Accepted Manuscript

Performance of mixture of ethylene glycol and glycine in inhibiting methane hydrate

formation

Zhen Long, Xuebing Zhou, Yong He, Dongliang Li, Deqing Liang

PII: S1875-5100(18)30234-8
DOI: 10.1016/j.jngse.2018.05.034
Reference: JNGSE 2592

To appear in: Journal of Natural Gas Science and Engineering

Received Date: 10 January 2018

Revised Date: 11 April 2018
Accepted Date: 25 May 2018

Please cite this article as: Long, Z., Zhou, X., He, Y., Li, D., Liang, D., Performance of mixture of
ethylene glycol and glycine in inhibiting methane hydrate formation, Journal of Natural Gas Science &
Engineering (2018), doi: 10.1016/j.jngse.2018.05.034.

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 ACCEPTED MANUSCRIPT

Performance of mixture of ethylene glycol and glycine in inhibiting methane hydrate

formation

Zhen Longa,b,c, Xuebing Zhoua,b,c, Yong Hea,b,c, Dongliang Li a,b,c, Deqing Liang a,b,c,*

a
CAS Key Laboratory of Gas Hydrate, Guangzhou Institute of Energy Conversion, Chinese

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Academy of Sciences, Guangzhou 510641, China

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b
Guangdong Provincial Key Laboratory of New and Renewable Energy Research and

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Development, Guangzhou 510640, China

c
Guangzhou Center for Gas Hydrate Research, Chinese Academy of Sciences, Guangzhou

510640, China
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*Corresponding Author: Phone: +86 20 8705 7669. Fax: +86 20 8705 7669.
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Email: liangdq@ms.giec.ac.cn（DQ. Liang）

ABSTRACT
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This study investigates synergistic hydrate inhibition performance of conventional

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thermodynamic hydrate inhibitors (THIs) combined with amino acids. For this purpose,
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hydrate-liquid-vapor equilibrium (HLVE) data for methane were measured in the presence of

mixed ethylene glycol and glycine using 1:1 mixtures at concentrations of 1wt% (0.5 wt%
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ethylene glycol +0.5 wt% glycine), 5 wt% (2.5 wt% ethylene glycol +2.5 wt% glycine), 10 wt% (5
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wt% ethylene glycol +5 wt% glycine), 20 wt% (10 wt% ethylene glycol +10 wt% glycine), and 30

wt% (15 wt% ethylene glycol +15 wt% glycine) by the isochoric pressure search method.

Thermodynamic inhibition efficiency has been investigated by observing the shifts in the hydrate

equilibrium curves and trends of the calculated hydrate suppression temperatures at various
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concentrations and pressures. The results were also obtained for ethylene glycol, glycine and ionic

liquids for comparison. An improving inhibition performance by mixing ethylene glycol and

glycine was observed, indicating the potential of amino acids as inhibition synergists in hydrate

exploitation, oil/gas transportation and flow assurance. Molar hydrate dissociation enthalpies were

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calculated by using the Clausius-Clapeyron equation and showed that the interaction of ethylene

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glycol and glycine has no impact on the hydrate structure.

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Keywords: methane hydrate; amino acids; synergistic effect; thermodynamic inhibition

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1. Introduction

Gas hydrates are crystalline solids that physically resemble ice and consist of water molecules

and gas molecules (CH4, C2H6, C3H8, CO2, etc.) trapped in hydrogen-bonded water cages at low

temperatures and high pressures (Sloan, 2003; Sloan and Koh, 2008). Huge deposits of naturally

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occurring gas hydrates have been found in permafrost and ocean sediments. The amount of natural

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gases stored in form of hydrates is estimated to approach twice that of all other fossil fuel reserves

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in worldwide areas (Sloan, 2003; Klauda and Sandler, 2005; Sloan and Koh, 2008; Boswell and

Collett, 2011). Due to high storage capacity (about 173 v/v), gas hydrate thereby obtains growing

