Journal of Molecular Liquids 180 (2013) 4550

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Journal of Molecular Liquids

journal homepage: www.elsevier.com/locate/molliq

Effect of CuO nanoparticle on dissolution of methane in water

Mostafa Keshavarz Moraveji , Milad Golkaram, Reza Davarnejad
Department of Chemical Engineering, Faculty of Engineering, Arak University, Arak 38156-8-8349, Iran

a r t i c l e

i n f o

Article history:
Received 31 July 2012
Received in revised form 29 October 2012
Accepted 9 December 2012
Available online 21 December 2012
Keywords:
CuO nanoparticle
Dissolution
Methane
Hydrate

a b s t r a c t
In this research, dissolution of methane in water with CuO nanoparticles was examined at temperatures of
20, 15, 10, 8, 6 and 3 C and at pressures of 10 and 15 bar. For this purpose, four samples including pure
water, water with surfactant and two nanouids with different concentrations were prepared. Each sample
volume was 200 cm 3. Methane was contacted with each solution in a reactor with no mixer. Addition of
0.05 wt.% SDS reduced surface and interfacial tensions by accumulating at the interface of immiscible uids.
This implies higher solubility of methane comparing with the pure water. The same procedure happened for
0.1 wt.% CuO nanoparticles, as well. It was concluded that high effective surface area of nanoparticles improved the solubility. Furthermore, adding 1 wt.% nanoparticle, increased methane solubility by 144% and
77.15% at pressures of 10 and 15 bar (compared with the pure water), respectively.
2013 Elsevier B.V. All rights reserved.

1. Introduction
Recently natural gas hydrates (NGH) have been paid much attention
for industrial utilization as a new method for storage and transport of
natural gas in the form of clathrate-hydrates and crystalline solid compounds. The natural gas hydrates originally contain 150180 volumes of
gas per volume of hydrate [1]. The industrial applications of NGH storage have been hindered by slow formation rate and volume of water
that did not react with methane gas that are results of very low solubility of methane gas in water (only a thin hydrate lm is formed at the interface between water and methane gas [2]).
There have been a number of approaches proposed to increase solubility of gas in the water that result enhancement of hydrate formation, including chemical and mechanical methods. The mechanical
methods use stirrer, liquid spraying by a nozzle and gas bubbling by
a pipe or orice plate [3,4] for solubility enhancement of gas in
water that result in hydrate formation. The agitation of water increases the watergas interfacial area and improves gas solubility
(hydrate formation).
In the chemical aspect, it is assumed that the hydrate formation
rate can be increased efciently by adding a certain quantity of thermodynamic or kinetic promoters. According to the literature, hydrate
storage properties can be improved by adding surfactants [57].
Surfactants are amphiphilic compounds which can reduce surface
and interfacial tensions by accumulating at the interface of immiscible uids. It can increase the solubility, mobility, bioavailability and
subsequent biodegradation of hydrophobic or insoluble organic compounds [6]. However, there are some limitations in the effective uses
of the above methods in practice.
Corresponding author. Tel.: +98 9363098063; fax: +98 861 4173450.
E-mail address: m-moraveji@araku.ac.ir (M.K. Moraveji).
0167-7322/$ see front matter 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.molliq.2012.12.014

Mandal and Laik studied effects of the anionic surfactants such as

SDS on ethane hydrate formation, dissociation and storage capacity in
a quiescent state system [7].
With the development of the synthesis technology of the nanometer
materials and the wide application of nanotechnology, the investigation
of its effect on the heat and mass transport processes, in chemical and
biochemical technologies became more and more important.
Recently, Olle et al. measured the oxygen absorption rate in the
presence of dispersed colloidal nanoparticles of magnetite (Fe3O4)
coated with oleic acid [8]. They found that the nanouid improved
the gasliquid oxygen mass transfer coefcient more than 1.6-fold,
while volumetric mass transfer coefcient increased up to 6-fold for
a nanouid (with volume fraction less than 1%) in an agitated and
sparged reactor.
Krisnamurthy et al. measured the dye diffusion in liquids containing
suspended nanoparticles. They investigated that mass transfer increased in a nanouid containing 20 nm Al2O3 nanoparticles (with volume fraction of 0.5%) in comparison with the pure water [9].
Nagy et al. investigated mass transfer coefcient in the nanouids
[10]. They improved gasliquid oxygen mass transfer coefcient to
200% in a 65 nm suspension of n-hexadecane droplets (with volume
fraction of 10%) while gasliquid oxygen mass transfer coefcient increased to 600% in a suspension of 20 nm Fe3O4. The same trend was
observed for the CO-water volumetric mass transfer coefcient when
mesoporous silica nanoparticles (with an average size of 250 nm)
were used [11].
Li et al. used nano-copper suspension to increase the refrigerants
water mass and heat transfer [12]. They experimentally showed that
the nano-copper addition increased heat and mass transfer during
HFC134a hydrate formation.
According to the literature, surface area enhancement and mass
transfer coefcient increment increase the mass transfer [9,13,14].

