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Energy Procedia 61 (2014) 75 79

The 6th International Conference on Applied Energy ICAE2014

Experimental Study on a Novel Way of Methane Hydrates

Recovery: Combining CO2 Replacement and Depressurization
Jiafei Zhao, Xiaoqing Chen, Yongchen Song *, Zihao Zhu, Lei Yang, Yunlong
Tian, Jiaqi Wang, Mingjun Yang, Yi Zhang
Key Laboratory of Ocean Energy Utilization and Energy Conservation of Ministry of Education, school of Energy and Power
Engineering, Dalian University of Technology, Dalian 116024, Liaoning, China

Abstract
A novel way to exploiting natural gas from methane hydrates combining carbon dioxide replacement and
depressurization was experimentally studied in a high pressure vessel of 255.254mL. Experiment results with or
without the procedure of depressurization were compared to reveal the effects of depressurization on final
replacement percent. Results show that making methane hydrates melt partially by depressurization will enhance
replacement reaction which is restricted by the diffusion and transportation of carbon dioxide. The key factors
affecting the replacement percent were investigated systematically for the first time, including: the saturation of
methane hydrate, and the pressure and temperature condition. Ten runs of non-depressurization and five runs of
depressurization replacement reaction were conducted with hydrate saturations ranging from 0.10 to 0.21,
temperature and pressure condition above phase equilibrium line of carbon dioxide hydrates. Results show that higher
saturation and temperature, and lower pressure enhance the methane exploiting and CO2 sequestration. Pressure and
temperature condition located between the phase equilibrium lines of methane hydrates and carbon dioxide hydrates
is most effective with the optimum methane recovery and carbon dioxide sequestration. The combined method
improves the replacement percent by about 10%, while, effects of depressurization on the stability of the sediments
remains to be explored. It is supposed that methane hydrates melt once, which provides path for carbon dioxide
penetrating into inner layer of hydrates.

by Elsevier
Ltd. This
an open access
2014
2014Published
The Authors.
Published
byisElsevier
Ltd. article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/3.0/).
Selection and/or peer-review under responsibility of ICAE
Peer-review under responsibility of the Organizing Committee of ICAE2014

Key words: methane hydrates; carbon dioxide; constant volume replacement;depressurization

1. Introduction

* Corresponding author. Tel.: +86-411-84706722; fax: +86-411-84706722.

E-mail address: songyc@dlut.edu.cn.

1876-6102 2014 Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/3.0/).
Peer-review under responsibility of the Organizing Committee of ICAE2014
doi:10.1016/j.egypro.2014.11.910

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Jiafei Zhao et al. / Energy Procedia 61 (2014) 75 79

