Gas storage characteristics of methane hydrate in micro-powder silica gel below the freezing point

doi:10.16085/j.issn.1000-6613.2024-1751

Abstract

Abstract:

Hydrates can effectively store cooling energy and gases, showing great potential for applications in the field of gas storage and transportation. This paper investigated the formation of methane hydrate in micro-powder silica gel below the freezing point, with pressure ranging from 4.0— 6.0MPa and temperature ranging from 253.1—268.1K. The study found that after the silica gel pores were saturated with water, the volume occupied by the interstitial spaces between particles constituted 45% of the total volume. It served as a pathway for gas diffusion. At a constant pressure ranging from 5.0—6.0MPa, in the first 280—300min before methane hydrate formation, the higher the temperature, the easier methane diffused into the ice, leading to a higher formation rate of methane hydrate. In comparison, the driving force for hydrate formation had a smaller impact on the gas consumption rate. However, during the formation of hydrates, the rate of gas consumption for hydrate formation was alternately controlled by the methane diffusion rate and the hydrate nucleation rate. NR₁₂₀ represented the relative gas consumption rate during the first 120min. At lower pressures, the overall NR₁₂₀ was higher, the time to consume 90% of the gas (T₉₀) was shorter, and the final reaction pressure was lower, indicating a lower energy requirement for hydrate formation. Under the conditions of 268.1K and 4MPa, the water conversion rate reached 77.93%. NR₁₂₀ was 44.40mol/(min·m³), T₉₀ was 198min, and the gas storage capacity relative to water at standard conditions reached 150.78m³/m³, which represented the optimal conditions for methane hydrate formation.

Key words: methane, hydrate, silica gel, gas storage, conversion

摘要：

水合物可以有效地储存冷能和气体，在气体储存运输领域具有巨大的应用前景。本文研究了冰点以下微粉硅胶（silica gel）中甲烷水合物的生成，压力范围为4.0~6.0MPa，温度范围为253.1~268.1K。研究发现，微粉硅胶孔内水饱和以后，颗粒之间体积占整体体积的45%，为气体扩散提供通道。在5.0~6.0MPa的相同压力下，甲烷水合物生成前280~300min，温度越高，甲烷越容易扩散进入冰中，导致甲烷水合物的生成速率越高，相比之下，水合物的生成驱动力对气体消耗速率影响较小。然而，在水合物生成过程中，甲烷扩散速率和水合物成核速率交替控制水合物气体的消耗速率。NR₁₂₀为前120min的相对气体消耗速率，压力越低，NR₁₂₀整体越高，完成90%气体消耗量的时间为T₉₀，整体越短，反应终结压力越低，所需生成水合物压缩能越低。在268.1K、4MPa的条件下，水的转化率为77.93%。NR₁₂₀为44.40mol/(min·m³)、T₉₀为198min，标准状态下相对于水的储气能力达到150.78m³/m³，是甲烷水合物生成的最佳条件。

关键词: 甲烷, 水合物, 微粉硅胶, 储气, 转化率

CLC Number:

TE89

LIU Jun, LAN Jiangchen, WANG Weiqiang, WANG Beifu, GAO Jianfeng, ZHENG Zhaoqi, CHENG Longsheng, LIANG Deqing. Gas storage characteristics of methane hydrate in micro-powder silica gel below the freezing point[J]. Chemical Industry and Engineering Progress, 2025, 44(11): 6290-6300.

刘军, 蓝江晨, 王卫强, 王北福, 高建丰, 郑兆棋, 程龙生, 梁德青. 冰点以下微粉硅胶中甲烷水合物储气特性[J]. 化工进展, 2025, 44(11): 6290-6300.