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worldwide attention as a new form to store methane, separate gas mixture or sequestrate
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greenhouse gases (CO2, CH4).
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On the other hand, it is reported that gas hydrates are also responsible for the problem of flow

assurance in the oil and gas industry (Hammerschmidt, 1934; Sloan, 2005; Sloan and Koh, 2008).
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Thermodynamic conditions in fluid transportation pipelines are often favorable for their formation.
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The occurrence of hydrate particles growth and aggregation easily leads to pipeline blockages and
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results in considerable production accidents and severe financial losses. Among a variety of

hydrate prevention methods (i.e., thermal heating, depressurization, and heat insulation), injection
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of chemicals is proposed to be the most common and practical way to control hydrate formation
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(Kelland, 2006). Thermodynamic hydrate inhibitors (THIs), like methanol and ethylene glycol, are

widely used in the industry. The addition of those materials into the aqueous phase directly lowers

the hydrate-liquid-vapor equilibrium (HLVE) temperature or increases HLVE pressure, keeping

the system operation conditions (P, T) far away from the hydrate-formation region. The dosage is
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higher up to 40-60 wt%, the safety zone is wider and the possibility of hydrate formation is lower

at the cost of increased operation capital (Koh, 2002; Gbaruko et al., 2007; Lafond et al., 2012;

Carroll, 2014). Most of alcohols are toxic, highly viscous and easily volatile, thereby causing

complex refining and recovery processes and leading to additional pumping costs (Carroll, 2014).

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For economic and environmental reasons, an alternative to THIs, the kinetic hydrate inhibitors

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(KHIs), based on water-soluble poly (N-vinylpyrrolidone) (PVP), poly-(N-vinylcaprolactam)

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(PVCap) and their analogues, have been identified and applied by various oil companies (Kelland,

2006). These KHIs are known to effectively delay hydrate nucleation or crystal growth at low

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concentration of 0.5-2.0 wt%. However, there are many challenges to be dealt with, including
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difficulty in preventing structure I hydrates, ineffectiveness at high subcooling (>10K) and poor
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biodegrability (Kelland et al., 2000; Storr et al., 2004; Kim et al., 2014).

The utilization of “green solvent” ionic liquids (ILs) opens up the possibility of seeking highly
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effective, environmentally friendly and economical inhibitors. Benefiting from their tunable
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structures, which can be selectively designed by a combination of huge databases of cations and
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anions available, most of ionic liquids shares such excellent characteristics as non-volatility, stable

thermos-physical properties, non-toxicity, and are preferred as gas/liquid separation media,

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catalysts, electrolytes (Tariq et al., 2014). Recent studies have revealed that some ILs, belonging to
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imidazolium (Xiao and Adidharma, 2009; Richard and Adidharma, 2013; Liu et al., 2011; Long et

al., 2015), pyrrolidinium (Kim et al., 2011; Kang et al., 2013, 2016), piperidinium (Cha et al.,

2016), and alkyl-ammonium families (Su et al., 2016; Mohammad et al., 2016), are able to act as

THIs or/and KHIs. However, poor thermodynamic inhibition performance of ILs has been pointed
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out, failing to exceed commercial THIs (Tariq et al., 2014).

Another novel class of natural hydrate inhibitors, amino acids, has successfully raised

researchers’ great attention, since they were first reported to significantly inhibit HLVE curve of

CO2 hydrate (Sa et al., 2011). Generally, there are 20 amino acids existing in living organism and

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they are organic compounds consisting of an amine (-NH2) and carboxylic acid (-COOH)

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functional groups with a characteristic side chain. Previous studies have suggested amino acids are

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capable of forming hydrogen bonding with water molecules due to the presence of the carboxylic

acid and amine groups (Madeira et al., 2014). Moreover, the phenomenon of amino acids behaving

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as zwitterions in aqueous phase contributes to electrostatic interaction between amino acids and
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water molecules. In accordance with the inhibition basic criteria, it is reasonable that amino acids
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are considered as potential hydrate inhibitors. Kinetic and thermodynamic inhibiting behaviors of

amino acids on CO2 (Sa et al., 2011, 2013, 2015; Park et al., 2014), ethane (Rad et al., 2015),
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tetrahydrofuran (Naeiji et al., 2014), methane and natural gas hydrates (Sa et al., 2016;
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Bhattacharjee et al., 2016; Bavoh et al., 2017) have been investigated through experimental or
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molecular dynamic (MD) simulation. Most of studied amino acids are found to play a dual role of

both KHIs and THIs. Surprisingly, some amino acids generate the opposite kinetic effects to
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different gas hydrate formers. For example, histidine, as a better CO2 hydrate KHI (Sa et al., 2015),
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becomes a good kinetic promoter for methane hydrate (Bhattacharjee et al., 2016). Leucine and

glycine are reported to act as KHIs for THF and ethane hydrates (Rad et al., 2015; Naeiji et al.,

