Fuel 235 (2019) 1266–1274

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Full Length Article

Experimental evaluation of RAFT-based Poly(N-isopropylacrylamide) T

(PNIPAM) kinetic hydrate inhibitors
Juwoon Parka, Hyunho Kima, Kelly Cristine da Silveirab,c, Qi Shengc,e, Almar Postmad,
⁎ ⁎
Colin D. Woodc, , Yutaek Seoa,
a
Department of Naval Architecture and Ocean Engineering, Research Institute of Marine Systems Engineering, Seoul National University, 1 Gwanak-ro, Gwanak-gu, Seoul
08826, Republic of Korea
b
Polytechnic Institute of Rio de Janeiro, Rio de Janeiro State University, Nova Friburgo, Brazil
c
CSIRO Australian Resources Research Centre, Kensington, WA 6152, Australia
d
CSIRO Manufacturing, Clayton, VIC 3168, Australia
e
Curtin University of Technology, Kensington, WA 6152, Australia

A R T I C LE I N FO A B S T R A C T

Keywords: As the oil and gas industry produces hydrocarbons from deeper waters and colder regions the issue of hydrate
Kinetic hydrate inhibitor formation becomes more serious. As a result, hydrate inhibition has focused on kinetic hydrate inhibitors (KHI)
PNIPAM and anti-agglomerants (AA) as an alternative to the existing approaches which involves injecting vast quantities
Polymer architecture of thermodynamic inhibitors. In this research, we evaluated the effect of different architectures (linear and
RAFT polymerization
branched) of poly(N-isopropylacrylamide) (PNIPAM) polymers synthesized using reversible addition−-
fragmentation chain-transfer (RAFT) polymerization. Unlike non-reversible deactivation radical polymerisation
(RDRP) synthetic routes this generates accurately controlled KHI candidates with target molecular weight,
narrow molecular weight distributions and controlled architecture, so that the effect on hydrate inhibition can
be more accurately assessed. The RAFT-based polymers (linear and branched) were compared to a commercially
available linear PNIPAM synthesized via non-RDRP radical polymerization and control groups (pure water, PVP,
and Luvicap). The hydrate experiments were performed in a high pressure autoclave with continuous cooling
under different cooling rates (0.25 K/min, 0.033 K/min, and 0.017 K/min). In addition, a cold restart was si-
mulated using constant subcooling. The results regarding subcooling temperature, onset time, and hydrate
fraction with resistance-to-flow were compared to known KHIs. These revealed that a linear PNIPAM-
MacroRAFT polymer delayed the hydrate nucleation with similar performance to known KHIs (eg., PVP and
Luvicap). However, a branched polymer showed the best performance in terms of hydrate fraction and re-
sistance-to-flow among all of the systems tested in this study. These data provide valuable information regarding
linear and branched PNIPAM-MacroRAFT polymers by demonstrating their ability to delay hydrate formation
but also in preventing hydrate agglomeration. These findings confirm that polymer architecture can effect hy-
drate inhibition.

1. Introduction
Gas hydrates are nonstoichiometric crystalline compounds that are
formed when water and light hydrocarbon molecules are present under
low temperature and high pressure conditions [1–3]. Recently, the
production of offshore oil and gas has moved to deeper and colder re-
gions which is more favorable for hydrate formation, increasing the risk
of hydrate blockage in flowlines. The most common method to prevent
hydrate formation is chemical injection. The injection of thermo-
dynamic inhibitors (THIs) such as monoethylene glycol (MEG) or
methanol has been conventionally used for hydrate prevention in the
subsea flowlines. These inhibitors function by shifting the hydrate
equilibrium conditions to a higher pressure and lower temperature re-
gion. The amount of THIs that are injected is dictated by the hydrate
equilibrium conditions and the amount of water in the flowlines
[1,4–7]. However, the search for new hydrocarbon sources has moved
the industry to more extreme environments that require higher THI
concentrations. This increases the CAPEX and OPEX [8] for new field
developments.
As a result, the oil and gas industry has been investigating other

⁎
Corresponding authors.
E-mail addresses: colin.wood@csiro.au (C.D. Wood), yutaek.seo@snu.ac.kr (Y. Seo).

