Experimental Study on the Structure Characteristics of CO2 in Gas Hydrate by Solid-State Nuclear Magnetic Resonance and Raman Spectroscopy

Juan FU; Jia-mei MO; Yi-song YU; Qing-zong ZHANG; Xiao-li CHEN; Pei-li CHEN; Shao-hong ZHANG; Qiu-cheng SU

doi:10.3964/j.issn.1000-0593(2022)02-0464-06

Journals >Spectroscopy and Spectral Analysis >Volume 42 >Issue 2 >Page 464 > Article

Spectroscopy and Spectral Analysis
Vol. 42, Issue 2, 464 (2022)

Experimental Study on the Structure Characteristics of CO₂ in Gas Hydrate by Solid-State Nuclear Magnetic Resonance and Raman Spectroscopy

Juan FU, Jia-mei MO, Yi-song YU, Qing-zong ZHANG, Xiao-li CHEN, Pei-li CHEN, Shao-hong ZHANG, and Qiu-cheng SU^*;

Author Affiliations

Key Laboratory of Gas Hydrate, Guangzhou Institute of Energy Conversion, Chinese Academy of Sciences, Guangzhou 510640, China

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DOI: 10.3964/j.issn.1000-0593(2022)02-0464-06 Cite this Article

Juan FU, Jia-mei MO, Yi-song YU, Qing-zong ZHANG, Xiao-li CHEN, Pei-li CHEN, Shao-hong ZHANG, Qiu-cheng SU. Experimental Study on the Structure Characteristics of CO₂ in Gas Hydrate by Solid-State Nuclear Magnetic Resonance and Raman Spectroscopy[J]. Spectroscopy and Spectral Analysis, 2022, 42(2): 464 Copy Citation Text

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Fig. 1. SEM photograph of ice (A), methane hydrate before replacement (B), after the decomposition of methane hydrate (C)

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Fig. 2. ¹³C NMR spectrum of CO₂-CH₄ hydrate

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Fig. 3. Raman spectrum of CO₂-CH₄ hydrate

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Fig. 4. ¹³C NMR spectrum of ¹³CO₂-H₂-CP hydrate and liquid CP

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Fig. 5. Raman spectrum of ¹³CO₂-H₂-CP hydrate

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水合物样品	温度/K	压力/MPa
CH₄	274.00	8
5%¹³CO₂-40%H₂-CP	274.15	8
CH₄-CO₂	274.00	6

Table 1. Experimental preparation conditions of hydrate samples

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气体水合物类型	Ⅰ		Ⅱ		H			纯物相
孔穴类型	小笼 5¹²	大笼 5¹²6²	小笼 5¹²	大笼 5¹²6⁴	小笼 5¹²	中笼 4³5⁶6³	大笼 5¹²6⁸
每个晶胞单元含有孔穴数	2	6	16	8	3	2	1
CH₄化学位移/ppm	-4.1~-4.5	-6.5~-6.7	-4.1~-4.5	-8.1~-8.2	-4.1~-4.5	-4.7~-4.9	-	-10.2
CO₂化学位移/ppm	-	125.6	124.8(本文)	-	-	-	-	125
CP化学位移/ppm	-	-	-	26.3	-	-	-	26.7

Table 2. Crystal structure and ¹³C NMR chemical shifts of common gas hydrate

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水合物种类	结构类型	$θ_{S, C H_{4}}$	$θ_{S, H_{2}}$	$θ_{S, C O_{2}}$	$θ_{L, C H_{4}}$	$θ_{L, C O_{2}}$	θ_{L, CP}	水合数n
CH₄	Ⅰ(NMR)	0.749 7	-	-	0.992 1	-	-	6.17
	Ⅰ(NMR)	0.097 5	-	-	0.317 2	-	-	-
CH₄+CO₂	Ⅰ(Raman)	0.059 3	-	-	0.009 5	0.978 2(费米低频共振)	-	7.61
	Ⅰ(Raman)	0.023 7	-	-	0.003 3	0.984 3(费米高频共振)	-	7.70
	Ⅱ(NMR)	-	-	0.783 1	-	-	0.971 6	6.70
CO₂-H₂-CP	Ⅱ(Raman)	-	0.124 8	0.304 2(费米低频共振)	-	-	0.997 8	9.16
	Ⅱ(Raman)	-	0.123 6	0.577 1(费米高频共振)	-	-	0.985 1	7.12

Table 3. Cage occupancy value obtained by ¹³C NMR and Raman

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