Accepted Manuscript

Title: Inhibition Effect of Ionic Liquids and their Mixtures

with Poly(N-vinylcaprolactam) on Methane Hydrate
Formation

Author: Wonhee Lee Ju-Young Shin Jong-Ho Cha Ki-Sub

Kim Seong-Pil Kang

PII: S1226-086X(16)30095-8
DOI: http://dx.doi.org/doi:10.1016/j.jiec.2016.05.007
Reference: JIEC 2927

To appear in:

Received date: 31-3-2016

Revised date: 4-5-2016
Accepted date: 7-5-2016

Please cite this article as: W. Lee, J.-Y. Shin, J.-H. Cha, K.-S. Kim, S.-P. Kang,
Inhibition Effect of Ionic Liquids and their Mixtures with Poly(N-vinylcaprolactam) on
Methane Hydrate Formation, Journal of Industrial and Engineering Chemistry (2016),
http://dx.doi.org/10.1016/j.jiec.2016.05.007

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Highlights
zIonic liquids prepared in this study acted as both thermodynamic and kinetic hydrate
inhibitors.
zExcessive dosage of ionic liquids (10 wt%) inhibited CH4 hydrate formation
thermodynamically.
zIonic liquids of pyrrolidinium and imidazolium cations with BF4- show the remarkable
kinetic inhibition effect.
zIonic liquids having alkyl chain with Br- show the weak kinetic inhibition
performance.

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zSeveral mixtures of ionic liquid and PVCap exhibited enhanced kinetic inhibition

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effectiveness.

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Page 1 of 28
 Inhibition Effect of Ionic Liquids and their

Mixtures with Poly(N-vinylcaprolactam) on

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Methane Hydrate Formation

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Wonhee Lee,a Ju-Young Shin,a Jong-Ho Cha,b Ki-Sub Kim,b,* Seong-Pil Kanga,*

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a
Climate Change Research Division, Korea Institute of Energy Research (KIER), 152

b
an
Gajeong-ro, Yuseong-gu, Daejeon 34129, Republic of Korea

Department of Chemical and Biological Engineering, Korea National University of

M
Transportation, 50 Daehak-ro, Chungju-si, Chungbuk 27469, Republic of Korea
d

*spkang@kier.re.kr, kks1114@ut.ac.kr
e

KEYWORDS: Gas hydrate, Ionic liquid, Polymeric inhibitor, Kinetic hydrate inhibitor,
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Synergetic effect
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Page 2 of 28
ABSTRACT

Various ionic liquids (ILs) were tested as CH4 hydrate inhibitors with/without polymeric

hydrate inhibitor, PVCap. Equilibrium dissociation conditions for CH4 hydrate were

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measured by the isochoric method in the presence of 10 wt% of ILs and they moved towards

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inhibition region as much as 1.4~1.8 K. Induction times of CH4 hydrate formation were also

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measured in the presence of the individual ILs at various concentrations, and of the mixtures

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of PVCap and ILs. Some ILs showed better CH4 hydrate inhibition behavior than did PVCap.

The mixtures of PVCap and several ILs exhibited enhanced kinetic inhibition effects for CH4

hydrate formation. an
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1. Introduction

Gas hydrates are crystalline solids consisting of various light gaseous guests within a

hydrogen-bonded, water-cage framework [1]. Because the guest molecules are trapped in the

water host cages, these are also called clathrates or inclusion compounds [1]. The

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representative crystal structures of the gas hydrates are categorized into structure I (sI),

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structure II (sII), and structure H (sH) according to their guest identity and size, as well as the

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cage types and combinations of unit cells [1]. The cubic unit cell of the sI hydrate is

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composed of 46 water molecules that create six 51262 and two 512 cages [1]. The sII hydrate

forms a cubic structure of 136 water molecules that create eight 51262 and sixteen 512 cages
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[1]. Unlike the sI and sII hydrates, the sH hydrate forms hexagonal unit cells composed of 34

water molecules that form three types (one 51268, two 435663, and three 512)of cages [1].
M
Among the three hydrate structures, only sI and sII hydrates have been found in oil/gas
d

flowlines, and thus, they lead to flow assurance issues [2]. The sII hydrate is more frequently
e

formed due to the presence of larger guest molecules, such as propane (C3H8) or isobutane (i-
pt

