustic levitator were used to study hydrate formation probability and rates of growth over
a range of system sizes for various gases, shear rates and inhibitor dosages. The resulting high resolution
probability curves are fitted with theoretical models demonstrating the ability to use the collected data for
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model validation and testing. Once validated, theoretical models for hydrate formation onset can be used as
the basis for more complete, industrially-applicable engineering models.

Statement of Theory and Definitions

In the experiments detailed here, we detect hydrate formation onset either visually or via a pressure reduction
(details given in the next section). Hydrate phase boundaries are calculated using the Cubic Plus Association
equation of state (CPA EoS), implemented in Multiflash 6.2 [2]. The calculated boundaries are used for
determining subcooling at formation onset. Subcooling is defined as ΔT = Tf – Teq where Tf is the formation
temperature and Teq is the equilibrium temperature at the formation pressure.
Comparisons will be made with theories for hydrate nucleation based on classical nucleation theory
(CNT) [3, 4]. These models predict an exponential distribution of induction times yielding the cumulative
probability of formation as a function of time as follows:
(1)
where J is a nucleation rate in s−1 and t is time. The nucleation rate can be written as:

(2)

In the above, Δse is the entropy of hydrate dissociation at Teq (per hydrate building unit; approximately 20
kB) and kB is the Boltzmann constant. A is a kinetic parameter proportional to the concentration of nucleation
sites whereas B' provides a measure of the nucleation work.
As will be shown below, fitting of eq (1) to induction time distributions enables extraction of the
nucleation rate, J. Subsequently, measuring J as a function of subcooling enables extraction of A and B' (as
demonstrated in [5]). These values, when measured for a specific production fluid, can then be used to
predict formation risk.

Description and Application of Equipment and Processes

We present or discuss formation data obtained with four different types of apparatus: high pressure stirred
automated lag time apparatus (HPS-ALTAs) [1, 5] (Figure 1), a high pressure visual autoclave HPVA (DB
Robinson-type sapphire cell, e.g. [6], Figure 2a) and a high pressure acoustic levitator [7] (Figure 2b). The
HPS-ALTA is a multi-cell apparatus (e.g. Figure 1b) which enables independent concurrent measurements
of hydrate formation in separate cells.
OTC-30710-MS 3

Figure 1—(a) 2nd (left) and 3rd (right) generation steel HPS-ALTA cells mounted on magnetic stirrers. (b) Four
3rd generation cells in a temperature controlled (32 °C) air bath (shown without top and front panels for clarity).

Figure 2—(a) HPVA and bath (adapted from [8]). The sapphire HPVA visible in the center of the bath with the stirrer motor
at the top of the image. (b) Acoustic levitator: cell internals (left), system schematic (center) and system photo (right).

In the HPS-ALTA and HPVA, onset is determined by a pressure reduction due to gas consumption by
the growing hydrate phase (detected via pressure transducers; see Figure 3a and b). Formation onset in
the levitator is detected visually (Figure 3c). Mechanical mixing is applied in both the HPS-ALTA (using
a cross-shaped magnetic flea) and HPVA (using a four-blade vane-and-baffle geometry impeller). Torque
measurements at fixed RPM can also be made in the HPVA.
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Figure 3—Hydrate formation onset via a pressure reduction during a constant cooling
experiment (a) or a fixed temperature, constant subcooling experiment (b) and via visual
detection of hydrate shell growth onset in a levitated water droplet (center image).

