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Article
Phase Equilibria and Dissociation Enthalpies of Methane
Hydrate in Imidazolium Ionic Liquid Aqueous Solutions
Zhen Long, Xuebing Zhou, Xiaodong Shen, Dong-Liang Li, and De-Qing Liang
Ind. Eng. Chem. Res., Just Accepted Manuscript • DOI: 10.1021/acs.iecr.5b03480 • Publication Date (Web): 02 Nov 2015
Downloaded from http://pubs.acs.org on November 6, 2015

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8 Phase Equilibria and Dissociation Enthalpies of
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Methane Hydrate in Imidazolium Ionic Liquid
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13 Aqueous Solutions
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17 Zhen Long1, Xuebing Zhou1,2, Xiaodong Shen1, Dongliang Li1,Deqing Liang1*
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Key Laboratory of Gas Hydrate, Guangzhou Institute of Energy Conversion, Chinese Academy of Sciences,
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23 Guangzhou 510640, China
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27 University of Chinese Academy of Sciences, Beijing 100049, China
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31 Abstract: This paper reports the thermodynamic inhibition effect of seven ionic liquids (ILs) on the methane
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34 hydrate formation. The isochoric multi-step heating dissociation pressure search method is applied for
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experimentally determining the phase boundary between hydrate-liquid-vapor (H-L-V) phases and liquid-vapor
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39 (L-V) phases in the pressure and temperature ranges of (3.45 to 13.28) MPa and (274.3 to 287.6) K, respectively.
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42 All the studied IL aqueous solutions are used at a mass fraction of 0.1. A comparison of the thermodynamic
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inhibitory performance of various ILs is carried out and reveals the predominant role of the type of anion of ILs.
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47 Considering the difficulty in directly measuring the dissociation enthalpies, the values of △H of methane hydrate are
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50 also calculated using the Clausius–Clapeyron equation. It is found that the mean dissociation enthalpies of methane
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hydrate in the presence of the seven ILs vary from 59.05 to 60.81 kJ·mol-1, and are very close to that in pure water.
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57 Keywords: methane hydrate, phase equilibria, enthalpy of dissociation, hydrate inhibitor, ionic liquid,
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4 1. INTRODUCTION
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8 Gas hydrates are ice-like crystalline compounds made of small gas molecules (guest), such as methane, ethane,
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10 carbon dioxide, or hydrogen sulfide, which are trapped in 3-dimensional lattices formed by hydrogen-bonded water
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13 molecules (host).1-3 Large deposits of natural gas (mostly methane) hydrate, which are considered as a possible
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16 alternative energy to fossil fuels, are estimated to abundantly exist in deep oceans and permafrost on a global
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18 scale.4-6 There are numerous areas of positive applications of gas hydrates, including refrigeration and air
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21 conditioning systems,7, 8 separation of close-boiling point compounds,9, 10 water treatment and desalination,11, 12 gas
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24 storage and seperation,13, 14, carbon dioxide capture,15, 16 etc. However, gas hydrates are also pointed out to be
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26 responsible for blockage of the pipelines, causing huge hazards as well as economic loss to production, transmission,
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29 and transportation system.17, 18A well-known example is the oil leakage of deep water drilling well in Gulf of
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32 Mexico, where the presence of water and favorable condition of high pressure and low temperature frequently result
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in the formation of gas hydrates. To mitigate the hydrate formation, the common method is to inject chemical
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37 inhibitors: thermodynamic hydrate inhibitor (THI) and kinetic hydrate inhibitor (KHI).19-21 Ethylene glycol (EG) and
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40 methanol (MeOH) are widely used as THI to effectively shift the hydrate phase boundary conditions towards lower
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temperature or higher pressure. Due to large quantities of usage, an expensive cost is inevitably spent,
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45 accompanying with environmental issue. For this reason, such KHI as polyvinylpyrrolidone (PVP) and
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48 polyvinylcaprolactam (PVCap) is proposed for managing the hydrate formed.1, 20, 22 Instead of completely avoiding
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the hydrate formation, they allow but delay the hydrate formation through slowing down the nucleation/growth rate
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53 of gas hydrates until the oil or gas is safely transported to non-hydrate zones. A low concentration of less than
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4 0.01mass fraction is enough active in under-inhibited KHI systems. The puzzling problem in the applications of KHI
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7 as the hydrate control strategy is that KHI will fail in hydrate inhibition under high subcoolings of up to 10 K.18, 20
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Recently, ionic liquids (ILs) as a new class of hydrate inhibitors have captured the researches’ great interests.
