J. Chem.

Thermodynamics 117 (2018) 48–53

Contents lists available at ScienceDirect

J. Chem. Thermodynamics
journal homepage: www.elsevier.com/locate/jct

The impact of amino acids on methane hydrate phase boundary and

formation kinetics
Cornelius B. Bavoh a,b, Omar Nashed a,b, Muhammad Saad Khan a,b, Behzad Partoon a,b, Bhajan Lal a,b,⇑,
Azmi M. Sharif a,b
a
Chemical Engineering Department, Universiti Teknologi PETRONAS, 32610 Bandar Seri Iskandar, Perak Darul Ridzuan, Malaysia
b
CO2 Research Centre (CO2RES), Universiti Teknologi PETRONAS, Bandar Seri Iskandar, 32610 Perak, Malaysia

a r t i c l e i n f o a b s t r a c t

Article history: The thermodynamic and kinetic effects of two amino acids (valine and arginine) on methane hydrate for-
Received 25 April 2017 mation was evaluated by measuring the dissociation temperature of methane hydrate in the range of 4.5–
Received in revised form 31 August 2017 10 MPa using the T-cycle method. The kinetics of methane hydrate formation was evaluated at 7.1 MPa
Accepted 1 September 2017
and 274.15 K. The experiments were conducted at concentrations of 0.01 and 0.05 mass fraction. Both
Available online 9 September 2017
amino acids showed a slight inhibition effect on the phase boundary of methane hydrate. The predicted
methane hydrate phase boundary data in the presence of amino acids was strongly correlated with the
Keywords:
experimental data with R = 0.9996 and an AAE less than 0.15 K. However, these amino acids also showed
Gas hydrate
Amino acids
hydrate formation rate enhancement compared to pure water. In addition, the total methane uptake at
Equilibrium phase boundary the end of the experiments was increased in the presence of these amino acids.
Kinetics Ó 2017 Elsevier Ltd.
Methane

1. Introduction
Gas hydrate are formed by the physical trapping of appropriate
gas molecules (such as methane, carbon dioxide etc.) in hydrogen
bonded water cages at lower temperatures and higher pressures
conditions. The gas molecules are held in the water molecules by
Van der Waal forces [1,2]. In oil and gas flow assurance, the forma-
tion of gas hydrate is unwanted, because it can lead to plugged
pipelines which consequently provoke high removal expense, stop-
page in production and in severe scenarios, the possible loss of
human life [3]. Generally, gas hydrates inhibitors and promoters
are the two main kinds of gas hydrate chemical additives [4–6] that
are usually applied to affects gas hydrate formation either thermo-
dynamically (by shifting the hydrate phase boundary conditions)
and/or kinetically (by delaying/enhancing the hydrate nucleation
and growth process) based on the required area of application.
Gas hydrate inhibitors are employed to mitigate gas hydrate
formation in pipelines. There are two main classes of gas hydrate
inhibitors: thermodynamic hydrate inhibitors (THIs) and low
dosage hydrate inhibitors (LDHIs). THIs are usually alcohol-based
(methanol and glycols) that inhibit hydrate formation by increas-
ing the hydrate free regions through the shifting of the hydrate
phase boundary conditions to higher pressures and/or lower tem-
⇑ Corresponding author at: Chemical Engineering Department, Universiti Tekno-
logi PETRONAS, 32610 Bandar Seri Iskandar, Perak Darul Ridzuan, Malaysia.
E-mail address: bhajan.lal@utp.edu.my (B. Lal).
peratures. However, THIs are volatile in nature and are applied in
huge quantities (up to over 0.4 mass fraction) [2,7,8], which makes
them expensive and environmentally unfriendly. LDHIs are mostly
polymers (PVP and PVCap) and are used in lower concentrations
(<0.02 mass fraction). They typically delay hydrate nucleation pro-
cess and/or total gas consumed in hydrate formation [1,9]. How-
ever, there is ongoing research for new and effective gas hydrate
chemical inhibitors to replace existing ones. Such research out-
comes would aid in an efficient application of gas hydrate based
technologies.
Recently, natural amino acids have been introduced as gas
hydrate inhibitors due to their zwitterionic behavior in water
and hydrogen bonding affinity for water molecules. Sa et al.
[10,11] reported that, in the concentration range of 0.001–
0.09 mol fraction, amino acids such as glycine, alanine, proline,
valine, and serine could thermodynamically inhibit methane and
carbon dioxide hydrate formation. Proline and valine were found
to show the highest inhibition impact for methane and carbon
dioxide hydrate, respectively. On the other hand, on the bases of
mass fraction, glycine has been reported to thermodynamically
inhibit methane hydrates better than alanine, proline, serine, and
arginine at 0.1 mass fraction [12]. Further study by Sa & co-
workers [13,14], showed that amino acids kinetically reduce car-
bon dioxide consumption compared to pure water via local water
perturbation. Since then, several studies [15–17] have also shown
that amino acids kinetically inhibits ethane and THF hydrates.
Most recently, Liu et al. [18] studied the effect of natural amino

http://dx.doi.org/10.1016/j.jct.2017.09.001
0021-9614/Ó 2017 Elsevier Ltd.
 C.B. Bavoh et al. / J. Chem. Thermodynamics 117 (2018) 48–53 49