The HPS-ALTA and HPVA are both run isochorically following initialization at a set temperature and
pressure. Autoclave temperature control is achieved using a variable temperature bath (cooling rates on the
order of K/h) whereas the HPS-ALTA cells are cooled and heated using thermoelectric (Peltier) elements
mounted on the 6 outer sides of each hexagonal cell (Figure 1a). The thermoelectric cooling allows for
cooling rates up to 5 K/min. Temperature is measured using 100Ω platinum resistance temperature detectors
(RTDs) located at the bottom of the liquid phase in the HPVA or in the wall of the steel HPS-ALTA cell. In all
measurements, the system is purged three times with the measurement gas prior to running the experiment.
In constant cooling measurements (HPS-ALTA and autoclave), the system is continuously cooled and
the temperature at which formation onset occurs is recorded (Figure 3a). A subcooling value can then be
calculated. Induction time measurements (detailed here for the HPS-ALTA only) are carried out at a fixed
temperature and pressure (following an initial rapid system cooling from outside the hydrate equilibrium
region). These measurements enable extraction of the induction time: the time required for hydrates to form
(induction time) since reaching that fixed subcooling condition (Figure 3b). The rapid cooling capability
in the HPS-ALTA ensures the time spent ramping the temperature down to achieve a target subcooling is
minimized. This minimizes the amount of time during the experiment where the driving force for hydrate
formation is changing.
For levitation measurements, the high pressure, visual levitation cell (L800, Borosa Acoustic Levitation
GmbH) is first pressurized with gas at a fixed temperature and pressure condition within the hydrate
equilibrium region. A water droplet is then introduced into the cell via a cannula and a high pressure, manual
syringe pump. A sonotrode (ultrasonic transducer) and reflector are used to generate a standing acoustic
wave that allows for levitation of the injected droplet. The latter is back illuminated and continuously imaged
(0.1 Hz imaging rate). Formation onset is identified based on the first appearance of visible solids on the
droplet (e.g. Figure 3c). This is followed by formation of a complete hydrate shell. Temperature is measured
in the wall of the levitation cell using a thermocouple, the cell being cooled via a circulation chiller which
drives coolant through a cooling jacket.
OTC-30710-MS 5

Data and results: impact of shear and subcooling

We will focus primarily on results from the 2nd generation HPS-ALTA [5], later making comparisons with
results obtained with the HPVA, levitator and a larger, 3rd generation HPS-ALTA. Some data from the 1st
generation HPS-ALTA will also be shown [1]. All measurements with the 2nd generation HPS-ALTA were
obtained with a 5 mL liquid loading (total cell volume is 10.9 mL).
The fast temperature ramping capability of the HPS-ALTA enables rapid collection of large numbers (100
or more) of independent hydrate formation events under constant cooling conditions (ramped temperature;
typically (1-2) K/min). Note that between each formation event, the system is heated to 40 °C for at least 5
minutes to ensure complete hydrate dissociation prior to running the next measurement. Each ramp yields a
value of the subcooling at formation with the resultant values binned to generate a histogram. This data can
then be converted into a cumulative probability distribution via numerical integration [9]. All processing is
carried out using an automated algorithm [1].
Example data from the 1st generation HPS-ALTA for a methane + water system (1 mL liquid loading,
total volume of 3 mL) [1] is shown in Figure 4a where we plot the cumulative probability of formation
within the hydrate equilibrium region as a function of subcooling for two different shear rates. Consistent
with the stochastic nature of nucleation, there is a significant spread in the range of subcooling values at
which formation is observed. The probability of observing formation increases with subcooling until a value
of 1 is reached at high subcooling.

Figure 4—(a) Calculated cumulative hydrate formation probability for methane and water as a function of
subcooling (constantly ramped temperature) at two shear rates [1]. (b) Shear rate dependence of the mean
subcooling extracted from a series of constant cooling experiments for methane + water. (c) Distributions
of initial hydrate growth rate for the data used to construct the probability distributions in panel (a) [1].

The data in Figure 4a can also be used to demonstrate the role of shear: lower shear leads to formation
occurring at higher subcooling values (i.e. deeper in the hydrate equilibrium region). Shear dependence was
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studied further in the 2nd generation HPS-ALTA. In Figure 4b, we plot the mean subcooling at formation
versus shear rate, again for a methane + water system. This dataset emphasizes the critical role of shear in
overcoming mass transfer limitations: below 400 RPM, the mean subcooling strongly increases, suggesting
that the observed probabilities are being influenced by mass transfer limitations. From a fundamental
perspective, the ability to collect such data enables the identification of the conditions under which extracted
nucleation rates are free of (system-dependent) mass transfer limitations. However, the ability to optionally
apply shear is also of direct relevance to understanding industrial systems, enabling an evaluation of the
reduction in formation probabilities associated with shut-in versus steady-state operation.
Post-formation time-dependent pressure data obtained with the HPS-ALTA (e.g. Figure 3a) can also be
used to extract hydrate growth rates, providing further insight into formation kinetics beyond nucleation-
limited formation onset. In Figure 4c, we show the rates of initial hydrate growth obtained for the hydrate
formation events used to generate the probability curves in Figure 4a. Again, shear plays a critical role:
despite formation occurring at higher values of subcooling (which, alone, would yield a higher growth rate;
e.g. [5, 10, 11]), the measurements obtained here under lower shear yielded lower rates of growth, again
demonstrating the important role of mass transfer limitations in defining measured kinetic quantities. All
other measurements presented here have been obtained at a shear rate of 700 RPM.
The increasing formation probability with increasing subcooling is due to an increasing nucleation rate
[3]. This can be seen directly from induction time measurements carried out at fixed subcooling values, as
shown in Figure 5. There we plot the cumulative formation probability for a sII-hydrate-forming gas mixture
(with water) as a function of time for four fixed subcooling values varying from 6.0 K to 9.8 K [5]. The
shortest formation times are seen at the highest subcooling. Consistent with predictions from CNT (eq 1),
the induction time distributions exhibit good agreement with an exponential distribution (also demonstrated
previously for a sII-forming gas mixture in [12]), enabling the extraction of a nucleation rate J which, as
expected, increases with subcooling (consistent with eq 2 [5]).