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In the present work, the effects of nanouids (CuO nanoparticles

with 40 nm diameter and weight fractions of 0.1% and 1% was dispersed in water) on the methane gas dissolution were studied. The
signicant goal of this research was to measure methane gas solubility in the nanouids under various operating conditions.

2. Experimental
2.1. Materials
Spherical copper oxide nanoparticles (with 40 nm nominal diameter, density of 6.32 g/cm 3 and purity of 99%) were purchased from
Merck Co. Methane gas (with purity of 99.95%) was purchased from
Technical Gas Services Co. (Iran) and deionized water (lab grade)
was used for the hydrate formation. An anionic surfactant [Sodium
Dodecyl Sulfonate (SDS) with purity of 98%] as dispersant was
obtained from Acros Co. (Belgium).

2.2. Nanouid preparation

Nanouids with particle weight percentages of 0.1% and 1% were
prepared by dispersing the specied amounts of CuO nanoparticles
in a base uid (deionized water). In order to stabilize the uid, the
procedure demands the surfactant (SDS) dissolution. The sample
without SDS was coagulated by 1 h. The sample coagulated within
1 day when 0.01% SDS was applied. The uid with 0.03% and 0.05%
was coagulated within 5 days and a week, respectively. More than
this amount of surfactant can inuence the experiment to fully remove the nanoparticles effect.
The samples were placed in an ultrasonic bath (Fritsch Ultrasonic,
Laborette 17, with frequency of 5060 Hz). It was used to break large
agglomerates of nanoparticles in the uid and prepare a stable suspension. The uniformed and stable dispersed nanouids were visually
obtained.

2.3. Apparatus
The schematic diagram of the experimental set-up which is a custom
fabricated apparatus is shown in Fig. 1. The cell was mounted on a pivot.
The main part of set-up is a cylindrical high-pressure stainless steel cell
with an inner diameter of 8.4 cm, length of 21.4 cm and a total available
volume of 1150 cm 3 which was tested up to 150 bar. The cell was
equipped with a magnetically coupled rotary impeller system that is a
disk impeller with six straight blades (Rushton turbine). The stirring
speed could vary between 0 and 1200 rpm which was kept at
400 rpm in this study. A water bath (model: E200, manufactured
by Lauda Co.), able to maintain the temperature with accuracy of
0.01 K from the set point, was also used. There was a cooling jacket
around the reactor through which ethylene glycolwater solution
could circulate out of the reactor. The high pressure cell was equipped
with a thermocouple (model: PT100 with accuracy of 0.01 K) and a
pressure transducer (model: 5436 Worenlos with accuracy of 0.1 bar
manufactured by Huba Control Co.) was used to measure the cell
temperature and pressure, respectively. Those measuring devices were
connected to a data-logger and a personal computer to record the temperature and pressure versus time. Temperature and pressure were
recorded every second throughout the experiments and averaged
every 60 s. The reactor had some valves for injecting and venting gas.
The other parts of the set-up were a vacuum pump to evacuate the cell
and a high pressure methane bottle to supply the methane.
2.4. Procedure
A required amount of nanouid was weighed on a digital balance
(up to 3 decimal points). The cell was rinsed with deionized water
twice. The solution was then poured into the cell. Air was removed
from the cell by a vacuum pump and methane purging. The methane
gas was then injected into the cell. Initial temperature of each test
was set at 15 C. When the equilibrium was obtained (temperature
and pressure remained constant), the cooling process without mixing
was operated to decrease the system temperature down to 3 C.

Fig. 1. Schematic diagram of methane hydrate formation apparatus.

M.K. Moraveji et al. / Journal of Molecular Liquids 180 (2013) 4550

There was a decrease in pressure due to dissolving methane gas in the

solution phase. Eight experiments (with pure water, mixture of water
and surfactant and two nanouids) were carried out twice and each
one was done in two different pressures.

3. Results and discussion

In this research, the experiments were carried out to investigate
the effects of nanoparticle concentrations on the methane dissolution

47

process. The results were analyzed in terms of methane pressure

reduction.
The cell reactor was lled up with the nanouid and then saturated with methane gas under the experimental conditions. The rate of
consumed gas by the systems (trapped methane in hydrate cages)
is equal to the methane pressure reduction. The experiments were
done in temperatures more than 3 C to prevent hydrate formation.
Fig. 2(af) shows the effect of nanoparticles on dissolution of
methane in water in various temperatures and at pressure of 10 bar.
Fig. 2(a) and (c) shows a dramatic change in dissolution which was

Fig. 2. a. Methane pressure versus time at P = 10 bar & T = 3 C. b. Methane pressure versus time at P = 10 bar & T = 6 C. c. Methane pressure versus time at P = 10 bar & T = 8 C.
d. Methane pressure versus time at P = 10 bar & T= 10 C. e. Methane pressure versus time at P = 10 bar & T = 15 C. f. Methane pressure versus time at P = 10 bar & T = 20 C.