Nomenclature

AAE average absolute error m number of data points

T temperature, K R universal gas constant, 8.314 J/(mol.K)
Tf(i) freezing point temperatures of water, 273.15 K DHFUS(i) heat of fusion of ice, 6008 J/mol
Tf freezing point temperatures of aqueous amino acid
solution, K Subscripts
P pressure, MPa aa amino acid
n hydration number, 6.0 w water
DHd dissociation enthalpy, kJ/mol Cal. calculated
a activity Exp. experimental

Table 1 Due to the requirement for new effective gas hydrate additives,
Chemical structures and details of studied amino acids. more understanding of the effect of amino acids on gas hydrate for-
mation is need. There are some amino acids whose thermodynamic
Amino Chemical structure Purity Supplier
acid and kinetic effect on gas hydrate formation have not been widely
studied. In addition, there is limited study on the prediction of gas
Arginine P 99% Sisco Research
Laboratories Pvt. Ltd
hydrate equilibrium phase boundary conditions in the presence of
amino acids. Thus, it is motivating to study the effect of such amino
acids on methane hydrate formation. Herein, the thermodynamic
Valine P 98% Sigma-Aldrich effect of arginine and valine on the methane hydrate equilibrium
phase boundary is predicted by adapting an existing model.

2. Experimental

acids as CH4 hydrate promoters at concentrations less than 0.01
mass fraction. They found that, leucine exhibited the highest pro-
motion effect. Their findings motivated Veluswamy et al. [19] to
further study the morphological changes mediated by leucine dur-
ing methane hydrate formation nucleation, growth and dissocia-
tion. They suggested that, no hydrate promotion was observed
below 0.003 mass fractions. In addition, Bhattacharjee et al. [20]
reported that, histidine (a polar amino acid) promotes methane
hydrate growth in the same range as SDS at 0.01 mass fraction.
However, histidine has also been reported as a kinetic inhibitor
for carbon dioxide hydrates [14,21], indicating that, the kinetic
inhibition and promotion effects of amino acids are dependent
on the type of guest molecules present.
2.1. Materials
The chemical structures and details of the amino acids used in
this study are shown in Table 1. All chemicals were used without
further purification. Methane gas with purity of 99.995% was sup-
plied by Gas Walker Sdn Bhd, Malaysia. All samples were prepared
using deionized water.
2.2. Apparatus and procedures
A hydrate sapphire cell rector as illustrated in Fig. 1 was used
for both hydrate equilibrium point and kinetic measurements. In
order to measure the hydrate equilibrium points, the isochoric

Fig. 1. Schematic diagram of the experimental setup.

50 C.B. Bavoh et al. / J. Chem. Thermodynamics 117 (2018) 48–53

T-cycle method [4] was employed. 18 ml of 0.05 mass fraction point temperatures of water (273.15 K) and water + aqueous amino
desired aqueous amino acid solution was pumped into the cell acid solution. Tf is calculated as suggested by Dickens and Quinby-
via a manual hand pump. A gas booster was then used to supply Hunt [28] using cryoscopic constant for water as 1.853 Kkg/mol.
the cell with methane at the desired pressure. When the system Hence, combining Eqs. (1) and (2), relates the temperature offset
stabilized, the magnetic torque stirrer was switched on, and the of methane hydrate phase condition and the temperature of the
system temperature reduced to 274.15 K (at 4 K/hr) to allow ice-water equilibrium condition in any amino acid solution at con-
hydrate formation. The hydrate formation is detected both visually stant pressure as follows;
and via observation by a rapid pressure drop in the system. When


hydrates were formed, the system temperature was first heated 1 1 nDHFUSðiÞ 1 1
 ¼  ð3Þ
fast (at 4 K/hr) to about 5 K close to the desired dissociation tem- T w T aa DHd T f ðiÞ T f
perature and then heated stepwise for 3 h at intervals of 0.5 K/step Therefore, Eq. (3) can be used to calculate Taa, the hydrate for-
[22–24]. The details of the experimental apparatus and procedures mation temperature in the presence of amino acids. The model’s
employed are previously reported elsewhere [12,25,26]. average absolute error (AAE) is calculated using Eq. (4).
To perform the kinetic measurements, the cell was cleaned, vac-
uumed and loaded with 18 ml of the desired aqueous amino acids. 1X m