Figure 5—Cumulative probability of sII hydrate formation as a function

of time for different subcooling values [5]. Solid lines are fits to eq (1).

Data and results: impact of KHIs on formation

Measurements of hydrate formation in the 1st and 2nd generation HPS-ALTA have also been used to
characterize the effect of KHIs (Luvicap EG and Luvicap 55W; BASF) on formation probability. Results
of measurements carried out under constant cooling are shown in Figure 6. Panels a and b demonstrate how
OTC-30710-MS 7

the probability curves both narrow and shift to higher values of subcooling in the presence of increasing
KHI concentrations. The curves in Figure 6b demonstrate good cell-to-cell reproducibility and highlight the
diminishing returns (in terms of inhibition) when increasing the KHI concentration beyond 1 wt%. Models
based on CNT have been successfully applied to reproduce the curves (Figure 6a).

Figure 6—(a) Formation probability as a function of subcooling under ramped temperature as

measured for Luvicap EG in the 1st generation HPS-ALTA for a sII-forming gas mixture (a) and
Luvicap 55W in the 2nd generation HPS-ALTA with methane + water (b). (c) shows the mean
subcooling as a function of KHI concentration for the data shown in panel (b). Concentrations in wt%.

While the above subcooling measurements are well suited to rapid performance screening when looking
(e.g.) at the effect of varying inhibitor concentration dependence or chemistry, measurements of induction
times are able to yield data that can be directly compared to flowline residence times that are encountered in
real-world production systems. In Figure 7, we show the induction time distribution obtained with methane
+ water (i.e. no KHI; panel a) and in a second experiment where the aqueous phase contained 1 wt% KHI
(Luvicap 55W; panel b). Data was obtained with the 2nd generation HPS-ALTA at pressures around 120
bara. While the KHI-free measurement again yields a distribution which remains consistent with eq 1 (see
data and solid black line fit in Figure 7a), this is not the case for the measurement in the presence of the KHI.
Indeed, for exponentially distributed data, the dataset's mean and standard deviation will be equal, leading
to a very large spread in the observed induction times, as observed in Figure 7a. In the presence of a KHI
however (here Luvicap 55W from BASF), we see a shifted and narrowed distribution (Figure 7b): despite
a mean induction time of 16,439 s, the standard deviation is significantly less, at 6,278 s. Consistent with
that seen under constant cooling conditions (Figure 6), the presence of a KHI fundamentally changes the
8 OTC-30710-MS

formation probability distribution. This has consequences for the definition of risk as well as the applicability
of existing models. These narrowed distributions are consistently seen over a range of subcooling values,
KHI concentrations and cells (Figure 8).

Figure 7—(a) Calculated cumulative formation probability as a function of time for a

methane + water system (a) and where the aqueous phase contained 1 wt% KHI (Luvicap
55W, BASF, also at 700 RPM) (b). The subcooling was 2.7 K in (a) and 6.4 K in (b).

Figure 8—Induction time distributions at KHI loadings (Luvicap 55W) of 0.3 wt% (upper left), 1 wt% (lower left), 2 wt% (upper
right) and 3 wt% (lower right) at various subcooling values. Different colors represent different subcoolings. Different
symbols represent different experimental cells. For each experiment, average subcooling is labelled next to the marker

Data and results: impact of KHIs on growth rates

In Figure 9 we show initial methane hydrate growth rates measured in the absence and presence of Luvicap
55W (1 wt%) under constant cooling conditions as a function of subcooling. Despite some spread in the
extracted growth rates (also seen in the induction time measurements detailed in [5]), the growth rates
increase roughly linearly with subcooling, qualitatively consistent with predictions from [10]. The plot also
provides an alternative method to visualize a KHI's inhibition effect: not only is formation shifted to higher
OTC-30710-MS 9

subcooling values but the fitted (linear-in-subcooling) growth rate is reduced approximately by a factor of
10.

