Chin. Phys. Lett.  2020, Vol. 37 Issue (4): 048201    DOI: 10.1088/0256-307X/37/4/048201
CH$_{4}$ Gas Extraction by CO$_{2}$: Substitution in Clathrate Hydrate through Bimolecular Iteration
Xiao-Hui Yu1†, Yuan Liu3,4†, San-Ya Du3†, Xu Zheng1, Jin-Long Zhu5,6**, Hong-Wu Xu2, Jian-Zhong Zhang2, Shi-Yu Du7, Xiao-Cheng Zeng3,4, J. S. Francisco4, Chang-Qing Jin1, Yu-Sheng Zhao5**, Hui Li3**
1National Lab for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, Beijing 100190
2LANSCE Division, Los Alamos National Laboratory, Los Alamos, New Mexico 87545, USA
3Beijing Advanced Innovation Center for Soft Matter Science and Engineering, Beijing University of Chemical Technology, Beijing 100029
4Department of Chemistry, University of Nebraska-Lincoln, Lincoln, Nebraska 68588, USA
5Department of Physics, Southern University of Science and Technology (SUSTech), Shenzhen 518055
6Center for High Pressure Science and Technology Advanced Research (HPSTAR), Beijing 100094
7Engineering Laboratory of Specialty Fibers and Nuclear Energy Materials, Ningbo Institute of Industrial Technology, Chinese Academy of Sciences, Ningbo 315201
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Xiao-Hui Yu, Yuan Liu, San-Ya Du et al  2020 Chin. Phys. Lett. 37 048201
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Abstract Methane clathrate hydrate (MCH) is a promising energy resource, but controllable extraction of CH$_{4}$ from MCH remains a challenge. Gradually replacing CH$_{4}$ in MCH with CO$_{2}$ is an attractive scheme, as it is cost efficient and mitigates the environmentally harmful effects of CO$_{2}$ by sequestration. However, the practicable implementation of this method has not yet been achieved. In this study, using in situ neutron diffraction, we confirm that CH$_{4}$ in the 5$^{12}6^{2}$ cages of bulk structure-I (sI) MCH can be substituted by gaseous CO$_{2}$ under high pressure and low temperature with a high substitution ratio ($\sim $44%) while conserving the structure of the hydrate framework. First-principles calculations indicate that CO$_{2}$ binds more strongly to the 5$^{12}6^{2}$ cages than methane does, and that the diffusion barrier for CH$_{4}$ is significantly lowered by an intermediate state in which one hydrate cage is doubly occupied by CH$_{4}$ and CO$_{2}$. Therefore, exchange of CO$_{2}$ for CH$_{4}$ in MCH is not only energetically favorable but also kinetically feasible. Experimental and theoretical studies of CH$_{4}$/CO$_{2}$ substitution elucidate a method to harness energy from these combustible ice resources.
Received: 30 September 2019      Published: 24 March 2020
PACS:  82.30.Hk (Chemical exchanges (substitution, atom transfer, abstraction, disproportionation, and group exchange))  
  82.40.Fp (Shock wave initiated reactions, high-pressure chemistry)  
  82.40.-g (Chemical kinetics and reactions: special regimes and techniques)  
  29.30.Hs (Neutron spectroscopy)  
Fund: Supported by the National Key R&D Program of China under Grant Nos 2016YFA0401503 and 2018YFA0305700, the National Natural Science Foundation of China under Grant Nos 11575288, 11775011, 21703006, 21773005, and the Youth Innovation Promotion Association of Chinese Academy of Sciences under Grant No 2016006. J. Zhu was supported by the National Thousand-Young-Talents Program and the National Science Associated Funding Grant U1530402. The experimental work has benefited from the use of the neutron source at Los Alamos Neutron Science Center (LANSCE), which is funded by the U.S. Department of Energy's Office of Basic Energy Sciences.
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Xiao-Hui Yu
Yuan Liu
San-Ya Du
Xu Zheng
Jin-Long Zhu
Hong-Wu Xu
Jian-Zhong Zhang
Shi-Yu Du
Xiao-Cheng Zeng
J. S. Francisco
Chang-Qing Jin
Yu-Sheng Zhao
Hui Li
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