2014), while leucine kinetically promotes methane hydrates formation (Liu et al., 2015;

Veluswamy et al., 2016). Besides, the choice of the studied concentration unit may result in
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significant variations of the order of inhibition effect of amino acids, which is found to depend on

their molecular weight. Glycine has been suggested to have the weakest thermodynamic inhibition

impact on both methane and natural gas (93% CH4, 5% C2H6, 2% C3H8) hydrates among tested

alanine, proline, and serine on the bases of mol% (at 1.3 mol%) (Sa et al., 2016). In contrast, an

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opposite trend of inhibition impact is observed that the strongest thermodynamic inhibitor for

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methane hydrate is glycine at the same mass concentration of 10 wt% (on the bases of wt%),

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whose molecular structure is the simplest and molecular weight is the smallest among twenty

natural amino acids (Bavoh et al., 2017). The use of wt% unit is regarded more suitable for

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industrial applications. Like ionic liquids, amino acids have not been competitive enough to
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replace commercial THIs (alcohols). The highest average depression temperature of amino acids is
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relatively lower, about 1.78 K for glycine when used alone at 10 wt%, while 2.5-5 K for

commercial THIs at the same concentration (Bavoh et al., 2017).

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To improve the inhibition performance of single THIs or KHIs, mixtures of novel THIs with
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conventional THIs, or commercial KHIs, have been often proposed (Kim et al., 2011, 2014; Kang
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et al., 2013, 2016; Richard and Adidharma, 2013; Lee et al., 2016). Several mixtures of

conventional THIs (sodium chloride + ethylene glycol, NaCl + methanol, methanol+ ethylene
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glycol) have been examined (Mohammadi and Richon, 2009, 2010; Lafond et al., 2012; Najibi et
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al., 2013). A combination of ionic liquids with conventional THIs (ethylene glycol) as well as with

other ionic liquids provides a strong synergistic thermodynamic inhibition effect at high pressures

(Richard and Adidharma, 2013; Long et al., 2017). In view of this, the potential synergistic effects

between ethylene glycol and glycine on thermodynamic inhibiting methane hydrate formation are
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investigated, which have never been studied and understood. Additionally, using the

Clausius-Clapeyron equation, the hydrate dissociation enthalpy has been determined from the

measured phase equilibrium data of methane hydrate in the presence of 0.5 wt% ethylene glycol

+0.5 wt% glycine, 2.5 wt% ethylene glycol +2.5 wt% glycine, 5 wt% ethylene glycol +5 wt%

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glycine, 10 wt% ethylene glycol +10 wt% glycine, and 15 wt% ethylene glycol +15 wt% glycine

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solutions.

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2. Experimental section

2.1. Materials
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Methane gas with 99.99% molar purity is supplied from South China Special Gases Ltd., Co.
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Ethylene glycol (AR grade) and glycine is purchased from Sigma Aldrich, with mass purities of

99.8% and 99.7%, respectively. The details of the chemicals are shown in Table 1. They are used
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without further purification in this work. Ultra-pure distilled water with a resistivity of 18.25
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mΩ·cm-1 made in laboratory is used in all experiments. All samples are prepared by weighing on
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an electronic analytical balance with an accuracy of ±0.0001 g, and the uncertainty for mass

fraction is less than ±5.0×10-4.

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Table 1 List of chemicals used in this work.