https://doi.org/10.1016/j.fuel.2018.08.036
Received 21 June 2018; Received in revised form 26 July 2018; Accepted 8 August 2018
Available online 05 September 2018
0016-2361/ © 2018 Elsevier Ltd. All rights reserved.
J. Park et al.
options to replace THIs including hydrate avoidance and risk manage-
ment [1,9–11]. Under the concept of risk management, several options
have been suggested such as under inhibition of THI [12–15], low do-
sage hydrate inhibitors (LDHIs) [3,4,7,16] and a combination of these
options [17,18]. Using the under inhibition of THI less THI is required
which reduces operational cost and complexity. However, the potential
of plugging with under inhibited systems increases because this relies
on the concentration of THI which determines the properties of the
hydrate slurry. The use of LDHIs has become an alternative to ther-
modynamic inhibitors due to the low concentrations required, usually
0.5–3.0 wt%, which offers an economic alternative to hydrate inhibi-
tion. LDHIs are classified as kinetic hydrate inhibitors (KHIs) and anti-
agglomerates (AAs) [3,4,7]. AAs allow hydrate to form but they prevent
the cohesion between hydrate particles resulting in hydrate slurries
that easily flow and are suitable for fluid transport. The surface of hy-
drate particle becomes hydrophobic with the AAs causing the disper-
sion of particles into the oil phase and the reduction of capillary in-
teractions. However, AAs are limited by the water cut (40–60%)
because the hydrate slurry becomes too viscous with high hydrate
fraction in the liquid phase. KHIs are water-soluble polymers that ty-
pically contain homo- or copolymers of N-vinylcarprolactam (VCap), N-
isopropylacrylamide (NIPAM) or N-vinylpyrrolidone (VP). These
structures are composed of the polyethylene backbone connected to a
pendant group. Groups containing hydrogen bonding sites such as
amide and imide can interact with the water molecules which defers the
hydrate nucleation. Research on KHIs has been conducted via mod-
ification or synthesis of well-known commercial polymers including
PVCap [19–21], PVP [22,23], and PNIPAM [24–26]. However, these
polymers have limited performance as evidenced by the low subcooling
temperature which is the difference between fluid and hydrate forma-
tion temperatures. The maximum subcooling for KHIs is reported to be
approximately 14 K, above which the KHI may not work effectively [4].
This problem can be overcome by synergistic inhibition with THIs such
as methanol and glycol.
To evaluate the performance of KHIs in delaying hydrate nucleation
the onset time and subcooling temperature are usually investigated.
The subcooling temperature and onset time indicate that hydrate for-
mation is delayed during the residence time of the fluids in the flow-
lines (onset time) even when there is a significant driving force derived
from the subcooling temperature. However, limitations exist with using
onset time for assessing KHIs because hydrate formation is stochastic.
Crystal growth inhibition (CGI) is an alternative method that has been
considered for the reliable and rapid evaluation of KHIs behavior.
Anderson et al. reported that the stochastic nature could be overcome
by focusing on the hydrate growth using the subcooling temperature
versus hydrate growth rate.[27] This was possible because KHIs func-
tion by adsorbing onto the hydrate surface which affects the hydrate
growth. The inhibition region which shows P_T is divided into 4 in-
cluding Complete Inhibition Region (CIR), Slow Growth Rate Region
(SGR), Rapid Growth Region (RGR) and Slow Dissociation Rate Region
(SDR). The growth rate during hydrate formation plays a significant
role in distinguishing the different growth stages [28]. Daraboina et al.
reported the formation and decomposition of natural gas hydrates in
the presence of KHIs using the high pressure calorimetry, the stirred
reactor, and the spectroscopic methods [39–42]. The crystal growth of
natural gas hydrates was also observed to investigate the effect of the
KHI on the hydrate crystal grwoth.
Recently, research has been conducted to develop more efficient
polymeric KHIs using chain growth polymerization techniques such as
reversible deactivation radical polymerization (RDRP), anionic or ca-
tionic polymerizations.[4] Among these methods, reversible addition-
fragmentation chain transfer (RAFT) has been investigated for synthe-
sizing polymeric KHIs with narrow polydispersity index (PDI) and
controlled molecular weight. It is well known that the performance of
KHIs is influenced by molecular weight [4], with molecular weight
control being accessible through RDRP techniques, and with RAFT
1267
Fuel 235 (2019) 1266–1274
showing a wide compatibility with functional monomers, it becomes an
obvious tool for developing finely tuned KHIs. Seo et al. synthesized
PVCap using RAFT and free radical polymerization (FRP) and showed
better inhibition performance with polymers of narrow molecular
weight distributions [29]. Reyes et al. suggested that polymers con-
taining predominantly non-amide-based monomers such as iso-
propenyloxazoline (IPOx) could be synthesized using RAFT and the
resulting polymers have high cloud points and they showed inhibition
of hydrate nuclei rather than growth inhibition [38]. Overall molecular
weight distribution is one of the factors that can influence the hydrate
inhibition efficiency.
In terms of polymer architecture there are limited investigations,
Del Villano et al. revealed that the tacticity of poly(N,N-dialkylacryla-
mide) influences the KHI performance [30]. The polymer tacticity af-
fected its interaction with water molecules, inducing different water
perturbation. A syndiotactic polymer showed better performance than
other tacticities. Chua et al. [31] reported that different tacticities of
PNIPAM with similar molecular weight changed the KHIs performance.
In this study, we investigated the effect of polymer architecture on
hydrate formation by comparing linear and branched polymers. In
particular, linear-PNIPAM and branched-PNIPAM that were synthe-
sized using RAFT polymerization. The results are compared to PNIPAM
synthesized with traditional radical polymerization, and commercial
KHIs (PVP and Luvicap). The results are presented in three sections: 1)
hydrate kinetics at a specific subcooling temperature and onset time, 2)
hydrate growth rate to observe the different growth characteristics, and
3) resistance to flow for the agglomeration of hydrate particles in the
presence of KHIs.
2. Experimental section
2.1. Materials
Deionized water and decane were supplied by OCI and Sigma-
Aldrich, respectively. Luvicap poly(N-vinylpyrrolidone) (PVP), com-
−
mercial linear poly(N-isopropylacrylamide) (PNIPAM) (Mn 30 000)
were used as control groups. Luvicap EG HM was supplied by BASF and
PVP [K-15, molecular weight (MW) = 9000 Da] was purchased from
Ashland Chemical Co. Those chemicals were used without further
purification. The synthetic natural gas used for hydrate formation (CH4:
90 mol%, C2H6: 6 mol%, C3H8: 3 mol%, and n-C4H10: 1 mol%) was
provided by Special Gas (Korea).
The following materials were purchased from Sigma Aldrich and
used for synthesis purpose: N-isopropylacrylamide (NIPAM, 97%),