The cell was then pressurized with methane to 7.1 MPa, and the AAE ¼ jT Exp:  T Cal: ji ð4Þ
m i¼1
stirrer is turned on. The system temperature was reduced to the
experimental temperature (4 K/hr) for hydrate to form simultane-
ously with the data acquisition system recoding the changes in
pressure and temperature of the system (every 10 s). The experi- 4. Results and discussion
mental temperature for all kinetic experiments were fixed at
274.15 K. The experiments were considered completed by observ- 4.1. Thermodynamic effect
ing a constant pressure and temperature in the cell for 2–3 h. The
induction time was determined as described in literature [26]. To The measured methane hydrate equilibrium boundary points in
calculate the moles of methane consumed, the real gas equation the presence of the amino acids are tabulated in Table 2 and graph-
was used with the compressibility factor, z, calculated from ically presented in Fig. 2. The presence of arginine and valine shifts
Peng–Robinson equation of state. The initial apparent rate constant the methane hydrate equilibrium phase boundary to higher
was determined by finding the gradient of the plot of calculated
methane mole consumed verses time [27]. Table 2
The experimental and predicted methane dissociation temperature (Ta) and pressure
(Pa) of amino acids at 0.05 mass fraction.
3. Model theory
Amino acid TExp/K TCal/K P/MPa
To predict the methane hydrate equilibrium phase points in the Arginine 278.80 278.61 4.55
presence of arginine and valine, the model by Dickens and Quinby- 281.30 281.19 6.15
Hunt [28] for electrolytes was adopted since most aqueous amino 283.30 283.22 7.50
285.90 285.89 9.84
acids show zwitterionic behavior. This zwitterionic behavior
makes them exhibit electrostatic behavior similar to normal elec- Valine 278.60 278.52 4.60
281.40 281.31 6.20
trolytes (salts) [29]. The model is a modification of the Pieroen 283.00 282.80 7.58
[30] model and has been previously adapted for modelling the 285.80 285.69 9.65
effect of electrolytes and ionic liquid solutions on the methane a
Standard uncertainties (U) are U(T) = ±0.15 K, U(P) = ±0.01 MPa, U(mass frac-
hydrate phase boundary by Javanmardi et al. [31,32] and Partoon
tion) = ±0.0003
et al. [4], and was developed from classical thermodynamic theory.
It assumes that, the amount of methane in the water phase is neg-
ligible, and vice versa. Also, the effect of arginine and valine on 11
methane hydrate formation solely decreases water activity (aw)
and at small temperature ranges, the hydrate enthalpy of dissocia-
10
tion (DHd) is constant. The derivation details are provided by Dick-
ens and Quinby-Hunt [28] and Pieroen [30].
Based on this model, the effect of amino acid on the methane 9
hydrate formation temperature can be represented as;
Pressure / Mpa