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Chemical name Chemical structure Chemical formula
(g·mol-1)
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ethylene glycol C2H6O2 62.07

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glycine C2H5NO2 75.07

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2.2. Experimental apparatus

The experimental setup used in this work is illustrated in Fig.1. It can operate up to 25 MPa and

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within the temperature range of 253.15-383.15 K. The apparatus contains two same
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cylinder-shaped autoclave hydrate reactors that run simultaneously. Each reactor is made of 316
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stainless steel with an effective volume of 175 mL. Two platinum resistance (PT100)

thermometers and a CYD-200 pressure transducer connected with each reactor are used for
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temperature and pressure measurements with accuracies of ±0.1 K and ±0.02 MPa, respectively. A
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magnetic stirrer is located in each cell to agitate the samples. All reactors are immersed into a
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programmable-control thermostat that uses ethylene glycol as coolant. The changes of temperature

and pressures are recorded by a computer connected with an Agilent data acquisition system every
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10s.
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Fig. 1. Schematic diagram of the apparatus

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2.3. Experimental procedure

The so-called isochoric step-heating pressure search method (Tohidi et al., 2000; Li et al., 2011;
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Najibi et al., 2013; Cha et al., 2016; Su et al., 2016; Mohammad et al., 2016) is employed for
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determining the phase equilibrium data. The details have been described in our previous studies
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(Long et al., 2015; Long et al., 2017). Before a fresh experiment, each autoclave hydrate reactor is

firstly washed with distilled water several times and dried, and then filled with about 60mL of
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prepared aqueous solutions. The whole experimental apparatus is vacuumized and flushed with
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methane three times in order to remove the undesired atmosphere gases. At room temperature,
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each test cell is charged with methane and pressurized by a gas booster to the target initial pressure.

Later, the mixture is cooled down to 273.65 K at a cooling rate of 10 K/h. The stirrer is also started

at a speed rate of 800 rpm to achieve a sufficient mixing. When enough amount of formed hydrate

is detected with a dramatic pressure drop and an abrupt temperature increase, the mixture within

each reactor is step-heated to dissociate the hydrates. After the completion of the experiment, the
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system returns to the initial state. The phase equilibrium point is identified by determining the

intersection point of the cooling and heating curves on a pressure-temperature plot according to the

before mentioned procedure (see Fig. 2). The hydrate dissociation point is the point where the

slope of P-T curve changes sharply and represents the phase boundary between liquid-vapor (L-V)

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and hydrate-liquid-vapor (H-L-V) phases.

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Fig. 2. Typical pressure-temperature traces for determining the hydrate phase equilibrium data for
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methane in presence of 10 wt% ethylene glycol +10 wt% glycine. Black dots are calculated
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dissociation points.
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2.4. Hydrate suppression temperatures

A statistic method is used to calculate the average hydrate depression temperature (Richard and

Adidharma, 2013; Long et al., 2017).


∆ = ∑

 ∆ (1)

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where N is the number of data points and △Ti is the temperature difference between measure

hydrate phase equilibrium temperature in the presence of various inhibitors and pure water at the

same dissociation pressure Pi. The temperature in pure water T0,Pi is calculated by CSMGem

model (Sloan and Koh, 2008).

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2.5. Dissociation enthalpy of methane hydrates

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The hydrate molar dissociation enthalpy, △Hdiss, is defined as the heat required for hydrate

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decomposition and to release 1 mol of guest gas molecule, which can be represented with the

following equation:

CH4 + n H2O—> CH4· nH2O

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where n is hydrate number. △Hdiss can be directly determined by calorimeter measurement. An
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alternative but indirect method is to obtain △Hdiss through the Clausisus-Clpeyron equation on the
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basis of measured phase equilibrium data (Sloan and Koh, 2008).

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() ∆
=− (3)
(/) 
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where P, T, z, and R are the pressure, temperature, compressibility factor and universal gas

constant, respectively. z is calculated using the Peng-Robinson equation of state (Peng and
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Robinson, 1976).
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3. Results and discussion

3.1. Validation of Apparatus and Procedure

Firstly, to check the accuracy and reliability of the experimental apparatus and procedure, a

comparison of the hydrate phase equilibria for 10 wt% ethylene glycol + methane between this
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work and those data from Mohammadi and Richon (2010), Robinson and Ng (1985), and Haghighi

et al. (2009) has been carried out. The measured methane hydrate phase equilibrium conditions in

the presence of 10 wt% ethylene glycol aqueous solution are presented in Table 2 and Figure 3.

The comparison result indicates that no significant difference is observed and there is a favorable

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agreement in the values obtained in this work and those data reported in literature.

