Accepted Manuscript

Title: Experimental and theoretical investigation of methane

hydrate induction time in the presence of triangular silver
nanoparticles

Authors: Mahboubeh Rahmati-Abkenar, Mehrdad

Manteghian, Hassan Pahlavanzadeh

PII: S0263-8762(17)30117-X
DOI: http://dx.doi.org/doi:10.1016/j.cherd.2017.02.023
Reference: CHERD 2586

To appear in:

Received date: 20-11-2016

Revised date: 5-2-2017
Accepted date: 20-2-2017

Please cite this article as: Rahmati-Abkenar, Mahboubeh, Manteghian, Mehrdad,

Pahlavanzadeh, Hassan, Experimental and theoretical investigation of methane hydrate
induction time in the presence of triangular silver nanoparticles.Chemical Engineering
Research and Design http://dx.doi.org/10.1016/j.cherd.2017.02.023

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 Experimental and theoretical investigation of methane hydrate induction time in the

presence of triangular silver nanoparticles

Mahboubeh Rahmati-Abkenar, Mehrdad Manteghian*, Hassan Pahlavanzadeh

Faculty of Chemical Engineering, Tarbiat Modares University, Tehran, Iran.

Abstract

Low formation rate of hydrates has restricted their industrial applications; however, new

promoters could be introduced as appropriate solutions. In this study, the nucleation of the

methane hydrate was theoretically and experimentally investigated in the presence of triangular

silver nanoparticles in an aqueous solution (4.5, 9, 18, 27 and 36 M) at initial pressures of 4.5,

4.8, 5, 5.3 and 5.5 MPa and temperatures of 275.15 and 276.15 K. The results revealed that these

nanoparticles reduced the induction time up to 97% in comparison with pure water. All of the

obtained data were put into the Kashchiev-Firoozabadi model; however, the calculated error was

not acceptable. As a result, a new model for calculating induction time in the presence of

nanoparticles was carried out. The average absolute deviation between measured and predicted

induction time was 13.82%. The methane hydrate/solution effective interfacial tension in the

presence of nanoparticles according to heterogeneous nucleation was estimated. The model

represented that increase in nanoparticles concentration contributes to declining of effective

interfacial tension of methane hydrate/solution.

Keywords: Methane hydrate; Silver nanoparticles; Induction time; Interfacial tension.

*
E-mail: manteghi@modares.ac.ir
Graphical Abstract
Highlights
Triangular silver nanoparticles reduce the induction time of methane hydrate severely.
A new model for calculation of the induction time in the presence of nanoparticles is
presented.
The hydrate/solution interfacial tension in the presence of silver nanoparticles is
estimated.
Nomenclature

A Kinetic factor (m-3s-1)

An Average surface area of nanoparticles (m2)
ah Cross sectional area of a hydrate building unit (m2)
b Dimensionless shape factor
C Numerical shape factor
Cn Concentration of nanoparticles (M)
Def Diffusion coefficient (m2/s)
G Growth rate (m/s)
J Nucleation rate (m-3s-1)
K Kinetic parameter (s)
k Boltzmann constant
kg Additive constant related to growth sites (M-1)
kg' Effective growth factor coefficient (m)
kn Additive constant related to nucleation sites (M-1)
kn' Effective nucleation factor coefficient (m)
m A number related to growth
Np,g Number of growth sites (#/mole)
Np,n Number of nucleation sites (#/mole)
nw Hydration number
P Pressure (MPa)
T Temperature (K)
ti Induction time (s)
Vn Average volume of nanoparticles (m3)

Greek letters
b Fraction of crystalized hydrate
Supersaturation
Sticking coefficient
hydrate/nanoparticle wetting angle (degree)
Interfacial tension (J/m2)
Volume (m3)
Fugacity coefficient

1 Introduction

Gas hydrates are formed by Van der Waals binding between water and small gas molecules

trapped in the cavities of water molecules under specific conditions (Sloan, 2003; Sloan and

Koh, 2007). Generally, Gas hydrates have potential for many industrial applications since

providing an applicable mechanism for gas storage and transportation, although low rate of their

formation is a challenging issue for using in industries (Sloan, 2003). Several methods such as:
applying ultrasonic (Park and Kim, 2013), and magnetic fields (Shu et al., 2004) and addition of

surfactants (Ganji et al., 2007a; Ganji et al., 2007b; Lin et al., 2004; ZareNezhad et al., 2014;

Zhang et al., 2004; Zhang et al., 2007; Zhong and Rogers, 2000) have been developed in order to

enhance hydrate formation rate. Various porous media such as mesoporous silica, porous glass

and carbon were studied to investigate pore effect on the methane, ethane and carbon dioxide

hydrate equilibrium conditions (Anderson et al., 2003; Pan et al., 2013; Uchida et al., 2002; Wei

et al., 2016).