azobisisobutyronitrile (AIBN, 98%), 1,4-dioxane (ACS reagent,
≥99.0%), n-heptane (LC-MS grade) and cyanomethyl dodecyl trithio-
carbonate (98% , HPLC grade), the inimer/transmer RAFT agent was
synthesized as described in the literature [32].
2.2. Polymerization of linear- and branched-PNIPAM via RAFT
NIPAM (1.012 g, 8.94 × 10−3 mol), RAFT agent cyanomethyl do-
decyl trithiocarbonate (0.0256 g, 9.06 × 10−5 mol), and AIBN (1.5 mg,
9.14 × 10−6 mol) were weighed in an ampule and dissolved in dioxane
(2.945 mL) to an approximate molar ratio of [NIPAM]:[RAFT]:
[AIBN] = 1000:10:1. The mixture was degassed with four free-
ze−pump−thaw cycles, sealed, and then heated at 333.15 K in a
thermostated oil bath for 19 h 11 min. The final polymers were purified
by repeated precipitation from the monomer/solvent mixture into n-
heptane until full removal of small molecule impurities and dried under
vacuum until constant weight.
The above procedure was adapted to synthesise the branched
macroRAFT, by replacing the commercial RAFT agent with the inimer/
transmer RAFT agent. [32] The cost of these RAFT agents will con-
tribute to the overall economics of the process and would need to be
J. Park et al.
considered. However, this is a proof-of-concept study to demonstrate
the utility of RAFT polymerisation and the economics would need to be
further investigated using more inexpensive agents that are emerging.
Gel permeation chromatography (GPC) was performed on a Shimadzu
system equipped with a CMB-20A controller system, an SIL-20A HT
autosampler, an LC-20AT tandem pump system, a DGU-20A degasser
unit, a CTO-20AC column oven, an RDI-10A refractive index detector,
and 4 × Waters Styragel columns (HT2, HT3, HT4, and HT5, each
300 mm × 7.8 mm2, providing an effective molar mass range of
100–4 × 106). N,N-Dimethylacetamide (DMAc) (containing 4.34 g L−1
lithium bromide (LiBr)) was used as an eluent with a flow rate of 1 mL/
− −
min at 353.15 K. Number (Mn ) and weight average (Mw ) molar masses
were evaluated using Shimadzu LC Solution software. The GPC columns
were calibrated with low dispersity poly(methymethacrylate) (PMMA)
standards (Polymer Laboratories) ranging from 1 110 to 2 136
000 g mol−1, and molar masses are reported as PMMA equivalents. A
3rd-order polynomial was used to fit the log Mp vs. time calibration
−
curve. The number average molar masses (Mn ) of linear-PNIPAM and
branched-PNIPAM were found to be 17 600 kDa and 35 200 kDa, re-
spectively, with a molar mass dispersity index of 1.07 and 1.48.
The molecular structure of polymers RAFT based PNIPAM is shown
in Fig. 1.
2.3. Experimental procedure for high pressure autoclave measurements
To evaluate the hydrate inhibition performance of the newly syn-
thesized polymers, hydrate formation characteristics including onset
time and growth rate were determined from experiments using a high
pressure autoclave. The reactor was equipped with a magnetic stirrer
coupling and anchor type impeller was made by 316 SUS having an
inner volume of 360 mL. The total volume of 80 mL liquid phase with
water cut 60% was loaded into the autoclave. Pure water, 0.5 wt% PVP
solution, and 0.5 wt% Luvicap solution were selected as control groups
to compare the inhibition performance. The PNIPAM-MacroRAFT
(branched and linear) as well as Linear PNIPAM (radical polymerization
PNIPAM) were evaluated at the concentration of 0.5 wt%. The auto-
clave was placed in a water bath connected to external water chiller
(Jeiotech RW2025G, Korea) to control the experimental temperature.
The temperature of the liquid phase in the autoclave was measured by
PT-100 Ω (accuracy: ± 0.15 K) and the pressure of the gas phase was
detected using a transducer (WIKA, A-10) (accuracy: ± 0.01 MPa over
0–20 MPa range). In addition, the torque was monitored using a torque
sensor (TRD-50KC, ± 0.3%) to observe the change of resistance-to-
flow. Temperature, pressure, and torque were recorded through a data
acquisition system.
The experimental procedure to study the hydrate formation char-
acteristics with continuous cooling is as follows:
S S
C12H25
S S
n n
HN O HN O HN
Free radical Linear
Fig. 1. Molecular structure of PNIPAM and RAFT based PNIPAM polymers. Free radical synthesized PNIPAM (left); RAFT synthesized linear (middle); and branched
(right).
Fuel 235 (2019) 1266–1274
1) The autoclave was filled with water and decane, then placed in the
water bath. The gas phase was slowly flushed three times at 1 MPa
with synthetic natural gas to remove residual air, which was then
pressurized by 12 MPa at 297.15 K.
2) The liquid phase was agitated at 600 rpm until pressure is stabilized
at 297.15 K. Once confirming the pressure stabilized, continuous
cooling was commenced to achieve target temperature 277.15 K
with a cooling rate of 0.25 K/min. Hydrate formation was observed
during or after the cooling process depending on the inhibition
performance of PVCap dissolved in water phase.
3) The temperature was kept for 10 h at 277.15 K, then ramped up to
301.15 K. Hydrate formation process was completed as seen in no
more pressure reduction in gas phase. The temperature was main-
tained for 3 h to eliminate the memory effect.
To simulate the cold-restart operation, the constant subcooling was
used in this work. The first procedure to stabilize the pressure was
identical, but the next procedures were as follows:
2) Once confirming the stabilized pressure, the temperature was cooled
down to 277.15 K without agitation and maintained for 4.5 h.
Hydrate formation was sometimes observed during this period, as
the thermal driving force was large enough to initiate the hydrate
nucleation. However, the hydrate fraction in liquid phase was small
due to limited mass transfer.
3) After 4.5 h of shut-in periods, the agitation was commenced at
600 rpm. Fast hydrate formation was observed from pressure re-
duction, which were studied to calculate the hydrate growth rate
and fraction in liquid phase.
A total of five repeat experiments were performed for each system
(Linear PNIPAM + decane + natural gas, PNIPAM-MacroRAFT (bran-
ched) solution + decane + natural gas, and PNIPAM-MacroRAFT
(linear) solution + decane + natural gas) to obtain the hydrate for-
mation characteristics and the hydrate inhibition performance.
Furthermore, the experiment for the control groups (pure water + de-
cane + natural gas, PVP solution + decane + natural gas, and Luvicap
solution + decane + natural gas) was also conducted five times. All
experiments were conducted under isochoric condition.
The constant subcooling method was also used to evaluate the
performance of linear and branched PNIPAM-MacroRAFT. After pres-
surizing the autoclave with natural gas to 12 MPa and saturating the
liquid phase by mixing at 600 rpm, the mixing was stopped and the
temperature was decreased from 297.15 to 277.15 K within an hour
without mixing. The temperature was maintained 277.15 K for five
hours, then mixing at 600 rpm was commenced to simulate a cold re-
start operation. For each PNIPAM-MacroRAFT, the constant subcooling
experiment was repeated five times.
p m
HN O
C 4H 9
CN S S
n
O
Branched
1268
J. Park et al.
3. Result and discussion
3.1. Effect of polymer architecture on hydrate formation kinetics