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12 According to the open studies, it is well recognized that ILs are made of organic cations (e.g., imidazolium-,
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15 pyrrolidinium-, ammonium-, and phosphonium-) and organic/inorganic anions.23, 24 Most of them are commonly less
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volatile, non-flammable, and highly thermally and chemically stable, and so on. Additionally, they are often
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20 characterized by environmental-friend due to their biodegradable feature, which are possible recovery technique of
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23 them.23 The tunability of cation and anion offers them designable structure for satisfying specific demands and
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various application areas. 24, 25 Xiao et al.26 presented the first discovery that imidazolium-based ILs were effective
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28 as THI as well as KHI for methane hydrate. The kinetic inhibition effect of [Emim][BF4] at 0.01 mass fraction was
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31 even much more excellent than those of Luvicap and PVCap. Since then, their study on the new class of ILs
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34 inhibitors was extended to dialkylimidazolium-based ILs with halide anions.27 ILs containing halide anions were
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36 reported to have strong thermodynamic inhibitory effects than ILs containing [BF4]–. Moreover, the thermodynamic
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39 inhibition effectiveness of ILs was demonstrated to be closely related to their electrical conductivity and/or the
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42 strength of hydrogen bonding with water, which was dependent on the type of cations and anions. Besides,
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44 [Emim][Cl] was observed to perform increased inhibition effectiveness with increased pressures and may surpass
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47 the thermodynamic inhibition effect of monoethyleneglycol (MEG) at high concentrations.28 Li et al.,29 Partoon et
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50 al.,30 and Sabil et al.31 all agreed that hydroxyl group could be beneficial for ILs to increase their electrostatic
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52 charges and make ILs possess better thermodynamic inhibition than typical imidazolium-based ILs without
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55 functional groups. In addition, Shin et al.32 studied the role of various anions and cations in determining the
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58 thermodynamic inhibition effectiveness of ILs. They found the anion was the main factor of improving the IL
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4 inhibitory capability. Compared to large phase equilibrium temperature shift by common THI (i.e., about 2-2.5 K by
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7 EG), the thermodynamic inhibition effect of these ILs at 0.1 mass fraction is yet very limited, which often depress
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the equilibrium temperature of methane hydrate less than 1.5 K. It is very difficult to practically apply ILs as gas
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12 hydrate inhibitors in the oil and gas industry. However, their dual inhibition functionality due to tunable structure
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15 provides a competitive potential over other type of hydrate inhibitors. So, knowledge of newly designed ILs as
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hydrate inhibitors is necessary that significantly contributes to an improved understanding of the inhibition
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20 mechanism and vice versa.
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23 In this work, the thermodynamic performance of imidazolium-based ILs as inhibitors on the gas hydrates is
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investigated. The dissociation conditions of methane hydrate in the presence of seven aqueous solutions of ILs are
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28 measured at pressures ranging from (3.45 to 13.28) MPa and temperatures ranging from (274.3 to 287.6) K. The
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31 seven ILs are 1-ethyl-3-methylimidazium perchlorate [Emim][ClO4], 1-ethyl-3-methylimidazolium thiocyanate
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34 [Emim][SCN], 1-ethyl-3-methylimidazolium acetate [Emim][Ac], 1-butyl-3-methylimidazolium acetate
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36 [Bmim][Ac], 1-hydroxyethyl-3-methylimidazolium perchlorate [OH-Emim][ClO4], 1-ethyl-3-methylimidazolium
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39 chloride [Emim][Cl] and 1-hydroxyethyl-2,3-dimethylimidazolium chloride [OH-Emmim][Cl]. The dissociation
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42 enthalpies are also calculated from the measured phase equilibrium data of methane hydrate in the presence of ILs
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44 using Clausius-Clapeyron equation.