Recently, some researchers have focused on nanofluids to improve the hydrate formation rate

and storage capacity (Arjang et al., 2013; Li et al., 2006; Mohammadi et al., 2014;

Pahlavanzadeh et al., 2016; Park et al., 2012; Park et al., 2010; Pasieka et al., 2013). Li and

coworkers indicated that employing of copper nanoparticles improves the heat and mass transfer

processes of HFC134a hydrate formation (Li et al., 2006). Using spherical silver nanoparticles

promoted the methane hydrate formation and storage capacity as well as reducing the induction

time (Arjang et al., 2013). Studies on multi-walled carbon nanotubes and oxidized carbon

nanofluids demonstrated a remarkable improvement in gas consumption during formation of

methane hydrate (Park et al., 2012; Park et al., 2010). Employing water-based copper nanofluids

increased the amount of methane in hydrate formation (Pahlavanzadeh et al., 2016). Addition of

sodium dodecyl sulfate and spherical silver nanoparticles significantly increased the storage

capacity of carbon dioxide.

In this study the induction time of methane hydrate in the presence of triangular silver

nanoparticles was measured. A kinetic expression for induction time based on Kashcheiv-

Firoozabadi (Kashchiev and Firoozabadi, 2003) model in the presence of nanoparticles was

presented. Since nucleation of hydrate is an interfacial phenomenon, interfacial properties such

as interfacial tension of gas hydrate and liquid may greatly affect the hydrate nucleation rate. So

the hydrate interfacial tension in the presence of silver nanoparticles was determined.

2 Material and methods

2.1 Materials

Hydrazine hydrate (N2H4.H2O), tri-sodium citrate dihydrate (C6H5Na3O7.2H2O) and silver nitrate

(AgNO3) were purchased from Merck, Merck and PanReac AppliChem, respectively. Methane

with purity of 99.9% was supplied from Varian Gas. De-ionized water was used in all

experiments. Aqueous solutions were prepared using an analytical balance with an accuracy of

0.1 mg.

2.2 Apparatus

The schematic diagram of the experimental apparatus is shown in Figure 1. The volume of

jacketed reactor is 460 cm3. An electromotor was used for mixing of the gas and aqueous

solution and cooling process of the system was done by mixture of water and ethylene glycol

which was circulated in the jacket of the reactor. A platinum resistance thermometer, PRT within

precision of 0.01 K and a BD pressure transducer within precision of 0.01 MPa inserted in the

reactor were used for measurement of temperature and pressure, respectively. Reactors

temperature and pressure were recorded in a desktop computer. In addition, the reactor was

evacuated by a JB Platinum vacuum pump.

 Figure 1 Schematic diagram of the experimental setup.

2.3 Synthesis of triangular silver nanoparticles

Silver nanoparticles were fabricated based on Ghaders procedure (Ghader et al., 2007). Briefly,

the mixture of 100 ml of silver nitrate (0.1 mM) and 5 ml of tri-sodium citrate dihydrate (34 mM

(1 wt%)) as the stabilizer was stirred for 5 min. Afterward, 5 ml of hydrazine hydrate (2 mM) as

the reducing agent was added to the mixture dropwise. After 5 min, the color of the solution

turned to green which indicated that triangular nanoparticles were formed. The UV-vis

absorption spectrum (OPTIZEN 3220UV spectrometer) of synthesized nanoparticles has been

plotted in Figure 2. According to the literatures a spectrum with four distinct peaks at the

wavelengths of 350, 420, 480 and 760 nm indicate that the shape of silver nanoparticles is

truncated triangular (Ghader et al., 2007; Jia et al., 2006; Ledwith et al., 2007). The dynamic

light scattering (DLS, Malvern Instruments) image of truncated triangular silver nanoparticles is

shown in Figure 3. It is observed that the size distribution of nanoparticles varied from 6 to 30
nm and the average particle size distribution is 14.6 nm. The transmission electron microscope

(TEM, Zeiss EM900) image shown in Figure 4 indicates that these nanoparticles were truncated

triangular.