Figures/Tables 12

参数	数值
硅胶种类	微粉硅胶
微粉硅胶球形颗粒平均直径/μm	40~75
微粉硅胶中平均孔径/nm	40.3
微粉硅胶比孔体积/m³·kg^-1	7.8×10^-4
微粉硅胶比表面积/m²·kg^-1	83.4×10³

序号	温度/K	压力/MPa	过冷度/℃	NR₁₂₀ /mol·min^-1·m^-3	T₉₀/min	实验结束		储气能力/m³·m^-3
序号	温度/K	压力/MPa	过冷度/℃	NR₁₂₀ /mol·min^-1·m^-3	T₉₀/min	NG _t /mol·mol^-1	转化率^②/%	GS_Si	$G S H 2 O$
1	268.1	4	9.35	44.40	198	0.121	77.93	58.59	150.78
2	268.1	5	11.85	50.23	145	0.127	81.47	61.25	157.64
3	268.1	6	13.65	49.48	175	0.128	82.27	61.85	159.17
4	263.1	4	14.35	45.50	308	0.132	84.84	63.78	164.16
5	263.1	5	16.85	33.63	329	0.114	73.51	55.26	142.22
6	263.1	6	18.65	28.59	558	0.120	76.93	57.83	148.84
7	258.1	4	19.35	48.37	260	0.130	83.33	62.64	161.22
8	258.1	5	21.85	30.93	497	0.124	79.82	60.01	154.44
9	258.1	6	23.65	24.39	594	0.119	76.75	57.70	148.49
10	253.1	4	24.35	39.88	414	0.137	88.20	66.30	170.64
11	253.1	5	26.85	31.72	537	0.131	84.24	63.33	162.99
12	253.1	6	28.65	22.66	834	0.156	100.00	75.18	193.47

序号	温度/K	压力/MPa	过冷度/℃	NR₁₂₀ /mol·min^-1·m^-3	T₉₀/min	实验结束		储气能力/m³·m^-3
序号	温度/K	压力/MPa	过冷度/℃	NR₁₂₀ /mol·min^-1·m^-3	T₉₀/min	NG _t /mol·mol^-1	转化率^②/%	GS_Si	$G S H 2 O$
1	268.1	4	9.35	44.40	198	0.121	77.93	58.59	150.78
2	268.1	5	11.85	50.23	145	0.127	81.47	61.25	157.64
3	268.1	6	13.65	49.48	175	0.128	82.27	61.85	159.17
4	263.1	4	14.35	45.50	308	0.132	84.84	63.78	164.16
5	263.1	5	16.85	33.63	329	0.114	73.51	55.26	142.22
6	263.1	6	18.65	28.59	558	0.120	76.93	57.83	148.84
7	258.1	4	19.35	48.37	260	0.130	83.33	62.64	161.22
8	258.1	5	21.85	30.93	497	0.124	79.82	60.01	154.44
9	258.1	6	23.65	24.39	594	0.119	76.75	57.70	148.49
10	253.1	4	24.35	39.88	414	0.137	88.20	66.30	170.64
11	253.1	5	26.85	31.72	537	0.131	84.24	63.33	162.99
12	253.1	6	28.65	22.66	834	0.156	100.00	75.18	193.47

