115 (2023) 205015

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Gas Science and Engineering

journal homepage: www.journals.elsevier.com/gas-science-and-engineering

Experimental and kinetic modelling studies on the gas hydrate inhibition

effect of PVP K-90 in drilling fluids
Moumita Maiti a, Ajoy Kumar Bhaumik b, Ajay Mandal a, *
a
Department of Petroleum Engineering, Indian Institute of Technology (Indian School of Mines), Dhanbad, India
b
Department of Applied Geology, Indian Institute of Technology (Indian School of Mines), Dhanbad, India

A R T I C L E I N F O A B S T R A C T

Keywords: The hydrate inhibitors play a very important role in preventing hydrate growth inside the drilling fluid systems,
Gas hydrate which is desirable for smooth drilling operation. It has been demonstrated in several scenarios that the water-
Inhibition soluble polymer such as polyvinyl pyrrolidone (PVP K-90) efficiently reduces hydrate formation rates. In this
Drilling fluid
study, the influence of on hydrate inhibition in predesigned drilling fluids in presence of a mixture gas of
Formation rate
Induction time
methane, ethane and propane has been investigated. As the concentration of the PVP K-90 increase, the induction
time continues to increase. The rheological studies of drilling fluids conducted at different temperature and
pressure condition with varying concentration of indicates their better performance. The chemical structure of
polymer is a single 5-membered lactam ring attached to a carbon backbone which is responsible for the inhi­
bition effect of the drilling fluid samples. The large concentration range tested allows unprecedented visuali­
zation of the shifting of formation rate in compare to pure water. Hydrate formation rate appears to reduce as
concentration of increases from 0.1 wt% to 0.7 wt%. The results suggest that increasing the concentration of the
inhibitor up to 0.7 wt% may reach to a level that saturates all the growth sites and there are enough PVP K-90
molecules available to block the hydrate crystal growth, which significantly reduces the formation rate. The
experimental investigation offers new understanding of the operational mechanics of kinetic hydrate inhibitor
(KHI) in drilling operations.

1. Introduction
Clean energy plays a significant role in social-economic growth as
the world economy is booming rapidly. The resources of typical oil and
gas mainly come from conventional fossil fuel resources and the utili­
zation of this energy surges fast (Chu and Lin, 2019; Jensen et al., 2004).
The growing demand has inspired to explore and commercialize the
unconventional source of natural gas such as natural gas hydrates and
interest remains in expanding the gas supply base (Riley et al., 2020).
Natural gas hydrates are ice-like crystalline solid where gas molecules
(guest molecules) are trapped inside polyhedral spaces of water mole­
cules (host molecules) under appropriate pressure and temperature en­
vironments (Wang et al., 2019). Gas hydrates can take the shape of many
lattice structures namely, sI and sII (cubic structure) and sH which is
hexagonal in shape (He et al., 2021). Majority of the gas hydrates are
distributed in some offshore regions and very little in the permafrost
regions.
Recent oil and gas investigation technologies indicate the presence of
gigantic oil and gas reservoir in some deep-water reservoirs. Thus, the
operations to exploit these energy sources are also expanding continu­
ously from offshore areas to deep-water reservoirs. However, as the
investigation of oil and gas resources continues to expand to a deeper
level of water, geological circumstances turn into a more complicated
process for drilling through that formation in deep-water areas (He
et al., 2021). The exploitation faces various drilling problems particu­
larly in deep-water conditions. The temperature starts to decrease and
submarine pressure starts to increase slowly as the operation goes
deeper into the water. Gas hydrate may also form within the drilling
pipe as the conditions of temperature and pressure are suitable for gas
hydrate formation and it causes some serious problems which could lead
to a blow-out, and subsurface instability.
To inhibit gas hydrate formation in such situations, suitable additives
are used to stop the nucleation of hydrate by shifting the thermodynamic
equilibrium curve or delaying the nucleation or agglomeration of hy­
drates (Kelland, 2011). Thermodynamic hydrate inhibitors (THIs) can
be used to achieve these criteria but it will be costly as they can work

* Corresponding author.
E-mail address: ajay@iitism.ac.in (A. Mandal).