Figure 2 UV-vis spectrum of the truncated triangular nanosilvers.

Figure 3 Size distribution analysis of silver nanoparticles by DLS.

 Figure 4 TEM image of synthesized silver nanoparticles.

2.4 Procedures

First the reactor was washed by de-ionized water and degassed by the vacuum pump and then,

100 cm3 of aqueous solution was injected into the reactor. After setting the reactor temperature to

275.15 or 276.15 K, methane was injected into the reactor to achieve the desired pressure of 4.5,

4.8, 5, 5.3 and 5.8 MPa. By obtaining the pressure the electromotor was utilized at speed of 25

rpm (frequency of 0.42 hertz) and the data acquisition of temperature and pressure was started

and recorded data at every 20 s. As shown in Figure 5, at first a slight pressure drop occurred due

to gas solubility. Then the pressure became constant for a while which is called induction time.

The pressure decline led to formation of hydrate crystallites. Hydrate crystallization was then

allowed to continue until no significant pressure decrease (less than 0.01 MPa h-1) was observed.

Summary of all experimental runs at different temperatures, pressures and nanoparticle

concentrations are given in Table 1.

Table 1 Experimental methane hydrate formation induction time for different situations.

Set Nanoparticles T (K) P (MPa) Average of Standard Deviation

Number Concentration Induction Time

(M) (min)

1 pure water 275.15 4.5 502.3 6.6

2 pure water 275.15 4.8 400.3 6.1

3 pure water 275.15 5 348.2 6.1

4 pure water 275.15 5.3 298.5 8.1

5 pure water 275.15 5.5 216.9 5.8

6 pure water 276.15 4.5 605 6.4

7 pure water 276.15 4.8 546.7 9.1

8 pure water 276.15 5 482.4 8.1

9 pure water 276.15 5.3 401.5 9.5

10 pure water 276.15 5.5 302 7.2

11 4.5 275.15 4.5 45.5 1.5

12 4.5 275.15 4.8 41.9 1.1

13 4.5 275.15 5 30 1.3

14 4.5 275.15 5.3 20.45 0.8

15 4.5 275.15 5.5 14.11 0.7

16 4.5 276.15 4.5 54.1 1.1

17 4.5 276.15 4.8 47.08 1.2

18 4.5 276.15 5 38.79 1.2

19 4.5 276.15 5.3 29.37 1.1

20 4.5 276.15 5.5 24.5 0.9

21 9 275.15 4.5 32.33 0.8

22 9 275.15 4.8 22.62 0.6

23 9 275.15 5 18.03 0.5

24 9 275.15 5.3 13.89 0.4

25 9 275.15 5.5 8.65 0.5

26 9 276.15 4.5 38.77 0.7

27 9 276.15 4.8 31.89 0.6

28 9 276.15 5 27.56 0.7

29 9 276.15 5.3 20.64 1.1

30 9 276.15 5.5 13.62 0.6

31 18 275.15 4.5 17.76 0.3

32 18 275.15 4.8 12.77 0.7

33 18 275.15 5 10.52 0.5

34 18 275.15 5.3 8 0.1

35 18 275.15 5.5 5.25 0.4

36 18 276.15 4.5 24.63 0.4

37 18 276.15 4.8 21.95 0.8

38 18 276.15 5 17.38 0.4

39 18 276.15 5.3 13.35 0.4

40 18 276.15 5.5 9.41 0.7

41 27 275.15 4.5 17.13 0.6

42 27 275.15 4.8 11.81 0.8

43 27 275.15 5 8.74 0.3

44 27 275.15 5.3 6.8 0.3

45 27 275.15 5.5 5.04 0.2

46 27 276.15 4.5 23.5 0.5

47 27 276.15 4.8 20.06 0.7

48 27 276.15 5 16.53 0.5

49 27 276.15 5.3 11.58 0.5

50 27 276.15 5.5 10.03 0.6

51 36 275.15 4.5 15.73 0.4

52 36 275.15 4.8 11.41 0.4

53 36 275.15 5 7.79 0.4

54 36 275.15 5.3 6.68 0.5

 55 36 275.15 5.5 5.04 0.1

56 36 276.15 4.5 21.94 0.7

57 36 276.15 4.8 19.34 0.4

58 36 276.15 5 14.77 0.4

59 36 276.15 5.3 11.5 0.4

60 36 276.15 5.5 9.35 0.4

3 Theory

Following equation indicates formation of methane hydrate:

CH 4 nw H 2O CH 4 .nw H 2O (1)

Where nw stands for hydration number which is 23/4 for methane hydrate.

According to the literature (Kashchiev and Firoozabadi, 2003) the induction time ti for gas

hydrate crystallization can be written as:

1
1 3m b 13m
ti 3m (2)
bG J

Where m is a number related to hydrate crystal growth, b is the fraction of crystalized hydrate, b

is a dimensionless shape factor, G is the growth rate and J is the nucleation rate. Generally, this

equation is used for progressive nucleation of gas hydrate. The progressive nucleation is a type

of nucleation in which hydrate crystals are continuously nucleated during the process (Kashchiev

and Firoozabadi, 2003).

As is observed, it can be clearly seen that, the errors attained based on the Kashchiev-

Firoozabadi model (Kashchiev and Firoozabadi, 2003) (shown in Table 3) were given high
values. Thus the mentioned model is not appropriate for calculating induction time in the

presence of nanoparticles.

The process of hydrate nucleation in the presence of nanoparticles can be considered as

heterogeneous nucleation. Based on this assumption the growth rate can be expressed by the

following equation:

G [Q(1 k g Cn )](e / kT 1) (3)

where kg is corresponding additive constant related to growth sites, Cn is the concentration of

nanosilvers in the hydrate system, k is Boltzmann constant and T is the temperature given in K.

Assuming the continuous growth (m=1):

Q ah Def C e (4)

Where is the sticking coefficient of building units to the crystallite surface, ah (m2) is the cross

sectional area of a hydrate building unit, Ce is the equilibrium solubility of the gas component

and Def (m2/s) is an effective diffusion coefficient characterizing the random events of transfer

hydrate building units across the crystallite/solution interface.

An
k g k g V S N P , g
Vn

(5)

Where Np,g is the number of growth sites, An is nanoparticles mean surface area, Vn is

nanoparticles mean volume and kg' is effective growth factor coefficient.

Considering the heterogeneous nucleation in the presence of silver nanoparticles, the nucleation

rate can be assumed as:

4C 3h2 ef3
J A (1 k n Cn ) e / kT exp( ) (6)
27kT 2
Where kn is corresponding additive constant related to nucleation sites, A (m-3s-1) is a kinetic

factor, C is a numerical shape factor (for cap-shaped nuclei in heterogeneous nucleation on nano-

substrates in the solution described in equation (8) (Kashchiev, 2000)) and ef (J/m2) represents

an effective specific surface energy.

An
k n k n V S N p ,n
Vn

(7)

Where Np,n is the number of nucleation sites and kn is the effective nucleation factor coefficient.

(1 cos )2
C (36 )1/3 (8)
4 2/3

ef

(9)

In above equation is hydrate/water surface energy and is a number between 0 and 1

calculated by:

1
[ (2 cos )(1 cos )2 ]1/3
4

(10)

Where is the hydrate/nanoparticle wetting angle with values from 0 to 180.

The supersaturation (J) for isothermally gas hydrate formation can be considered

as:(Kashchiev and Firoozabadi, 2003)

(P,T) P
kT ln[ ] e (P Pe ) (11)
(Pe ,T) Pe

Where

e nw w h (12)
Where e is the difference between nw water molecules in the solution and the volume of a

hydrate building unit at the equilibrium pressure. P (Pa) and Pe are the pressure of gas phase and

hydrate equilibrium pressure respectively. Here is the fugacity coefficient of gas which is

determined by Peng-Robinson equation of state.