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Table 2 Hydrate dissociation data for methane in the presence of 10 wt% ethylene glycol aqueous

solutiona

T/K P/MPa
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277.7 4.98
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279.9 6.46

282.0 8.15
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283.7 9.96
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285.0 11.67
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Uncertainties u are u(T)= ±0.1 K and u(P)= ±0.02 MPa.
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Fig.3. Hydrate equilibrium curves obtained from the apparatus used in this work for methane in

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the presence of 10 wt% ethylene glycol along with data from literature for validation purposes. (□)

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This work; (■) Mohammadi and Richon (2010); (●) Robinson and Ng (1985); (▲) Haghighi et al.
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(2009).
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3.2. Hydrate equilibrium in the presence of mixed inhibitors of ethylene glycol and glycine
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To investigate the thermodynamic effect of mixture on hydrate formation, the methane

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hydrate phase equilibrium conditions are obtained in the presence of mixed ethylene glycol and

glycine using 1:1 mixtures at concentrations of 1wt% (0.5 wt% ethylene glycol +0.5 wt% glycine),
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5 wt% (2.5 wt% ethylene glycol +2.5 wt% glycine), 10 wt% (5 wt% ethylene glycol +5 wt%
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glycine), 20 wt% (10 wt% ethylene glycol +10 wt% glycine), and 30 wt% (15 wt% ethylene glycol
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+15 wt% glycine) in the pressure range of 4.78 to 12.20 MPa and temperature range of 273.3 to

287.8 K. Those measurement results are illustrated in Table 3 and Fig. 4. As shown in Fig.4,

compared with pure water system, the addition of mixture shifts the methane HLVE curves

towards lower temperature/higher pressure regions. The phenomenon can be explained in the way

that ethylene glycol, as a kind of traditional THIs, is well recognized to inhibits hydrate via
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disrupting water activity through hydrogen bonding. Glycine is surrounded by a strong

electrostatic field caused by NH3+ and COO- moieties of its zwitterionic structure, which results in

strong hydrogen bonding with water molecules and lowers the activity coefficient of water, thus

leading to thermodynamic inhibition. Due to smaller hydrophobic group and higher charge density

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in case of glycine, hydrogen bonding interaction increases. (Sa et al., 2016; Bavoh et al, 2017).

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MD simulation study also has ever revealed that the presence of amino acids can affect the

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reorientation behavior of water molecules during hydrate formation (Laage et al., 2011). Moreover,

the thermodynamic inhibition effect increases with increased concentrations. The effect of

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ethylene glycol and glycine on water activity increases as the inhibitors content in water increases,
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resulting in further reduction in bulk water reorientation dynamics, which is more unfavorable for
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hydrate formation.
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Table 3 Hydrate dissociation data for methane in the presence of mixed solution of ethylene glycol
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and glycinea
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T/K P/MPa

0.5 wt% ethylene glycol +0.5 wt% glycine

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279.7 5.05
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282.4 6.61

284.9 8.83

286.0 9.95

287.8 12.20
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2.5 wt% ethylene glycol + 2.5 wt% glycine

279.1 5.11

281.8 6.63

283.4 8.22

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285.2 10.03

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286.7 11.98

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5 wt% ethylene glycol + 5 wt% glycine

277.1 4.78

280.1
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282.4 8.22
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284.4 10.03

285.4 11.47
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10 wt% ethylene glycol + 10 wt% glycine

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274.7 4.88
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277.3 6.50

279.3 8.14
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281.0 9.81
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282.2 11.47

15 wt% ethylene glycol + 15 wt% glycine

273.3 4.81

275.1 6.33
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277.6 8.41

278.7 9.63

279.9 11.15

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Uncertainties u are u(T)= ±0.1 K and u(P)= ±0.02 MPa.

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Fig. 4. Phase equilibrium conditions of methane hydrate in the presence of 1:1 ethylene glycol +
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glycine mixture at various concentrations. (◄) 1 wt%; (▼) 5 wt%; (●) 10 wt%; (▲) 20 wt%; (■)

30 wt%; (○) pure water (Long et al., 2015).