https://doi.org/10.1016/j.jgsce.2023.205015
Received 27 December 2022; Received in revised form 27 February 2023; Accepted 11 May 2023
Available online 13 May 2023
2949-9089/© 2023 Elsevier B.V. All rights reserved.
M. Maiti et al.
only at high concentrations (up to 40 wt% THIs are required depending
on the water cut). They are also environmentally very toxic. Therefore,
low dosage hydrate inhibitors (LDHIs) with concentration in the range
of 0.1–1.0 wt% is very effective. Some polymers such as Poly­
vinylpyrrolidone (PVP K-90) and Polyvinylcaprolactam (PVCap) are
generally known as LDHIs and they are widely used in the industry
(Frostman et al., 2003). Multiple studies have reported that, LDHIs can
change the formation and dissociation behaviour of gas hydrates (Tang
et al., 2010; Perrin et al., 2013). The inhibition effect of these additives
has already been documented in some literature, although their mech­
anism is not clear about how these additives work on inhibiting the gas
hydrate formation. Daraboina et al. (2011) concluded in their study that
some LDHIs were able to inhibit the hydrate formation as well as
improve the kinetics of methane hydrate decomposition. Whereas,
Bruusgaard et al. (2009) revealed through their experiments on hydrate
formation and dissociation, that PVP K-90 and PVCap act as hydrate
preservers because of their higher memory effect; and the dissociation
rate was also very low in contrast to pure water. Therefore, the inves­
tigation of the kinetics of hydrate decomposition of such additives are
important as it can help to understand the mechanism with which these
additives change the surface characteristics of the water-hydrate
boundary.
High-pressure and low-temperature conditions are suitable for gas
hydrates to be stable but it gets disturbed by changes in geostatic stress,
the heat, created by the drill bit cuttings and the resistance of the drill bit
to the wellbore during the drilling operation (Schofield et al., 1997).
Therefore, the formation surrounding the wellbore collapses as gas hy­
drates adjacent to the wellbore dissociate. Besides, the gas hydrate
dissociation releases a large amount of gas and water, which raises the
pore pressure and lowers the strength of the formation. The gas that
released during the dissociation process gets mixed with the drilling
fluid and reduces its density, thus losing its ability to support the well­
bore, causing wellbore instability. This gas also can regenerate gas hy­
drate within the drilling fluid at a suitable temperature and pressure
conditions during the static mode of the wellbore. As a result of this, the
blowout preventer and pipeline become clogged (Wang et al., 2019).
Hence, while drilling through sediments that contain hydrates, one of
the main challenges the drilling industry has to deal with is hydrate
dissociation.
Drilling fluid is classified among the most important components in
the drilling industry for assuring the effectiveness and safety of the
procedure while drilling through gas hydrate bearing formations.
Temperature, pressure and characteristics of the drilling mud have a
significant impact on the stability of hydrates (Zhao et al., 2019). In
theory it has been found that, lower temperature and higher density has
a better effect on drilling fluid to enhance the stability of the hydrates.
But, as the density of the drilling mud increases it can invade and
rupture the formation. However, dissociation of hydrates cannot be
prevented only by a reduction in temperature. For example, despite the
low temperature and high pressure of the drilling fluid in the arctic re­
gion, dissociation of hydrates occurred and caused some serious prob­
lems (Schofield et al., 1997). The density of the drilling fluid was raised
to boost the stability of the hydrates. But the column pressure was much
higher than the fracture pressure, which causes loss in circulation. The
chemical and physical characteristics of the drilling fluid are extremely
important in preventing hydrate dissociation.
In the current work, we conducted a number of studies to find out the
impact of PVP K-90 polymer on the formation and decomposition ki­
netics of gas hydrates. The information on the number of moles of gas
consumption during the hydrate formation, the rate of hydrate forma­
tion, rate constant, water to hydrate and gas to hydrate conversion are
being evaluated using the pressure temperature data collected from the
experimental results. The effect of PVP K-90 based drilling fluid on the
induction time of hydrate formation has been further investigated. The
influence of PVP K-90 on rheological properties of drilling fluid and their
dependence on varying temperature and pressure were also evaluated.
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Gas Science and Engineering 115 (2023) 205015
2. Materials and methods
2.1. Materials
Bentonite was acquired from Loba Chemie Pvt. Ltd. Sodium chlorite
was provided by Finer Chemicals Limited., Ahmedabad. Calcium Car­
bonate and Boron Nitride nanoparticles (BN) were purchased from SRL
Pvt. Ltd. Guar gum (function as a viscosifier) and Polyvinyl pyrrolidone
K-90 (utilized as a kinetic hydrate inhibitor) were provided from Sigma-
Aldrich Chemie GmbH and Central Drug House (P) Ltd. Respectively.
Structure of PVP K-90 polymer is mentioned in Fig. 1. PVP K-90 is more
biodegradable and greener KHIs (Ke et al., 2016). PVP K-90 as a KHIs is
very effective as very low concentration (0.1–1 wt%) is very effective to
inhibit the hydrate formation. Combined gas (90 mol% Methane, 7 mol
% Ethane and 3 mol% Propane) was supplied by Advance Gas Solution,
Gujarat, India. Table 1 contains all the additives with the specific con­
centration in the conventional drilling fluid (DF). All the concentration
chose in this study have been optimized from our previous study based
on their optimized rheological properties (Maiti et al., 2021).
3. Apparatus and procedure
3.1. Rheological measurements
The rheological analysis of different drilling fluid samples was con­
ducted in a rheometer (MCR 102) of Anton Paar with cup and bob ge­
ometry system., The torque of this rheometer ranges from 2 nNm to 200
mNm with a minimum and maximum angular deflection of 0.5 and ∞
respectively. Variations in viscosity may be caused by sample underfill.
Sample underfill can be brought on by a sample not being completely
filled or by a sample being lost to evaporation. Manual sample moni­
toring is required during the trials in order to prevent these errors. Ex­
periments were conducted with different drilling fluid samples and
varied temperature but with a constant pressure (2000 psia).
4. Stability characterization of the drilling mud using the optical
method
The stability of the drilling mud was evaluated using the dynamic
light scattering theory by the TURBISCAN Lab Expert stability analyzer
(Formulation Company, France). The test was conducted at 30ᵒ C. The
analyzer has synchronous optical sensors that measure the strength of
back scattered light and a pulsed near infrared light source (BS). Fig. 2
provides an illustration of the work concept.
5. Hydrate formation and dissociation experiments
Vinci Technologies autoclave system equipment was used to inves­
tigate the stability behaviour of gas hydrate as depicted in Fig. 3. The
capacity of the cell is 350 ml. There was a thermal bath to regulate the
autoclave’s temperature and it was measured using two temperature
sensors attached to the autoclave with a precision of ±0.5 ◦ C. One
pressure gauge is attached to the pressure sensor with the system to
display the internal pressure of the cell and the accuracy of the pressure
sensor is ±0.01 MPa. The volume of sample placed inside the reactor
was 120 ml.
Isochoric pressure search method was used to carry out the hydrate
formation and dissociation studies (Smith, 2015). To prevent any
contamination, the reactor cell was cleaned with deionized water. A
vacuum pump was used to remove any foreign gas that might have been
inside the cell. After that, the cell was filled with 120 ml of sample and
was pressurized with mixture gas to 12.55 MPa. At the beginning, the
temperature inside the reactor was 288.52 K. The system was left on for
nearly an hour to stabilize. As the pressure is constant, the temperature
of the system was lowered until the hydrate formation is being observed.
The abrupt pressure drop and temperature rise are signs of hydrate
M. Maiti et al. Gas Science and Engineering 115 (2023) 205015

Fig. 1. Polymer structure of PVP K-90 in 2D and 3D.