A general expression for induction time in the presence of nanoparticles is obtained by applying

both mentioned assumptions and substituting J and G in equation (2):

K -1
4C 3 h2 ef3
t i,n = 1
[S(S - 1) 3m ] 1+3m exp[ ] (13)
3m 1+3m
27(1 + 3m)kT 2
[(1 + k g C n ) (1 + k nC n )]

In which

S exp( ) (14)
kT

And K stands for a kinetic parameter calculated by this assumption that it is independent of the

presence of nanoparticles

(1 3m )d 113m
K [ ] (15)
bQ 3A

4
b (16)
3
As is observed, if Cn=0, the equation (13) turns into the induction time equation represented by

Kashchiev-Firoozabadi (Kashchiev and Firoozabadi, 2003). The values of parameters used in

this model and Kashchiev-Firoozabadi model are illustrated in Table 2.

Table 2 The values of parameters used in the current work and Kashchiev-Firoozabadi model.

Parameters Value
An (nm2) 123
ah (nm2) 0.435
Def (m2/s) 1.6E-9
nw 23/4
Vn (m3) 0.615
1
 h (nm3) 0.216
w (nm3) 0.03

4 Results and Discussion

In this work, 600 induction time data points at initial pressures of 4.5, 4.8, 5, 5.3 and 5.5 MPa

and temperatures of 275.15 and 276.15 K and five different nanoparticles concentrations were

experimentally measured. Since the nucleation is stochastic, each experiment was repeated ten

times to increase the reliability of induction time data. The average of measured induction time

and standard deviation for each set of experiments are listed in Table 1. In this study, the

induction time reflects the period of time from the initial equilibrium state to the initial formation

of gas hydrate. As shown in Figure 5, in this period of time the pressure of the reactor is constant

and the end of induction time is accompanied by reduction in gas pressure and the growth

process starts with a slight rise in gas temperature.

Figure 5 Representative pressure and temperature profiles of hydrate formation (experiment #11).
According to Table 1, scattering of induction time in pure water systems was more than

nanoparticles containing systems. The presence of silver nanoparticles in the system led to

heterogeneous nucleation since silver nanoparticles provided numerous new nucleation sites. In

addition to improving nucleation rate, these sites increased the nucleation probability which

contributed to decreasing distribution of induction time. These nanoparticles significantly

decreased the induction time and there was a reverse relationship between induction time and

concentration of nanoparticles. Also, silver nanoparticles notably increased the available surface

area which enhanced the aqueous solution mass transfer capability. The surface activity of small

nanosilvers is an important factor for nucleation process. Silver nanoparticles improved the heat

transfer of the solution due to their high thermal conductivity. All of these properties led to

decrease in induction time. The triangular silver nanoparticles could diminish the induction time

up to 97% which is more than the result obtained by spherical silver nanoparticles (Arjang et al.,

2013). Total free energy of spherical nanoparticles is less than other shapes (Henry, 2005;

Lehtinen and Zachariah, 2001). Non-spherical nanoparticles tend to minimize their free energy

which is achievable by the formation of gas hydrate nuclease on the corner or rough parts of

these types of particles. Since, the triangular silver nanoparticles provide more appropriate places

for nucleation, they can reduce induction time more than spherical nanoparticles. Besides, the

decline in the methane hydrate induction time using triangular silver nanoparticles is much more

than the results presented by studies which have used some nanoparticles such as copper

nanoparticles (Pahlavanzadeh et al., 2016) (0.72% reduction) or mixture of SDS (sodium

dodecyl sulfate) and copper oxide nanoparticles (Najibi et al., 2015) (0.88% reduction) and some

surfactants such as CTAB (Pahlavanzadeh et al., 2016) (cetyl trimethyl ammonium bromide,

0.74% reduction) or SDS (keshavarz Moraveji et al.) (0.84% reduction). The superiority of silver
nanoparticles over copper ones could be linked to higher thermal conductivity of silver compared

to copper. Because of this feature, silver nanofluid can transfer the heat released in the hydrate

formation process more quickly. As a result, silver nanoparticles reduced induction time more

than copper nanoparticles. The variation in the density of used nanoparticles leads to change in

the attraction between nanoparticles and water molecules. In fact, the Van der Waals forces of

the liquid surface and the following interfacial tension are influenced by the density of

nanoparticles (Bhuiyan et al., 2015). These results confirm that the type of nanoparticles plays an

important role in nucleation of methane hydrate. Figure 6 compares the experimental and

predicted induction time of methane hydrate in the presence of triangular silver nanoparticles. As

shown in Figure 6 and according to R2-value which is equal to 0.96, the presented model related

to induction time was accurate and reliable.

