Article

Cite This: Energy Fuels 2019, 33, 6335−6349 pubs.acs.org/EF

Formation and Dissociation Kinetics of Methane Hydrate in

Aqueous Oilfield Polymer Solutions (Polyacrylamide, Xanthan Gum,
and Guar Gum) and Their Performance Evaluation as Low-Dosage
Kinetic Hydrate Inhibitors (LDHI)
Pawan Gupta and Jitendra S. Sangwai*
Gas Hydrate and Flow Assurance Laboratory, Petroleum Engineering Program, Department of Ocean Engineering, Indian Institute
of Technology Madras, Chennai 600 036, India
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ABSTRACT: Hydrate formation and deposition during drilling offshore oil and gas wells has been one of the major challenges
faced by the oil and gas industry. The use of low-dosage hydrate inhibitor (LDHI), such as water-soluble polymers, has become
an established technique to prevent hydrate plugging during drilling and transportation. Commonly used oilfield polymers, such
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as polyacrylamide (PAM), xanthan gum (XG), and guar gum (GG), have not yet been clearly investigated individually and
compared for their possible role as LDHI. The present study aims to investigate the performance evaluation of various water-
soluble oilfield polymers as LDHI by performing hydrate formation and dissociation kinetic experiments. Two different
molecular weights and varying concentrations of polymer in water were considered for the investigations. These are PAM (Mw:
1.1 × 106 g/molPAM-1 and 1.5 × 105 g/molPAM-2); XG (Mw: 6.4 × 105 g/molXG-1 and 2.4 × 105 g/molXG-2);
and GG (Mw: 1.7 × 106 g/molGG-1 and 6 × 105 g/molGG-2), with 100, 200, and 500 ppm. These are referred to as high
molecular weight polymers (PAM-1, XG-1, and GG-1) and relatively low molecular weight polymers (PAM-2, XG-2, and GG-
2). The experiments were performed at an initial pressure of 8 MPa and a constant temperature of 274.15 K (i.e., at 10−11
degree of subcooling conditions). The hydrate nucleation (induction) time, gas consumption and its rate, gas-to-hydrate and
water-to-hydrate conversion during formation experiments, and moles of gas released and its rate during hydrate dissociation
were reported. The growth kinetics of gas hydrate were studied and reported up to 20 h after hydrate nucleation, while the
dissociation kinetics were investigated for few selected polymers. From the study, it was observed that the molecular weight and
concentration of polymer does play a major role in hydrate growth (consumption of gas) and the rate of gas consumed. PAM-1
exhibits excellent kinetic hydrate inhibition properties among the polymers studied. Other polymers such as XG-1 and GG-1 at
500 ppm also performed well as LDHI. Low molecular weight polymers, such as PAM-2, XG-2, and GG-2, did not result in
much hydrate inhibition as compared to relatively high molecular weight polymers (PAM-1, XG-1, and GG-1). These
observations have special significance for flow assurance, safer offshore drilling, and drilling fluid design and analysis particularly
during degassing operations.

1. INTRODUCTION during drilling process resulting in well kick, enhanced

Gas hydrate formation and deposition in pipelines and
wellbore has been one of the major flow assurance challenges
faced by the upstream offshore oil and gas industry.1−4 They
usually form under high pressure and low temperature
conditions, such as in permafrost and subsea environments.
Formation of hydrates during drilling offshore wells is also a
major concern. The presence of any hydrate zone that may be
encountered during drilling also complicates the issue.
Typically hydrate formation in drilling fluid occurs when
drilling is suspended for a while, as the gas may seep in from
the reservoir.5−7 Thermodynamic conditions during this
period are mostly favorable, as there is an adequate time for
the hydrate equilibrium to be reached. During drilling and
production of deepwater−oil and gas wells, the potential
complications caused by natural gas hydrates primarily include
blocking of choke and kill lines, plugging blowout preventers,
block around the drill string, clogging pipelines, and
obstructing drilling fluid circulation.8 The hydrate generally
produces a large amount of gas when dissociated. The
produced gas severely affects the quality of drilling fluid
wellbore pressure, wellbore instability, etc.9,10 In recent
times, these issues have been amplified because of a rise in
the deepwater−oil and gas exploration.11 In addition, because
of stringent environmental norms, the oil and gas industry is
now moving toward water-based drilling fluids over oil-based
drilling fluids, which also add challenges for hydrate inhibition
while drilling.12,13 There are a number of well-documented
hydrate-related problems during offshore/deepwater drilling
with case histories. To mention a few, a case of hydrate
formation occurred off the United States (U.S.) West coast at a
depth of 1150 ft at a temperature of 280.15 K. The gas entered
the well causing hydrate formation in the blowout preventer,
choke line, kill line, and riser. The kill operation had lasted for
7 d. Another case was of hydrate formation that occurred in
the Gulf of Mexico at a depth of 3100 ft at a temperature of
277.15 K. A lengthy workover operation lasted more than 48 h
Received: April 17, 2019
Revised: June 17, 2019
Published: July 1, 2019