Reversible Addition Fragmentation chain Transfer (RAFT) is a
controlled radical polymerization technique that uses as a chain
transfer agent (RAFT agent) to control the growth of the molecular
chains. This allows polymers with controlled molecular weight, narrow
molecular weight distributions, specific architectures and high end-
group fidelity to be generated. The RAFT agent remains at the end of
the polymerization as an end-group. The generation of the linear
PNIPAM was via polymerizing NIPAM with a commercial RAFT agent,
whilst the dendritically branched PNIPAM was accessed using an in-
imer/transmer RAFT agent.
The subcooling temperature (ΔTsub) is the driving force for hydrate
nucleation and has been used to evaluate the performance of KHIs. It is
defined as the difference between the equilibrium and hydrate onset
temperatures. The kinetics of hydrate formation are dependent on the
subcooling temperature and onset time. For the polymers under in-
vestigation various cooling rates were used to determine the effect of
polymer architecture on the performance of the KHI. The hydrate onset
is determined as the point where the pressure decreases substantially
during the cooling process or at the target temperature. In this study,
the cooling rate was varied from 0.25 K/min to 0.033 K/min and then
0.017 K/min. With a slow cooling rate, the subcooling temperature
decreased and the onset time increased. Faster cooling rate indicates a
larger driving force for hydrates to form during the cooling process at a
certain time, hence it results in a shorter onset time and higher sub-
cooling temperature. Each experiment was repeated over five cycles
and the mean value and standard deviation for the subcooling tem-
perature (ΔTsub) and onset time (tonset) were obtained (Table 1).
The ΔTsub of the linear PNIPAM-MacroRAFT under 0.25 K/min,
0.033 K/min, and 0.017 K/min was 11.64 K, 10.60 K, and 9.26 K. For
the branched PNIPAM-MacroRAFT polymer the ΔTsub was 10.60 K,
9.97 K, and 8.96 K under 0.25 K/min, 0.033 K/min, and 0.017 K/min,
respectively. The ΔTsub of PNIPAM-MacroRAFT was higher than in pure
water (4.71 K, 3.30 K, and 3.25 K under 0.25 K/min, 0.033 K/min, and
0.017 K/min) which indicates a kinetic inhibition for the PNIPAM. To
estimate the effect of the RAFT group on the kinetic hydrate inhibition,
the kinetics of Linear PNIPAM also showed ΔTsub of 10.07 K, 10.44 K,
and 9.38 K under the studied cooling rates.
Commercial KHIs were also investigated including Luvicap and poly
(N-vinylpyrrolidone) (PVP) to compare their performance to the syn-
thesized polymers. While the ΔTsub of 0.5 wt% PVP solution varied from
8.46 K to 12.52 K under cooling rates between 0.017 K/min and 0.25 K/
min, the ΔTsub of Luvicap was 11.58 K, 11.43 K, and 7.93 K under the
same cooling rates. PVP showed the best performance with the sub-
cooling temperature of 12.52 K for 0.25 K/min and Luvicap was the best
Table 1
Hydrate kinetic characteristics of 0.5 wt% PNIPAM solutions (Linear and
Branched PNIPAM-MacroRAFT, and Linear PNIPAM.) under various cooling
rates (0.25 K/min, 0.033 K/min, and 0.017 K/min). The value in parenthesis is
the standard deviation. Data for pure water, 0.5 wt% PVP, and 0.5 wt% Luvicap
solutions were presented in our previous work [26].
Cooling rate ΔTsub (K) tonset (min)
(K/min)
Linear PNIPAM-macroRAFT 0.25 11.64 (0.19) 77.33 (3.75)
0.033 10.4 (0.89) 358.13 (12.65)
0.017 9.26 (0.14) 566.43 (11.43)
Branched PNIPAM-macroRAFT 0.25 10.60 (0.09) 67.33 (2.96)
0.033 9.97 (0.25) 309.36 (7.68)
0.017 8.96 (1.42) 532.77 (79.19)
Linear PNIPAM 0.25 10.07 (0.09) 48.83 (1.65)
0.033 10.44 (0.60) 323.86 (20.54)
0.017 9.38 (0.47) 576.63 (30.95)
1269
Fuel 235 (2019) 1266–1274
for 0.033 K/min. Linear PNIPAM-MacroRAFT showed the highest ΔTsub
of 9.26 K for 0.017 K/min. For the inhibition of hydrate nucleation,
linear PNIPAM-MacroRAFT and commercial KHIs showed better per-
formance under fast cooling rate, suggesting the linear structure may
provide high energy barrier for hydrate nucleation. The rank of the
inhibition performance from the ΔTsub for each cooling rate is as fol-
lows:
0.25 K/min: PVP > linear PNIPAM-MacroRAFT ≈ Luvicap
> branched PNIPAM-MacroRAFT > linear PNIPAM
0.033 K/min: Luvicap > Linear PNIPAM-MacroRAFT ≈ Branched
PNIPAM-MacroRAFT ≈ PVP ≈ Linear PNIPAM
0.017 K/min: Linear PNIPAM-MacroRAFT ≈ Branched PNIPAM-
MacroRAFT ≈ Linear PNIPAM > PVP > Luvicap
Even though the branched PNIPAM-MacroRAFT shows a slightly
weaker KHI performance compared to the linear PNIPAM-MacroRAFT,
both PNIPAM-MacroRAFT materials have comparable kinetic inhibition
performance to commercial KHIs (Luvicap and PVP).
3.2. Hydrate formation characteristics under continuous cooling
Hydrate growth rate and hydrate volume fraction in the liquid
phase were measured to study the hydrate formation with PNIPAM-
MacroRAFT (linear and branched), Linear PNIPAM and control groups
(pure water, PVP and Luvicap solutions). Recent studies have revealed
that KHIs also affect the hydrate growth due to their adsorption onto
the hydrate crystal surface. The gas consumption during the hydrate
formation was calculated for each system by measuring the difference
in pressure between the experimental pressure and estimated pressure
without hydrate formation [33].
Pexp Vcell
ΔnH , t = ⎛ ⎜ ⎟
⎞ −⎛ Pcal Vcell ⎞
⎝ zRT ⎠t ⎝ zRT ⎠t
where, ΔnH , t is the mole of gas consumption for hydrate formation at a
certain time, Pexp is an experimental pressure, Vcell is gas volume, R is the
gas constant, T is gas temperature, Pcal is calculated pressure with no
hydrate assumption, z is compression factor simulated by Cubic Plus
Association EOS from Multiflash [34].
The hydrate volume fraction of the liquid phase is calculated by the
following equation.
Vhyd
Φhyd =
Vhyd + Vdecane + Vresid, water
where Φhyd is a hydrate volume fraction, Vhyd is a volume of hydrate,
Vresid, water is a volume of residual water after water conversion to hy-
drate. For calculation of the hydrate volume fraction, a hydration
number of 6.5 was used which was obtained by cage occupancy of
structure II hydrate [35]. The relative torque was also calculated from
the ratio of torque at specific moment (τexp, t ) to torque when there was
no hydrate (τnohyd, to ), suggesting how resistance-to-flow increased.
τexp, t
τrel =
τnohyd, to
Table 2 presents initial growth rate, hydrate volume fraction at
100 min after the onset, and the amount of water converted into hy-
drate while varying the cooling rate. Fig. 3 shows the hydrate volume
fraction as a function of time until 100 min after the nucleation as the
initial growth rate is important to evaluate the performance of the KHIs.
The time zero indicates the moment of hydrate nucleation. The hydrate
fraction of pure water recorded the highest conversion from water to
hydrate under three different cooling rates. The initial growth rate for
pure water was 8.9 × 10−3 vol.frac./min and the hydrate fraction
reached 0.43 at 0.25 K/min cooling rate. With the addition of Luvicap,
the growth rate was reduced to 4.9 × 10−3 vol.frac./min while
achieving the fraction 0.13 under 0.25 K/min cooling rate. The addition
of PVP also showed that the hydrate volume fraction and the growth
J. Park et al. Fuel 235 (2019) 1266–1274