C4H10) that cannot occupy the sI cages [2]. Some fields possess sufficient amounts of CH4

that sI hydrate can be formed [3]. In this case, blockage by the sI hydrate could prevent the
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flow of gas. In particular, the sI hydrate flow assurance issue would also occur in CH4
Ac

hydrate reservoirs located deep in the oceans during the CH4 production in the future. The

offshore production of the CH4 hydrate has been investigated using various methods, such as

depressurization,[4-6] thermal stimulation,[5, 7] and CH4-CO2 replacement [8]. Whatever

methods might be applied, CH4 hydrate would be formed by a reaction with water produced

under specific conditions, particularly, low temperature and high pressure.

During gas/oil production and transport, methanol (MeOH) and monoethylene glycol

(MEG), which are called thermodynamic hydrate inhibitors (THIs), have conventionally been

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Page 4 of 28
used to prevent hydrate problems [2]. These chemicals possess hydrogen bond sites that

interact with water molecules, thereby shifting the phase equilibrium conditions for hydrate

formation to higher pressures and lower temperatures [2]. However, the thermodynamic

hydrate inhibition strategy has to utilize a substantial amount of THIs, leading to immoderate

operating cost [2]. Hence, another type of hydrate inhibitors called low dosage hydrate

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inhibitors (LDHIs) were developed and have been applied in the field to reduce the

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production cost [3]. LDHIs are classified into two types of chemicals: kinetic hydrate

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inhibitors (KHIs) and anti-agglomerants (AAs) [3]. In general, the KHIs are polymeric

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materials that kinetically retard the nucleation and growth of hydrate crystals, whereas the

AAs are surfactants that bind to hydrate particles and preventing the hydrate agglomeration
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[3]. The calculation based on the standard nucleation theory indicated that the hydrate

nucleation is difficult to stop indefinitely when the subcooling is above 10 K [3, 9]. In
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practice, the KHIs was found quite advantageous at subcooling below 10 K during field tests

[9]. Various test programs for kinetic hydrate inhibition performance were carried out within
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an industry project [10]. Recently, combination of KHI and THI has been investigated for
e

more effective hydrate flow assurance [11]. Additionally, removal of KHI from produced
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water has been also researched to prevent KHI precipitation prior to MEG regeneration [11].
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Among the various KHIs, poly(N-vinylcaprolactam) (PVCap) is used as a standard

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chemical to compare KHI performance [3]. This polymeric KHI is known to exhibit better

inhibition performance for sII natural gas hydrate than for sI CH4 hydrate [3], which implies

that the kinetic hydrate inhibition effectiveness of PVCap is crystal structure-dependent. In

practice, some fields contain very high portion of CH4 leading to the formation of sI hydrate

rather than sII [3]. Because most studies and development of KHIs are focused on sII hydrate

formation, general polymeric hydrate inhibitors exhibited weak KHI performance for sI

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Page 5 of 28
hydrate [3, 12-15]. Therefore, it is necessary to develop effective KHIs for sI hydrate

formation.

Ionic liquids (ILs) have recently received interest as novel types of hydrate inhibitors that

exhibit dual inhibition effects, that is, both thermodynamic and kinetic inhibition

performance [16, 17]. The previous studies experimentally revealed that some ILs exhibited

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higher hydrate anti-nucleation performance for sI CH4 hydrate than did PVCap [18, 19].

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Furthermore, their combinations showed much enhanced kinetic inhibition effect on CH4

hydrate formation [19]. In this study, CH4 hydrate phase equilibria with 10 wt% of the

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various ILs were measured. The kinetic inhibition experiments for CH4 hydrate were

extended using the ILs at various concentrations; then using mixtures containing the ILs and
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PVCap. The induction times for the CH4 hydrate formation were evaluated in the presence of
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a variety of additives and the effects of them on the hydrate growth were also tested. The

experimental results were compared with those in the previous study [18].
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2. Experimental

2.1. Reagents

Pure CH4 (99.999 %) was purchased from Anjeon Gas (Korea). PVCap was obtained from

the Luviskol Plus (BASF, PVCap dissolved in ethanol) through ethanol evaporation using a