© 2019 American Chemical Society 6335 DOI: 10.1021/acs.energyfuels.9b01204

Energy Fuels 2019, 33, 6335−6349
Energy & Fuels
due to malfunctioning of the blowout preventer because of
hydrates.6,14 It has also been speculated that the major blowout
of British Petroleum (BP) that occurred at the Macondo Gulf
of Mexico in the year 2010 was due to the possible formation
of gas hydrate in the wellhead. Significant stress generated due
to methane hydrate dissociation has been blamed for damaging
drilling rig foundation.15,16 The challenges triggered by hydrate
formation in deepwater environment during drilling operation
and oil and gas flow through pipelines must be carefully
considered for successful and safer operations.
Primarily, two different methods for hydrate prevention (in
pipelines) have been employed, which are, first, using water
dehydration, which can be done by sending the gas stream
through dehydrator and, second, by shifting the pressure and
temperature conditions to hydrate unstable region. The second
method can be achieved by insulating the pipelines, thermal
heating, and the addition of chemical inhibitors.2 Chemical
inhibitors are most commonly used and preferred among the
other hydrate inhibition techniques because of the practic-
ability over other methods.17 Chemical inhibitors have been
categorized into two main types: thermodynamic hydrate
inhibitors (THIs) and kinetic hydrate inhibitors (KHIs). THIs
are capable of shifting the thermodynamic phase conditions of
hydrate toward high pressure and low temperature conditions,
where hydrates are unstable, thus not favoring hydrate
formation. The common THIs used by the oil and gas
industry are methanol, glycols, and electrolytes. A shift in the
oil and gas production from onshore to a more harsh
environment in deep offshore has increased the use of
conventional THIs (methanol) to as high as 50 wt %.18,19
More severe conditions, such as in offshore, demand more
usage of THIs, which not only increases the cost but also leads
to storage and handling problems of methanol due to space
constraints. Excessive usage of methanol is also ecologically not
suitable.20 Because of the severity in the application of THIs
under harsh conditions, the oil and gas industry is now using
kinetic hydrate inhibitors, which are also branded as low-
dosage hydrate inhibitors (LDHIs or KHIs) and antiagglom-
erates.21,22 LDHI/KHIs are typically water-soluble polymers
that retard the kinetics of hydrate formation but do not affect
thermodynamic phase stability of hydrate significantly. Most of
the studies relating to the polymer as kinetic hydrate inhibitor
suggest that the KHIs tend to delay hydrate nucleation and
rate of growth of hydrate crystals. For their effective usage in
gas transport facilities, the time taken for hydrate formation in
the presence of kinetic hydrate inhibitors is greater than their
residence time.23 The use of LDHIs/KHIs has become an
established technique to prevent hydrate plugging in oil and
gas well/pipelines.
Water-soluble polymers are also used for designing drilling
fluids and enhanced oil recovery processes, as they impart
suitable properties such as density and viscosity. Among
several water-soluble polymers, polyacrylamide (PAM),
xanthan gum (XG), and guar gum (GG) are most commonly
used in upstream oil and gas industry. Polyacrylamide is
extensively used in enhanced oil recovery applications, drilling
fluid design, etc. Guar gum and xanthan gum are high
molecular weight polysaccharides known to impart various
properties to drilling fluids. They are primarily added to
control the rheology of the aqueous systems. In deepwater
drilling as well as in hydrate-bearing sediments and production
operations, polymers can delay and/or reduce hydrate growth
in pipelines and borehole and thus help to prevent flow
6336
Article
assurance issues and maintain borehole stability/well integrity.
Khodaverdiloo and co-workers have studied the synergetic
effect of PAM, few nonionic surfactants, and polymers on the
formation kinetics of ethane hydrate at subcooling temperature
of 10.5 K. It has been found that the synergism between PAM
(15 000−20 000 g/mol) and surfactants strongly inhibited the
ethane hydrate formation.24 Jokandan et al. examined the
synergism between PAM, hydroxyethyl cellulose, and poly-
(ethylene glycol) (PEG) as potentially strong hydrate
inhibiting system as compared to poly(vinylpyrrolidone).
They found that the addition of PAM, hydroxyethyl cellulose,
and PEG help to increase hydrate inhibition (in terms of
hydrate induction time) of the system by a factor of 2−8
times.25 Kelland and co-workers have investigated polymers of
alkylacrylamides plus blends of these with other synergists (N-
vinyl caprolactam monomer or N-vinylpyrrolidone monomer)
and found that polymers of these monomers show high
performance as KHIs.21 Exxon filed a patent in the year 1999
on different classes of polymers having amide groups. These
include polyalkylacrylamides, polyallylamides, polydialkylacry-
lamides, polyvinylamides, polymaleimides, and polyacylalkyle-
neimines. The best hydrate inhibition was observed with
acrylamide polymers possibly due to the optimum size of alkyl
group. They also observed that adding a methyl group to the
backbone of acrylamide increased the hydrate inhibition
performance.26 In an another effort, Abrahamsen and Kelland
worked out to identify the better polymeric kinetic hydrate
inhibitor for sI and sII hydrate. They found that best KHIs for
sII hydrates are N-vinylcaprolactam polymers and that the best
KHIs for SI hydrates were a N-isopropylacrylamide homopol-
ymer along with N-vinylcaprolactam polymers.27 The poly-
saccharides, such as gum xanthan, gum arabic, gum karaya, and
gum locust, were investigated for hydrate growth inhibition,
but these polysaccharides were not able to stop hydrate
agglomeration.28 Lee and co-workers studied the effect of a
number of cationic starches on the kinetics of hydrate
inhibition using methane and other gas mixtures. The starches
were found to display weak inhibiting effect as compared to
tapioca starch, which enlarged the hydrate induction time by
an order of magnitude. The addition of poly(ethylene oxide)
(PEO) has further enhanced the performance of starches as
kinetic hydrate inhibitors.29 Talaghat has investigated the effect
of starches in the presence of PEO and poly(propylene oxide)
on hydrate growth. They found that starches are able to reduce
the rate of hydrate growth.30 Kumar et al. investigated the
effect of polysaccharides (chitosan) on methane hydrate
formation and dissociation. They found that chitosan was
found to be better than the other conventional kinetic hydrate
inhibitors in reducing nucleation and the growth rate at 1 wt %
concentration.31 In a recent work by our group, a water-soluble
polymer PEG was found to be a good thermodynamic as well
as kinetic hydrate inhibitor suitable for drilling fluids.5,32 In our
subsequent study,33 we found that the inhibition and
dissociation results are extremely important for their possible
application for methane recovery studies from hydrate
reservoir. Methane recovery from hydrate has been studied
by using different methods such as inhibitor injection,
depressurization, CO2 injection, and thermal methods.34−39
Methane production from inhibitor injection along with
polymer seems to be a promising method. In our recent
work, PEG acted as a good hydrate inhibitor as well as a better
sweeping agent for methane recovery.33
DOI: 10.1021/acs.energyfuels.9b01204
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Energy & Fuels Article

Table 1. Details of the Oilfield Polymers Used for Low-Dosage Kinetic Hydrate Inhibitors (LDHI) Investigations
number-average monomer number of
molecular weight polydispersity molecular repeating
polymers abbreviation (g/mol) index (PDI) molecular formula weight unites source
polyacrylamide PAM-1 1.1 × 106 1.16 (C3H5NO)n 71 15 493 Oil and Natural Gas
Corporation, Mumbai
PAM-2 1.5 × 105 1.30 2133 Sigma-Aldrich, U.S.
xanthan gum XG-1 6.4 × 105 1.06 (C35H49N29)n 875 731 Oil and Natural Gas
Corporation, Mumbai
XG-2 2.4 × 105 1.23 274 Halliburton, U.S.
guar gum GG-1 1.7 × 106 1.16 (C10H14N5Na2O12P3)n 535 3178 The Energy and
Resources Institute,
Delhi
GG-2 6.0 × 105 1.09 1121 Sisco Research
Laboratories,
Mumbai

Figure 1. FTIR spectra of the oilfield polymers used in this study. (a) Polyacrylamide (PAM-1, PAM-2). (b) Xanthan gum (XG-1, XG-2). (c) Guar
gum (GG-1, GG-2).

