CIESC Journal ›› 2019, Vol. 70 ›› Issue (3): 1042-1047.doi: 10.11949/j.issn.0438-1157.20180821

• Energy and environmental engineering • Previous Articles     Next Articles

Microscopic measurements on methane hydrate dissociation

Xuebing ZHOU1,2,3,4(),Chanjuan LIU1,2,Jinqiong LUO1,2,Deqing LIANG1,2()   

  1. 1. Guangzhou Institute of Energy Conversion, Chinese Academy of Sciences, Guangzhou 510640, Guangdong, China
    2. CAS Key Laboratory of Gas Hydrate, Guangzhou 510640, Guangdong, China
    3. Guangdong Provincial Key Laboratory of New and Renewable Energy Research and Development, Guangzhou 510640, Guangdong, China
    4. Guangzhou Center for Gas Hydrate Research, Chinese Academy of Sciences, Guangzhou 510640, Guangdong, China
  • Received:2018-07-18 Revised:2018-10-17 Online:2019-03-05 Published:2018-12-10
  • Contact: Deqing LIANG E-mail:zhouxb@ms.giec.ac.cn;liangdq@ms.giec.ac.cn

RichHTML

1

PDF (PC)

74

Abstract:

The decomposition process of methane hydrate was measured by laser Raman and X-ray powder diffraction (PXRD) at 253 K under normal pressure. The results showed that the methane hydrates at the surface dissociated into Ⅰh ice in the initial 30—50 min and then the ice film covered the hydrate phase which triggered the “self-preservation” effect and finally led to a dramatic decrease in dissociation rate of methane hydrate. During the dissociation, the ratio of methane content in large and small hydrate cages obtained from Raman spectra remained stable at around 3.2 which was generally in accord with the ratio of large to small cages in methane hydrate, while the characteristic peaks of hydrate lattice planes in the powder X-ray diffraction patterns decreased in the same profile, suggesting that the methane hydrate dissociated as a whole crystal unit. However, the characteristic peaks of Ⅰh ice lattice planes increased in different ways. The intensity of (002) plane was found to increase linearly up to 370% of its original value in 60 min while the intensity of (100) plane kept steady at about 200% of its original value after the first 20 min, indicating that the ice inclined to grow into horizontal plates instead of columnar growth. Combining with the transport characteristics of water molecules on the ice surface under low temperature, the growth of ice film covered on the inner hydrate cores was suggested to cultivate the “self-preservation” effect.

Key words: methane, hydrate, kinetics, microscale

CLC Number: 

  • TK 123

Fig.1

Schematic diagram of sⅠ hydrate structure"

Fig.2

Schematic diagram of hydrate forming device"

Fig.3

Typical Raman spectrum of CH4 hydrate"

Fig.4

In situ Raman spectra of CH4 hydrate in dissociation"

Fig.5

Ratio of integrated intensities of CH4 in large and small cages (AL/AS)"

Fig.6

Percentage of integrated intensities of CH4 in large hydrate cages"

Fig. 7

PXRD patterns of CH4 hydrates and Ⅰh ice"

Fig.8

In situ PXRD patterns of CH4 hydrate in dissociation"

Fig.9

Percentage of characteristic peaks of crystal plane for CH4 hydrate and Ⅰh ice"