Table 2
Hydrate formation characteristics of 0.5 wt% PNIPAM solutions (linear
PNIPAM-MacroRAFT, branched PNIPAM-MacroRAFT, and, linear PNIPAM)
under various cooling rates (0.25 K/min, 0.033 K/min, and 0.017 K/min).
Standard deviation values in parenthesis.
Cooling rate rini (min−1) ϕhyd,100min ϕhyd,600min
(K/min)

Linear PNIPAM-MacroRAFT 0.25 9.0 × 10−3 0.28 (0.05) 0.39 (0.05)

0.033 8.2 × 10−3 0.18 (0.08) 0.36 (0.05)
0.017 1.6 × 10−3 0.22 (0.02) 0.39 (0.05)
Branched PNIPAM-MacroRAFT 0.25 1.9 × 10−3 0.16 (0.07) 0.36 (0.06)
0.033 2.0 × 10−3 0.16 (0.02) 0.38 (0.07)
0.017 0.4 × 10−3 0.03 (0.02) 0.28 (0.04)
Linear PNIPAM 0.25 3.8 × 10−3 0.13 (0.04) 0.26 (0.02)
0.033 5.8 × 10−3 0.09 (0.01) 0.22 (0.02)
0.017 1.1 × 10−3 0.06 (0.01) 0.22 (0.02)