As discussed above, most of the oilfield polymers, such as polymers and have shown better results. The use of
polyacrylamide, have been used as a synergist along with other polysaccharides for kinetic hydrate inhibition cannot also be
6337 DOI: 10.1021/acs.energyfuels.9b01204
Energy Fuels 2019, 33, 6335−6349
Energy & Fuels
Figure 2. Schematic of the experimental setup used for the performance evaluation of oilfield polymers as LDHI.
ruled out, as these polysaccharides are one of the cheap
hydrophilic polymers and are commercially available. These
polymers are significantly being used as drilling fluid additives.
However, studies on the individual effect of these oilfield
polymers on gas hydrate formation and dissociation kinetics
are still unknown. Also, in most of the literature, the molecular
weight of the polymers used in the study of hydrate kinetics is
either low or not mentioned.
The present study aims to investigate the performance
evaluation of various water-soluble oilfield polymers as LDHI
by performing methane hydrate formation and dissociation
kinetic experiments. Water-soluble polymers, such as PAM,
XG, and GG with two different molecular weights and varying
concentrations in water, were considered for the investigations.
These are PAM (Mw: 1.1 × 106 g/molPAM-1 and 1.5 × 105
g/molPAM-2); XG (Mw: 6.4 × 105 g/molXG-1 and 2.4
× 105 g/molXG-2); and GG (Mw: 1.7 × 106 g/molGG-1
and 6 × 105 g/molGG-2), with varying concentrations of
100, 200, and 500 ppm in aqueous solution. These are referred
to as high molecular weight polymers (PAM-1, XG-1, and GG-
1) and relatively low molecular weight polymers (PAM-2, XG-
2, and GG-2).
2. EXPERIMENTAL SECTION
2.1. Materials. Methane gas with a purity of 99.95 mol %
(obtained from Bhuruka gas agency) was used in the study. Deionized
water is used for preparing aqueous solutions, which is obtained from
Labostar (Siemens). The details of the polymers used in the study
with their terminologies are given in Table 1.
2.2. Polymer Analysis. The oilfield polymers utilized in the
present work were acquired from different places. Consequently, it is
important to characterize them before use. The aim of conducting this
exercise is to find the molecular weight and associated functional
group of the polymers.
2.2.1. Gel Permeation Chromatography. The molecular weight of
polymers was measured by gel permeation chromatography
(Shimadzu, Japan), with refractive index sensor (RID-10A) and
Polysep column. A concentration of 0.1 molal sodium nitrate was
used as a carrier phase at a flow rate of 1 mL/min. The molecular
weight of the sample was determined by using a typical curve of
known molecular weight prepared using pullulan standards. The
measured molecular weights of the polymers are reported in Table 1.
6338
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2.2.2. Fourier-Transform Infrared Spectroscopy (FTIR) Analysis.
The functional group distribution of polymers was obtained from
FTIR analysis. Cary 660 FTIR spectrometer (Agilent Technologies, at
NCCRD, IIT Madras) is utilized for the measurement. Figure 1
shows the FTIR analysis of different polymers. FTIR analysis of
polyacrylamide discloses the presence of strong and medium N−H
group stretching, C−H group stretching, and C−O group bending.
FTIR analysis of xanthan gum indicated the presence of hydrogen-
bonded O−H stretching groups, C−H stretching, O−H bending
group, C−O stretching, and benzene derivative (Figure 1). The FTIR
spectrum of guar gum shows strong O−H stretching, the presence of
strong C−H stretching, medium CC stretching, strong C−O
stretching modes, and C−H bending polymer backbone. The FTIR
spectrum acquired for PAM-2, XG-2, and GG-2 show analogous
peaks with respect to their corresponding relatively high molecular
weight polymers PAM-1, XG-1, and GG-1. Thus, the polymers that
are being used in this work are of similar types.
2.3. Experimental Setup. Figure 2 shows a typical diagram of the
experimental setup used in this study. A high-pressure reactor with a
capacity of 250 mL, made of SS-316 and a working pressure 10 MPa,
was used. A Thermo Haake water bath (model A 25) circulates
cooled water−glycol mixture through the jacket encompassing the
reactor and maintains the desired temperature. A temperature sensor
(Pt-100) and a pressure transducer (Wika A-10) are used to measure
the temperature and pressure within the reactor. These devices have
the uncertainty of ±0.05 K and ±0.005 MPa, respectively. An
externally powered magnetic stirrer rotating at 1000 rpm is used to
increase the heat and mass transfer between gas and liquid interface
within the reactor. Also, a syringe pump (500 D, Teledyne Isco, U.S.)
is employed to inject and enhance the pressure of the gas in the
reactor up to the experimental pressure. A data acquisition system
records the data at every 30 s and sends it to the computer for
analysis.
2.4. Experimental Procedure. Isothermal formation kinetic
study on methane hydrate was performed using various aqueous
solutions of water-soluble polymers reported in Table 1. Table 2
reports the details of experiments performed along with the
nomenclature used. All the experiments were performed at 8 MPa
and 274.15 K. The temperature and pressure are selected in such a
way that it should lie in the hydrate formation (stable) region, that is,
above the hydrate phase equilibrium curve for the respective polymer
aqueous solutions as reported in our recent work.40 The reactor vessel
was appropriately cleaned and dried before the start of each
experiment. The water−glycol mixture is circulated through an
enclosed jacket of the reactor to keep the anticipated temperature of
the reactor. Once the temperature of the reactor reaches the set value
DOI: 10.1021/acs.energyfuels.9b01204
Energy Fuels 2019, 33, 6335−6349
Energy & Fuels Article