1 SunC, LiW, YangX, et al. Progress in research of gas hydrate[J]. Chinese Journal of Chemical Engineering, 2011, 19(1): 151-162.
2 EnglezosP, LeeJ D. Gas hydrates: a cleaner source of energy and opportunity for innovative technologies[J]. Korean Journal of Chemical Engineering, 2005, 22(5): 671-681.
3 SloanE D. Clathrate Hydrates of Natural Gases[M]. 2nd ed. New York: Marcel Decker, 2008: 532-535.
4 周雪冰, 陈玉凤, 易莉芝, 等. CH4-CO2混合气体水合物生成过程[J]. 石油化工, 2013, 42(5): 479-481.
ZhouX B, ChenY F, YiL Z, et al. Formation of hydrates of CH4-CO2 mixtures[J]. Petrochemical Technology, 2013, 42(5): 479-481.
5 周雪冰, 龙臻, 何勇, 等. CH4-CO2混合气体水合物在NaCl溶液中生成过程[J]. 工程热物理学报, 2016, 37(9): 1829-1833.
ZhouX B, LongZ, HeY, et al. Crystallization of the CH4-CO2 mixed gas hydrates in NaCl solutions[J]. Journal of Engineering Thermophysics, 37(9): 1829-1833.
6 LeeS, ParkS, LeeY, et al. Thermodynamic and 13C NMR spectroscopic verification of methane-carbon dioxide replacement in natural gas hydrates[J]. Chemical Engineering Journal, 2013, 225: 636-640.
7 LiangS, KusalikP G. Communication: structural interconversions between principal clathrate hydrate structures[J]. Journal of Chemical Physics, 2015, 143(011102): 1-5.
8 HansenT C, FalentyA, KuhsW F. Lattice constants and expansivities of gas hydrates from 10 K up to the stability limit[J]. Journal of Chemical Physics, 2016, 144(5): 1-11.
9 WalshM R, KohC A, SloanE D, et al. Microsecond simulations of spontaneous methane hydrate nucleation and growth[J]. Science, 2009, 326(5956): 1095-1098.
10 MimachiN, TakeyaS, YoneyamaA, et al. Natural gas storage and transportation within gas hydrate of smaller particle: size dependence of self-preservation phenomenon of natural gas hydrate[J]. Chemical Engineering Science, 2014, 118: 208-213.
11 MimachiN, TakahashiM, TakeyaS, et al. Effect of long-term storage and thermal history on the gas content of natural gas hydrate pellets under ambient pressure[J]. Energy & Fuels, 2015, 29: 4827-4834.
12 FalentyA, KuhsW F, GlockzinM, et al. “Self-preservation” of CH4 hydrates for gas transport technology: pressure-temperature dependence and ice microstructures[J]. Energy & Fuels, 2014, 28: 6275-6283.
13 TakeyaS, RipmeesterJ A. Dissociation behavior of clathrate hydrates to ice and dependence on guest molecules[J]. Angewandte Chemie-International Edition, 2008, 120: 1296-1299.
14 KomaiT, KangS, YoonJ, et al. In situ Raman spectroscopy investigation of the dissociation of methane hydrate at temperatures just below the ice point[J]. Journal of Physical Chemistry B, 2004, 108: 8062-8068.
15 ZhouX, LongZ, LiangS, et al. In situ Raman analysis on the dissociation behavior of mixed CH4-CO2 hydrates[J]. Energy & Fuels, 2016, 30: 1279-1286.
16 TakeyaS, MuromachiS, YamamotoY, et al. Preservation of CO2 hydrate under different atmospheric conditions[J]. Fluid Phase Equilibria. 2016, 413: 137-141.
17 ZhouX, LinF, LiangD. Multiscale analysis on CH4-CO2 swapping phenomenon occurred in hydrates[J]. Journal of Physical Chemistry C, 2016, 120: 25668-25677.
18 LeeY, KimY, SeoY. Enhanced CH4 recovery induced via structural transformation in the CH4/CO2 replacement that occurs in sH hydrates[J]. Environmental Science &Technology, 2015, 49: 8899-8906.
19 曹潇潇, 苏艳, 赵纪军, 等. 烷烃客体分子(CnHm, n≤6, m≤14)在51262和51264水笼中的稳定性与拉曼光谱的密度泛函理论计算[J]. 物理化学学报, 2014, 30(8): 1437-1446.
CaoX X, SuY, ZhaoJ J, et al. Stability and Raman spectroscopy of alkane guest molecules (CnHm, n≤6, m≤14) in 51262 and 51264 water cavities by density functional theory calculations[J]. Acta Physico-Chimica Sinica, 2014, 30(8): 1437-1446.
20 LiuC, LuH, YeY, et al. Raman spectroscopic observation on the structural characteristics and dissociation behavior of methane hydrate synthesized in silica sands with various sizes[J]. Energy & Fuels, 2008, 22: 3986-3988.
21 QinJ, KuhsW F. Quantitative analysis of gas hydrates using Raman spectroscopy[J]. AIChE J., 2013, 59(6): 2155-2167.