Table 1
Drilling fluids with various additives concentrations.
Drilling Additives Concentration Function
Fluid (DF) (wt%)
Bentonite 4 Base mud, work as a
lubricant and cools the
cuttings
NaCl 3.5 Anti-freezing agent
CaCO3 6 Weighting agent
Guar gum 0.4 Viscosifier
BN (Boron 0.4 Fluid loss controller
nitride)
PVP K-90 0 Kinetic hydrate inhibitor

Fig. 3. Schematic representation of a high-pressure autoclave system.

( )
Pi Pt
Δn↓,H = Vg \ – (1)
Zi RT Zt RT

Fig. 2. Schematic of measuring principle of TURBISCAN stability analyzer.
formation (Rajnauth et al., 2010; Wang et al., 2020). As the pressure
stabilizes after the complete formation of hydrates, the temperature is
increased stepwise to dissociate the hydrate until the cooling and
heating curve converged. This point refers to as hydrate equilibrium
point.
Equation (1) given below is used to calculate the gas consumption
during hydrate formation (Bhawangirkar et al., 2021):
Here, Δn↓,H denotes the amount of gas that was used during the for­
mation of hydrate at time t, the gas volume inside the cell is indicated by
Vg, Pi and Pt stand for the initial cell pressure and the pressure at any
given time, Zi denotes the starting compressibility factor and Zt repre­
sents the compressibility factor at any time t, T is the temperature and R
is the universal gas constant. For simplicity, the volume change of gas
phase is ignored while calculating gas consumption value (Mekala et al.,
2014). The capacity of the sample to prevent the hydrate formation is
known as the induction time. The retention period of hydrate-free mud
circulation can be estimated by mud engineers; hence the induction time
is crucial when drilling through hydrate-bearing formation. It is also
helpful to know how long one sample may tolerate in shut in condition
without forming hydrates. The induction time is the amount of time
between the start of the experiment and the first nucleation point. It can
be described as follows
ti = th – ts (2)
Where ts represents the initial time of the experiment, while ti is the
induction time, the initial hydrate nucleation started at this time (th).
The hydrate formation rate and rate constant can be evaluated using the
equations mentioned in the previous literature (Maiti et al., 2022).