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Table 4 Average suppression temperature of studied inhibitor solution systems

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Components △Tav/K

0.5 wt% ethylene glycol +0.5 wt% glycine (1 wt% mixture) 0.3

2.5 wt% ethylene glycol +2.5 wt% glycine (5 wt% mixture) 1.1

5 wt% ethylene glycol +5 wt% glycine (10 wt% mixture) 2.2

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10 wt% ethylene glycol +10 wt% glycine (20 wt% mixture) 5.2

15 wt% ethylene glycol +15 wt% glycine (30 wt% mixture) 7.2

5 wt% glycine (Bavoh et al., 2017) 1.0

10 wt% glycine (Bavoh et al., 2017) 1.8

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10 wt% ethylene glycol 2.7

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10 wt% ethylene glycol (Mohammadi and Richon, 2010) 2.6

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15 wt% glycine (Bavoh et al., 2017) 2.3

20 wt% glycine (Bavoh et al., 2017) 2.9

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Fig. 5. Temperature shifts △T calculated from experimental hydrate dissociation pressures for 1:1
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ethylene glycol + glycine with those for the individual components at the same concentration. (■)

1 wt% mixture (this work); (○) 5 wt% glycine ( Bavoh et al., 2017); (●) 5 wt% mixture (this work);

(◇) 5% ethylene glycol obtained from CSMGem model (Sloan and Koh, 2008); (▲) 10 wt%

mixture (this work); (△) 10 wt% ethylene glycol (Mohammadi and Richon, 2010); (☆) 10 wt%
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glycine (Bavoh et al., 2017); (▼) 20 wt% mixture (this work); (▽) 20 wt% ethylene glycol

(Mohammadi and Richon, 2010); (×) 20 wt% glycine (Bavoh et al., 2017); (◆) 30% mixture (this

work); (◄) 30 wt% ethylene glycol (Robinson and Ng, 1985).

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Following are quantitative analyses on inhibition efficiency by calculating trends of hydrate

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suppression temperature (△T) in the studied experimental conditions to better evaluate the

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synergistic effects of mixed inhibitors. The average △Tav calculated by Eq. 1 in the presences of

mixture at studied concentrations are presented in Table 4. Fig. 5 depicts the relationship of the

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dissociation pressure and calculated temperature shift of mixed solution at the mass concentrations
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of 1 wt%, 5 wt%, 10 wt%, 20 wt% and 30 wt% together with the individual components from
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literature for comparison. As illustrated in Fig. 5, similar to hydrate-inhibiting behavior of ethylene

glycol and glycine, the mixture system demonstrates relatively constant inhibition effectiveness
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throughout the studied pressure range (4-12MPa). At low concentration of 1 wt%, the magnitude
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of shift (△T) is very small or negligible, falling to 0.3 oC. Despite of lack of HLVE experimental
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data in the presence of 5 wt% ethylene glycol, the calculated temperature shift by CSMGem model

(Sloan and Koh, 2008) at the same pressures with 5 wt% mixture systems is provided and
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compared. At 5 wt%, △T for the mixture is almost equivalent to those for single glycine and
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ethylene glycol, with the close magnitude of 1.1 oC. It suggests that the partial substitution of

ethylene glycol by glycine can help reduce the environmental pollution from the large usage of

glycol inhibitors, without affecting thermodynamic inhibition effect. Additionally, based on HJ

505-2009 standards and GB/T 11914-1989 standards of China, the measurement of BOD5 and
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COD have been carried out. When the value of BOD5/COD is less than 0.20, the organic

compound in wastewater is usually considered as hardly biodegradable. When the organic

compound is completely utilized by the microorganism, the value of BOD5/COD is almost close to

0.6 (He et al., 2007). From the above point, BOD5/COD value of 5 wt% ethylene glycol was 0.28,

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which is not easy to be biodegraded. Biodegradability of 5wt% ethylene glycol plus 5 wt% glycine

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was 0.36. Glycine can improve the biodegradability of ethylene glycol by 22.2%. In the case of 30

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wt%, the mixture shows weaker inhibition efficiency than ethylene glycol, with magnitudes of 7.2

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C and 9.4oC, respectively. It is possibly associated with the solvation behavior of glycine in the