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vacuum pump (Mn,PVCap = 5100, polydispersity = 1.303). Deionized (DI) water was acquired

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from water purification equipment (Zeneer Power II, Human Corporation). Fig. 1 shows the

structures of the ILs used for the present work. Among the nine ILs for the CH4 hydrate

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inhibition tests, N-ethyl-N-methylimidazolium tetrafluoroborate (EMIM-BF4), and 1-ethyl-1-

methylpyrrolidine chloride (EMP-Cl) were purchased from C-TRI, and the other ILs were
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synthesized. The materials used for the synthesis of the ILs were as follows: 1-
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methylpyrrolidine (Sigma-Aldrich, 98%), bromoethane (Sigma-Aldrich, 99%), 1-

chlorobutane (Sigma-Aldrich, 99.5%), 1-bromobutane (Sigma-Aldrich, 99.5%), sodium

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tetrafluoroborate (Aldrich, 98%), dichloromethane (SAMCHUN, 99.5%), acetone

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(SAMCHUN, 99.8%), and acetonitrile (JUNSEI, 99.5%).

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2.2. Synthesis of ILs

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Four ILs, 1-hydroxyethyl-1-methylpyrrolidinium chloride (HEMP-Cl), 1-hydroxyethyl-1-

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methylpyrrolidinium tetrafluoroborate (HEMP-BF4), 1-butyl-1-methylpyrrolidinium bromide

(BMP-Br), and 1-butyl-1-methylpyrrolidinium tetrafluoroborate (BMP-BF4), were

synthesized using the same procedures reported in a previous study [18]. The rest three other

ILs were synthesized by the following procedures.

1-ethyl-1-methylpyrrolidine bromide (EMP-Br): Drops of 1-methylpyrrolidine (0.5 mol,

53.23 ml) in 200 mL of acetonitrile were added to bromoethane (0.5 mol, 37.32ml) in a three-

necked round-bottom flask. The mixture was refluxed under nitrogen gas for 48 h at 343.15

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Page 7 of 28
K. The EMP-Br was washed three times with acetone, and dried on a rotary evaporator for 5

h at 323.15 K under low pressure. The solid product was dried under vacuum at 323.15 K for

more than 48 h. The 1H-NMR (DMSO, ߜ /PPM, relative to TMS) spectrum included the

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following peaks: 1.25-1.30 (t, 3H), 2.07-2.08 (s, 4H), 2.99 (s, 3H), and 3.39-3.51 (m, 6H).

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1-ethyl-1-methylpyrrolidine tetrafluoroborate (EMP-BF4): EMP-Br (0.2 mol) in acetone

was reacted with 0.2 mol of sodium tetrafluoroborate in a round-bottom flask. After 24 h of
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stirring, the resulting NaBr precipitate was filtered through a plug of filter paper, and the

volatiles were removed using a rotary evaporator at 323.15 K. The product was dissolved in
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dichloromethane, and the organic phase was washed with dichloromethane twice to ensure
d

complete removal of the bromide salt. Then, the product was dried for more than 24 h under
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vacuum at 323.15 K. The 1H-NMR (D2O, ߜ /PPM, relative to TMS) spectrum included the
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following peaks: 1.31-1.36 (t, 3H), 2.14-2.18 (d, 4H), 2.98 (s, 3H), 3.35-3.43 (t, 2H), 3.45-

3.49 (s, 4H).

1-butyl-1-methylpyrrolidine chloride (BMP-Cl): Drops of 1-methylpyrrolidine (0.5 mol,

53.23 ml) in 200 mL of acetonitrile was added to 1-chlorobutane(0.5 mol, 52.25 ml) in a

three-necked round-bottom flask. The mixture was refluxed under nitrogen gas for 72 h at

343.15 K. BMP-Cl was washed three times with acetone, and dried on a rotary evaporator for

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Page 8 of 28
5 h at 323.15 K under low pressure. The solid product was dried under vacuum conditions at

323.15 K for more than 48 h. The 1H-NMR (D2O, ߜ /PPM, relative to TMS) spectrum

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included the following peaks: 0.85-0.89 (t, 3H), 1.26-1.36 (m, 2H), 1.66-1.74 (m, 2H), 2.12 (s,

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4H), 2.95 (s, 3H), 3.22-3.27 (m, 2H), 3.39-3.44 (s, 4H).

