Research progress on influencing factors and strengthening mechanism of CO2-CH4 hydrate replacement in porous media system

doi:10.16085/j.issn.1000-6613.2021-2632

Chemical Industry and Engineering Progress ›› 2022, Vol. 41 ›› Issue (10): 5259-5271.DOI: 10.16085/j.issn.1000-6613.2021-2632

• Energy processes and technology • Previous Articles Next Articles

Research progress on influencing factors and strengthening mechanism of CO₂-CH₄ hydrate replacement in porous media system

ZHANG Xuemin¹^,²^,³(), ZHANG Shanling¹^,²^,³, LI Pengyu¹^,²^,³, HUANG Tingting¹^,²^,³, YIN Shaoqi¹^,²^,³, LI Jinping¹^,²^,³, WANG Yingmei¹^,²^,⁴

^1.School of Energy and Power Engineering, Lanzhou University of Technology, Lanzhou 730050, Gansu, China
^2.Key Lab of Complementary Energy System of Biomass and Solar Energy Gansu Province, Lanzhou 730050, Gansu, China
^3.Western China Energy & Environment Research Center, Lanzhou University of Technology, Lanzhou 730050, Gansu, China
^4.Northwest Institute of Eco-Environment and Resources, Chinese Academy of Sciences, Lanzhou 730000, Gansu, China

Received:2021-12-27 Revised:2022-02-15 Online:2022-10-21 Published:2022-10-20
Contact: ZHANG Xuemin

多孔介质中CO₂-CH₄水合物置换的影响因素及强化机理研究进展

张学民¹^,²^,³(), 张山岭¹^,²^,³, 李鹏宇¹^,²^,³, 黄婷婷¹^,²^,³, 尹绍奇¹^,²^,³, 李金平¹^,²^,³, 王英梅¹^,²^,⁴

^1.兰州理工大学能源与动力工程学院，甘肃兰州 730050
^2.甘肃省生物质能与太阳能互补供能系统重点实验室，甘肃兰州 730050
^3.兰州理工大学西部能源与环境研究中心，甘肃兰州 730050
^4.中国科学院西北生态环境资源研究院冻土工程国家重点实验室，甘肃兰州 730000

通讯作者: 张学民
作者简介:张学民（1987—），男，博士，副教授，硕士生导师，主要从事气体水合物生成与分解动力学方面的研究。E-mail：zxm2010lut@163.com。
基金资助:
国家自然科学基金(51906093);中科院天然气水合物重点实验室开放基金(Y907ke1001);兰州理工大学“红柳优秀青年人才支持计划”（2018）

Abstract

Abstract:

Natural gas hydrate has become one of the most promising clean energy sources in the future due to its huge reserves, clean and pollution-free.CO₂ replacement method can realize the safe exploitation of natural gas hydrate and the storage of greenhouse gas. However, the replacement process of CO₂-CH₄ hydrate in porous media is characterized by long reaction period, slow rate and low efficiency, which has become a bottleneck restricting the efficient exploitation of natural gas hydrate. In this paper, the displacement characteristics of CO₂-CH₄ hydrate in porous media system are reviewed, and the displacement mechanism and dynamic process of CO₂-CH₄ hydrate are analyzed. On this basis, the effects of different factors on the efficiency of CO₂-CH₄ hydrate replacement in porous media and their strengthening mechanisms are described in detail, including thermal stimulation, displacement pressure, small molecule gas and chemical additives. Finally, the shortcomings and future development direction of CO₂-CH₄ hydrate replacement enhancement technology in porous media system are pointed out. Further research is needed to understand the strengthening mechanism and dynamic mechanism of CO₂-CH₄ hydrate replacement in porous media.

Key words: gas hydrate, porous media, displacement characteristics, CO₂ sequestration, strengthening mechanism

摘要：

天然气水合物因其储量巨大、清洁无污染而成为未来最具潜力的清洁能源之一，CO₂置换法可实现天然气水合物的安全开采和温室气体的地层封存。然而，多孔介质中CO₂-CH₄水合物的置换过程存在反应周期长、速率慢、效率低等特点，已成为制约天然气水合物高效开采的瓶颈问题。本文全面综述了多孔介质体系中CO₂-CH₄水合物的置换特性，分析了CO₂-CH₄水合物的置换机理及其动力学过程。在此基础上，详述了不同因素对多孔介质中CO₂-CH₄水合物置换效率的影响规律及强化机理，包括热刺激、置换压力、小分子气体、化学添加剂等的作用机理及其规律。最后指出了多孔介质体系中CO₂-CH₄水合物置换过程强化技术存在的不足和未来的发展方向。对多孔介质体系中CO₂-CH₄水合物置换过程的强化机理及其动力学机制的认识仍需进一步研究。

关键词: 天然气水合物, 多孔介质, 置换特性, CO₂封存, 强化机理

CLC Number:

TK01⁺9

ZHANG Xuemin, ZHANG Shanling, LI Pengyu, HUANG Tingting, YIN Shaoqi, LI Jinping, WANG Yingmei. Research progress on influencing factors and strengthening mechanism of CO₂-CH₄ hydrate replacement in porous media system[J]. Chemical Industry and Engineering Progress, 2022, 41(10): 5259-5271.