3
M. Maiti et al.
6. Results and discussion
6.1. Stability of the drilling fluid
The Turbiscan stability index (TSI) analysis was done to evaluate and
characterise the physical stability of additives which can track insta­
bility of kinetics in drilling fluids. The TSI analysis used in this investi­
gation for different drilling fluid with varying concentrations of PVP K-
90 were acquired using a stability monitor, and the outcomes of the
experiment are depicted in Fig. 4. Drilling fluid without PVP K-90 (DF)
shows higher stability index and stability starts to decrease as PVP K-90
is added to the DF. The higher stability of the DF sample is a result of the
large surface area and thus negative surface charge of bentonite particles
following the separation of small particles and Na+ saturation. Bentonite
have high electrostatic repulsion (Al Juhaiman et al., 2010). The water
loss value of the DF decreases in presence of 0.1 wt% PVP K-90, then
increases with higher PVP K-90 concentration. This happens as PVP K-90
and water molecules come into conflict on the clay surface, changing the
structure of the suspension close to the clay surfaces. As a result,
bridging between each polymeric molecule individually on the surfaces
of multiple particles is thought to be involved. As a result of this linking,
the particles form loose aggregates that are sedimented quickly,
lowering the stability (Al Juhaiman et al., 2010). The stability increases
again at larger concentrations (more than 0.1 wt%), which reduces the
flocculation efficiency and possibly stabilize the suspension perma­
nently. This outcome is caused by the induced charges that are produced
when steric stabilization occurs in the presence of a high polymer
concentration.
7. Effect of PVP K-90-based drilling fluid on rheological
properties
Rheological properties play one of the most significant roles in the
drilling process. The ability of the drilling fluid to carry cuttings is
determined by its rheological qualities (Adesina et al., 2017). The vis­
cosity should not be too high or too low since excessive viscosity of the
drilling mud may cause a number of issues including high flow resis­
tance, which will slow down the drilling process (Medhi et al., 2020).
Drilling fluids are not able to transport the cuttings if their viscosity is
very low and is more likely to cause wellbore collapse and other safety
hazards during drilling. Shear stress and viscosity measurements were
used at a wide range of shear rate (0.001–1020 1/s) and temperature
(273.15K–310.15 K) with a fixed pressure of 2000 psia to examine the
Fig. 4. The variation of stability of DF at different PVP K-90 concentration.
4
Gas Science and Engineering 115 (2023) 205015
rheological behaviour. As shown in Fig. 5, fluid samples with behaved as
non-Newtonian fluids with a high shear thinning behaviour as their
viscosity decreased with the increased shear rate. The level of shear
thinning can be assessed using the flow index behaviour (n). The flow
curve is fitted with different non-Newtonian model to see which model is
fitted the best. It is clear to see that, the flow curve is fitted best to the
Herschel-Bulkley model with a correlation coefficient (R2) ranging be­
tween 0.986 and 0.997 than the power-law model whose R2 value
ranges from 0.974 to 0.995 (as shown in Table 2). The compared values
of these two model’s parameters are given in Table 2. The importance of
yield stress in the Herschel-Bulkley model is crucial as it indicates the
flow behaviour of the drilling fluid at low shear rate. Yield stress is
dependent on the polymer and its concentration used in the system. The
values of yield stress are observed to increase with addition of PVP K-90
polymer to the drilling fluid. As temperature reduces, yield stress in­
creases. Higher consistency index indicates higher viscosity. Higher
consistency index might lead to an issue in opening the pump whereas
lower consistency index will not be able to carry rocky debris, which
might create a blockage within the borehole (Ofei, 2016). The activation
of PVP K-90 caused the consistency index (K) to rise with reducing
temperature while keeping almost the same shear-thinning character­
istics. The high shear thinning behaviour of drilling fluid is advanta­
geous because it reduces the susceptibility of frictional pressure loss to
changes in flow rate. The variation of plastic viscosity (PV), yield point
(YP), and apparent viscosity (AV) as a function of temperature are
shown in Fig. 6. Viscosity of the sample increases with further addition
of the PVP K-90 into the sample. Plastic viscosity (PV) of the drilling
fluid rises as the temperature reduces from 293.15 K to 273.15 K. Plastic
viscosity is particularly sensitive to temperatures below 298.15 K (Zhao
et al., 2017). The ratio of rheological parameters at 273.15 and 293.15 K
was chosen to illustrate how drilling fluid rheology is affected by lower
temperature. The addition of led to a rapid rise in PV, YP, and AV. It has
been found that the effect of temperature on Yield points is only mar­