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2.3. Procedure

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Fig. 2 shows a schematic diagram of the apparatus for the measurement of hydrate phase

equilibrium points and CH4 hydrate inhibition tests with ILs and the mixtures of PVCap with
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the ILs. The CH4 for hydrate formation was supplied from a gas cylinder. The CH4 was

pressurized by a gas booster to the specific experiment pressure of the autoclave hydrate
d

reactors. These were placed in an ethylene glycol bath where the temperature was controlled
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by the chiller. The temperature and pressure inside the autoclave were measured during the
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experiments by a data acquisition system.

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The hydrate equilibrium dissociation conditions were measured with the aqueous solutions

containing 10 wt% of the ILs, to determine their thermodynamic hydrate inhibition

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performance. The aqueous solutions of ILs (90 mL) were injected into the autoclave reactor.

The air existing in the reactor was removed under vacuum at a specified temperature. Then,

the autoclave cell was pressurized to a specified pressure using CH4. The reactor temperature

was gradually reduced and the system pressure was also decreased by the contraction of gas

volume and increase in the solubility of the gas. During the cooling stage, the gradient of

pressure decrease became suddenly high due to the CH4 hydrate formation. Once the pressure

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Page 9 of 28
stabilized, the reactor was held at the same pressure for some time. Then, the temperature of

the autoclave was increased by 0.1 K/h stepwise to induce dissociation of the formed CH4

hydrate. The hydrate equilibrium dissociation conditions were determined from the pressure-

temperature trajectory as the intersection of the hydrate dissociation line and thermal

expansion trace. The hydrate phase equilibrium data in the presence of 10 wt% of EMIM-BF4

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in the previous study [18] lies on almost the same equilibrium curve in the previous research

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by Xiao et al. [16]. Because all of the phase equilibrium data in the present work were

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obtained using the same method in the former research [18], the hydrate dissociation

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temperature data is reliable.

The procedures of the CH4 hydrate inhibition tests of this work are basically the same as
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those in a previous study [19]. To evaluate the inhibition performance of the ILs (0.5, 1.0, 2.0,
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or 3.0 wt%) or their mixtures with PVCap (0.5 wt% ILs + 0.5 wt% PVCap) to hydrate

nucleation, they were dissolved in water at specified concentrations and 90 mL of the

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aqueous solutions were charged in a 220 mL autoclave hydrate reactor equipped with a
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magnetic drive. The remnant gases inside the reactor were removed under vacuum at 274.15
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K. Then, CH4 was charged into the autoclave to 7.0 MPa. The temperature inside the reactor

was maintained at 274.15 K during the tests. Under this hydrate formation condition, the
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subcooling temperature was 8.9 K, which is near the maximum subcooling (10 K) during the
Ac

field tests, above which hydrate nucleation is difficult to prevent [3, 9]. KHI-containing

solutions were agitated at 700 rpm after the autoclave pressure was stabilized. The induction

time of the CH4 hydrate formation were measured during four or five repeated tests, and their

values averaged. The induction time was defined as the time difference between the the

moment of the first hydrate formation and the time zero, when the agitation was started.

Hydrate formation was recognized by the pressure decrease inside the autoclave due to

consumption of the CH4. The pressure traces during CH4 hydrate formation were recorded by

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the data acquisition system to compare CH4 hydrate growth in the presence of the different

ILs, or mixtures of PVCap and ILs.