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due to existing SDS particles. However, nano-CuO particles can tangibly assist methane dissolution. There was no signicant change in
two various concentrations of nano-CuO. Furthermore, all gures
show that solubility reached the steady state condition. This was
due to mass transfer and diffusion of methane through the nanouid.
In addition, the steady state condition is obtained during 15 min at
8 C while it was around 25 min at 3 C. This is due to temperature effect on methane mobility in the nanouid. The mobility led to higher
rate of mass transfer. As shown in Fig. 2(b), a signicant change was
observed by addition of different nanoparticle concentrations at

pressure of 10 bar and temperature of 6 C. This showed that concentrated solution highly causes methane dissolution at this pressure and
temperature. Fig. 2(d) and (e) shows the effect of nanoparticles at
pressure of 10 bar and at temperatures of 10 and 15 C, respectively.
According to these gures, the higher temperature decreased methane solubility. This output is also supported by Mohammadi et al.
[15]. Fig. 2(f) illustrates that SDS and nanoparticles with higher
concentration (1 wt.%) increased methane solubility at pressure of
10 bar and at temperature of 20 C compared with the other solutions. Fig. 3(af) shows the effect of nanoparticles on dissolution of

Fig. 3. a. Methane pressure versus time at P = 15 bar & T = 3 C. b. Methane pressure versus time at P = 15 bar & T = 6 C. c. Methane pressure versus time at P = 15 bar & T = 8 C.
d. Methane pressure versus time at P = 15 bar & T= 10 C. e. Methane pressure versus time at P = 15 bar & T = 15 C. f. Methane pressure versus time at P = 15 bar & T = 20 C.

M.K. Moraveji et al. / Journal of Molecular Liquids 180 (2013) 4550

49

Fig. 6. Relative enhancement percentage of methane dissolution in 0.1% and 1%

nano-CuO solutions at P0 = 10 bar.
Fig. 4. Enhancement percentage of methane dissolution versus temperature at P0 =
10 bar in SDS, 0.1% and 1% nano-CuO solutions.

methane in water in various temperatures and at pressure of 15 bar.

According to Fig. 3(ad), there was a little change in methane dissolution compared with the SDS solution. Fig. 3(e) and (f) indicates
that time is a signicant parameter in the dissolution. Furthermore,
the rate and capacity of methane dissolution increased in the aqueous
solutions with surfactant and nanoparticles in comparison with the
pure water in particular at 3 C (suitable for hydrate formation) and
at pressures of 10 and 15 bar. The solubility at 15 bar was more
than that of 10 bar. Figs. 4 and 5 show the solubility reduction versus
temperature enhancement at pressures of 10 and 15 bar, respectively. The best operating temperature for methane dissolution is 3 C.
Maximum percentages of methane dissolution are 144% and 142.1%
for 0.1 wt.% and 1 wt.% nanouid, respectively. As shown in Fig. 5,
the best temperature was 3 C that 77.15% enhancement in methane
dissolution at 0.1 and 1 wt.% nanoparticles was obtained, although
54.57% for SDS solution was found (in comparison with water).
Fig. 6 illustrates that methane dissolution percentages were 22.2%
and 24.1% for 0.1 and 1 wt.% nanoparticles respectively compared
with the SDS solution. Fig. 7 illustrates that methane dissolution enhancement is 22.58% for 0.1 and 1 wt.% nanouid at pressure of
10 bar. Therefore, nanoparticle addition into the SDS solution increased its capability although this was not as sharp as SDS added
into the pure water. It was due to surface reduction and interfacial
tension of SDS by accumulating at bigger surface and interface of immiscible uids. This implies higher solubility of methane compared
with the pure water. According to the literature, 0.5 wt.% cyclodextrin

Fig. 5. Enhancement percentage of methane dissolution versus temperature at P0 =

15 bar in SDS, 0.1% and 1% nano-CuO solutions.

addition into the water increased the methane solubility around

14.63% at temperature of 1 C and at pressure of 3 bar [15].
The solubility enhancement percentage is calculated using the following equation:


2 P i P j  100


%Enhancement
Pi Pj

where, Pi is the equilibrium pressure for the basic material (pure

water). Pj is the methane pressure for SDS solution and nanouids.

4. Conclusions
A dramatic enhancement in methane solubility was observed in SDS
solution and nanouid (with 0.1 wt.% CuO) in comparison with the
pure water. This enhancement was more signicant in low temperatures and at high pressure. The surface and interfacial tensions reduced
when 0.05 wt.% SDS was used. This caused higher solubility of methane
compared with the pure water. The same procedure happened when
0.1 wt.% nanoparticles was used however highly effective surface area
of nanoparticles dramatically improved the solubility. The optimum
concentration was 1 wt.% CuO and 0.05 wt.% SDS. The best pressure
and temperature were 10 bar and 3 C, respectively. It led to 144% enhancement in solubility compared with the pure water although it
was 24.1% compared with the SDS solution.

Fig. 7. Relative enhancement percentage of methane dissolution in 0.1% and 1%

nano-CuO solutions at P0 = 15 bar.

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