张学民, 张山岭, 李鹏宇, 黄婷婷, 尹绍奇, 李金平, 王英梅. 多孔介质中CO₂-CH₄水合物置换的影响因素及强化机理研究进展[J]. 化工进展, 2022, 41(10): 5259-5271.

Figures/Tables 8

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CH₄回收率 /%	置换时初始压力 /MPa	热刺激方式	研究者
68.8	3.3	加热功率为100W	Tupsakhare等^［52］
49.42	8.03	每两小时加热15min（共加热三次）	Ouyang等^［20］
64.6	2.13	温度从273.65K提升到279.15K并维持2h	Zhang等^［49］
75~93	2	温度升到289.15K并保持200min	Yang等^［97］
82.2	3	温度设置成275.65K并保持18h	Stanwix等^［6］
60	3	温度在271.15~278.15K循环	Tupsakhare等^［98］
44	7.8	升高温度直至观察到分解时刻	Gambelli等^［46］

CH₄回收率 /%	置换时初始压力 /MPa	热刺激方式	研究者
68.8	3.3	加热功率为100W	Tupsakhare等^［52］
49.42	8.03	每两小时加热15min（共加热三次）	Ouyang等^［20］
64.6	2.13	温度从273.65K提升到279.15K并维持2h	Zhang等^［49］
75~93	2	温度升到289.15K并保持200min	Yang等^［97］
82.2	3	温度设置成275.65K并保持18h	Stanwix等^［6］
60	3	温度在271.15~278.15K循环	Tupsakhare等^［98］
44	7.8	升高温度直至观察到分解时刻	Gambelli等^［46］

CH₄回收率 /%	置换时初始温度 /K	压力或减压方式	研究者
32.66	273.65	每次减压时压力从2.92MPa降到1.74MPa并维持30min（共减压三次）	Sun等^［60］
63.3	274.15	通过减压使水合物分解比为20%时再进行置换	Lee等^［56］
71	274.15	CO₂气体分压为1.8MPa	Ding等^［58］
66	276.2	压力降至2MPa直至置换反应结束	Sun等^［99］
85.3～89.1	279.15	通过多级减压将压力从6MPa降至3MPa	Gao等^［100］
49	277.2	实验压力为3.5MPa	Liu等^［101］
31	276.15	CO₂气体分压为4.5MPa	Xu等^［55］

CH₄回收率 /%	置换时初始温度 /K	压力或减压方式	研究者
32.66	273.65	每次减压时压力从2.92MPa降到1.74MPa并维持30min（共减压三次）	Sun等^［60］
63.3	274.15	通过减压使水合物分解比为20%时再进行置换	Lee等^［56］
71	274.15	CO₂气体分压为1.8MPa	Ding等^［58］
66	276.2	压力降至2MPa直至置换反应结束	Sun等^［99］
85.3～89.1	279.15	通过多级减压将压力从6MPa降至3MPa	Gao等^［100］
49	277.2	实验压力为3.5MPa	Liu等^［101］
31	276.15	CO₂气体分压为4.5MPa	Xu等^［55］

方法	温度/K	压力/MPa	反应时间/h	CH₄回收率/%	研究者
气态CO₂	273	3.36	100	20	Ota等^［26］
气态CO₂	272.2	3.6/4.0/4.5	150	8.63/10.89/13.2	Zhang等^［102］
气态CO₂	275	2.91/2.93	225/200	23/6	Li等^［103］
气态CO₂	274	4.5	34	35	Ryou等^［89］
液态CO₂	273.2	4	700	26.4	Wang等^［104］
液态CO₂	282.2	6	288	45	Li等^［103］
液态CO₂	275	9	80	40.2	Lee等^［105］
CO₂乳化液	281.2	5	96	27.1	Zhou等^［12］
CO₂+N₂（25∶75）	274.2	10	280	25	Pan等^［106］
CO₂+N₂（20∶80）	274	17	72	39	Choi等^［74］
CO₂+N₂（60∶40）	274	4.5	192	73.42	Xu等^［43］
CO₂+N₂（21∶79）	285.2	12/15	200	86/75	Li等^［107］
CO₂+H₂（60∶40）	274.15	4.5	192	70.21	Ding等^［58］
CO₂+H₂（18∶82）	275.65	5	300	70	Wang等^［108］
CO₂+H₂（40∶60）	274	4.5	192	78.02	Xu等^［43］
CO₂+H₂（56∶44）	276.12～276.23	3.70～3.80	4	61～75	Sun等^［99］
CO₂+H₂（43∶57）	276	3.67	320	61	Sun等^［109］
CO₂+H₂（0∶100）	276	3.67	320	63	Sun等^［109］
CO₂+CH₃OH	274.41	3.3	56.62	92	Khlebnikov等^［82］
CO₂+Rhamnolipid（鼠李糖脂）	276.15	3.1	92	18.02	Heydari等^［84］
CO₂+TMACl（四甲基氯化铵）	274.15	6	24	83	Moujdin等^［21］