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mixed solvent of water and nonaqueous ethylene glycol. The solubility of glycine in alcohol-water
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binary solvent mixtures has been found to be less than in water, which attributes to partial
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dehydration of the hydration shells of glycine zwitterion and diol hydroxyl groups caused by

chemical interaction of solute molecules in aqueous medium (Korolev, 2012). It is negative to the
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inhibition performance of glycine. On the other hand, the reported saturated solubility of glycine in
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pure water at 298.15 K and under atmospheric pressure is 3.447 mol·kg-1. As a result of a
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preferential hydration in pure water, glycine shows a salting-out effect at mass concentrations

higher than 21 wt% (Hossain et al., 2017). So it is impossible to prepare 30wt% glycine for
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comparison. For 10 wt% and 20 wt%, △T is in the following decreasing order of magnitude:
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ethylene glycol > mixture > glycine. Moreover, for systems with 10 wt% and 20 wt% mixture, △T

is found to exceed the arithmetic mean of the temperature shifts for the individual components at

the same mixture inhibitor concentration, indicating the presence of synergistic inhibition effect

(Richard and Adidharma, 2013; Long et al., 2017). Despite of unwanted dehydration effect, this
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may because hydrophobicity of diol alkyl groups result in reinforcing hydrogen bonds between

water molecules surrounding these nonpolar groups. The cooperativity of hydrogen bonds

reinforces the interaction between water molecules in hydration layers and hydroxyl groups which

are combined with nonpolar groups in the diol molecule (Korolev, 2012). The hydrogen bonding

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between the H3N+ and COO− groups of α-amino acid and -OH groups of ethylene glycol possibly

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help strengthen the disruption of free water molecules. Further researches are necessary to

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investigate the synergetic mechanism between them existing in a certain concentration range.

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Fig. 6. Comparison of methane HLVE data in the presence of different inhibitors at 10 wt%. (■)
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mixture (this work); (*) ethylene glycol (this work); (□) glycine (Bavoh et al., 2017); (+) methanol
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(Mohammadi and Richon, 2010); (▽) [OH-Emim][Cl] (Li et al., 2011); (◇) [OH-Emmim][Cl]

(Long et al., 2015); solid line represent pure water (Long et al., 2015).

Fig. 6 compares the methane HLVE curves of mixed ethylene glycol and glycine with
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conventional thermodynamic inhibitors (methanol and ethylene glycol) from literature Robison

and Ng (1985), Mohammadi and Richon (2010), and Bavoh et al. (2017) and imidazolium-based

ionic liquids ([OH-Emim][Cl] and [OH-Emmim][Cl]) from literature Li et al. (2011) and Long et

al. (2015) at the same concentration of 10 wt%. The inhibition effect of mixture is found to be

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weaker than methanol, but almost close to ethylene glycol. It is clear from the plots that the

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performance of mixture working as methane hydrates inhibitor is slightly superior to ionic liquids

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and glycine. Despite of being more expensive than alcohols, amino acids are well known to be

more environmentally friendly and cheaper than ionic liquids, and most of amino acids and ionic

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liquids produce a little thermodynamic effect when applied alone at high concentrations.
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According to the comparison results, it can be inferred that amino acids can be used as synergists
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to enhance the inhibition performance when mixed with traditional thermodynamic inhibitors. It is

believed that the inhibition effect of mixture depends on the structures of amino acids and the
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mixing ratio between amino acids and alcohols. How does the synergy effect play and achieve
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maximum in suppressing the hydrate equilibrium? -will be discussed in the next researches.
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3.3. Dissociation enthalpy of methane hydrates

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As described in the methodology, the HLVE P-T data listed in Tables 2 and 3 are plotted as ln P
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versus 1/T. Theses curves exhibit linear trends that show satisfactory correlation coefficients (R2)

in Fig. 7. The average molar dissociation enthalpies △Hdiss of methane hydrate in studied inhibitors

and pure water are calculated and presented in Table 5. It is clear from Table 5 that the value of

△Hdiss for methane hydrates in 10 wt% ethylene glycol this work is in favorable agreement with that
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obtained from literature. It is noted that these slight differences in △Hdiss values can be related with

small uncertainty in measured equilibrium values, which can result in large errors in calculation of

compressibility factor z and d(ln P) / d(1/T). But no significant difference happens between the

average values of △Hdiss in the presence of the mixture of ethylene glycol and glycine and that for

