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Frontiers in Energy

Front. Energy    2020, Vol. 14 Issue (3) : 443-451
Efficient promotion of methane hydrate formation and elimination of foam generation using fluorinated surfactants
Quan CAO1(), Dongyan XU2, Huanfei XU3, Shengjun LUO1(), Rongbo GUO4()
1. Shandong Industrial Engineering Laboratory of Biogas Production and Utilization, Key Laboratory of Biofuels of Chinese Academy of Sciences, Qingdao Institute of Bioenergy and Bioprocess Technology, Chinese Academy of Sciences, Qingdao 266101, China
2. Faculty of Engineering, Qingdao University of Science and Technology, Qingdao 266042, China
3. Faculty of Engineering, Qingdao University of Science and Technology, Qingdao 266042, China; College of Chemical Engineering, Qingdao University of Science and Technology, Qingdao 266042, China
4. Shandong Industrial Engineering Laboratory of Biogas Production and Utilization, Key Laboratory of Biofuels of Chinese Academy of Sciences, Qingdao Institute of Bioenergy and Bioprocess Technology, Chinese Academy of Sciences, Qingdao 266101, China; Dalian National Laboratory for Clean Energy, Dalian 116023, China; Faculty of Engineering, Qingdao University of Science and Technology, Qingdao 266042, China
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Methane hydrate preparation is an effective method to store and transport methane. In promoters to facilitate methane hydrate formation, homogeneous surfactant solutions, sodium dodecyl sulfate (SDS) in particular, are more favorable than heterogeneous particles, thanks to their faster reaction rate, more storage capacity, and higher stability. Foaming, however, could not be avoided during hydrate dissociation with the presence of SDS. This paper investigated the ability of five fluorinated surfactants: potassium perfluorobutane sulfonate (PBS), potassium perfluorohexyl sulfonate (PHS), potassium perfluorooctane sulfonate (POS), ammonium perfluorooctane sulfonate (AOS), and tetraethylammonium perfluorooctyl sulfonate (TOS) to promote methane hydrate formation. It was found that both PBS and PHS achieve a storage capacity of 150 (V/V, the volume of methane that can be stored by one volume of water) within 30 min, more than that of SDS. Cationic ions and the carbon chain length were then discussed on their effects during the formation. It was concluded that PBS, PHS, and POS produced no foam during hydrate dissociation, making them promising promoters in large-scale application.

Keywords methane hydrate      fluorinated surfactants      homogeneous promoter      foam elimination      stability     
Corresponding Author(s): Quan CAO,Shengjun LUO,Rongbo GUO   
Online First Date: 13 July 2020    Issue Date: 14 September 2020
 Cite this article:   
Quan CAO,Dongyan XU,Huanfei XU, et al. Efficient promotion of methane hydrate formation and elimination of foam generation using fluorinated surfactants[J]. Front. Energy, 2020, 14(3): 443-451.
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Quan CAO
Dongyan XU
Huanfei XU
Shengjun LUO
Rongbo GUO
Fig.1  Scheme 1 Graphical representation of hydrate formation apparatus.
Fig.2  Surface tension of fluorinated surfactants at 20°C.
Fig.3  Contact angles of fluorinated surfactant solutions at 20°C.
Fig.4  Methane consumption versus time for fluorinated surfactants at 300 r/min, a temperature of 2°C, and a pressure of 6 MPa.
Fig.5  Effects of salts added on hydration formation at 300 r/min, a temperature of 2°C, and a pressure of 6 MPa.
Surfactant Concentration/(m·mol·L1) Viscosity/(mPa·S)
PBS 40 2.9
PHS 10 3.1
POS 4 2.8
AOS 1 3.4
AOS 4 6.7
AOS 7 8.2
TOS 1 3.6
TOS 4 7.1
TOS 7 8.7
Tab.1  Viscosities of surfactant solutions at 20°C
Fig.6  Photographs of hydrate dissociation.
Fig.7  Photographs taken five minutes after violently shaking the surfactant solutions (from left to right: PBS 30 mmol/L; PHS 10 mmol/L; SDS 1 mmol/L; SDS 4 mmol/L).
Fig.8  Hydrate formation at 300 r/min, different temperatures, and pressures.
Fig.9  Reactions with PHS (10 mmol/L) without stirring and its recycling at a temperature of 2°C and a pressure of 6 MPa.
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