References 25

[1]	周印洁, 吉思蓓, 何松阳, 等. 机器学习辅助高通量筛选金属有机骨架用于富碳天然气中分离CO₂ [J]. 化工学报, 2025, 76(3): 1093-1101.
	ZHOU Yinjie, JI Sibei, HE Songyang, et al. Machine learning-assisted high-throughput screening approach for CO₂ separation from CO₂-rich natural gas using metal-organic frameworks[J]. CIESC Journal, 2025, 76(3): 1093-1101.
[2]	向腾龙, 王治红, 汪贵, 等.液化天然气冷能梯级利用的多功能集成系统研究[J].化工学报, 2024, 75(10): 3401-3413.
	XIANG Tenglong, WANG Zhihong, WANG Gui, et al. Research on multifunctional integrated system for cold energy cascade utilization of liquefied natural gas[J]. CIESC Journal, 2024, 75(10): 3401-3413.
[3]	刘军, 马贵阳, 潘振, 等. 水合物晶核充分发展对水合物生成量影响的实验研究[J]. 工程热物理学报, 2016, 37(5): 941-945.
	LIU Jun, MA Guiyang, PAN Zhen, et al. A experimental study on the change of the number of hydrate formation affected by hydrate nucleation fully development[J]. Journal of Engineering Thermophysics, 2016, 37(5): 941-945.
[4]	王谨航, 何勇, 史伶俐, 等. 气体水合物阻聚剂研究进展[J]. 化工进展, 2023, 42(9): 4587-4602.
	WANG Jinhang, HE Yong, SHI Lingli, et al. Progress of gas hydrate anti-agglomerants[J]. Chemical Industry and Engineering Progress, 2023, 42(9): 4587-4602.
[5]	张准顺, 潘振, 包瑞新, 等. 掺氢比对天然气管道泄漏扩散影响的模拟研究[J]. 辽宁石油化工大学学报, 2024, 44(4): 44-50.
	ZHANG Zhunshun, PAN Zhen, BAO Ruixin, et al. Simulation study on the influence of hydrogen blending ratio on natural gas pipeline leakage and diffusion[J]. Journal of Liaoning Petrochemical University, 2024, 44(4): 44-50.
[6]	陈旭阳, 杨帆, 姜文全, 等. 基于LNG冷能的卡琳娜-三级有机朗肯循环性能分析[J]. 辽宁石油化工大学学报, 2024, 44(5): 90-96.
	CHEN Xuyang, YANG Fan, JIANG Wenquan, et al. Performance analysis of the kalina-three-stage organic rankine combined cycle based on LNG cold energy[J]. Journal of Liaoning Petrochemical University, 2024, 44(5): 90-96.
[7]	刘礼豪, 黄婷, 雍宇, 等. 含粉砂盐水体系甲烷水合物生成与固相沉积规律[J]. 化工学报, 2024, 75(5): 1987-2000.
	LIU Lihao, HUANG Ting, YONG Yu, et al. CH₄-hydrate formation and solid-phase deposition in salt-sand coexisting flow systems[J]. CIESC Journal, 2024, 75(5): 1987-2000.
[8]	樊栓狮, 刘发平, 郎雪梅, 等. CO₂捕集与置换开采天然气水合物中甲烷的研究进展[J]. 天然气化工 — C₁化学与化工, 2022, 47(4): 1-10.
	FAN Shuanshi, LIU Faping, LANG Xuemei, et al. Research progress of CO₂ capture and replacement of methane from natural gas hydrates[J]. Natural Gas Chemical Industry, 2022, 47(4): 1-10.
[9]	姚国宝, 李占东, 范瑞彬, 等. 外部扰动促进气体水合物生成方法的研究进展[J]. 能源化工, 2023, 44(4): 8-15.
	YAO Guobao, LI Zhandong, FAN Ruibin, et al. Research progress on methods for promoting gas hydrate formation through external disturbances[J]. Energy Chemical Industry, 2023, 44(4): 8-15.
[10]	刘军, 潘振, 马贵阳, 等. 降低“固封” 对甲烷水合物生成的影响[J]. 化工进展, 2016, 35(5): 1410-1417.
	LIU Jun, PAN Zhen, MA Guiyang, et al. Experimental study on decreasing the effect of the solid seal on methane hydrate[J]. Chemical Industry and Engineering Progress, 2016, 35(5): 1410-1417.
[11]	HE S, LIANG D Q, LI D L, et al. The formation of natural gas hydrate from SDS-solutions and decomposition by microwave heating in a static reactor[J]. Petroleum Science and Technology, 2013, 31(16): 1655-1664.