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47 2. EXPERIMENTAL SECTION
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50 2.1 Materials. The seven ILs studied in this work are obtained from Lanzhou Institute of Chemical Physics. They
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52 are water-soluble and used without further purification. Table 1 shows the chemical structures and purities of these
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55 ILs. The mass fractions of ILs used are 0.1. Methane gas with a purity of 0.9999 mole fraction is supplied by South
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58 China Special Gases Ltd., CO. Deionized water with a resistivity of 18.25 mΩ·cm-1 is made by an ultrapure water
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4 system and used for preparing all of the sample solutions. Samples are weighed using an electronic analytical
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7 balance with an accuracy of ±0.1 mg.
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2.2 Apparatus and Procedure. The apparatus used in this work is the same as that described in our previous
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12 study.33 The apparatus allows the measurement conditions within the pressure range of (0 to 20) MPa with an
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15 uncertainty of ±0.02 MPa and the temperature range of (233.15 to 383.15) K with an uncertainty of ±0.1 K. The
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cylindrical hydrate crystallizer is made of 316 stainless steel and has an effective volume of 175 mL. The samples in
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20 the crystallizer are fully mixed through an electrically-driven magnetic stirrer, which is coupled with a magnet
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23 mounted outside the cell. The stirring speed is set to 800 rpm. The system temperature is controlled by a
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programmable air bath with an uncertainty of ±0.1 K and measured by a platinum resistance (Pt100) thermometer.
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28 The system pressure, which is measured by a CYB-20S pressure transducer, can be controlled by injection or
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31 withdrawal of water using a high-pressure pump. The data of temperature and pressure are real-time recorded and
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34 displayed in a computer via an Agilent data acquisition system. A schematic diagram of the experimental apparatus
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39 The hydrate dissociation points are determined by an isochoric equilibrium step-heating pressure search
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42 method.33-37 The method has been verified to be reliable and employed for obtaining data in many experimental
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44 systems.38-42 Briefly speaking, it operates in a three-step process. The first step includes the preparation of the ionic
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47 liquid aqueous solution, washing and drying the crystallizer and all connected pipelines, evacuating the crystallizer,
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50 and introducing the methane gas into the crystallizer until the desired initial experimental pressure at the room
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52 temperature. The following is lowering the temperature and starting the stirrer to facilitate the formation of gas
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55 hydrate. At the onset of gas hydrate formation, a sharp pressure drop is often observed, along with an evident
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58 temperature increase. With the accumulating gas hydrate formed, the last but important is to stepwise increase the
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4 temperature to make the gas hydrate dissociate. At every heating step, it often takes enough time (i.e. 6 h to 10 h) to
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7 achieve a steady equilibrium state. When the system temperature is increased beyond the hydrate formation region,
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the pressure versus temperature exhibits an approximately linear trend again. The experiment ends until the system
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12 returns to initial stable state. In this way, the dissociation point, where the slope of P-T curve changes sharply, is
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15 determined (see Figure 2) and represents the boundary between liquid-vapor (L-V) phases and hydrate-liquid-vapor
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(H-L-V) phases.33-37
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20 3. RESULTS AND DISCUSSION
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23 3.1 Validation of Apparatus and Procedure. The methane hydrates phase equilibrium conditions in pure water are
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measured in the pressure range of (3.40 to 13.27) MPa and temperature range of (275.8 to 288.5) K and presented in
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28 Table 2 and Figure 3. Also plotted in Figure 2 are those reported from Adisasmito et al. 43 Mohammadi et al.,44 and
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31 Keshavarz et al.45 by using isochoric step-heating pressure search method. The data from the present study are
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34 observed to agree well with those given in literature. It validates that our experimental apparatus and approach are
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36 well established and reliable.