Clathrate hydrates are of three types of structure-- SI, SII and SH [1]. As is decided by the molecule
diameter, both methane and carbon dioxide can only form SI hydrate respectively [2] and will not form
stable structure II as binary mixtures [3]. SI methane hydrate constitution can be expressed by the formula
8CH446H2O. Note that methane hydrates formed in the lab are probably not ideal, the value of 6 as
hydrate number allows for the possibility of empty cages [4].
In the process of exploiting natural gas from methane hydrates, researchers have explored four ways to
decompose the crystalline inclusion compounds: depressurization, thermal stimulation, inhibitor injection
and CO2 replacement [5]. Among these four methods, carbon dioxide replacement offers stable long-term
storage of a greenhouse gas while benefiting from methane production without requiring heat [6]. Such
conception has revealed a tempting prospect and attracted many researches on this issue. The process of
methane hydrates swapped by carbon dioxide has been proved feasible kinetically [7] and
thermodynamically [8].
Current researches are mainly focused on the field of improving the replacement rate and finding more
practical displacer to exchange CH4. Three types of displacer have been used experimentally: gaseous
CO2, liquid CO2 and CO2 emulsion. Xitang Zhou et al. [9] compared the replacement rate as the
equilibrium condition changed. Carbon dioxide in emulsion phase in region B of phase equilibrium
diagram [7] was found to be the most efficient condition compared with gaseous phase and liquid phase
due to better conductivity and diffusibility of the CO2 emulsion. Qing Yuan et al. [10] compared the
replacement percent in the literature using different displacers. CO 2 emulsion is the most effective
displacer with the most CH4 replaced and CO2 liquid exchanged the second most CH4 replaced while the
gaseous CO2 the least replacement percent. While in this study, replacement reaction conditions are
discussed instead of different kinds of displacer, since different phase of CO2 is due to certain pressure
and temperature condition. Besides, the usage of emulsion is limited by the high cost and complexity of
emulsion formation. Our effort is mainly laid on enhancing the recovery of CH4 with pure CO2 supply. A
novel way is put forward and studied in the procedure of CO 2 replacement by combining depressurization.
2. Experiment apparatus and procedures
The adapted schematic diagram of the experimental apparatus is shown in figure 1. It consists of 4
parts: reaction cell (1,2,3), a signal conversion device to record pressure and temperature (4,5,6,7), gas
supplying system (8,9,10,11,12), and mass analyzer to analyze the gas composition (13,14,15).The
reactor is made of stainless steel and has a pair of quartz windows on either side for direct observation of
the process of hydrate forming and dissociation. The inner volume of the cell is 255.254 mL with
diameter of 50 mm and height of 130 mm. The designed maximum pressure is 30MPa. The temperature
of the cell during the experiment is controlled by glycol bath.
x First step: in-situ methane hydrates formation in porous media.
x Second step: constant volume replacement reaction.
x Third step: gas composition analysis.
The procedure of depressurization combined method was the same for the first and third step except
that 2 hours depressurization was added to the second step. Constant volume replacement reaction
underwent for 15 hours with gaseous CO2 at certain temperature (273K) and pressure. Then the
temperature was set 267K to reduce hydrates decomposition when lowing pressure to 1.6MPa, which is
below methane hydrate phase equilibrium line but above CO 2 hydrate phase equilibrium line. Then the
temperature was reset to be 273K. This procedure lasted for 2 hours and then cooled CO2 was injected to
the original pressure before depressurization. As was reported by literatures, the replacement rate dropped
dramatically after the first 5 minutes of reaction. The first stage of replacement reaction explained as
surface reaction is about 10 hours. [11] The combined method is designed to tackle this problem by
breaking through throats to increase the diffusion of CO 2 when replacement rate declines.

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Jiafei Zhao et al. / Energy Procedia 61 (2014) 75 79

Fig. 1. (a)Schematic diagram of the experimental apparatus; (b) replacement conditions and phase equilibrium diagram

3. Results and discussion

Typical phase diagrams of methane (gas/hydrates) and carbon dioxide (gas/liquid/hydrates) are shown
in Fig.1(b)[7]. Target zones of this study are located at zone A(above L_(CO2)-V_(CO2)), B(between
L_(CO2)-V_(CO2) and water-H_(CH4)-V_(CH4)) and C(between water-H_(CH4)-V_(CH4) and waterH_(CO2)-V_( CO2)). It can be seen that zone C is an optimum condition for replacement reaction where
CO2 hydrates exist and CH4 hydrates decompose. In the process of depressurization, temperature and
pressure condition will be changed from zone B to zone C for 2 hours to melt methane hydrates partially.
Fig.2 (a) shows the replacement percent of ten runs of non-depressurization reaction. Conditions in
zone B where CO2 is in liquid phase and C where the optimum zone locates have higher replacement
percent, while zone C is relatively more effective. There is a tendency that as saturation increases,
replacement percent will increase first and decrease when reaching certain degree, which is in consistence
with studies in [12].
Five groups of experiments on combined method were conducted with the same duration of 50 hours.
Temperature and pressure condition is nearly the same except methane hydrates saturation ranging from
0.11 to 0.22. Data is shown in table 1 with calculated saturation and replacement percent in.
Effective and whole replacement percent is analyzed in Fig.3(b). It is found that the effective
replacement percent is much higher than runs without depressurization when replacement condition is
located at zone B. Replacement percent of runs only by CO2 replacement are below 0.2 shown in Fig.3(a),
while runs with depressurization in addition are more than 0.3. For higher saturation, amount of methane
decomposed by depressurization is larger, while the effective replacement percent is on average level.
Results reveal that method with depressurization is effective to enhance methane hydrates recovery. It can
be explained that 2 hours depressurization will make certain amount of methane hydrate dissociate and
porous sediment loose to support the replacement reaction.
Table 1. Data of five runs with depressurization combined method
Runs with combined method