22 LuH, MoudrakovskiI, RiedelM, et al. Occurrence and structural characterization of gas hydrates associated with a cold vent field, offshore Vancouver Island[J]. Journal of Geophysical Research-Solid Earth, 2005, 110(B10204): 1-9.
23 SchicksJ, Luzi-HelbingM. Cage occupancy and structural changes during hydrate formation from initial stages to resulting hydrate phase[J]. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 2013, 115: 528-536.
24 TakeyaS, RipmeesterJ A. Anomalous preservation of CH4 hydrate and its dependence on the morphology of hexagonal ice[J]. Chemphyschem, 2010, 11: 70-73.
25 SmitW J, BakkerH. The surface of ice is like supercooled liquid water[J]. Angewandte Chemie- International Edition, 2017, 56(49): 15540-15544.
26 WeberB, NagataY, KetzetziS, et al. Molecular insight into the slipperiness of ice[J]. Journal of Physical Chemistry Letters, 2018, 9(11): 2838-2842.
[1] Jingchun YAN, Laihong SHEN, Shouxi JIANG, Huijun GE. Chemical looping combustion of high-sodium coal and gasification kinetics of coal char [J]. CIESC Journal, 2019, 70(5): 1913-1922.
[2] Zhixin SHANG, Xianglan ZHANG. DFT study on effects of hydrolysis degrees of 3-mercaptopropyltriethoxysilane on grafting mechanisms of nano-silica [J]. CIESC Journal, 2019, 70(5): 1663-1673.
[3] Linchen ZHOU, Zhigao SUN, Ling LU, Sai WANG, Juan LI, Cuimin LI. Formation and stability of HCFC–141b hydrate in organic phase change emulsion [J]. CIESC Journal, 2019, 70(5): 1674-1681.
[4] Dikun HONG, Zheng CAO, Changmin YANG, Liang LIU, Xin GUO. Catalytic effect of calcium on reaction of phenol using reactive molecular dynamics simulation [J]. CIESC Journal, 2019, 70(5): 1788-1794.
[5] Shuai REN, Xing LI, Jing ZHANG, Xiaohan WANG, Daiqing ZHAO. Investigation on combustion characteristics of ethanol and dimethyl ether micro-jet flames [J]. CIESC Journal, 2019, 70(5): 1973-1980.
[6] Desheng LI, Chao ZHANG, Shihai DENG, Zhifeng HU, Jinlong LI, Yuanhui LIU. Experimental study on effective nitrate removal from sewage by ZVI-based catalyzed reduction [J]. CIESC Journal, 2019, 70(3): 1065-1074.
[7] Xiaoxue CAO, Shaochang JI, Wenjie KUANG, Anping LIAO, Ping LAN, Jinyan ZHANG. Solubility and ternary phase diagram of azithromycin dihydrate in water-organic solvent [J]. CIESC Journal, 2019, 70(3): 817-829.
[8] Yongfei XUE, Yalin WANG, Bei SUN, Qianzhong LI, Jiazhou SUN. Improved state transfer algorithm-based kinetics parameter estimation for cascaded plug flow reactors [J]. CIESC Journal, 2019, 70(2): 607-616.
[9] Yan WANG, Lei SHI, Jiaqi FAN, Fei CHEN, Jie YAO, Guangwen XU. High-efficiency catalytic synthesis of polyoxymethoxy dimethylether from sulfolane-treated sulfonic acid resin [J]. CIESC Journal, 2019, 70(1): 116-127.
[10] ZHOU Kan, LI Wei, LI Junye, ZHU Hua, SHENG Kuang, BAI Guanghui, CHANG Hao. Flow boiling heat transfer characteristics of superhydrophilic modified surface in microchannels [J]. CIESC Journal, 2018, 69(S2): 82-88.
[11] XUE Chao, MAO Yanpeng, WANG Wenlong, SONG Zhanlong, ZHAO Xiqiang, SUN Jing, WANG Yanxiang. Treatment of phenol wastewater by microwave catalytic wet oxidation under high pressure [J]. CIESC Journal, 2018, 69(S2): 210-217.
[12] XU Xiaoying, YOU Hao, WANG Wen. Numerical simulations of desublimation of CO2 or water vapor in liquid methane with cellular automata method [J]. CIESC Journal, 2018, 69(S2): 402-407.
[13] ZOU Huiming, LI Xuan, TANG Mingsheng, SHAO Shuangquan, TIAN Changqing. Experimental investigation on refrigeration performance of R290 linear compressor [J]. CIESC Journal, 2018, 69(S2): 480-484.
[14] XU Jiaxing, CHAO Jingwei, LI Tingxian, WANG Ruzhu. Preparation and characterization of expanded graphite/metal organic frameworks composite sorbent [J]. CIESC Journal, 2018, 69(S2): 492-499.
[15] LUO Kai, WANG Jianhua, YU Junhuo, WENG Jun. Effect of methane concentration on diamond film in high power microwave plasma system [J]. CIESC Journal, 2018, 69(S2): 505-511.
Viewed
Full text