rate were decreased to 0.29 and 6.4 × 10−3 vol.frac./min, respectively.

These results indicated that Luvicap showed better performance than
PVP in term of slow growth rate and less hydrate fraction in the liquid
phase [26]. For the cooling rate of 0.033 K/min and 0.017 K/min, Lu-
vicap also outperformed PVP.
Although linear PNIPAM-MacroRAFT showed the best performance
for delaying the hydrate onset as shown in Fig. 2, it did not effectively
suppress the growth of hydrate crystals. The initial growth rate for
linear PNIPAM-MacroRAFT was 9.0 × 10−3 vol.frac./min under
0.25 K/min cooling rate, which was close to that of pure water and was
higher than that of both Luvicap and PVP. The hydrate fraction was also
high enough to demonstrate that it was not effective at inhibiting hy-
drate growth. When the cooling rate was 0.017 K/min, the growth rate
was 1.6 × 10−3 vol.frac./min while the hydrate fraction was still 0.22.
However, the branched PNIPAM-MacroRAFT outperformed both Lu-
vicap and PVP. The initial growth rate was 1.9 × 10−3 vol.frac./min
and 2.0 × 10−3 vol.frac./min under 0.25 K/min and 0.033 K/min
cooling rate, respectively. The hydrate fraction reached approximately
0.15 for both cooling rates. For the 0.017 K/min cooling rate, the initial
growth rate was 0.4 × 10−3 vol.frac./min with hydrate fraction of 0.03
at 100 min. The growth curve for Linear PNIPAM was placed between
the linear and branched PNIPAM-MacroRAFT in early stage of hydrate
formation. For cooling rates of both 0.25 and 0.033 K/min, an inflection
point was observed for branched PNIPAM-MacroRAFT in Fig. 3 when
the hydrate fraction reached 0.03, after which the growth rate picked
up, resulting in a higher hydrate fraction than Linear PNIPAM.
Fig. 3 shows hydrate growth curves 3 for each KHI and demon-
strates that the structure of the polymer had a significant impact on the
hydrate inhibition performance. Our previous work suggested that
torque could be used to estimate the flowability of a hydrocarbon fluid
in the presence of hydrate particles [26]. When the hydrate fraction
increased to more than 0.10 in the liquid phase an increase in torque is
induced for pure water due to the agglomeration of hydrate particles. Fig. 2. Subcooling temperature of 0.5 wt% polymer groups (Linear PNIPAM,
Luvicap and PVP showed relatively stable torque during the hydrate linear PNIPAM-MacroRAFT and branched PNIPAM-MacroRAFT and control
formation under 0.25 K/min cooling rate, however, the torque fluc- groups (pure water, PVP, and Luvicap solutions) under various cooling rates (a)
tuated under 0.033 and 0.017 K/min, which may indicate the hydrate 0.25 K/min, (b) 0.033 K/min, and (c) 0.017 K/min.
particle were separated rather than a homogeneous dispersion in the
liquid phase. The torque changes as a function of hydrate fraction in the agglomeration of hydrate particles. The torque remained stable at
liquid phase for newly RAFT-synthesized PNIPAM are shown in Fig. 4. 0.017 K/min cooling rate in the presence of all synthesized PNIPAM
The branched PNIPAM-MacroRAFT showed slow torque increase polymers. Overall, the branched PNIPAM-MacroRAFT suppressed the
until the hydrate fraction reached 0.10 for 0.25 and 0.033 K/min, then torque during the hydrate formation. The linear PNIPAM-MacroRAFT
the torque either decreased steadily or rapidly returned to the baseline. showed limited performance in terms of controlling torque increase
However, the linear PNIPAM-MacroRAFT showed a rapid increase in when the subcooling temperature was varied. These results suggest that
torque during the early stages of hydrate formation before decreasing to the agglomeration of hydrate particles might be controlled in the pre-
the baseline with hydrate fraction 0.10 for 0.25 K/min cooling rate. The sence of effectively designed KHI molecules. The branched polymer
rapid torque increase was repeated for 0.033 K/min cooling rate when structure induces slow hydrate growth and can inhibit the agglomera-
the hydrate fraction was higher than 0.15. The Linear PNIPAM showed tion of hydrate particles as show in Figs. 3 and 4. KHIs synthesized
similar performance to those of branched PNIPAM-MacroRAFT, using conventional free radical polymerization have promising perfor-
suggesting that the branched functional groups can inhibit the mance but further improvements in the performance can be achieved