Figure 9—Initial hydrate growth rates as a function of subcooling as determined from the gas consumption
rate in the absence and presence of a KHI. Values determined from constant cooling experiments with a 1 K/
min cooling rate. Blue lines are linear fits with constrained x-axis intercept (zero growth rate at zero subcooling).

The growth rates can also be binned and represented as histograms, as shown in Figure 10. Here,
diminishing returns are again seen as the KHI concentration is increased (now in terms of growth rather
than nucleation inhibition): the distributions exhibit only a weak concentration dependence from 0.3 wt%
onwards.

Figure 10—Initial growth rate (Gi) distributions for methane hydrate at various KHI concentrations. Repeats with
different cells are shown (full and half shaded) for each KHI concentration. The scale of the axes in panels (c-f)
are different to those in panels (a,b) with the growth rate axis being reduced in range by a factor of 5 for the latter.

Data and results: apparatus dependence

Nucleation rates extracted with the HPS-ALTA for a sII-hydrate-forming gas mixture exhibit good
consistency with those extracted at comparable pressures by Ke et al [12] for a sII-hydrate-forming gas
mixture determined using an autoclave with a volume several times that of the HPS-ALTA, as shown
in Figure 11a [5]. The consistency between such different apparatus with different scales suggests that
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nucleation rates might be less scale-dependent than has previously been assumed, particularly once a critical
system size has been reached. This suggests that it may be possible to directly use nucleation rates measured
in the laboratory to predict those that will be observed in production systems. The subcooling-dependence of
the nucleation rate is consistent with the theoretical model derived from nucleation theory (eq 2), as shown in
Figure 11b. Fitting such laboratory data and extracting values of the kinetic and thermodynamic parameters,
A and B' [here (1.6 ± 0.4) × 10−3 s−1 and (3.6 ± 0.4) × 104 K3, respectively] could enable to quantitative
predictions to be made for production systems using engineering models tuned to fluid-specific data.

Figure 11—Nucleation rates extracted from induction time distributions measured using
the 2nd generation HPS-ALTA compared with data from [12] (a) and fitted with eq 2 (b).

Additional evidence that nucleation rates may scale only very weakly can be found by comparing
nucleation rates observed for mm-scale levitated droplets with those measured using the HPS-ALTA [7].
Figure 12 shows nucleation rates for sII hydrates determined by the two apparatus over a wide range of
subcoolings, which have been scaled by the gas-water interfacial area. In the case of the levitated droplets,
the imaging software allows a direct measurement of this interfacial area, which is on the order of 13 mm2.
This is about three orders of magnitude smaller than the interfacial area present in the HPS-ALTA cells;
to construct Figure 12 we have assumed a constant value of 11 cm2 based on the dimensions of the cells.
Further research is required to investigate the validity of the assumption but the apparent consistency of
the log-linear trend apparent in Figure 12 for the two very different apparatus is promising. Further, the
observation of comparable area-normalized nucleation rates in freely levitated droplets and in a sheared
water volume in contact with a steel containing vessel thus suggest that shear (either mechanical or via an
acoustic field) is more important than water-solid contact (and the associated solid defects) in determining
the nucleation rate.
OTC-30710-MS 11

Figure 12—Nucleation rates normalized by the gas-water interfacial area estimated for two different
apparatus as a function of subcooling. For the HPS-ALTA, the interfacial area was assumed to be 11
cm2 while for the high-pressure acoustic levitator it was measured in both cases (» 11 mm2 and 16 mm2)

Constant cooling experiments with the 1" sapphire HPVA at UWA also yield subcooling values at
formation similar to those observed in the 2nd generation HPS-ALTA cells, which have the same internal
diameter (ID) but quite different volumes and solid surfaces in contact with the fluids (sapphire vs steel).
Furthermore, preliminary measurements made with the recently commissioned 3rd generation HPS-ALTA
(Figure 1, 42 mm ID) have yielded subcooling distributions for methane + water that, as shown in Figure
13, are largely comparable to those seen in the smaller, 2nd generation HPS-ALTA (24 mm ID). Before firm
conclusions can be drawn, detailed shear dependence studies, induction time measurements and thermal
gradient characterizations need to be carried out with the 3rd generation cells. Nevertheless, when taken
collectively, all of these results indicate that it should be possible in the near future to develop a field-
applicable method of predicting gas hydrate nucleation rates, for example via interfacial area estimates and/
or through the parameters A and/or B' in eq (2).