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39 3.2 Hydrate Phase Equilibrium Conditions in the Presence of Ionic liquid. The phase equilibrium data of
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42 methane hydrate in the presence of ILs with the mass fraction of 0.1 are measured at pressures from 3.45 to 13.28
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44 MPa. The obtained experimental results are listed in Table 3. First, to study the effect of cations of ILs on their
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47 thermodynamic inhibition performance, four cations [Emim]+, [Bmim]+, [OH-Emim]+, and [OH-Emmim]+ are
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50 selected for analysis. According to the anion type in each group, groups A-C are formed, represented in
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52 [Cation][ClO4], [Cation][Ac], and [Cation][Cl], respectively. The available P-T data for each group are plotted
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55 in Figures 4a-c. It is clearly visible that the inhibition effect of ILs containing [Emim]+ is slightly stronger than
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58 that of ILs containing [Bmim]+. The same behavior also happens in groups [Cation][BF4],26, 32
[Cation][Br],27
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4 and [Cation][I].29 Those results suggest that dialkylimidazolium-based ionic liquids with a shorter alkyl in the
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7 cation have better thermodynamic inhibition effectiveness than ionic liquids with a longer alkyl. A possible
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explanation for the finding is that the introduction of longer alkyl chains to the imidazolium cation can increase
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12 hydrophobicity of ionic liquids and therefore hinder the formation of hydrogen bonding with water molecules.
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15 The comparisons between [OH-Emim][ClO4] and [Emim][ClO4], [OH-Emim][Cl] and [Emim][Cl] verify
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that the substitution of hydroxyl group in the cation can enhance the ability of the ionic liquid to form
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20 hydrogen-bonding with water, thereby contributing to the increased inhibitory effects.29-31 However, the
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23 addition of hydroxyl group into the cation [Emim]+ increases the size of cation itself, which may be negative to
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26 the incorporation of the ionic liquids into the hydrogen-bonding network of water. Thus, the increase of
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28 inhibition strength due to the presence of hydroxyl group is found to be not significant.29, 30 In contrast to the
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31 positive effect of hydroxyl group on ILs’ inhibition ability, the introduction of [OH-Emmim][Cl], where the
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34 position-2 hydrogen in the imidazolium cation ring is replaced by a methyl group, displays weaker inhibition
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36 effect than [Emim][Cl] and [OH-Emim][Cl], as illustrated in Figure 4c.
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39 Following are the inhibitory effects of various anions of ionic liquids containing the same cation [Emim]+ on the
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42 methane hydrate formation investigated. Figure 5 shows the phase equilibrium data of methane hydrate in the
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44 presence of [Emim][ClO4], [Emim][SCN], [Emim][Ac], and [Emim][Cl], which are compared with those in
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47 [Emim][HSO4] from Zare et al.,46 [Emim][NO3] from our recent study33 and pure water. Those ionic liquids present
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50 similar inhibition behavior that the inhibitory effect increases with the increased pressure. The order of the
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52 effectiveness of each anion in thermodynamic methane hydrate inhibition is as follows: [Cl]– > [Ac]– > [NO3]– >
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55 [SCN]– > [ClO4]– > [HSO4]–. It appears that the thermodynamic inhibition tendency is closely related to the anion
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58 size. Smaller is the size of anion, the ion charge density is higher at the same mass fraction of aqueous solution. This
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4 can result in stronger electrostatic interaction between IL and water molecules and may make the IL more effectively
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7 suppress hydrate formation.32
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To better evaluate the thermodynamic inhibition effectiveness of these ILs, a standard statistical method is used to
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12 calculate the average shift temperature △Tave as follows: 27, 31, 46
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n
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∆Tave =
n ∑ ∆T
i =1
i (1)