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Results and Discussion

3.1. Thermodynamic hydrate inhibition of ILs

The phase equilibrium conditions of the CH4 hydrate dissociation were measured in the

presence of 10 wt% of ILs and the results are shown in Fig. 3. The blank circles are the phase

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equilibrium points of the pure CH4 hydrate in the literature [20]. Fig. 3 includes CH4 hydrate

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dissociation points with 10 wt% EMIM-BF4, BMP-BF4, and HEMP-BF4 from the previous

study [18]. All of the samples exhibited a shift of the thermodynamic conditions towards the

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hydrate inhibition region. In a previous study, EMIM-BF4 moved the equilibrium curve about

1.0 K at the same pressure, and in this study, this matched the worst thermodynamic hydrate
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inhibition performance [18]. EMP-Cl, EMP-Br, EMP-BF4, BMP-Cl, BMP-Br, and BMP-BF4
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[18] shifted the CH4 hydrate equilibrium curve as much as 1.5, 1.8, 1.6, 1.5, 1.7, and 1.4 K,

respectively. The hydrate equilibrium curves in the presence of 10 wt% of HEMP-BF4 [18]
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and HEMP-Cl almost overlapped and their shift from the pure CH4 hydrate was about 1.5 K.
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Even though bromide-based ILs exhibited slightly higher thermodynamic inhibition

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performance, it was hard to determine if the variation trends were dependent on the cations or

the anions. In general, thermodynamic hydrate inhibition is reported to be caused by strong

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hydrogen bonding between the inhibitor and water molecules [2]. The hydrogen bond or
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interaction strength between the anions of the ILs and water molecules is quite different

depending on the anion identities. In addition, structures, functional groups, or alkyl chains of

the cations could influence the hydrophobicity or hydrophilicity of ILs, which leads to

variation of the hydrogen bond or interactions of IL with water molecules. Hence, the

interactions between ILs and water molecules are quite complicated, which may make it

difficult to find any apparent relationship between ILs and thermodynamic inhibition

performance.

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3.2. Kinetic hydrate inhibition of ILs and IL-PVCap mixtures

Fig. 4 displays the average induction time for CH4 hydrate formation at various

concentrations of ILs and PVCap. Additionally, Fig. 5 compares the induction times in the

presence of 0.5 or 1.0 wt% of ILs and their mixtures with PVCap (0.5 wt% IL + 0.5 wt%

PVCap). Table 1 summarizes the average induction time values and their ranges. In the case

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of the experiments with 0.5 or 1.0 wt% EMIM-BF4, BMP-BF4, HEMP-BF4, or PVCap, and

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the IL/PVCap mixtures or pure water (Figs. 4 and 5; Table 1), induction time data were

obtained from the previous study for comparison [19].

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All of the ILs delayed the nucleation of CH4 hydrate formation, based on increased
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induction times, in comparison with that of pure water. The functions of the ILs on the CH4

hydrate inhibition are thought to be different from that of PVCap due to the structural
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differences. PVCap and other polymer KHIs inhibit hydrate formation by adsorption on

hydrate particles [3]. However, ILs are composed of small cations and anions which are
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dispersed in aqueous solutions and interact with water molecules, which could retard CH4
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hydrate nucleation and growth [18].

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EMIM-BF4 tested in a previous study [19] and in this study, showed very high kinetic
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hydrate inhibition performance in comparison with PVCap. As the concentration of EMIM-

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BF4 increased, the induction time of CH4 hydrate formation was also increased over the

concentration range from 0.5 to 3 wt%. In particular, its mixture with PVCap (each 0.5 wt%)

significantly delayed hydrate nucleation (the induction time was 120.3 min) [19].

Three EMP-based ILs (EMP-BF4, EMP-Br, and EMP-Cl), were tested for their hydrate

nucleation inhibition performance. Unlike EMIM-BF4, the induction time for CH4 hydrate

formation in the presence of EMP-BF4 decreased as its concentration increased. Its inhibition

performance was higher than that of PVCap at the concentrations less than 2.0 wt%, but

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Page 13 of 28
lower at 3.0 wt%. However, because KHIs are generally used in up to ~1.0 wt% of water

phase [3], their performance as a KHI is better than PVCap. Furthermore, the mixture of

EMP-BF4 and PVCap (each 0.5 wt%) exhibited an induction time of 104.3 min, which is four

times longer than that of CH4 hydrate formation with 1 wt% PVCap [19]. On the whole,

EMP-BF4 is a better KHI than PVCap, but is inferior to EMIM-BF4.