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pure water. Similar values of △Hdiss indicate that the hydrate structure and guest occupancy of

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methane hydrate formation in the presence of mixed inhibitors is similar to the simple methane

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hydrate, and only sI methane hydrate is formed in the studied systems. It is also inferred that most

of the thermal energy is consumed to break down the hydrogen-bonded network formed by water

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molecules present in hydrate phase. In the similar pressure and temperature range, the slight
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difference in the △Hdiss values is consistent with the trends of △T and concentration.
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Fig. 7. Plots of lnP versus 1/T for methane hydrate in absence and presence studied inhibitors. (◇)

pure water (Long et al., 2015); (●) 1% mixture; (△) 5 wt% mixture; (○) 10 wt% mixture; (◄) 20

wt% mixture; (■) 30 wt% mixture; (□) 10 wt% ethylene glycol. Solid lines represent the regressed

curves by a modified correlation equation of lnP=A+B*(1/T)

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Table 5 Clausius-Clapeyron calculated molar dissociation enthalpies of methane hydrate in the

absence and presence of ethylene glycol and mixed aqueous solutions with glycine at studied

conditions in this work

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△Hdiss
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Components P/MPa T/K slope R

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/kJ·mol-1

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pure water (Long et al., 2015) 3.40−13.27 275.8−288.5 −8505.42 0.996 59.82

10 wt% ethylene glycol (Mohammadi and

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4.00−9.93 275.5-283.4 -8256.37 0.995 57.51
Richon, 2009)
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10 wt% ethylene glycol 4.98−11.67 277.7−285.0 -9108.12 0.999 62.13
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0.5 wt% ethylene glycol + 0.5 wt% 5.05−12.20 279.7−287.8 -8781.43 0.999 60.05

glycine
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2.5 wt% ethylene glycol + 2.5 wt% 5.11-11.98 279.1−286.7 -9012.08 0.995 65.34
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glycine
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5 wt% ethylene glycol + 5 wt% glycine 4.78−11.47 277.1−285.4 -8274.44 0.998 56.56

10 wt% ethylene glycol + 10 wt% glycine 4.88−11.47 274.7−282.2 -8720.51 0.998 59.09
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15 wt% ethylene glycol + 15 wt% glycine 4.81−11.15 273.3−279.9 -9555.39 0998 64.44
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4. Conclusions

In this work, dissociation measurements for methane hydrate in the presence of 0.5 wt%

ethylene glycol +0.5 wt% glycine, 2.5 wt% ethylene glycol +2.5 wt% glycine, 5 wt% ethylene
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glycol +5 wt% glycine, 10 wt% ethylene glycol +10 wt% glycine, and 15 wt% ethylene glycol +15

wt% glycine solutions have been performed by using an isochoric step-heating pressure search

method in the pressure and temperature ranges of 4.81-12.20 MPa and 273.3-287.8 K, respectively.

The combined inhibitor having 1:1 weight ratio ethylene glycol with glycine demonstrates a

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progressive thermodynamic inhibition effect as the concentration increases. Like ethylene glycol

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and glycine, the pressure has no significant effect on the inhibition of their mixtures. A comparison

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between the depression temperature for the mixture and the arithmetic mean of the temperature

shifts for the individual components presents that a synergistic thermodynamic inhibition effect

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occurs in systems with 5 wt% ethylene glycol + 5 wt% glycine and 10 wt% ethylene glycol + 10
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wt% glycine, suggesting the potential of glycine applicable for industrial application as an
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excellent inhibition synergist. The mixture system of 1:1 ethylene glycol + glycine exhibits a

stronger inhibition impact than ionic liquids at the same concentration. Furthermore, calculated
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methane molar dissociation enthalpies in the presence of the mixed aqueous solutions indicate that
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the interaction between ethylene glycol and glycine does not affect the hydrate structure.
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Acknowledgements

This work was supported by the National Natural Science Foundation of China (Grant Nos.
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51506202, 41374149, 41276043), and Scientific cooperative project by CNPC and CAS (Grant No.
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2015A-4813).

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►The phase behavior of methane hydrate with ethylene glycol and glycine is studied.

►Glycine has weaker inhibitory effect than glycol while can act as a good synergist.

► Adding glycine can improve biodegradability of ethylene glycol.

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