Table 2. Details on the Methane Hydrate Formation Experiments in the Presence of Aqueous Solutions of Water-Soluble
Polymers
average gas-to- average gas- water-to- average water- average cumulative average cumulative
average induction hydrate to-hydrate hydrate to-hydrate gas consumed gas consumed
expt polymer expt induction induction time conversion conversion conversion conversion (mol/mol of (mol/mol of
no. system run time (h) time (h) (min) (%) (%) (%) (%) water) water)
1 pure water run 1 0.20 1.43 86 58.0 57.6 ± 0.4 15.9 15.8 ± 0.1 0.025 0.025 ± 0.0
2 run 2 2.65 57.2 15.7 0.025
3 PAM-1_ run 1 1.05 2.42 145 27.0 27.5 ± 0.5 6.9 7.0 ± 0.1 0.011 0.011 ± 0.0
100 ppm
4 run 2 3.78 28.0 7.0 0.011
5 PAM-1_ run 1 14.0 12.15 729 13.0 14.5 ± 1.5 3.4 3.8 ± 0.4 0.005 0.006 ± 0.001
200 ppm
6 run 2 10.3 16.0 4.2 0.007
7 PAM-1_ run 1 NHF NHF NHF NHF NHF NHF NHF NHF NHF
500 ppm
8 run 2 NHF NHF NHF NHF
9 PAM-2_ run 1 2.65 2.65 159 48.0 48.0 13.0 13.0 0.021 0.021
200 ppm
10 run 2
11 PAM-2_ run 1 0.49 0.75 45 52.2 53.6 ± 1.4 14.4 14.3 ± 0.1 0.023 0.024 ± 0.001
500 ppm
12 run 2 1.00 55.0 14.2 0.024
13 XG-1_ run 1 6.24 7.49 449 43.5 37.8 ± 5.7 11.1 9.6 ± 1.5 0.018 0.016 ± 0.003
100 ppm
14 run 2 8.73 32.0 8.1 0.013
15 XG-1_ run 1 0.10 0.35 21 44.0 39.0 ± 5 11.0 9.5 ± 1.5 0.013 0.015 ± 0.002
200 ppm
16 run 2 0.60 34.0 8.0 0.017
17 XG-1_ run 1 0.02 0.04 2 21.9 21.4 ± 0.5 5.7 5.4 ± 0.3 0.010 0.010 ± 0.001
500 ppm
18 run 2 0.06 20.9 5.1 0.009
19 XG-2_ run 1 0.02 0.03 2 54.0 53.5 ± 0.5 14.4 14.2 ± 0.2 0.023 0.022 ± 0.001
200 ppm
20 run 2 0.04 53.0 13.9 0.021
21 XG-2_ run 1 0.03 0.04 2 37.0 36.0 ± 1 9.7 9.3 ± 0.4 0.016 0.015 ± 0.001
500 ppm
22 run 2 0.05 35.0 8.8 0.014
23 GG-1_ run 1 0.21 0.21 13 49.6 49.6 13.6 13.6 0.022 0.022
100 ppm
24 run 2
25 GG-1_ run 1 1.09 1.09 65 44.3 44.3 12.0 12 0.019 0.019
200 ppm
26 run 2
27 GG-1_ run 1 15.80 10.71 643 32.8 36.4 ± 3.6 8.7 9.4 ± 0.6 0.016 0.015 ± 0.001
500 ppm
28 run 2 5.62 40.0 10.0 0.014
29 GG-2_ run 1 1.16 1.68 101 46.0 45.5 ± 0.5 13.0 12.5 ± 0.5 0.022 0.021 ± 0.001
200 ppm
30 run 2 2.20 45.0 11.9 0.020
31 GG-2_ run 1 5.40 3.00 180 43.4 44.1 ± 0.6 11.9 11.9 ± 0 0.019 0.019 ± 0.0
500 ppm
32 run 2 0.60 44.7 11.9 0.019

of 274.15 K, methane gas is purged in aqueous solution of polymer to
remove any traces of dissolved and atmospheric air within the reactor.
During purging, the magnetic stirrer is kept on at 1000 rpm. After the
temperature inside the reactor becomes stable, the reactor is
pressurized with methane gas up to the desired pressure (8 MPa),
and the stirrer was again switched on at 1000 rpm.
Figure 3 demonstrates various events during hydrate formation
experiment in the presence of PAM-2_500 ppm aqueous solution.
The figure is divided into three zones; zone 1 represents the time
taken for hydrate nucleation; zone 2 is the hydrate growth period;
zone 3 shows hydrate formation is in the steady-state condition. The
induction time (time at which the first hydrate nucleation occurs) is
manifested in terms of the rise in the temperature (due to exothermic
hydrate formation process) and sudden decrease in the pressure of the
reactor (zone 1, Figure 3). Gas is consumed after nucleation due to
hydrate growth (zone 2, Figure 3). Hydrate formation was then
continued for ∼20 h after the onset of the hydrate formation. When
the pressure of the reactor remains steady (when the pressure
differential of the reactor remains steady at ∼0.001 MPa/h; zone 3,
Figure 3), hydrate formation is assumed to be completed. Thereafter,
hydrate is allowed to dissociate completely by increasing the
temperature from 274.15 to 299.15 K (hydrate dissociation
experiment). The methane gas in the reactor is vented out safely,
and the reactor is made ready for the next run.
2.5. Calculations. 2.5.1. Gas Consumed. The gas consumed
during hydrate formation (hydrate growth) is estimated from the
difference of gas inside the reactor initially and the residual gas after
methane hydrate formation at time tf (time is measured after hydrate
nucleation). The moles of gas consumed in a hydrate formation
experiment is given by eq 1. The gas present initially is calculated by
the first term in eq 1, and the residual gas at any time is calculated by
second term in eq 1 (see below for example calculation).

6339 DOI: 10.1021/acs.energyfuels.9b01204

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Energy & Fuels Article

where Vg is the volume of gas in the system, Δng is the number of

Figure 3. Pressure and temperature profile for kinetics of methane
hydrate formation in the presence of PAM-2_500 ppm aqueous
moles of gas consumed (mole) at time tf, PR represents the reactor
pressure at given time tf, T is the temperature, Z is the compressibility
factor, and R denotes the universal gas constant. Compressibility
factor (Z) is computed using Pitzer correlation. For each experiment,
we plotted gas consumption (N in mol/mol), which is the ratio of
moles of gas consumed at any given time (Δng) to the number of
moles of water initially present (nw) versus time.
A sample calculation for gas consumption is shown below:
The amount of gas consumed in the presence of PAM-2 at 200
ppm:
Initial pressure and temperature of the reactor, P = 8050 kPa, T =
274.15 K.
Z factor calculated from Pitzer correlation = 0.8157.
Volume of the reactor = 90 cm3.
R = 8314 cm3 kPa·mol−1·K−1.
Number of initial moles of gas: first term of eq 1 = 0.389 26 mol.
Final pressure and temperature of the reactor at the end of hydrate
formation after hydrate induction (after ∼20 h from hydrate
induction): P = 4590 kPa, T = 274.65 K.

ÄÅ ÉÑ
solution.

ÅÅ P Ñ
Z factor calculated from Pitzer correlation = 0.8949.

ÅÅji R zy i PR zy ÑÑÑ
j
Volume of the reactor = 90 cm3, R = 8314 cm3 kPa·mol−1·K−1.
Δng = VgÅÅÅjj zz − jj zz ÑÑÑ
ÅÅÅÇk ZRT {t f = 0 k ZRT {t f ÑÑÑÖ
Number of moles of residual gas; second term of eq 1 = 0.202 31
(1) mol.
Moles of gas consumed/Moles of water = (0.389 26 − 0.202 31)/
8.88 = 0.021 05 − 0.021 mol/mol.

Figure 4. Cumulative moles of gas consumed during formation of methane hydrate in the presence of high molecular weight polymer aqueous
solutions at different concentrations of 100, 200, and 500 ppm. (a) PAM-1; (b) XG-1; (c) GG-1.