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While EMP-BF4 showed quite high hydrate nucleation inhibition performance, EMP-Br

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exhibited the worst performance among the ILs tested in this study. Over the EMP-Br

concentration range in this study, the induction times were less than 10 min. Although the

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induction time in the presence of various concentration range of EMP-Br shows maximum

points, the consideration of this trend is meaningless due to too short induction time. Even its
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mixture with PVCap (each 0.5 wt%) delayed the nucleation of the hydrate formation about
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only ~9.3 min. The hydrate nucleation inhibition of EMP-Cl was higher than that of PVCap

at all the concentrations tested. Even though the average induction time at 3.0 wt% of EMP-
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Cl (70.0 min) is slightly lower than that at 2.0 wt% (72.1 min), the difference is very small.
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Additionally, the difference of standard deviations at 2.0 wt% (9.4 min) and 3.0 wt% (10.0
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min) is also very small. This implies that the induction time in the presence of EMP-Cl

increased at low concentration (less than 2.0 wt%) and converged at around 2.0 wt%. At 0.5
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wt% of EMP-Cl in the solution, the induction time was shorter than that of EMP-BF4 at the
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same concentration. At the other concentrations, it delayed hydrate nucleation more

effectively than EMP-BF4. However, the hydrate nucleation inhibition of the mixture of

EMP-Cl with PVCap (each 0.5 wt%) was considerably reduced. The mixture delayed hydrate

nucleation for only 26.2 min, which is quite similar to the induction time of CH4 hydrate

formation with 1.0 wt% PVCap. The induction time was significantly reduced from 63.9 min

for 1.0 wt% EMP-Cl, to 26.1 min for the mixture.

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Page 14 of 28
 Three BMP-based ILs were also used to evaluate their hydrate nucleation inhibition

performance and to compare the experimental results with those of the EMP-based ILs. As in

the case of the EMIM-BF4, the induction time of CH4 hydrate formation using BMP-BF4

increased with increasing concentration of BMP-BF4, and its nucleation inhibition

performance was higher than that of PVCap all over concentrations tested. The hydrate

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nucleation inhibition of the BMP-Cl and PVCap mixture (each 0.5 wt%) was also more

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effective than 1 wt% of individual BMP-Cl or PVCap, and the induction time of the mixture

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was 65.8 min. However, the use of BMP-halide ILs exhibited quite poor hydrate nucleation

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inhibition performances. In particular, BMP-Br showed the worst inhibition performances

among the three BMP-based ILs; the induction time was 12.3 min at 1.0 wt% of BMP-Br.
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Additionally, its mixture with PVCap (each 0.5 wt%) delayed the hydrate nucleation for only

14.8 min; induction time was extended only 2.5 min. BMP-Cl was slightly better than BMP-
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Br as a KHI, yet it was inferior to PVCap. In particular, the mixing of BMP-Cl and PVCap

(each 0.5 wt%) reduced inhibition performance achieved by of 1.0 wt% of either individual
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BMP-Cl or PVCap.
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Two HEMP-based ILs (HEMP-BF4 and HEMP-Cl) were also tested. The induction time

for CH4 hydrate formation using either of the HEMP-based ILs increased, as the
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concentrations of the ILs were increased. In a previous study, HEMP-BF4 and its mixture
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with PVCap (each 0.5 wt%) exhibited the best hydrate nucleation inhibition performance

among the other ILs and mixtures [18, 19]. Furthermore, there are no KHI candidates better

than HEMP-BF4 even in this study. HEMP-Cl exhibited slightly lower inhibition

performance than PVCap when it was used individually. However, its mixture with PVCap

was much more effective (induction time 75.1 min).

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Page 15 of 28
 From the experimental results of the induction time measurement using the ILs in this

study, it is quite difficult to determine clear trends of induction time variations and the

hydrate nucleation inhibition performance in relation to anions or cations. This is also true of

the IL combinations and the mixtures with PVCap, even though all of the ILs used, extended

the induction time of CH4 hydrate formation. Nonetheless, the ILs containing BF4- exhibited

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better inhibition performance than the other halide-containing ILs and PVCap. Moreover, the

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mixtures of the BF4-based ILs and PVCap created excellent synergetic inhibition effects.