ginal (Chilingarian et al., 1986). When temperature is low during
offshore drilling, the addition of PVP K-90 in the drilling fluid can clearly
increase the viscosity. They are high molecular-weight polymers, which
causes exceptional molecular entanglement to take place at low tem­
peratures and produce high viscosity. The drilling fluid is more sensitive
to temperature changes as PVP K-90 is added to the DF sample (as seen
in Fig. 7). Thus, when the temperature decreases from 293.15 K to
273.15 K, the relative viscosity of the samples increases for DF samples
with PVP K-90 compared to DF samples without PVP K-90. Table 3
shows the rheological parameter ratios of different DFs with
M. Maiti et al.
Fig. 5. Shear rate versus shear stress curve of different drilling fluids at varying temperature and constant pressure (13.78 MPa).
temperature (in DF: PV273.15: PV293.15 = 2.2, in DF + 0.7 wt% PVP K-90:
PV273.15: PV293.15 = 1.32). Both drilling fluids have a definite tacking
effect when the temperature is low but drilling fluid with PVP K-90 has a
stronger tackifying effect than drilling fluid without PVP K-90. Zhao
et al. (2017) discussed in their study developed a CMC (carboxymethyl
cellulose) based drilling fluid and conducted the influence of different
concentration of this polymer on rheological properties of drilling fluid.
Drilling fluid with 0.75 wt% CMC concentration shows similar range
(23.4 mPa s) of AV as this study. Rheological performance of PNBAM
polymer has been investigated by Wang et al. (2020). The amide group
of PNBAM adsorbs to the clay at low temperatures, leading to an in­
crease in low temperature viscosity. Base fluid with PNBAM also show
similar range of PV and AV (Wang et al., 2020) According to the rheo­
logical properties, drilling fluids have an unavoidably negative tacki­
fying effect at low temperature. Thus, drilling fluid with PVP K-90 shows
better performance as the temperature decreases.
8. Microscopic structure of drilling fluid
The outcomes of the microscopic study of morphological observation
are displayed in Fig. 8. The microscopic examination demonstrates that
the connected hydrophobic polymer is still in the form of tiny beads in
aqueous solution, primarily forming intramolecular interactions at low
concentrations. The molecular chains are not entirely stretched, as seen
in Fig. 8(b). As the polymer concentration rises, the intramolecular and
intermolecular interaction become more perceptible, and intermolec­
ular interaction develop throughout time as seen in Fig. 8(c). As the
concentration is raised, the intramolecular and intermolecular connec­
tions in the polymer solution interchange. The self-assembly among the
5
Gas Science and Engineering 115 (2023) 205015
hydrophobic side chains of the macromolecules is visible in Fig. 8(d),
resulting in a dense network structure. However, the network structures
are visible under CAC (critical association concentration) circumstances.
The hydrophobic group engages, causing the molecules to engage an
intramolecular to intermolecular interaction. This alters the rheological
behaviour as well as the network structure of the drilling fluid as the
polymer concentration exceeds the critical association concentration
(Chilingarian et al., 1986).
9. The behaviour of gas hydrate formation in presence of
inhibitor
The behaviour of hydrate formation and dissociation is illustrated in
Fig. 9. In the case of pure water (Fig. 9(a)), as the temperature reached
284.2 K, a sudden reduction in pressure was noticed indicating the
nucleation of hydrate crystals. The pressure inside the reactor continues
to decrease with slow reduction of temperature which implies different
stages of hydrate formation. When the temperature reaches 269 K
temperature, no significant pressure drop was observed which indicates
no further formation of gas hydrate took place. As the dissociation cycle
started with increasing the temperature, pressure starts to increase.
Dissociation of hydrate continues until temperature reaches 289 K
where the dissociation curve meets the formation curve. That intersec­
tion point is considered the maximum temperature at which all the three
phases remain in equilibrium. Because the related gas and liquid phases
are disordered on a molecular level, whereas the hydrate crystals are
arranged orderly, there is a basic difference in hydrate initiation and
dissociation. Entropy always prefers chaos over order. Thus, the initial
hydrate formation is delayed by a metastable period which is called
M. Maiti et al. Gas Science and Engineering 115 (2023) 205015

273.15

273.15
28.24
0.977

36.13
0.974
8.95
0.39

0.36
278.15

278.15
30.27

29.84
0.990
3.19
0.29

0.99

0.29
281.15

281.15
19.89
0.994

19.31
0.994
1.65
0.29

0.29
283.15

283.15
12.66
0.995

12.15
0.995
1.06
0.29

0.29
293.15

293.15
0.995

0.995
0.57
0.31
6.58

0.31
6.57

Fig. 6. Influence of PVP K-90 concentration on drilling fluid viscosity at

DF + 0.7 wt% PVP K-90

305.15 K

various low temperature and constant 13.78 MPa pressure.