Figure 6 Comparison between experimental and predicted induction time data.

Since the gas/liquid interfacial tension plays an important role in hydrate formation process

especially in nucleation, in this work the effect of concentration on hydrate effective interfacial

tension was investigated. It is assumed that the effect of silver nanoparticles on the effective

diffusion coefficient of methane is inconsiderable. The optimum value of effective interfacial

tension (ef) regarding methane hydrate/solution and mentioned hypothesis was determined by

minimizing the difference between calculated and measured induction time according to the

following root mean squared error equation:

N
t i ,n t i ,n
( t
j 1
(pred.) j
ti 0
(exp.) j ) 2
RMSE i0
(17)
N

Where ti0 is the induction time in pure water, N is the number of data points. (pred.) and (exp.)

stand for predicted and measured values respectively. The effective interfacial tension values of

methane hydrate in pure water and in the presence of nanoparticles were determined by genetic

optimization algorithm and presented in Table 3. Average absolute deviation for prediction

accuracy is defined as:

1 N t exp. j t pred . j
AAD %
N

j 1 t exp. j
100 (18)

Since the obtained values of m were approximately equal to 1, the assumption of continuous

growth in the presence of silver nanoparticles applied in the model was correct.

Table 3 Optimum kinetic parameter and effective interfacial tension of methane in pure water and in the
presence of triangular silver nanoparticles.

ADD%
Nanoparticle ADD% (Kashchiev and Firoozabadi,
m ef (J/m2)
concentration (M) (degree) (this work) 2003) based on their optimized
parameters
Pure water 1 0.020 - - -
4.5 0.99142 1.43E-05 19 11.29 11.88
 9 1.00168 1.21E-07 5.6 12.96 28.77
18 0.99994 1.04E-08 3 13.21 74.32
27 0.9964 4.64E-09 2.5 16.68 74.06
36 0.99474 3.24E-09 2.3 14.95 68.75
average - - - 13.82 51.56
The calculated values of methane hydrate/pure water effective interfacial tension (ef0) are

illustrated in Figure 7. The results showed that the obtained ef0 values at operating pressures and

temperatures were very close together with the average of 20 mJ/m2. Thus in these operating

conditions interfacial tension of methane hydrate is almost independent of temperature and

pressure.

Figure 7 Calculated value of methane hydrate/pure water interfacial tension at different operating
conditions.

It was found that the triangular silver nanoparticles significantly impact the effective interfacial

tension of methane. The variation of ef/ef0 versus nanoparticles concentrations is depicted in

Figure 8. As shown in Figure 8, it can be seen that the effective interfacial tension of methane

hydrate/solution decreases severely by addition of nanoparticles. This implies that methane

adsorption on the gas/liquid interface in the presence of silver nanoparticles is more remarkable

than its adsorption in pure water. This reduction is due to decrement of the interaction force of

liquid surface layer in the presence of triangular silver nanoparticles. In general, the effective

interfacial tension of methane hydrate/solution decreases by increasing triangular silver

nanoparticles; however, its sharp declining trend turns into the steady one while nanoparticles

concentrations rise.

Figure 8 Variation of ef/ef0 versus nanoparticles concentration.

5 Conclusion

In this study, the effect of triangular silver nanoparticles on methane hydrate induction time was

experimentally and theoretically studied. The results showed that methane hydrate induction time

in the presence of nanoparticles declined up to 97% in comparison with pure water. Since the

Kashchiev-Firoozabadi model was not desirable for data related to nanoparticles, a new model
for determining induction time was used for predicting the effective interfacial tension of

methane hydrate/solution. The ADD between predicted and measured induction time in the

presence of silver nanoparticles was 13.82%. The effective interfacial tension of methane

hydrate/solution greatly decreased by addition of nanoparticles. It can be concluded that the

presence of silver nanoparticles not only facilitated hydrate nucleation but also decreased

effective interfacial tension of methane hydrate.

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