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However, some halide ILs reduced the nucleation inhibition performance of PVCap and

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shortened induction time. In particular, the Br-based ILs were the worst KHI candidates. In

the previous report by Xiao et al., Cl--containing ILs exhibited better inhibition effects when
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compared to Br--containing ILs [17], which contradicts with the finding in this study.

However, those ILs in the previous report [17] are not the same compounds used in this work.
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Depending on the cation, the effects of ILs on the hydrate formation kinetics could be

completely different. As an extreme example, 1-hydroxyethyl-1-methylmorpholinium

d

chloride (HEMM-Cl) promotes CH4 hydrate formation rate, whereas 1-hydroxyethyl-1-

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methylmorpholinium tetrafluoroborate (HEMM-BF4) inhibits CH4 hydrate nucleation [21].

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Even though this example shows the comparison of BF4-- and Cl--containing ILs (not Cl--
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containing and Br--containing ILs), Cl--containing ILs in this study, at least, did not increase

CH4 hydrate formation rate. Therefore, the hydrate inhibition performance of ILs should be
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experimentally determined.

Fig. 6 shows the representative results of pressure traces during CH4 hydrate formation

with/without 0.5 wt% of several ILs, 1.0 wt% of PVCap or the mixture of HEMP-BF4 and

PVCap (0.5/0.5 wt%). This figure also includes the magnified diagram showing the pressure

traces for 20 min from the test start to represent clearly short induction time obtained in the

presence of EMP-Br and in the absent of any ILs. For all of the tests, slight pressure decrease

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Page 16 of 28
is observed at the very beginning of the hydrate inhibition experiments. This arises from the

dissolution of CH4 into aqueous solution due to agitation. This figure also shows that ILs

containing BF4- acted as excellent hydrate anti-nucleators due to the long induction times

when they were used as KHIs. In comparison with PVCap, the BF4-based ILs more

effectively retarded the sI CH4 hydrate nucleation, as shown in Fig. 6. In particular, the

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mixture of HEMP-BF4 and PVCap (0.5/0.5 wt%) exhibited the best anti-nucleation

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performance. A more interesting point is that the hydrate growth rate after the initial hydrate

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formation. EMP-BF4, HEMP-BF4, and especially the mixture of HEMP-BF4 and PVCap

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effectively reduced the CH4 hydrate formation rate, which resulted in a low slope of the

pressure trace, compared to that of pure CH4 hydrate growth. In contrast, EMP-Br showed
an
not only very short induction time but also more rapid pressure decrease than that in the

presence of other additives. Furthermore, the hydrate formation rate after 110 min suddenly
M
increased, which originated from catastrophic hydrate growth, leading to a higher slope of the

pressure trace than that of pure CH4 hydrate formation. This result indicates that EMP-Br is a
d

very poor KHI candidate in comparison with EMP-BF4. Although the ILs containing Br-
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exhibited slightly better thermodynamic hydrate inhibition performances, their kinetic

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inhibition effectiveness was the worst. Therefore, further research related to thermodynamic
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modelling or molecular dynamics simulations should be performed for better understanding

of the interactions of the ILs and water molecules that affect thermodynamic and kinetic
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hydrate inhibition performance.

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Page 17 of 28
Conclusions

In the present study, a variety of ILs were synthesized and used as THIs and KHIs for sI

CH4 hydrate formation. The hydrate equilibrium conditions were inhibited as much as 1.4-1.8

K by 10 wt% ILs. Among the tested ILs, Br-based ILs showed slightly better thermodynamic

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inhibition performance for CH4 hydrate formation, whereas they exhibited the worst kinetic

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hydrate inhibition effectiveness. All ILs synthesized in the present work delayed the

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induction time of CH4 hydrate formation. In particular, BF4-based IL showed the best kinetic

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hydrate inhibition performance. The mixing of several ILs with PVCap further extended the

induction time or reduced the CH4 hydrate growth rate. However, the other ILs rather
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decreased the kinetic inhibition effectiveness of PVCap. From the thermodynamic hydrate

dissociation and kinetic hydrate formation measurements, it is difficult to determine the trend
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of the phase equilibrium/induction time data in relation to the anions or cations of ILs.

Therefore, more research in relation to modelling or simulations should be conducted to shed

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light on the interactions of the IL, PVCap, and water molecules that influence the
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thermodynamic and kinetic hydrate inhibition performance.