Figure 13—Subcooling distributions for methane hydrate in the 2nd (24 mm ID) and 3rd generation (42 mm ID) HPS-ALTA cells.
12 OTC-30710-MS

Conclusions
Improved measurement technology has been developed and used to allow more detailed and reliable
investigations of hydrate formation probability. These measurements allow more holistic characterizations
of kinetic inhibitor performance and provide new insight into their operational mechanisms. Such data
sets should both facilitate the development of more effective KHIs and also provide robust cost-benefit
analyses regarding KHI dosage rates and associated risk suppression, based on both quantifiable reductions
in nucleation and growth rates.
The similarity of nucleation rates measured over a wide range of length scales using very different
apparatus suggests that the scale-dependence of gas hydrate formation may be smaller than thought
previously. By using the framework of well-established Classical Nucleation Theory as applied to gas-
hydrates, it might soon be possible to provide robust predictions of hydrate formation probability in
production systems if the relevant fluids are characterized appropriately using the HPS-ALTA methodology
presented here.

Acknowledgements
This work was supported by Shell and the Australian Research Council (DP150100341, IC150100019,
LE170100174, FT180100572 and DE140101094). The authors are grateful to Daniel Crosby, Gert
Haandrikman and Ishan Rao for guidance and stimulating discussions and to Andrew Pelc for contributions
to the measurements and analysis.

Nomenclature
A kinetic nucleation parameter (s−1)
B' thermodynamic nucleation parameter (K3)
J hydrate nucleation rate (s−1)
kB Boltzmann constant (1.3806 × 10−23 J/K)
P cumulative probability of hydrate formation
Δse entropy of hydrate dissociation (J/K)
t time at fixed temperature and pressure (s)
ΔT subcooling (K)
Teq equilibrium temperature at the hydrate formation pressure (K)
Tf hydrate formation temperature (K)

References
1. May, E.F., et al, Gas Hydrate Formation Probability Distributions: The effect of shear &
comparisons with nucleation theory. Langmuir, 2018. 34: p. 3186.
2. MultiFlash 6.2. 2016, Infochem/KBC Advanced Technologies plc.
3. Kashchiev, D. and A. Firoozabadi, Nucleation of gas hydrates. Journal of Crystal Growth, 2002.
243(3-4): p. 476–489.
4. Kashchiev, D. and A. Firoozabadi, Induction time in crystallization of gas hydrates. Journal of
Crystal Growth, 2003. 250(3-4): p. 499–515.
5. Metaxas, P.J., et al, Gas hydrate formation probability distributions: Induction times, rates of
nucleation and growth. Fuel, 2019. 252: p. 448–457.
6. Aman, Z.M., et al, Methane Hydrate Bed Formation in a Visual Autoclave: Cold Restart and
Reynolds Number Dependence. Journal of Chemical and Engineering Data, 2015. 60(2): p.
409–417.
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7. Jeong, K., et al, Hydrate nucleation and growth on water droplets acoustically-levitated in high-
pressure natural gas. Physical Chemistry Chemical Physics, 2019. 21(39): p. 21685–21688.
8. Akhfash, M., et al, Gas Hydrate Thermodynamic Inhibition with MDEA for Reduced MEG
Circulation. Journal of Chemical and Engineering Data, 2017. 62(9): p. 2578–2583.
9. May, E.F., et al, Quantitative kinetic inhibitor comparisons and memory effect measurements
from hydrate formation probability distributions. Chemical Engineering Science, 2014. 107: p.
1–12.
10. Turner, D., et al, Development of a hydrate kinetic model and its incorporation into the
OLGA2000 transient multi-phase flow simulator, in Fifth International Conference on Gas
Hydrates. 2005: Trondheim, Noway.
11. Englezos, P., et al, Kinetics of Gas Hydrate Formation from Mixtures of Methane and Ethane.
Chemical Engineering Science, 1987. 42(11): p. 2659–2666.
12. Ke, W., et al, Inhibition-Promotion: Dual Effects of Polyvinylpyrrolidone (PVP) on Structure-II
Hydrate Nucleation. Energy & Fuels, 2016. 30(9): p. 7646–7655.