[12]	LIU Weiguo, LI Yanghui, XU Xiaohu. Influence factors of methane hydrate formation from ice:Temperature, pressure and SDS surfactant[J]. Chinese Journal of Chemical Engineering, 2019, 27(2): 405-410.
[13]	LI Xingxun, LIU Ming, LI Qingping, et al. TBAB hydrate formation and growth in a microdevice under static and dynamic conditions[J]. Petroleum Science, 2024, 21(2): 1396-1404.
[14]	SHI Bohui, SONG Shangfei, CHEN Yuchuan, et al. Rheological study of methane gas hydrates in the presence of micron-sized sand particles[J]. Chinese Journal of Chemical Engineering, 2024, 70: 149-161.
[15]	邝若谷, 吴良猛, 谢凤梅, 等. 活性炭+THF溶液体系中CO₂水合物生成特性研究[J]. 低碳化学与化工, 2023, 48(5): 109-114, 134.
	KUANG Ruogu, WU Liangmeng, XIE Fengmei, et al. Study on characteristics of CO₂ hydrate formation in activated carbon+THF solution system[J]. Low-Carbon Chemistry and Chemical Engineering, 2023, 48(5): 109-114, 134.
[16]	DONG Lin, LIU Xiaoqiang, GONG Bin, et al. Geomechanical properties of hydrate-bearing strata and their applications[J]. Advances in Geo-Energy Research, 2024, 11(3): 161-167.
[17]	ZHOU Xueqing, WU Shiguo, BOSIN Aleksandr, et al. Evaluation of CO₂ hydrate storage potential in the Qiongdongnan Basin via combining the phase equilibrium mechanism and the volumetric method[J]. Advances in Geo-Energy Research, 2024, 11(3): 220-229.
[18]	LIU Jun, LIANG Deqing. Investigation on methane hydrate formation in silica gel particles below the freezing point[J]. RSC Advances, 2019, 9(26): 15022-15032.
[19]	郎雪梅, 姚柳眉, 樊栓狮, 等. 多孔材料中甲烷水合物生成的传热数值模拟研究[J]. 化工学报, 2022, 73(9): 3851-3860.
	LANG Xuemei, YAO Liumei, FAN Shuanshi, et al. Numerical simulation of methane hydrate formation and heat transfer in porous materials[J]. CIESC Journal, 2022, 73(9): 3851-3860.
[20]	SEO Yongwon, LEE Huen, UCHIDA Tsutomu. Methane and carbon dioxide hydrate phase behavior in small porous silica gels: Three-phase equilibrium determination and thermodynamic modeling[J]. Langmuir, 2002, 18(24): 9164-9170.
[21]	ZHONG Dongliang, LI Zheng, LU Yiyu, et al. Investigation of CO₂ capture from a CO₂ + CH₄ gas mixture by gas hydrate formation in the fixed bed of a molecular sieve[J]. Industrial & Engineering Chemistry Research, 2016, 55(29): 7973-7980.
[22]	ZHU Yujie, CHEN Yuzhou, XIE Yan, et al. Microscopic experimental study on the effects of NaCl concentration on the self-preservation effect of methane hydrates under 268.15K[J]. Chinese Journal of Chemical Engineering, 2024, 73:1-14.
[23]	DUAN Jun, ZHONG Keyi, JIANG Shuyi, et al. Insight into the micro-mechanism of hydrate-based methane storage from active ice[J]. Fuel, 2025, 381: 133-154.
[24]	KANG Seong-Pil, LEE Jonghyub, SEO Yutaek. Pre-combustion capture of CO₂ by gas hydrate formation in silica gel pore structure[J]. Chemical Engineering Journal, 2013, 218: 126-132.
[25]	ZARIFI Mojdeh, JAVANMARDI Jafar, HASHEMI Hamed, et al. Experimental study and thermodynamic modelling of methane and mixed C₁ + C₂ + C₃ clathrate hydrates in the presence of mesoporous silica gel[J]. Fluid Phase Equilibria, 2016, 423: 17-24.