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19 where n is the number of data points and △Ti is the shift in the hydrate phase equilibrium temperature measured in
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the presence of the ionic liquid relative to that in pure water at the same pressure. Considering that the experimental
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24 data for various ionic liquids are available at different pressures, the dissociation temperatures in the pure water at
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27 the same pressures are calculated by the model of CSMGem.1 The results for the ionic liquids studied are listed in
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Table 4. From Table 4, [Emim][Cl] is the strongest thermodynamic inhibitor among all the studied ionic liquids,
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32 shifting the phase equilibrium curve by 1.7-1.9 K. Since the uncertainty of the temperature measurement in our
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35 experiments is ±0.1 K, it seems that the inhibition effects of [Emim][SCN], [Emim][ClO4] and [OH-Emim][ClO4]
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38 are approximately the same as seen in Table 4. Despite of longer alky chain in the cation, [Bmim][Ac] is found to be
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40 more effective than the three ionic liquids mentioned above as inhibitors. In this way, it demonstrates a more
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43 significant correlation between the overall inhibition effect and anion type rather than cation type, which is
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46 consistent with the results from Shin et al.32 However, it is considered as inconclusive because of insufficient cation
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48 and anion types. Another is noticed that ILs as effective inhibitors, are generally synthesized in laboratories. Their
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51 use as inhibitors may be expensive in comparison with traditional THIs like methanol and ethylene glycol. Therefore,
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54 more researches should be carried out to make their use economical.
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56 3.3 Dissociation Enthalpy of Methane Hydrates. For oil and gas industry, the thermal properties such as enthalpy
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4 of dissociation and specific heat are important for predicting the heat requirement for hydrate dissociation. It is
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7 meanwhile to assess the molar enthalpy of dissociation, which is defined as the enthalpy change when one molar of
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hydrate is transformed into gas and water. In this work, it is calculated by using Clausius-Clapeyron equation
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12 expressed as: 47, 48
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d (1 T ) zR
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where R is the universal gas constant, and z is the compressibility factor of methane gas, which can be determined
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20 by the Peng-Robinson (PR) equation of state 49 The left side in Eq. 2 can be solved by plotting the experimental data
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23 in the ionic liquids as lnP versus 1/T. A good linear relationship, with the correlation coefficient R2 close to 1, can be
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seen by observation of Figure 6. The value of d(lnP)/d(1/T) is assumed equal to the slope of the regressed curve. The
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28 average dissociation enthalpies of methane hydrate in these ionic liquids and pure water are summarized in Table 5.
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31 It is noted that due to small measurement uncertainties of the phase equilibrium data, this can lead to the large errors
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34 in the compressibility factor z and d(lnP)/d(1/T). Within the errors in values of △H, the calculated △H value for
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36 methane hydrate in pure water agrees well with those reported in literature. Compared with that in pure water
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39 systems, there is no significant difference in the molar dissociation enthalpy for ILs-contained systems. The molar
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42 dissociation enthalpy of the ILs does not demonstrate an apparent relationship with the thermodynamic inhibition
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44 effectiveness of the ILs. The slope of the hydrate dissociation lines (lnP versus 1/T), which is related to the cavity
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47 size occupied by the guests, is also found to be similar for the systems with and without ILs. It is assumed that the
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50 simple methane hydrate is formed in the presence of ILs aqueous solutions, which do not participate in the cage
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52 structures. More important evidences are required throughout our next work.