Abstract

Cited
  Shared   
  Discussed   
[1] LING Lixia, ZHANG Riguang, WANG Baojun, XIE Kechang. Pyrolysis Mechanisms of Quinoline and Isoquinoline with Density Functional Theory[J]. , 2009, 17(5): 805 -813 .
[2] LEI Zhigang, LONG Aibin, JIA Meiru, LIU Xueyi. Experimental and Kinetic Study of Selective Catalytic Reduction of NO with NH3 over CuO/Al2O3/Cordierite Catalyst[J]. , 2010, 18(5): 721 -729 .
[3] SU Haifeng, LIU Huaikun, WANG Fan, LÜXiaoyan, WEN Yanxuan. Kinetics of Reductive Leaching of Low-grade Pyrolusite with Molasses Alcohol Wastewater in H2SO4[J]. , 2010, 18(5): 730 -735 .
[4] WANG Jianlin, XUE Yaoyu, YU Tao, ZHAO Liqiang. Run-to-run Optimization for Fed-batch Fermentation Process with Swarm Energy Conservation Particle Swarm Optimization Algorithm[J]. , 2010, 18(5): 787 -794 .
[5] SUN Fubao, MAO Zhonggui, ZHANG Jianhua, ZHANG Hongjian, TANG Lei, ZHANG Chengming, ZHANG Jing, ZHAI Fangfang. Water-recycled Cassava Bioethanol Production Integrated with Two-stage UASB Treatment[J]. , 2010, 18(5): 837 -842 .
[6] Gao Ruichang, Song Baodong and Yuan Xiaojing( Chemical Engineering Research Center, Tianjin University, Tianjin 300072). LIQUID FLOW DISTRIBUTION IN GAS - LIQUID COUNTER - CONTACTING PACKED COLUMN[J]. , 1999, 50(1): 94 -100 .
[7] Su Yaxin, Luo Zhongyang and Cen Kefa( Institute of Thermal Power Engineering , Zhejiang University , Hangzhou 310027). A STUDY ON THE FINS OF HEAT EXCHANGERS FROM OPTIMIZATION OF ENTROPY GENERATION[J]. , 1999, 50(1): 118 -124 .
[8] Luo Xiaoping(Department of Industrial Equipment and Control Engineering , South China University of Technology, Guangzhou 510641)Deng Xianhe and Deng Songjiu( Research Institute of Chemical Engineering, South China University of Technology, Guangzhou 5106. RESEARCH ON FLOW RESISTANCE OF RING SUPPORT HEAT EXCHANGER WITH LONGITUDINAL FLUID FLOW ON SHELL SIDE[J]. , 1999, 50(1): 130 -135 .
[9] Jin Wenzheng , Gao Guangtu , Qu Yixin and Wang Wenchuan ( College of Chemical Engineering, Beijing Univercity of Chemical Technology, Beijing 100029). MONTE CARLO SIMULATION OF HENRY CONSTANT OF METHANE OR BENZENE IN INFINITE DILUTE AQUEOUS SOLUTIONS[J]. , 1999, 50(2): 174 -184 .
[10]

LI Qingzhao;ZHAO Changsui;CHEN Xiaoping;WU Weifang;LI Yingjie

.

Combustion of pulverized coal in O2/CO2 mixtures and its pore structure development

[J]. , 2008, 59(11): 2891 -2897 .
Copyright © 2019 CIESC Journal, All Rights Reserved.
Powered by Beijing Magtech Co. Ltd