 8
DHd 1 1
In aw ¼  ð1Þ
nR T w T aa
7
where,

 6
DHFUSðiÞ 1 1
In aw ¼  ð2Þ
R T f ðiÞ T f
5
where aw represents water activity, DHd denotes the dissociation
enthalpy of methane (58.88 kJ/mol [22]), n is methane hydrate 4
hydration number (6.0 [33]), R is the universal gas constant, and 278 279 280 281 282 283 284 285 286 287
Tw and Taa are the hydrate formation temperatures in pure water
Temperature / K
and water + amino acid solution. The pure water methane hydrate
dissociation temperature can be calculated by any hydrate predic- Fig. 2. Methane hydrate equilibrium phase boundary in the presences of amino
tion model as described in literature [9] or CSMGem. DHFUS(i) is acids: (d) Pure water this wok, (s) Pure water Sabil et al. [2], ( ) Arginine, ( )
the heat of fusion of ice (6008 J/mol), Tf(i) and Tf are the freezing Valine.
 C.B. Bavoh et al. / J. Chem. Thermodynamics 117 (2018) 48–53
11
10
Pressure / Mpa
7
6 20
5
4
278 280 282 284 286
Temperature / K
Fig. 3. Experimental and predicted methane hydrate equilibrium phase boundary
in the presences of amino acids: (d) Pure water this wok, (s) Pure water Sabil et al.
[2], ( ) Arginine, ( ) Valine, ( ) Arginine predicted, ( ) Valine predicted.
pressures and lower temperatures regions. An average methane
hydrate equilibrium temperature shift of about 0.5 K is observed,
suggesting a thermodynamic methane hydrate inhibition effect.
There was a minor inhibition impact (Fig. 2) likely because the
amino acids are tested at low concentration (0.05 mass fraction)
compared to concentrations of known THIs (>0.15 mass fraction)
used in academic laboratories and industrial applications. The inhi-
bition mediated by both arginine and valine was found to be in the
same range, with valine slightly higher than arginine. It is possible
that the thermodynamic inhibition impact of arginine and valine is
due to their ability to form hydrogen bonding with water mole-
cules [11], and therefore influences the activity of water to com-
pete in hydrate formation. This findings further extends and
supports the study of Sa et al. [11] and Bavoh et al. [12] on amino
acids as THIs for methane hydrate formation. Furthermore, the
slight inhibition impact of valine over arginine could be due to
their side chain alkyl length and properties [12]. This resulted in
a slight improvement of the miscibility of valine with water.
The proposed model was then used to predict the impact of
arginine and valine on the methane hydrate and for comparison
with the equilibrium phase condition point. The predicted and
experimental methane hydrate equilibrium points are presented
in Fig. 3. As shown in Fig. 3, the model predictions are in good
agreement with the experimental data with an AAE of 0.09 K and
0.12 K for arginine and valine, respectively. In addition, a very
strong correlation (R = 0.9996 at 95% confidence level) was
observed between the experimental and predicted hydrate dissoci-
ation temperatures. This further validates the accuracy of the
model and thus, supports the used of the model in predicting the
hydrate phase behavior in amino acids.
4.2. Kinetic effect
The induction time, initial apparent rate of hydrate formation
and the total methane moles consumed are studied as kinetic inhi-
bition indicators. Since kinetics studies of gas hydrate is probabilis-
tic, the experiments were repeated two times to ensure
repeatability of the experimental results. Induction time was used
to evaluate the effect of amino acids on the methane hydrate
nucleation process until a detectable hydrate is formed. The induc-
tion time in this study is determined as described in literature [26].
Valine showed a longer induction time than pure water. However,
51
60
50
Induction time / min
40
30
10
288
0
Arginine Valine SDS
Fig. 4. The induction time of methane hydrates in the presence of arginine, valine
and SDS; the solid line represents pure water sample.
the induction time of arginine and water were found to be in the
same range as shown in Fig. 4. The effect of arginine and valine
on the initial rate of hydrate is estimated and illustrated in Fig. 5.
Interestingly, both arginine and valine delayed the rate of hydrate
formation compared to pure water. Valine showed the highest
methane hydrate formation rate reduction, as it could delay the
hydrate formation rate about 3 times more than arginine and 6
times more than pure water.
Due to the stochastic nature of hydrate induction time mea-
surements, the use of induction time alone can sometimes be mis-
leading. Therefore, the total methane moles consumed was used to
further investigate the effects of arginine and valine on methane
hydrate formation. The total methane consumed is taken as the
point where the system pressure became stable after hydrate for-
mation. However, in most cases, the stability of the system pres-
sure in hydrate formation is either due to kinetic or
thermodynamic constrains. The hydrate formation stability or con-
stant pressures of all experiments were found to be above the
hydrate equilibrium pressure of the experimental temperature
(274.15 K) as shown in Fig. 6. This suggests that, the hydrate for-
mation stability or completion is not due to thermodynamic con-
straints but rather, on kinetics. The influence of 0.01 mass
fraction of arginine and valine on the total moles of methane con-
sumed is presented in Fig. 7. Contrary to the thermodynamic inhi-
bition effect (shown in Fig. 2), it is observed in Fig. 7 that, the
Pure water
Arginine
Valine
SDS
0 0.02 0.04 0.06 0.08 0.1 0.12
Initial apparent rate of formation / min-1
Fig. 5. The initial apparent rate of methane hydrate formation in the presence of
arginine, valine and SDS.
52 C.B. Bavoh et al. / J. Chem. Thermodynamics 117 (2018) 48–53