305.15

0.975

0.986
0.27
0.28
1.45

0.31
1.11
310.15 K
310.15

0.820

0.961
0.52
0.21
1.12

0.31
0.54
273.15

273.15
19.83
0.997

20.12
0.996
0.32
0.39

0.39
278.15

278.15
0.996

0.995
0.62
0.27
9.85

0.27
9.62
281.15

281.15
0.992

0.989
0.68
0.34
2.32

0.31
2.94
283.15

283.15
0.988

0.974
0.57

0.75

0.46
1.04
0.5
293.15

293.15
0.987

0.986
0.20
0.49
0.48

0.45
0.58

Fig. 7. Effect of PVP K-90 on the viscosity of drilling fluid at different tem­
peratures and constant shear rate of 150 s− 1.
305.15 K

305.15 K
0.993

0.994
0.07
0.39
0.38

0.41
0.36

Table 3
Parameter ratios of drilling fluid with and without DF.
310.15 K
310.15
Flow index and consistency index of different drilling fluid.

0.986

Parameter Ratios DF DF + 0.7 wt% PVP K-90

0.06
0.37
0.25
0.98

0.38
0.24
DF

PV273.15:PV293.15 2.2 1.32

AV273.15:AV293.15 1.6 1.25
YP273.15:YP293.15 1.35 1.26
Herschel-Bulkly model

Power Law model

induction time. During this time, gas and liquid phases that were in
disorder phase rearranged into the orderly hydrate crystal structure. On
the other hand, dissociation starts rapidly when the hydrate is removed
Model

from their stability region (Gao et al., 2019; Nakamura et al., 2003).
There is no hydrate left after that point. The first nucleation of hydrate in
the case of drilling fluid without PVP K-90 started at a temperature of
Consistency Index (K)

Consistency Index (K)

283.84 K which was lower than the first nucleation point for pure water.
There was a second sudden pressure drop at 266.19 K after almost
Temperature (K)

Temperature (K)
Yield stress (τ0)
Flow Index (n)

Flow Index (n)

constant pressure. No substantial pressure drop was noticed within the

range of temperature from 280 K to 266.19 K, indicating a very slow rate
of hydrate growth. It signifies that there were some water molecules still
Sample
Table 2

available to form gas hydrate for the second time. The first nucleation
R2

R2

6
M. Maiti et al.
Fig. 8. Visualization of different additives used in the drilling fluids (a) DF, (b) DF + 0.1 wt% PVP K-90, (c) DF + 0.3 wt% PVP K-90 (d) DF + 0.7 wt% PVP K-90.
point for DF with the addition of 0.1 wt% PVP K-90 is observed at
281.85 K. Nucleation temperature in case of PVP K-90-based drilling
fluid was lower than both the pure water and drilling fluid without PVP
K-90. It was seen that during the hydrate dissociation hydrate decom­
position begins at a lower temperature as the concentration of PVP K-90
increases. Formation and dissociation behaviour of the drilling fluid
with 0.3 wt% PVP K-90 shows a different cycle from the previous one. It
is noted that the pressure suddenly drops when the nucleation starts
around 280.52 K with an abrupt rise in temperature. As seen in the
figure (Fig. 9(d)) where the formation curve hits the dissociation curve
and attempts to reach the equilibrium state when a significant quantity
of hydrate is created. This outcome indicates that as a significant volume
of hydrate generates, the system attempts to reach the phase equilib­
rium. After that, the experiment was repeated with a higher concen­
tration of PVP K-90 in the drilling fluid. Fig. 9(e) depicts the hydrate
forming cell’s isochoric operation. The hydrate instability region (point
A) is where the preliminary system temperature and pressure are
established. When the cell temperature is initially dropped, cell pressure
also drops to point B. The pressure now instantly drops much more as
hydrate crystals start to form (point C). After that, the temperature is
gradually raised, which causes the hydrate crystals to dissociate and
raise the pressure. All of the gas is released from the crystals once the
hydrates have entirely dissociated, and the temperature and pressure are
then recorded as the dissociation conditions (point D) (Gayet et al.,
2005; Smith, 2015). This method is independent of visual observation
and since the setup is a closed system, it is safer to operate at higher
pressures (Sloan and Koh, 2008). Nucleation temperature shows to be
278.48 K which is much lower than the previously used drilling fluid
with a lower percentage of PVP K-90. Drilling fluid without PVP K-90
has the highest pressure drop due to encapsulation of gas while drilling
mud with the highest concentration of PVP K-90 has theowest pressure
drop. When PVP K-90 is added to the drilling fluid, the amount of
mixture gas that is captured by hydrates is reduced. At the end of the
test, the hydrate blockage was noticed (Fig. 10). As depicted in Fig. 10,
DF with 0.7 wt% PVP K-90 shows better results in inhibiting the hydrate
formation as the hydrate plug form in this case is very less in compare to
other samples.
7
Gas Science and Engineering 115 (2023) 205015
10. Influence of PVP K-90 on the induction time of drilling fluid
In this study, from the starting period of the agitation (500 rpm) to
the point of a sudden temperature rise and a drastic drop in the pressure
gradient is regarded as the induction time of the hydrate formation (He
et al., 2021). Fig. 11 depicts an outcome of the experiment of hydrate
formation temperature and pressure fluctuations in drilling fluid. As
hydrate formation is an exothermic process, it resulted in a considerable
increase in temperatures as shown in Fig. 11. The first abrupt pressure
drop happened 0.78 h after the experiment indicating first nucleation of
hydrate. The temperature continues to rise for about 3–4 min and then
gradually reduces due to the ongoing cooling of the water bath. How­
ever, the pressure continues to drop which suggests the continuous
formation of the hydrate. The pressure and temperature inside the cell
were steady after 2 h, indicating that hydrate formation had ceased and
that neither water nor free gas was available for further hydrate for­
mation (He et al., 2021). Similar experimental studies have been con­
ducted with other drilling fluid samples and it was found that the PVP
K-90 has the capability to extend the induction time of the hydrate
formation as shown in Fig. 12. As the concentration of the PVP K-90
increases, the induction time continues to increase. The chemical
structure of PVP K-90 polymer is a single 5-membered lactam ring
attached to a carbon backbone and it is responsible for the inhibition
effect of the drilling fluid samples. One hydrogen bond is created be­
tween the carbonyl oxygen atom of PVP K-90 molecules and water
molecules of the cage. According to Fig. 13, the open hydrate cages can
partially capture PVP K-90 because of their greater cage width, and
expansion of the lactam ring can enhance the capacity of the inhibitor to
bind. KHIs situated in the gas–liquid phase interface is discussed further
to better understand the inhibition mechanism of the PVP K-90 (Cha
et al., 2013a,b). PVP K-90 molecules contain both hydrophilic and hy­
drophobic groups and they typically alter their traits to fit the nearby
chemical environment. From Fig. 13, it is to be seen that the polymer
molecules are consistent at the boundary between gas and liquid phase
with the hydrophilic groups in close proximity to the water molecules
and the hydrophobic groups to the mixture gas (guest molecules). Both
of the pyrrolidone rings are totally submerged in the fluid phase, and the
double-bond oxygen atoms on the pyrrolidone rings of PVP K-90
molecule forms H-bonds with water molecules. The increasing
M. Maiti et al. Gas Science and Engineering 115 (2023) 205015