6340 DOI: 10.1021/acs.energyfuels.9b01204

Energy Fuels 2019, 33, 6335−6349
Energy & Fuels Article

Figure 5. Cumulative moles of gas consumed during formation of methane hydrate in the presence of relatively low molecular weight polymer
aqueous solutions at different concentrations of 200 and 500 ppm. (a) PAM-2; (b) XG-2; (c) GG-2.

2.5.2. Gas-to-Hydrate Conversion. The gas-to-hydrate conversion (Δn′) at any given time td (time measured from start of hydrate
(cumulative) at the end of hydrate formation experiment is given by dissociation) is estimated by the difference between number of moles
eq 2: of gas in the reactor at time td and initial number of moles of gas in
the reactor at td = 0, which is represented by eq 5. The rate of gas

ÄÅ ÉÑ
Δng × 100

ÅÅ P Ñ
release is given by eq 6.

ij PR yz ÑÑÑ
gas‐to‐hydrate conversion =
ÅÅij R yz
moles of gas recovered = Δn′ = VgÅÅÅjj z − jj z ÑÑÑ
ni (2)
z
ÅÅk ZRT {t z
ÅÇ k ZRT {td = 0ÑÑÑÖ
where ni is the moles of gas at the start of the experiment.
2.5.3. Water-to-Hydrate Conversion. The water-to-hydrate d
conversion (cumulative) at the end of the experiment is given by (5)

i dN ′ yz
gas release rate = jjj
eq 3:
zz =
d(Nt′d +Δt − Nt′d)
k {
Δng × h × 100
water‐to‐hydrate conversion = d t dt (6)
nw (3)
where N′ (mol/mol) is the ratio of moles of gas released at any given
where h is the hydration number (∼6.1 for methane hydrate).41 time (Δn′) to the number of moles of water initially present (nw), and
2.5.4. Rate of Gas Consumption. The rate of gas consumed is Δt is the time between two different observations.
calculated using eq 4:

i dN zy
rate of gas consumed, jjj zz =
d(Nt f +Δt − Nt f ) 3. RESULTS AND DISCUSSION
k dt { dt (4) In this study, to understand the performance of various oilfield
polymers as LDHI, formation and dissociation kinetic
where N (mol/mol) is the ratio of moles of gas consumed at any
experiments of methane hydrate in the presence of various
given time (Δng) to the number of moles of water initially present
(nw), and Δt is the time between two different observations. The rates aqueous solutions of oilfield polymers, such as PAM, XG, and
are averaged for the time period of 1 h and plotted. GG, were reported. Total 32 experiments were performed as
2.5.5. Gas Recovered During Dissociation and Rate of Gas reported in Table 2. Two different molecular weight of
Release. The moles of gas recovered during hydrate dissociation polymers (one high and other relatively low) with varying
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Figure 6. Rate of gas consumption during hydrate formation in the presence of aqueous solutions of various polymers at different concentrations of
100, 200, and 500 ppm. (a) PAM-1; (b) XG-1; (c) GG-1.
concentrations (viz., 100, 200, 500 ppm) of each were tested.
The experiments were performed at an initial pressure of 8
MPa and a constant temperature of 274.15 K. The nucleation
(induction) time, gas consumption (hydrate growth) and its
rate, gas-to-hydrate and water-to-hydrate conversion during
formation experiments, and moles of gas released and its rate
during hydrate dissociation were reported. The growth kinetics
of gas hydrate were studied and reported up to 20 h after
hydrate nucleation, while the dissociation kinetics were
investigated for a few selected polymers after onset of hydrate
dissociation. Most of the experiments were repeated twice, and
the results are provided with error bar to show the repeatability
of the experiments.
3.1. Kinetics of Methane Hydrate Formation. 3.1.1. Ef-
fect of Polymer Concentration on Gas Consumption. The
formation kinetics of methane hydrate in the presence of PAM,
XG, and GG aqueous solutions was investigated for high
molecular weight polymers (PAM-1, XG-1, GG-1; 100, 200,
500 ppm) and relatively low molecular weight polymers
(PAM-2, XG-2, GG2; 200 and 500 ppm). Table 2 shows the
average moles of gas consumed (cumulative) in mol/mol of
water. Figure 4 shows cumulative moles of methane consumed
during hydrate formation in the presence of PAM-1, XG-1, and
GG-1 for a period of 20 h after hydrate nucleation at three
concentrations of 100, 200, and 500 ppm. The cumulative
moles of gas consumed in PAM-1 aqueous solution at 100 and
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200 ppm is 0.011 and 0.006 mol/mol of water, respectively,
while no hydrate formation (NHF) is observed at 500 ppm
(Figure 4a). Also, the cumulative gas consumed in pure water
system without any polymer is observed to be 0.025 mol/mol
of water (pure water case). It was observed that all the three
concentrations of PAM-1 reduced the hydrate growth
substantially as compared to the pure water case. In other
words, the presence of PAM-1 significantly inhibited the
hydrate formation. The hydrate inhibition in the presence of
PAM-1 follows the order: 500 >200 >100 ppm. In the case of
XG (Figure 4b), it was found that all three concentrations of
XG-1 inhibited the hydrate formation. The cumulative moles
of gas consumed in the presence of XG-1 aqueous solution at
100, 200, and 500 ppm are observed to be 0.016, 0.015, and
0.010 mol/mol of water, respectively. XG-1_500 ppm resulted
in higher methane hydrate inhibition as compared to the other
two concentrations of XG-1. The order of hydrate inhibition in
the presence of XG-1 follows the same order as that of PAM-1,
that is, 500 > 200 > 100 ppm. Similarly, gas consumed in GG-1
aqueous solution at 100, 200, and 500 ppm is found to be
0.022, 0.019, 0.015 mol/mol of water, respectively (Figure 4c).
The hydrate inhibition in the presence of GG-1 also follows a
similar trend as that of PAM-1 and XG-1.
Figure 5 shows the moles of methane consumed during
hydrate formation in the presence of relatively low molecular
weight polymers, PAM-2, XG-2, and GG-2. The gas
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Figure 7. Comparison of cumulative moles of gas consumed during hydrate formation for different aqueous polymer systems, effect of molecular
weight.
consumption in the presence of PAM-2 at 200 and 500 ppm is
0.021 and 0.024 mol/mol of water, respectively (Figure 5a).
The gas consumption in the presence of XG-2 at 200 and 500
ppm is 0.022 and 0.015 mol/mol of water, respectively (Figure
5b). Also, the gas consumption in the presence of GG-2 at 200
and 500 ppm is 0.021 and 0.019 mol/mol of water, respectively
(Figure 5c). Gas consumption seems to be higher (almost
equivalent to that of pure methane hydrate) for initial period of
5 h in the case of GG at both 200 and 500 ppm. Subsequently,
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the gas consumption was decreased in longer run of hydrate
formation. Initially, the rapid hydrate formation occurred due
to possible polymer entanglement, during which, free water
availability is high for the hydrate formation. Later, as the
hydrate formation matures, polymer molecules may get
adsorbed onto the hydrate crystal preventing further growth
of the crystals. In the case of GG, the carbon chain length is
quite high as compared to PAM (see Table 1), due to which
rapid hydrate formation was observed in the case of GG and
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Figure 8. Comparison of cumulative moles of gas consumed and the rate of gas consumption in the presence of aqueous solutions of different
relatively high molecular weight polymers (PAM-1, XG-1, GG-1).
not in PAM. Also, because of possible polymer entanglement
(which is expected to be more in case of GG due to its higher
chain length), the overall gas consumption is observed to be
higher in the case of GG as compared to PAM.
Though all the polymers with relatively low molecular
weight have shown a reduction in gas consumption during
hydrate formation, there is not much difference in gas
consumption in the cases of PAM-2 and GG-2 at both the
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concentrations of 200 and 500 ppm, as compared to pure
water case.
3.1.2. Effect of Polymer Concentration on the Rate of
Hydrate Formation. Figure 6 shows the rate of gas
consumption during hydrate formation at different concen-
trations of PAM-1, XG-1, GG-1, and pure water. The initial
rate of gas consumption is very slow in case of PAM-1_100
and 200 ppm as compared to pure water system (Figure 6a),
while it is almost negligible in the case of PAM-1_500 ppm.
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Figure 9. Gas-to-hydrate conversion (%) in the presence of different aqueous polymer systems.
The rate of gas consumption in the presence of PAM-1_100
ppm is higher than that with PAM-1_200 ppm. All
concentrations of PAM-1 attain a steady state in hydrate
formation in an ∼7−9 h post-hydrate nucleation. For XG-1,
the rate of gas consumption is initially higher at 100 ppm
followed by 200 ppm, while the rate of gas consumption is
quite slow in case of XG-1_500 ppm (Figure 6b). The rate of
gas consumption for XG-1 is fairly low at all concentrations as
compared to the rate of gas consumption in a pure water
system. The steady state in hydrate formation was reached in
an ∼12−15 h postnucleation for almost all the concentrations
of XG-1. For GG-1, the initial rates of gas consumption are
reasonably high for all the concentrations for initial 2−2.5 h,
which are almost comparable to that of pure water (Figure 6c).
As the concentration of GG1 increases (GG-1_100 to 500
ppm), the rate of hydrate growth decreases after 2−2.5 h
postnucleation. The steady state was reached in ∼13−15 h for
almost all the concentrations of GG1.
From the above study, it was observed that the
concentration of polymer does play a major role in hydrate
growth (gas consumption) and growth rate. Also, the rate of
gas consumption in case of different polymers seems to be
concentration-dependent. Higher concentration of relatively
high molecular weight polymer is effective in slowing the
hydrate growth and rate of gas consumption. The amount of
gas consumed during hydrate formation in the presence of
polymer solutions depends on many factors such as heat and
mass transfer, surface area, turbulence, subcooling, water
history, and the geometry of the system during hydrate
formation. As the concentration of polymer increases, the heat
and mass transfer limitation dominates and also possible
adsorption of polymer molecules onto the hydrate surface
limiting the hydrate growth.18,42