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55 4. CONCLUSIONS
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58 In this work, the measurements of the phase equilibrium data of methane hydrate in the presence of seven ILs are
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4 carried out by using the isochoric step-heating pressure search method. All the ionic liquids present a
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7 thermodynamic inhibition effect to shift the formation condition of methane hydrate to lower temperatures and
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higher pressures. The depression temperature among the studied ILs is about between 0.84 and 1.69 K. Although
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12 some functional group in the cation, i.e., hydroxyl group, can help strengthen the interaction of the ILs with water,
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15 the overall inhibitory performance of the ILs is found to be primarily dependent on the type of anion. Taking use of
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the available experimental data, the calculated average molar dissociation enthalpies of methane hydrate with and
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20 without ILs are obtained. Within the statistical errors of △H, the results show a good agreement of our values with
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23 literature data in pure water and no much difference of the dissociation enthalpy is observed due to the addition of
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various ILs. There is also no apparent relationship between the dissociation enthalpy of the ILs with their
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28 thermodynamic inhibition effectiveness.
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31 AUTHOR INFORMATION
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34 Corresponding Author
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36 *Phone: +86 20 8705 7669. Fax: +86 20 8705 7669. Email: liangdq@ms.giec.ac.cn (D.Q. Liang)
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39 ACKNOWLEDGMENTS
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42 This work is supported by the National Natural Science Foundation of China (No. 51376182), and the Chinese
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44 Academy of Sciences Key Development Program (No. KGZD-EW-301).
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47 Notes
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50 The authors declare no competing financial interest.
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52 REFERENCES
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55 (1) Sloan, E. D.; Koh, C. A. Clathrate Hydrates of Natural Gases, 3 rd ed.; CRC Press-Taylor & Francis: New
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39 tributylmethylphosphonium methylsulfate ionic liquid. J. Chem. Eng. Data 2011, 56, 3620-3629.
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52 hydrate formation. Chem. Eng. Sci. 2013, 87, 270-276.
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7 [EMIM]-Cl and [OH-C2MIM]-Cl on methane hydrate equilibrium line. Fluid Phase Equilib. 2013, 337, 26-31.
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36 thermodynamic modeling of methane hydrate dissociation conditions in the presence of aqueous solution of
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39 ionic liquid. Fluid Phase Equilib. 2013, 354, 312-318.
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47 square well equation of state. Fluid Phase Equilib. 2013, 341, 61-69.
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50 (47) van der Waals, J. H.; Platteeuw, J. C. Clathrate solutions. Adv. Chem. Phys. 1959, 2, 1.
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52 (48) Sloan, E. D.; Fleyfel, F. Hydrate dissociation enthalpy and guest Size. Fluid Phase Equilib. 1992, 76, 123-140.
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4 (50) Handa, Y.P. Compositions, Enthalpies of dissociation, and heat capacities in the range 85 to 270 K for clathrate
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7 hydrates of methane, ethane, and propane, and enthalpy of dissociation of isobutane hydrate, as determined by
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a heat-flow calorimeter. J. Chem. Thermodyn. 1986, 18, 915-921.
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4 Table 1. Ionic liquid studied in this work
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7 Symbol Chemical name Chemical structure Mass
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10 fraction
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12 purity
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15 [Emim][ClO4] 1-ethyl-3-methylimidazolium perchlorate
16 0.99
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19 [OH-Emim][ClO4] 1-hydroxyethyl-3-methylimidazolium
20 0.99
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22 perchlorate
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24 [Emim][SCN] 1-ethyl-3-methylimidazolium thiocyanate
25 0.98
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28 [Emim][Ac] 1-ethyl-3-methylimidazolium acetate
29 0.985
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32 [Bmim][Ac] 1-butyl-3-methylimidazolium acetate
33 0.985
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36 [Emim][Cl] 1-ethyl-3-methylimidazolium chloride
37 0.99
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40 [OH-Emmim][Cl] 1-hydroxyethyl-2,3-dimethylimidazolium
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42 0.99
43 chloride