Run1

Run2

Run3

Run4

Run5

Reaction pressure(MPa)

2.98

2.97

2.78

3.16

2.68

Reaction temperature(K)

272.3

272.6

272.3

273.5

273.7

Methane hydrates saturation

0.148

0.128

0.118

0.213

0.182

Whole replacement percent

0.347

0.343

0.498

0.554

0.421

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Jiafei Zhao et al. / Energy Procedia 61 (2014) 75 79

Fig. 2. Comparison of replacement percent of runs without (a) and with (b) depressurization (a: diamond: reaction condition in zone
A; square points: in zone B; triangle points: in zone C. b: stars: whole replacement percent; square points: effective replacement
percent; diamond: percentage of hydrates decomposed not by replacement)

4. Conclusions
Reaction conditions in zone A and C have larger effective replacement percent compared with zone B,
where CO2 is gaseous. When combining depressurization, replacement percent in zone B can reach as
high as zone C. Replacement percent climbs up first but declines as methane hydrates saturation increases.
It is confirmed that the combined method is effective in enhancing methane hydrate exploitation.
References
[1] Servio P, Lagers F, Peters C, Englezos P. Gas hydrate phase equilibrium in the system methanecarbon dioxideneohexane
and water. Fluid phase equilibria 1999; 158: 795-800.
[2] Lee H, Seo Y, Seo YT, Moudrakovski IL, Ripmeester JA. Recovering methane from solid methane hydrate with carbon
dioxide. Angewandte Chemie International Edition 2003; 42 (41): 5048-5051.
[3] Staykova DK, Hansen T, Salamatin AN, Kuhs WF. In Kinetic diffraction experiments on the formation of porous gas
hydrates. Proceedings of the Fourth International Conference on Gas Hydrates, Yokohama, May 19, 2002, p 537-542.
[4] Sloan Jr, ED, Koh C. Clathrate hydrates of natural gases. 3rd ed. CRC press; 2007.
[5] Lee J, Park S, Sung W. An experimental study on the productivity of dissociated gas from gas hydrate by depressurization
scheme. Energy Conversion and Management 2010; 51 (12): 2510-2515.
[6] Ersland G, Huseb J, Graue A, Kvamme B. Transport and storage of CO< sub> 2</sub> in natural gas hydrate reservoirs.
Energy Procedia 2009; 1 (1): 3477-3484.
[7] Goel N. In situ methane hydrate dissociation with carbon dioxide sequestration: Current knowledge and issues. Journal of
petroleum science and engineering 2006; 51 (3): 169-184.
[8] Ota M, Abe Y, Watanabe M, Smith JrRL, Inomata H. Methane recovery from methane hydrate using pressurized CO< sub>
2</sub>. Fluid Phase Equilibria 2005; 228: 553-559.
[9] Zhou X, Fan S, Liang D, Du J. Replacement of methane from quartz sand-bearing hydrate with carbon dioxide-in-water
emulsion. Energy & Fuels 2008; 22 (3): 1759-1764.
[10] Yuan Q, Sun CY, Yang X, Ma PC, Ma ZW, Liu B, Ma QL, Yang LY, Chen GJ. Recovery of methane from hydrate
reservoir with gaseous carbon dioxide using a three-dimensional middle-size reactor. Energy 2012; 40 (1): 47-58.
[11] Ota M, Saito T, Aida T, Watanabe M, Sato Y, Smith RL, Inomata H. Macro and microscopic CH4CO2 replacement in CH4
hydrate under pressurized CO2. AIChE Journal 2007; 53 (10): 2715-2721.
[12] Yuan Q, Sun CY, Liu B, Wang X, Ma ZW, Ma QL, Yang LY, Chen GJ, Li QP, Li S. Methane recovery from natural gas
hydrate in porous sediment using pressurized liquid CO< sub> 2</sub>. Energy Conversion and Management 2013; 67: 257-264.

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Biography
Xiaoqing, Chen, female, born in 1989, graduate student dedicated to the study of methane
hydrates exploitation by CO2 replacement method in Key Laboratory of Ocean Energy
Utilization and Energy Conservation of Ministry of Education, school of Energy and Power
Engineering, Dalian University of Technology.

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