3.1.3. Effect of Polymer Molecular Weight on Hydrate
Formation. Figure 7 shows the effect of different molecular
weight of each polymer (at the same concentration) on gas
consumption during hydrate formation. The amount of gas
consumed drastically decreases in case of PAM-1 as compared
to PAM-2 (see Figure 7a,b). No hydrate formation was
observed in case of PAM-1_500 ppm, while the gas
consumption in the presence of PAM-2_500 ppm is ∼0.024
mol/mol of water (which is nearly equal to the pure water
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system, i.e., 0.025 mol/mol; also see Table 2), Figure 7a. A
significant difference between the gas consumed in case of
PAM-1_200 ppm (0.006 mol/mol of water) and PAM-2_200
ppm (0.021 mol/mol of water) was also observed, Figure 7b.
XG-1 is also found to be effective in reducing the gas
consumption in hydrate as compared to its relatively low
molecular weight polymer XG-2 (Figure 7c,d). Gas con-
sumption was found to be 0.010 mol/mol in the presence of
XG-1_500 ppm, while it is 0.015 mol/mol of water in the
presence of XG-2_500 ppm, Figure 7c, so is the similar
observation for XG-1_200 ppm and XG-2_200 ppm, Figure
7d. For GG, the gas consumption was found to be 0.015 and
0.019 mol/mol of water in the presence of GG-1 and GG-2 at
500 ppm, respectively (Figures 7e). In the case of GG-1 and
GG-2 at 200 ppm, gas consumption was found to be 0.019 and
0.021 mol/mol of water, respectively (Figure 7f, Table 2). In
terms of percentage reduction, it was observed that a 97%
reduction in gas consumption is observed in the presence of
high molecular weight polymer, PAM-1_500 ppm, as
compared to PAM-2_500 ppm. Almost 72% reduction in gas
consumption is observed in the presence of PAM-1_200 ppm
as compared to PAM-2_200 ppm. A reduction of 57% in gas
consumption is observed in XG-1_500 ppm as compared to
XG-2_500 ppm. A reduction of ∼26% in gas consumption is
observed in GG-1_500 ppm as compared to GG-2_500 ppm.
This indicates the relative effect of different types of polymers
having different molecular weight on the hydrate growth.
From the above result, we observe that molecular weight of
polymers affects the gas consumption during hydrate
formation. The relatively high molecular weight polymers are
very effective in inhibiting hydrate growth. A careful look at
Table 1 shows that PAM-1 is almost 7 times higher in
molecular weight than that of PAM-2. Therefore, such a large
difference in gas consumption with a change in PAM molecular
weight is anticipated. Again, the molecular weight of XG-1 is
almost 3 times higher than that of XG-2, and molecular weight
of GG-1 is also almost 3 times higher than that of GG-2.
Available literature says that when water-soluble polymers are
added in water, they may form hydrogen bonding with water
molecules to inhibit hydrate.8,31,43−45 In this case, we also
expect that the polymers with high molecular weight give rise
to more water and polymer interactions (possibly with more
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Figure 10. Methane hydrate induction time (min) in the presence of different aqueous polymer systems.
hydrogen bonding between polymer and water molecules),
thus leading to reduced hydrate growth and gas consumption
with an increase in molecular weight of the polymers.
3.1.4. Comparison of Gas Consumption and the Rate of
Hydrate Formation. A comparison was made for relatively
high molecular weight polymers by observing their perform-
ance as LDHI. Figure 8 shows cumulative moles of gas
consumed (Figure 8a−c) and the rate of gas consumption
(Figure 8d−f) during hydrate formation in the presence of
relatively high molecular weight polymers (PAM-1, XG-1, GG-
1). As shown in Figure 8a, at 500 ppm, the order of hydrate
inhibition in the presence of polymer aqueous system is PAM-
1 > XG-1 > GG-1. This order of hydrate inhibition in polymer
aqueous system remains the same at 200 and 100 ppm
(Figures 8b,c). The initial hydrate formation rates are higher
for GG-1_500 ppm followed by XG-1_500 ppm and PAM-
1_500 ppm (Figure 8d). The steady state in hydrate formation
was observed after 8−9 h of hydrate induction in case of GG-
1_500 ppm and XG-1_500 ppm, while no significant hydrate
was formed for PAM-1_500 ppm (Figure 8d). The initial
hydrate growth rate is higher for GG-1_200 ppm followed by
XG-1_200 ppm and PAM-1_200 ppm. The GG-1and XG-1 at
200 ppm attain similar rates after 4 h of hydrate induction,
until the steady state is reached after ∼13−15 h of hydrate
induction. As compared to XG-1 and GG-1 at 200 ppm, the
rate of gas consumption is lower in the case of PAM-1 (Figure
8e). GG-1_100 ppm has shown higher initial rates of hydrate
formation followed by XG-1_100 ppm and PAM-1_100 ppm
(Figure 8f). PAM-1_100 ppm maintained a slow rate of
hydrate formation throughout and attains a steady state after
∼10 h post-hydrate nucleation. The use of aqueous solution of
PAM-1 in water resulted in lower gas consumption and the
rate of hydrate growth as compared to XG-1 and GG-1. The
performance of PAM-1 is superior even at a low concentration
of 100 ppm followed by XG-1_500 ppm and then followed by
other concentrations of PAM-2, XG-2, GG-1, GG-2. The
possible reason for the above observation is explained later.
3.1.5. Gas-to-Hydrate Conversion, Water-to-Hydrate
Conversion, and Induction Time. Figure 9 and Table 2
show gas-to-hydrate conversion in the presence of various
aqueous solutions of polymers with varying concentrations. It
was observed that the gas-to-hydrate conversion is highest for
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the pure water system. The gas-to-hydrate conversion is
observed to be lowest (negligible) in case of PAM-1_500 ppm
followed by (in increasing trend) PAM-1_200 ppm, XG-1_500
ppm, PAM-1_100 ppm, XG-2_500 ppm, GG-1_500 ppm, and
so on. Table 2 also shows water-to-hydrate conversion, and it
can be observed that the trend of water-to-hydrate conversion
is similar to gas-to-hydrate conversion. Although all polymers
at all concentrations show hydrate inhibition as compared to
the pure water system, PAM-1 demonstrated higher inhibition
(best LDHI) in terms of hydrate growth at all three
concentrations used in this investigation.
Figure 10 shows the information on induction (nucleation)
time for hydrate formation in the presence of various polymer
aqueous solutions. The highest induction time is observed in
the case of PAM1_500 ppm (negligible hydrate formation),
followed by (in decreasing trend) PAM-1_200 ppm, GG-
1_500 ppm, XG-1_100 ppm, etc. It can be observed that
induction time in case of PAM-1 and GG-1 follows a particular
trend. In these cases, as the concentration is reduced, the
induction time also gets reduced. However, a reduction in the
concentration of GG-1 from 500 to 200 and 100 ppm resulted
in a significant decrease in induction time. In the case of XG,
with an increase in concentration, the induction time reduced
significantly for XG-1, while it is negligible in the case of XG-2.
Hydrate inhibition in terms of induction time follows a general
trend in the presence of PAM-1 aqueous solution. In case of
relatively low molecular weight polymers, the time for hydrate
induction (nucleation) is significantly lower.
From the above studies, PAM-1 was demonstrated to be a
good kinetic hydrate inhibitor (LDHI) up to 10−11 degrees of
subcooling conditions in the essence of hydrate nucleation,
hydrate growth, and hydrate growth rate. Moreover, XG-1 and
GG-1 at 500 ppm also performed as decent hydrate inhibitors
in lowering the hydrate growth. PAM-2, XG-2, and GG-2
(relatively low molecular weight polymers) did not result in
much hydrate inhibition as compared to the former group.
A study by Koh and co-worker demonstrated that hydrate
formation is an interfacial phenomenon. They also found that
polymers as kinetic hydrate inhibitors are capable of
controlling bulk and surface nucleation.46 In case of PAM,
there is carbonyl group in amide functional group (also see
Table 1), which is capable of forming hydrogen bond with
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Figure 11. Rate of hydrate dissociation in the presence of different aqueous polymer systems after the start of dissociation process: (a) PAM-1, 100
and 200 ppm; (b) XG-2, 200 and 500 ppm; (c) GG-1, 200 and 500 ppm.
water molecule, and the number of such hydrogen bonding
former increases with the molecular weight of the poly-
mer.43,45,47 PAM (say with a single unit as a monomer) is small
enough and can interact in a much better way with water
molecules and get adsorbed onto hydrate crystal more
potentially than the longer chain monomers such as xanthan
gum and guar gum (see Table 1). The number of monomers