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J. Park et al.
Fig. 3. Average hydrate volume fraction of 0.5 wt% polymer (Linear PNIPAM,
Linear PNIPAM-MacroRAFT and Branched PNIPAM-MacroRAFT) and 0.5 wt%
control groups (pure water, PVP, and Luvicap) under various cooling rates (a)
0.25 K/min, (b) 0.033 K/min, and (c) 0.017 K/min. Time 0 means the onset
moment [26].
by controlling the structure of the KHI using RAFT polymerization. The
difference in hydrate inhibition performance between linear and
branched PNIPAM-MacroRAFT clearly suggests that the design of KHI
structures is vital to achieve the desired inhibition performance. This is
in line with our previous work [25,26] which also demonstrated that
controlling the structure of KHIs can modulate the peformance, which is
not easily accessible using conventional free radical techniques.
3.3. Hydrate formation characteristics in cold restart operation
As presented above, KHIs can delay hydrate nucleation, reduce its
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Fuel 235 (2019) 1266–1274
Fig. 4. Relationship between hydrate volume fraction and torque to observe the
resistance to flow during hydrate formation under (a) 0.25, (b) 0.033, and (c)
0.017 K/min cooling rate. (Red) Linear PNIPAM, (Blue) Linear PNIPAM-
MacroRAFT, (Green) Branched PNIPAM-MacroRAFT. (For interpretation of the
references to colour in this figure legend, the reader is referred to the web
version of this article.)
growth rate, and are able to inhibit the agglomeration of hydrate par-
ticles if the structure of the polymer is controlled. However, industry
reports [3,4] have suggested that their performance might be limited
under high subcooling conditions i.e. more than 14 K, especially if the
hydrocarbon fluid resides inside the hydrate formation region for pro-
longed duration. Aman et al. observed that a hydrate film was formed
without mixing and this played a role of hydrate nucleation for fast
hydrate growth during a cold restart operation [36]. Our previous work
suggested that Luvicap may be effective at interacting with hydrate
nuclei at 1.0 wt% to suppress their nucleation and growth in the early
stages, at a low mixing rate of 200 rpm. But loosing its efficacy when
the mixing rate increased to 600 rpm [37], where the onset time was
J. Park et al. Fuel 235 (2019) 1266–1274

Table 3
Hydrate growth rate of mixing at start moment and hydrate volume fraction at
100 min and final moment.
rmax rlinear ϕhyd, ϕhyd,final τmax
(min−1) (min−1) 100min