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4 Table 2. Experimental dissociation data for methane hydrate in the presence of pure watera
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7 T /K P /MPa
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10 275.8 3.40
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13 279.6 4.97
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282.0 6.32
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20 284.4 8.21
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23 288.5 13.27
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26 a
Uncertainties u are u(T)=±0.1 K, u(P)=±0.02 MPa
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4 Table 3. Experimental dissociation data for methane hydrate in the presence of 0.1 mass fraction of ionic liquid
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7 aqueous solutionsa
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Ionic liquid T /K P /MPa Ionic liquid T /K P /MPa
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12 [Emim][ClO4] 275.3 3.54 [Emim][SCN] 275.2 3.52
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15 278.6 4.88 278.6 4.95
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18 281.3 6.45 281.5 6.44
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20 283.4 8.13 283.8 8.51
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23 287.6 13.21 287.5 13.15
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26 [OH-Emim][ClO4] 275.0 3.45 [Emim][Cl] 274.3 3.47
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28 278.6 4.94 277.7 4.85
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31 281.3 6.44 280.3 6.43
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34 283.5 8.34 282.5 8.06
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36 287.4 12.96 286.7 13.17
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39 [Emim][Ac] 274.5 3.51 [OH-Emmim][Cl] 274.7 3.51
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42 277.8 4.95 278.1 4.91
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44 280.3 6.34 280.5 6.27
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47 282.7 8.38 283.2 8.24
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50 286.6 13.08 287.4 13.28
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52 [Bmim][Ac] 274.9 3.49
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4 280.5 6.37
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7 283.1 8.41
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286.8 13.04
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12 a
Uncertainties u are u(T)=±0.1 K, u(P)=±0.02 MPa
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4 Table 4. Average shift temperature △Tave for studied ionic liquid at 0.1 mass fractions
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7 Ionic liquid △Tave /K
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10 [Emim][ClO4] 0.8
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12 [Emim][SCN] 0.9
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15 [OH-Emim][ClO4] 0.9
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18 [Bmim][Ac] 1.4
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20 [Emim][Ac] 1.7
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23 [Emim][Cl] 1.7
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26 [OH-Emmim][Cl] 1.7
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4 Table 5. Average enthalpies of methane hydrate dissociation for (methane+water) and (methane+ILs) (0.1 mass
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7 fraction)-water systema
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Enthalpy
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11 Ionic liquid P/MPa T/K Slope R2
12 △H/kJ·mol-1
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Pure water (Handa et al.)50 1.013 273.15 - 54.19b -
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19 Pure water (Sloan Fleyfel,
20 1.013 273.15 - 56.9c -
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1992)
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24 Pure water (this work) 3.40-13.27 275.8-288.5 -8505.42 59.82 0.996
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27 [Emim][ClO4] 3.54-13.21 275.3-287.6 -8476.30 59.46 0.996
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30 [OH-Emim][ClO4] 3.45-12.96 275.0-287.4 -8429.62 59.11 0.996
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33 [Emim][SCN] 3.52-13.15 275.2-287.5 -8429.30 59.05 0.993
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35 [Bmmim][Ac] 3.49-13.04 274.9-286.8 -8685.67 60.81 0.998
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38 [Emim][Ac] 3.51-13.08 274.5-286.6 -8542.60 59.77 0.997
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41 [Emim][Cl] 3.47-13.17 274.3-286.7 -8449.31 59.20 0.997
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43 [OH-Emmim][Cl] 3.51-13.28 274.7-287.4 -8247.01 57.81 0.997
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45
a
46 Uncertainties u are u(T)=±0.1 K, u(P)=±0.02 MPa, u(H)=±3.49 kJ·mol-1; b measured value via calorimetry; c

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24 Figure 1. Schematic of experimental apparatus. V1-V7, valves; T, resistance thermometer; P, pressure
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Figure 3. Experimental dissociation conditions for methane hydrate in the presence of pure water.
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39 Figure 4. Effect of cation of 0.1 mass fraction ionic liquids on the phase equilibrium curves of methane hydrates. (a)
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Figure 5. Phase equilibrium conditions of methane hydrate in the presence of 0.1 mass fraction Emim ionic liquids.
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