(repeating units) in the case of PAM are quite large with a
molecular weight in the range of 1.1 × 106 g/mol. Thus, the
number of repeating units for PAM-1 is ∼15 493 in this case
(see Table 1 for details on repeating unit); as a result, the
number of interactions with water molecules is expected to
increase significantly as compared to other systems. This may
be the possible reason why PAM-1 has inhibited hydrate
significantly as compared to other polymers studied in this
work.
There are few reports which advocate that acrylamide
polymers are good kinetic hydrate inhibitors. Exxon had
patented some of the acrylamide polymers and suggested that
the hydrophobic group of the polymer (monomer unit) would
form hydrate cavities around it, whereas the oxygen atom of
carbonyl group of acrylamide would form hydrogen bonds
with water molecules.26 A polymer was required for making
these interactions larger. The inhibitor could therefore
interfere the nucleation of hydrates in the water phase. Our
results are satisfactorily in line with some of the literature that
shows that amide group of polyacrylamide has a good tendency
to inhibit hydrate, while polysaccharides are not as good
performers as polyacrylamide.26,28,47,48
3.2. Kinetics of Methane Hydrate Dissociation. The
purpose of hydrate dissociation kinetics is important to
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understand how the gas will release during dissociation once
the hydrates are formed in aqueous polymer solutions. This
has special significance for drilling fluid design and analysis,
particularly during degassing operations. Figure 11 shows the
rate of gas release for various polymer systems at various
concentrations plotted after the start of dissociation process. It
was observed that PAM-1_100 ppm showed faster gas release
rate and early release of gas from hydrate than PAM-1_200
ppm. In case of PAM-1_200 ppm, the release of gas from
hydrate is delayed by 0.25 h (∼15 min) compared to PAM-
1_100 ppm. The peak in rate was attained at 0.13 and 0.38 h
(∼7.8 and 22.8 min) in case of PAM-1_100 ppm and PAM-
1_200 ppm, respectively, from the start of dissociation process.
In XG-2_200 ppm aqueous solution (Figure 11b), the release
of gas from hydrate is delayed by ∼0.12 h (∼7.2 min), while in
case of XG-2_500 ppm it is delayed by 0.25 h (15 min) from
start of the dissociation process. XG-2_200 ppm resulted in
higher dissociation rates as compared to XG-2_500 ppm. The
peaks in the gas release rate is observed at 0.63 and 0.75 h
(∼37 to 45 min) for XG-2_200 ppm and XG-2_500 ppm,
respectively. In case of GG-1_200 ppm (Figure 11c), the gas
release from hydrate is delayed by 0.13 h (∼7.8 min), while it
is delayed by 0.3 h (∼18 min) for GG-1_500 ppm. Again, the
lower concentration of GG-1_200 ppm resulted in higher
dissociation rates as compared to GG-1_500 ppm. Also, the
peaks in the gas release rate is observed at 0.75 and 0.63 h
(∼45 and 37 min) for GG-1_200 ppm and GG-1_500 ppm,
respectively.
From the dissociation kinetics, it was observed that the rate
of gas release during hydrate dissociation attains a peak value
when it is closer to near-hydrate equilibrium conditions. For
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example, the time at which the peak occurs in hydrate
dissociation rate curve in case of PAM-1_200 ppm (Figure
11a), the corresponding temperature (T) and pressure (P) at
that time are 282.3 K and 7.04 MPa, respectively, which are
close to methane hydrate equilibrium conditions for the said
polymer aqueous systems (Teq = 282 K, Peq = 7.05 MPa) as
reported in our recent work.40 Similar are the observations for
other polymer systems. This outcome has a special significance
for determining early gas kick during offshore drilling
operations and designing of drilling fluids. The stability
conditions of hydrate in the drill pipe are dynamic and do
keep changing during mud circulation. Consequently, there are
different hydrate dissociation regions encountered during the
circulation, which may result in variable in situ pressures and
possible gas kick during drilling operation. Operator can take
appropriate precautions if it is observed that the in situ
conditions of pressure and temperature are approaching near-
hydrate equilibrium conditions.
It was also observed that the low concentration of polymers
(viz., PAM-1_100 ppm, XG-2_200 ppm, GG-1_200 ppm)
resulted in slightly high hydrate dissociation rates and early
release of gas as compared to their respective high
concentration of polymer (e.g., PAM-1_200 ppm, XG-2_500
ppm, GG-1_500 ppm). The reason for high rates of gas release
and slightly early release of gas during methane hydrate
dissociation in case of low concentration of the polymers can
be attributed to increased heat and mass transfer of the system
as compared to higher concentrations. Also, at high
concentration, the polymers have high viscosity with limited
heat and mass transfer conditions, which is attributed to the
delayed gas release during dissociation. The above information
on hydrate dissociation is crucial for safer drilling operation.
4. CONCLUSION
Oilfield polymers such as PAM, XG, and GG have not yet been
explored for their use as LDHI, which is the aim of this study.
Various experiments on the kinetics of methane hydrate
formation and dissociation have been performed in aqueous
solutions of these polymers. Two different molecular weights
with varying concentrations (100, 200, and 500 ppm) have
been considered for the investigations. These are PAM (Mw:
1.1 × 106 g/molPAM-1 and 1.5 × 105 g/molPAM-2); XG
(Mw: 6.4 × 105 g/molXG-1 and 2.4 × 105 g/molXG-2);
and GG (Mw: 1.7 × 106 g/molGG-1 and 6 × 105 g/mol
GG-2). The experiments were performed at an initial pressure
of 8 MPa and at a constant temperature of 274.15 K (i.e., at
10−11 degrees of subcooling conditions). The growth kinetics
of gas hydrate have been studied up to 20 h after hydrate
nucleation, while the dissociation kinetics have been performed
for the selected polymers. The nucleation (induction) time, gas
consumption and its rate, gas-to-hydrate and water-to-hydrate
conversion during formation experiments, and moles of gas
released and its rate during hydrate dissociation have been
studied. The following conclusions can be drawn from the
study:
(1) It has been observed that the concentration of polymer
does play a major role in hydrate growth (consumption
of gas) and the rate of gas consumed. Higher
concentration of relatively high molecular weight
polymer is effective in slowing the hydrate growth and
the rate of gas consumption. This may be attributed to
increase in heat and mass transfer limitation due to
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increase in the concentration of polymer and also
because of possible adsorption of polymer molecules
onto the hydrate surface limiting the gas consumption
and the rate of gas consumption.
(2) It has been found that the molecular weight of polymer
affects the gas consumption during hydrate formation.
The relatively high molecular weight polymers of the
same species are very effective in inhibiting hydrate
growth and the rate of hydrate growth. For example,
PAM-1 inhibited the hydrate formation more than
PAM-2, and similar is the case with XG and GG.
(3) A comparative study between different high molecular
weight polymers (PAM, XG, and GG) on the kinetics of
methane hydrate formation shows that the use of PAM-1
resulted in lower gas consumption and the rate of
hydrate growth against XG-1 and GG-1. The perform-
ance of PAM-1 is superior even at a lower concentration
of 100 ppm followed by XG-1_500 ppm as compared to
other concentrations of PAM-2, XG-2, GG-1, and GG-2.
Among all the polymers studied in this work, PAM-1
also demonstrated higher induction time for hydrate
nucleation. Higher hydrate inhibition is possibly due to
large number of monomer units of PAM-1 interacting
with water molecules.
(4) The rate of hydrate dissociation in the presence of
polymers has shown that the high concentration
polymers are effective in delaying the release of gas
and hence delays the occurrence of hydrate dissociation
peak. This observation has special significance for
drilling fluid design and analysis, particularly during
degassing operations and safer drilling operations.
(5) This study has implications in flow assurance, designing
of hydrate inhibitive drilling fluids, and other industrial
applications where kinetics of hydrate inhibition play a
vital role.
■
AUTHOR INFORMATION
Corresponding Author
*E-mail: jitendrasangwai@iitm.ac.in. Phone: +91-44-2257
4825. Fax: +91-44-2257 4802.
ORCID
Jitendra S. Sangwai: 0000-0001-8931-0483
Notes
The authors declare no competing financial interest.
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