6
Pressure / Mpa

Fig. 8. Pictures of produced methane hydrate from pure water, arginine, valine, and
2
SDS during hydrate growth.
272 274 276 278 280 282 284
Temperature / K which according to Sa et al. [13], a hydrate kinetic promotion
impact is sometimes exhibited as amino acids side chain alkyl
Fig. 6. The hydrate formation stability pressures of all experiments in this work
against methane hydrate equilibrium condition: (d) Pure water run 1, (s) Pure
length increases. Also, the longer alkyl side chains of amino acids
water run 2, ( ) Arginine run 2, ( ) Arginine run 2, ( ) Valine run 2, ( ) Valine make them good candidates to develop bio-surfactants. Thus, just
run 2, ( ) SDS run 1, ( ) SDS run 2. like surfactants (e.g. SDS) effect on hydrate formation, arginine
and valine may restrict the aggregation of hydrate at the liquid –
vapor interface during hydrate formation. This facilitates the
0.025 movement of more methane into the liquid phase, therefore,
increasing the moles of methane in hydrate formation [27]. This
mechanism is supported by the visual observation made during
hydrate formation until completion (see Fig. 8). In all experiments
0.02
containing arginine, valine, and SDS it was visual observed that, the
stirrer in the cell continue to rotate till completion. Whereas in
Methane consumed / mole

experiments without additives, the stirrer stops rotating upon

0.015
0.01
0.005
0
0 100 200 300 400
Time / min
Fig. 7. Mole of methane consumed during hydrate growth: (d) Pure water (
Arginine, ( ) Valine, ( ) SDS.
presences of arginine and valine significantly increased the total
moles of methane consumed compared to pure water. However,
valine showed the highest impact on methane hydrate promotion.
Valine enhanced methane hydrate formation about 10 times more
than water. The surprising contrasting behavior of arginine and
valine on the thermodynamics and kinetics of methane hydrate
formation is similar to methanol (a commercially used thermody-
namic hydrate inhibitor). Methanol is well known as a good ther-
modynamic hydrate inhibitor, however several studies [34] have
shown that, methanol sometimes kinetically promotes hydrate for-
mation depending on the applied concentration [35].
The methane hydrate kinetic promotion behavior of arginine
and valine is similar to the mechanism of surfactants [18,36]. In
addition, both arginine and valine have longer alkyl side chains,
hydrate formation at the liquid/water interface, suggesting hydrate
aggregation suppression behavior as the possible cause of the
methane hydrate promotion effect in arginine and valine. In addi-
tion, the observed promotion variation of arginine and valine is
attributed to their different side chain properties. The higher
methane hydrate promotion of valine than arginine is because,
the methyl R-groups in valine can become incorporated as guests
in hydrate cages [37]. This could provide some stability for hydrate
formation, hence result in higher hydrate formation than arginine.
The surprising high methane hydrate kinetic promotion effect
of arginine and valine observed in this study is further compared
500 600 with SDS (a commercial hydrate promoter) as shown in Figs. 4, 5,
and 6. On the bases on induction time, arginine and valine per-
formed poorly as methane hydrate formation nucleation promot-
) ers in comparison with SDS (see Fig. 4). On the other hand, the
impact of SDS on the initial rate of methane hydrate formation is
in the same range as arginine (see Fig. 5). However, both arginine
and valine were found to promote methane hydrate uptake more
than SDS as shown in Fig. 7. The average methane consumed in
the hydrate in the presence of valine is 1.3 times that of SDS. This
results agrees with Bhattacharjee et al. [20] suggesting that, the
impact of some amino acids (Histidine) on the total moles of
methane consumed are in the range with SDS. Furthermore, the
methane promotion effect of valine agrees with the findings of Per-
feldt et al. [38] who suggested that valine does not kinetically pro-
mote methane hydrate formation.
5. Conclusions
The effect of arginine and valine on the thermodynamics and
kinetics of methane hydrate formation is studied in an isochoric
 C.B. Bavoh et al. / J. Chem. Thermodynamics 117 (2018) 48–53
high pressure sapphire cell reactor. It was found that both arginine
and valine thermodynamically inhibits methane hydrate formation
by shifting the phase boundary to higher pressures and lower tem-
peratures region. An average dissociation temperature shift of
0.5 K is observed in the presence of both arginine and valine. Fur-
thermore, the predicted and experimental methane hydrate equi-
librium phase temperature were in good agreement with an AAE
of less than 0.15 K. In contrary to the thermodynamic inhibition
effect, both arginine and valine kinetically enhanced the total mole
of methane consumed compared with pure water and SDS (i.e.
kinetic methane hydrate promotion effect). Valine showed the
highest average methane hydrate promotion impact of about 10
and 1.3 times higher than pure water and SDS. The findings in this
study should be useful for gas hydrate based technological applica-
tion research such as flow assurance and gas transportation and
storage.
Acknowledgement
This work is support by the Universiti Teknologi PETRONAS
through FRGS Research grants (Grant No. FRGS-0153AB-K77) from
the Ministry of Higher Education, Malaysia.
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JCT 17-342