Fig. 9. Typical P-T curve for mixture hydrate formation in presence of different drilling fluid.

interaction area between the PVP K-90 molecules and guest molecules is
advantageous to boosting the inhibition ability of the inhibitors. The
presence of NaCl in the drilling fluid is slightly responsible for increase
in induction time of the drilling fluid as its ions dissolved in water causes
electrostatic interaction with dipoles of water molecules to form a
cluster (Kakati et al., 2016). Only a few water molecules are able to form
hydrate clusters as ionization occur and delays the hydrate nucleation.
The mechanism by which PVP K-90 can delay the hydrate growth is
either forming a hydrogen connection with the hydrate crystal or by
disrupting the local water structure which raises the barrier to nucle­
ation (Anderson et al., 2005). The significant interaction of the PVP K-90
functional group with the accessible cages on the hydrate surface, which

8
M. Maiti et al.
Fig. 10. Hydrate plug was observed after the completion of the experiment.
Fig. 11. An example of a temperature-pressure vs time graph showing how to
calculate a typical induction time drilling fluid.
destabilizes potential growth sites, prevents the absorption of the gas
molecule into the water framework. The PVP K-90 latches or binds to the
hydrate network as hydrates continue to expand in all directions and
start to inhibit hydrate growth (Posteraro, 2016).
11. Hydrate dissociation behaviour of different drilling fluid
systems
The equilibrium pressure and temperature of hydrate dissociation
were measured in the presence of drilling fluid with and without in­
hibitors and the results are shown in Fig. 14. The plot suggests that there
is a definite shift in the thermodynamic equilibrium curve towards the
higher pressure and lower temperature region which is the inhibition
region. As can be seen from Fig. 14, the temperature range of the
mentioned equilibrium curve is between 281.15 and 290.15 K. The
figure displays a collection of phase equilibrium temperature and pres­
sure values obtained during mixed hydrate formation and decomposi­
tion tests of different samples in a high-pressure reactor. The hydrate
equilibrium curve for drilling fluid without PVP K-90 and with PVP K-90
9
Gas Science and Engineering 115 (2023) 205015
Fig. 12. Induction time of different drilling fluid samples with different PVP K-
90 concentration.
(0.1 wt%) almost overlapped and their shift from the pure water curve
was significant. It can be interpreted that; the drilling fluid sample
shows lower-temperature and higher-pressure equilibrium curve in
compare to pure water. The curve exhibits to shift toward higher inhi­
bition regions as the concentration of the PVP K-90 increases. Drilling
fluid with 0.7 wt% PVP K-90 shows higher thermodynamic inhibition
performance compared to all the other drilling fluids. The result reflects
that the drilling fluid samples have an inhibition effect. Strong hydrogen
interaction between the inhibitor and water molecules is thought to
induce thermodynamic hydrate inhibition (Koh et al., 2011). Cha et al.
(2013) discussed in their study on how the equilibrium curve shifts to
the left of the original curve when MEG is added to the aqueous phase,
indicating a lower formation temperature at corresponding pressure.
Khan et al. 2019. recently discovered Tetraethylammonium chloride
(TMACl), an A-ionic liquid to reduce the temperature of CH4 hydrate by
0.9 K when used at a concentration of 10 wt%. Research on quaternary
M. Maiti et al.
Fig. 13. Schematic interaction of PVP K-90 molecules (ring structure in the
middle) with guest molecules (yellow colour) and water molecules (red colour).
ammonium salts (QASs) as thermodynamic hydrate inhibitors for CH4
hydrates was undertaken in the prior study (Qasim et al., 2019), and it
was found that the inhibitory effect of QAS rises with increasing con­
centration. All the equilibrium curve mentioned below shows thermo­
dynamic hydrate inhibition effect on hydrate formation as they are able
to shift the equilibrium curve to higher pressure and lower temperature.
But in this work, the equilibrium curve shifted to much higher pressure
and lower temperature zone in compare to other reported data
mentioned below in the graph.
12. Influence of PVP K-90 on gas consumption
Hydrate plug formed inside the drilling fluid is strongly dependent
on gas consumption but not reliant on the induction time. Therefore, the
total gas consumption for all the drilling fluid was estimated separately
to understand the potential of hydrate plug inside the drilling mud. The
hydrate formation experiments were performed for different drilling
fluids with different concentrations of PVP K-90 at 6–10 MPa pressure
and 275.15–277.15 K temperature. In this study, the total amount of gas
consumed during the hydrate formation was calculated, and the results
are shown in Fig. 15. Each component of the figure depicts the con­
sumption of gas over time at various temperatures and pressures. The
figure shows a higher slope in case of pure water and it gets gentle in the
Fig. 14. Hydrate phase equilibrium of (a) drilling fluid with and without PVP K-90 and (b) Comparative study of three phase V-Lw-H equilibrium conditions reported
in this work and compared with other reported data based on the thermodynamic hydrate inhibitors.
10
Gas Science and Engineering 115 (2023) 205015
case of drilling fluid alone and drilling fluid with varying concentrations
of PVP K-90. The addition of PVP K-90 into drilling fluid results in a
gentle slope, which indicates that PVP K-90 can slow down the growth
rate of hydrate nucleation. From Fig. 15 it is evident that the consumed
gas in all the drilling fluid samples show a decreasing trend as the
concentration of PVP K-90 increases. All the PVP K-90 based drilling
fluid systems inhibit the gas uptake compared with the pure water and
base mud. This is possible because of the complex molecular structure of
the PVP K-90 polymer which can arrange the drilling fluid system in a
well-structured manner to resist high gas dissolution in the bulk drilling
fluid system. Molecular weight of PVP K90 is 111.14 g/mol. The force
field parameter is a function of torsion angle between hydrogen-oxygen
of the nearest water (hydrogen bonded) (Choudhary et al., 2016). Ni­
trogen and oxygen atoms available in PVP K-90 polymer are more
interactive with free water compared to hydrated water as water mol­
ecules present in the solid hydrates are saturated with hydrogen bonds
and have less mobility in compare to liquid water. These results suggest
that, in comparison to any monomers, long polymeric chains have a
stronger affinity for the hydrate surface. Pendent group of PVP K-90 is
encaged inside half cage of hydrate surface. Choudhary et al. (2016)
suggested in their study that there are more interaction sites with a
higher molecular weight of PVP K-90 than lower molecular weight as it
has a stronger affinity for the surface of the methane hydrate.
13. Gas hydrate formation rate in presence of PVP K-90
It has been found that the hydrate formation region is split into three
temporal zones for all samples, as illustrated in Fig. 16 after nucleation.
This could be because of varying rates of hydrate formation because of
hindrance of gas diffusion (Saw et al., 2014). As observed, a first-order
reaction is consistent with the exponential behaviour of the slope of the
curve. A first order reaction is defined by the following equations (3) and
(4) (Lekvam and Ruoff, 1993).
N = No e − kt
(3)
Utilizing the logarithm on each sides,
( )
N
ln = − kt (4)
No
where, N represents the total number of free moles at time t and No is the
initial number of moles, t represent the time in minutes and k denotes
rate constant in min− 1. Here, slope is used to compute the rate constant,
which may also be calculated using equation (4). This curve consists of
M. Maiti et al.
Fig. 15. Gas consumption of different drilling fluids with and without the
presence of PVP K-90.
three sections. The first phase is known as nucleation, the second as the
hydrate formation region, and the third as the hydrate growing zone.