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FIGURES

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Fig. 1. Structures of the various ILs and PVCap used in this study: Y indicates one of the BF4-,
Br- and Cl-.
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Fig. 2. Schematic diagram of the apparatus.
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Fig. 3. CH4 hydrate phase equilibria in the presence of 10 wt% of various ILs: The data
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denoted by the asterisk (*) and double asterisks (**) were obtained from references [20] and
[18], respectively.
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Fig. 4. Average induction time variation for CH4 hydrate formation depending on the
concentration of ILs: The induction times measured in the presence of 0.5 and 1.0 wt% of
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EMIM-BF4, BMP-BF4, and HEMP-BF4 were obtained from a previous study [19].
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Fig. 5. Comparison of the induction times for CH4 hydrate formation in the presence of 0.5
and 1 wt% ILs and the mixture of IL with PVCap (0.5/0.5 wt%). The data denoted by the
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asterisks (*) was obtained from a previous study [19].

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Fig. 6. Pressure trace as a function of time due to CH4 hydrate formation: The data denoted
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by asterisk (*) was obtained from a previous study [19]. Pressure trace for 15 min from the
test start is shown in the magnified diagram.
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Table 1. Average induction times and ranges for CH4 hydrate formation in the presence of
various ILs and the mixture of ILs and PVCap (0.5/0.5 wt%).
Induction time (min)

Ionic liquid 0.5 wt% IL + 0.5

0.5 wt% 1.0 wt% 2.0 wt% 3.0 wt%
wt% PVCap

62.1* 79.4* 89.8 95.5 120.3*

EMIM-BF4

t
(47.4í (48.3í (69.4í (84.2í (112.4í

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56.3 52.0 45.6 44.1 104.3
EMP-BF4

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(38.2í (35.6í (30.8í (31.4í (88.5í

5.0 7.0 6.9 4.5 9.3

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EMP-Br
(2.8í (3.7í (4.8í (3.6í (7.5í

42.1 63.9 72.1 70.0 26.1

EMP-Cl
(28.4í59.2)

40.4*
(50.3í76.2)

47.2*
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64.4
(62.5í81.4)

77.0
(13.5í37.4)

65.8*
BMP-BF4
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(33.8í (43.2í (53.8í77.2) (66.7í85.7) (39.4í

3.6 12.3 11.9 15.2 14.8

BMP-Br
(0.7í (8.8í (9.2í (13.1í (11.8í
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20.4 21.9 26.4 27.9 18.1

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BMP-Cl
(9.7í29.7) (12.4í28.8) (14.3í30.3) (16.2í31.5) (9.3í28.4)
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78.8* 91.2* 112.2 139.4 184.9*

HEMP-BF4
(65.2í (70.3í (108.3í (121.4í (166.6í
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17.5 24.4 35.3 51.6 75.1

HEMP-Cl
(11.4í (17.6í (23.5í (44.8í (59.2í
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Water 2.6*

(no additive) (1.5í

22.8* 26.2* 39.2 53.5

PVCap -
(18.6í (22.6í (34.6í (47.2í

The data denoted by asterisks (*) were obtained from a previous study [19]. Numbers in
parentheses indicate range of induction time. (T = 274.15.ǻ7VXE-cooling) = 8.9 K, P =
7.0 MPa).

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AUTHOR INFORMATION

Corresponding Author

*E-mail: spkang@kier.re.kr, kks1114@ut.ac.kr

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ACKNOWLEDGMENT

This work was supported by the Industrial Strategic Technology Development Program (No.

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10045068) of Korea Evaluation Institute of Industrial Technology funded by the Ministry of

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Trade, Industry and Energy.

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REFERENCES

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[19] S.-P. Kang, E.S. Kim, J.-Y. Shin, H.-T. Kim, J.W. Kang, J.-H. Cha, K.-S. Kim, RSC
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[20] W.M. Deaton, E.M. Frost, U.S. Bureau of Mines Monograph, 8 (1946) 101.
[21] W. Lee, J.-Y. Shin, K.-S. Kim, S.-P. Kang, Energy & Fuels, (2016).
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Graphical Abstract

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