Linear PNIPAM-MacroRAFT 7.6 × 10−2 4.3 × 10−2 0.19 0.22 3.5

Branched PNIPAM-MacroRAFT 7.2 × 10−2 3.0 × 10−2 0.17 0.21 1.5

dropped to 4.2 min. In this work, we performed hydrate formation

experiments to investigate the performance of both linear and branched
PNIPAM-MacroRAFT under a simulated cold restart operation with
high subcooling condition of 16 K. The concentration of PNIPAM was
maintained at 0.5 wt%, and the PNIPAM solution was kept at 277.15 K
and 10.5 MPa (subcooling temperature of 16 K) for approximately five
hours before commencing the mixing at 600 rpm.
Table 3 presents the hydrate fraction, maximum growth rate upon
mixing, linear growth rate before reaching an inflection point, hydrate
fractions at 100 min and at the end of experiments, and maximum re-
lative torque observed during the experiment. Fig. 5 (a) and (b) shows
the hydrate fraction along with the torque changes upon mixing as a
function of time for linear PNIPAM-MacroRAFT and branched PNIPAM-
MacroRAFT, respectively. It was observed that a thin hydrate film
formed on the surface of PNIPAM solutions during the period when the
system was not mixed. Upon commencing stirring (600 rpm), the hy-
drate film broke up into small pieces and dispersed into the liquid phase
due to turbulent mixing, this was followed by rapid hydrate formation
as shown in Fig. 5. For both linear and branched PNIPAM-MacroRAFT,
the initial growth rates were 7.6 × 10−2 and 7.2 × 10−2, respectively,
and the rates were about eight times larger than that of the linear
PNIPAM-MacroRAFT, in the continuous cooling experiment,
9.0 × 10−3 min−1. This result is in agreement with our previous work
and of those from Aman et al., observing fast hydrate growth initiated
from the previously-formed hydrate pieces. [36] Both the linear and
branched PNIPAM-MacroRAFT showed limited inhibition performance
on hydrate nucleation when the solution was maintained at the high
subcooling condition of 16 K for five hours.
However, once the hydrates started to grow the branched PNIPAM-
MacroRAFT showed better performance on hydrate growth inhibition
than the corresponding linear PNIPAM-MacroRAFT. The initial growth
rate quickly reduced from 7.6 × 10−2 to 4.3 × 10−2 for linear
PNIPAM-MacroRAFT before reaching an inflection point at 18 min. The Fig. 5. Relationship between hydrate growth and relative torque during a si-
mulated cold restart. Time zero indicates start of mixing. (a) Linear PNIPAM-
hydrate fraction was about 0.17 and the relative torque showed a
MacroRAFT; (b) Branched PNIPAM-MacroRAFT. (c) Resistance to flow with
maximum of 3.5 at the inflection point, indicating the highest re-
increasing hydrate fraction.
sistance-to-flow. After the inflection point, the hydrate growth rate
reduced and the relative torque returned to the original value. For the
branched PNIPAM-MacroRAFT, the growth rate was reduced to the autoclave wall by the impeller. After that the contact area between
3.0 × 10−2 after the initial fast growth and the hydrate fraction at the the slurry and the impeller was reduced. In the case of the branched
inflection point was at 0.10. The torque increased to 1.5 around the PNIPAM-MacroRAFT (Fig. 6 (b)) the hydrate particles appear to be
inflection point, but decreased slowly while increasing hydrate fraction. brittle and well crushed into small pieces by the impeller. The second
These results suggest that the hydrate formation characteristics were image shows the viewing window covered with hydrate particles but
different in linear and branched PNIPAM-MacroRAFT solutions. Fig. 5 not a slurry, thus these hydrate particles did not induce an increase of
(c) depicts the torque changes as a function of hydrate fraction in the liquid phase viscosity. These images clearly show the different hydrate
liquid phase. Linear PNIPAM-MacroRAFT showed increasing relative properties in the presence of linear and branched PNIPAM-MacroRAFT.
torque with increasing hydrate fraction, but branched PNIPAM-Mac- Further investigations will be carried out, however, these results sug-
roRAFT showed little increase in relative torque. gested that branched polymer structure may better interact with
Fig. 6 shows images captured during the hydrate formation. The growing hydrate crystals than a linear analogue. More studies will also
first images were taken when the mixing was initiated, with the second be carried out to quantitatively analyze the effect of polymer structure
images taken 20 min after. The final images were taken at the end of the on the growth and agglomeration of hydrate particles.
experiment. For linear PNIPAM-MacroRAFT, Fig. 6 (a), growing hy-
drate particles in the liquid phase induced a viscosity increase due to 4. Conclusions
interaction between hydrate particles and liquid phase. As seen in the
image at 20 min, which is just after the inflection point in growth curve, This work investigated the kinetic hydrate inhibition performance
the hydrate and liquid mixture looked like a slurry being pushed toward of RAFT synthesized PNIPAM, using hydrate onset conditions, growth

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J. Park et al.
(a)
[t = 0 min]
(b)
[t = 0 min]
Fig. 6. Images of hydrate phase during hydrate formation. (a) Linear PNIPAM-MacroRAFT; (b) Branched PNIPAM-MacroRAFT.
rate, hydrate fractions, and torque changes while varying the cooling
rate. Both linear and branched PNIPAM-MacroRAFT show the sub-
cooling behavior similar to those of commercial KHIs, Luvicap and PVP.
Once the hydrate forms, a branched PNIPAM-MacroRAFT was effective
in reducing the growth rate and maintaining well-dispersed hydrate
particles in the liquid phase. When decreasing the cooling rate the
subcooling temperature slightly changed but hydrate growth rate de-
creased significantly, suggesting the importance of the thermal driving
force to form the hydrate crystals. A cold restart was simulated using a
high subcooling (16 K) for both linear and branched PNIPAM-
MacroRAFT which showed a significant impact on the hydrate growth
rate and torque changes as the branched PNIPAM-MacroRAFT was ef-
fective in interacting with growing hydrate particles. Research on KHIs
have primarily been focusing on their performance to delay the hydrate
onset. However, our results suggested that KHIs would play an im-
portant role in controlling the hydrate growth rate and the interaction
between hydrate particles.
Acknowledgment
This work was partially supported by CNPq, Brazil through PDJ
grant to Kelly Cristine da Silveira (Proc. 150710/2017-8) and also
supported by the Technology Innovation Program (10060099) funded
by the Ministry of Trade, Industry & Energy (MI, Korea).
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