The number of gas molecules that are converted to hydrate at a certain
pace is typically used to express the formation rate (Hussain et al.,
2006). The rate at which hydrates form is represented by the following
equation:
dN
= − No ke− kt
(5)
dt
The rate constant is calculated from these three time zones sepa­
rately. Each of the three time zones has a different hydrate forming
process. At first, the formation rate is rapid (0–50 min after nucleation)
(Fig. 16), then it slows down exponentially over time. The rate constant
(k) of hydrate formation is determined by the slope of the ln (N/No) vs.
time curve as shown in Fig. 17. The rate of hydrate formation is seen to
be decreased as PVP K-90 is added to the drilling fluid compared to pure
water and DF sample without PVP K-90 (Fig. 18). To visualize hydrate
formation inhibition at higher PVP K-90 concentration, a bar diagram
plot was used with different time zones. The wide range of concentra­
tions tested allow unprecedented visualization of the shifting of for­
mation rate in compare to pure water system. At 0.1 wt% concentration,
it is possible that no sufficient inhibitor is there to drastically alter the
formation rate. Even though all the available PVP K-90 molecules might
adhere to the surface of the hydrate crystal to slow down the formation
rate, but not enough to influence the formation rate as the number of
growth sites present are more than the available PVP K-90 molecules to
inhibit them. However, as the concentration increases, the presence of
PVP K-90 molecules is much more than before to inhibit the formation
rate of hydrates. The change in shift happens when PVP K-90 concen­
tration increases to 0.7 wt% where there are sufficient inhibitor mole­
cules available to block the hydrate crystal growth which significantly
reduces the formation rate. It reaches a saturation point when all growth
sites are affected and very little formation is occurred. Posteraro (2016)
also reported similar trends in their results. The hydrate formation rate
decreases with progressive time. Fig. 16 indicates that experiments with
pure water have the highest formation rate in compare to other samples.
It implies the strong inhibition effect of PVP K-90 on hydrate formation
inside the drilling fluid. Long polymeric chain of PVP K-90 is responsible
for such inhibition effect on drilling mud. Once the inhibitor molecules
(PVP K-90) bind to one side of the hydrate nanocrystal, the growth along
that side is slowed down significantly. Thus, the formation rate of hy­
drate seems to reduce as concentration of PVP K-90 increases.
11
Gas Science and Engineering 115 (2023) 205015
14. Conversion of water and gas to hydrate
Water to hydrate and gas to hydrate conversion for all the different
drilling fluid samples are shown in Fig. 19. The conversion of water to
hydrate is carried out to determine the amount of water that has been
converted into hydrate at the conclusion of the tests. Equation (6) is used
to perform this computation (Bhawangirkar et al., 2021).
100
Water to hydrate conversion = Δn↓,H × hydration number × (6)
nwater
where, Δn↓H is the amount of gas consumed during hydrate formation
(measured in moles), and the hydration number used in this study is
5.67 (Shu et al., 2011), nwater indicates how many moles of water were
present in the cell at the beginning of the experiment. It can be observed
from the figure that, water to hydrate conversion in case of pure water is
highest and lowest for drilling fluid with 0.7 wt% PVP K-90. Conversion
value of water to hydrate in case of drilling fluid with 0.7 wt% PVP K-90
is 16.58% which indicates 77.43% decrease compared to the pure water
(73.47%). The reason for this decrease compared to pure water is the
reduction in the reaction kinetic velocity and the amount of gas
consumed by the PVP K-90 based drilling fluid. The reduction in reac­
tion kinetic velocity and the quantity of gas consumed by the PVP
K-90-based drilling fluid are what causes this drop when compared to
pure water system. Higher gas consumption for pure water is responsible
for higher water to hydrate conversion which might be explained by the
numerous nucleation phenomenon and the sharp growth zones of the
hydrates that are noticed during hydrate formation (Fig. a). No
numerous nucleation sites were found during the hydrate formation in
case of PVP K-90 based drilling fluid. This is due to the presence of PVP
K-90 in the solution which inhibits multiple hydrate nucleation sites.
Thus, the water to hydrate conversion is relatively low when drilling
fluid containing PVP K-90 polymer is compared to pure water. Similarly,
the gas to hydrate conversion percentage is observed to be lower for
drilling fluid with 0.7 wt% PVP K-90 in compare to pure water.
15. Conclusions
In this work, the effect of PVP K-90 on rheological characteristics of
drilling fluid were investigated. The enhanced rheological properties of
base fluid (DF) by PVP K-90 are due to their influence on the colloidal
activities of the base mud. It was found that the addition of PVP K-90 has
a very significant effect on the rheological properties of drilling fluid
with a high dependency on the temperature. Thus, when the tempera­
ture decreases from 293.15 K to 273.15 K, the relative viscosity of the
samples increases for DF samples with PVP K-90 compared to DF sam­
ples without PVP K-90. Gas hydrate formation and dissociation experi­
ments were started at pressure and temperature of 13 MPa and 290 K
respectively. In case of drilling fluid with 0.7 wt% PVP K-90 polymer,
gas consumption during the hydrate formation seems to be lower in
compare to pure water. By increasing the PVP K-90 concentration from
0.1 wt% to 0.7 wt%, the hydrate formation rate further decreases
significantly. At 0.1 wt% concentration, no sufficient inhibitor is there in
the system to significantly affect the formation rate. As the concentra­
tion increases, the presence of PVP K-90 molecules starts to inhibit the
formation rate of hydrates. The change in shift happens when PVP K-90
concentration increases to 0.7 wt% where there are sufficient inhibitor
molecules available to block the hydrate crystal growth which signifi­
cantly reduces the formation rate. The results demonstrate that the
drilling mud with 0.7 wt% PVP K-90 used in this study is able to prevent
the hydrate nucleation kinetically as evidenced by the long induction
time and a slowing rate of hydrate formation. Thermodynamic equi­
librium curve is transitioned to high pressure and low temperature re­
gion in presence of PVP K-90 in the drilling fluid in compare to pure
water and drilling fluid without PVP K-90. These findings support that,
PVP K-90 inhibits the hydrate formation both kinetically and
M. Maiti et al. Gas Science and Engineering 115 (2023) 205015

Fig. 16. Change of moles of methane during hydrate formation in presence of PVP K-90.

thermodynamically.

Credit author statement

Moumita Maiti: Data curation; Formal analysis; Writing - original

draft, Ajoy Kumar Bhaumik: Investigation; Analysis of data; review &
editing, Ajay Mandal: Resources; Project administration; Conceptuali­
zation; Supervision; Validation; review & editing.

Declaration of competing interest

Fig. 17. Semi-logarithmic figure showing the change in gas moles during hy­
drate formation at various PVP K-90 concentrations. The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence

12
M. Maiti et al.
Fig. 18. Hydrate formation rate and rate constant of drilling fluid in presence of different concentration of PVP K-90.
Fig. 19. The percentage conversion of water and gas to hydrate in the presence
of pure water and different drilling fluids.
the work reported in this paper.
Data availability
Data will be made available on request.
Acknowledgment
We gratefully acknowledge the financial assistance provided by
Earth System Science Organization, Ministry of Earth Sciences, Gov­
ernment of India, New Delhi (MoES/36/OOIS/Extra/65/2016) to the
Department of Petroleum Engineering, Indian Institute of Technology
(ISM), Dhanbad, India.
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