泡沫铜强化甲烷水合物生成动力学实验研究

doi:10.11949/0438-1157.20210662

摘要/Abstract

摘要：

提高水合物生成速率和储气密度对天然气水合物技术应用非常重要。将三种孔密度的泡沫铜（CF）分别浸入十二烷基硫酸钠（SDS）溶液中构建水合储气强化体系，在高压静态反应釜中研究泡沫金属对甲烷水合物生成动力学特性。实验结果表明，泡沫铜骨架能为水合物生成提供充足的结晶点，同时可作为水合物生长过程水合热迁移的“高速公路”。甲烷水合物在SDS/CF体系中可快速生成，最大水合储气速率分布在19.24~21.04 mmol·mol^-1·min^-1之间，其中添加15 PPI泡沫铜的SDS溶液储气量最高（139 mmol·mol^-1），且达到最大储气量90%所用时间最短（10.1 min）。在6.0~8.0 MPa压力下，相比SDS溶液，添加15 PPI泡沫铜的SDS溶液储气量提高了8.8%~35.6%，储气速率提高了4.7%~40.4%；特别在压力为5.0 MPa时，该孔密度SDS/CF体系储气量甚至比SDS溶液增加13倍，储气速率增加16倍。

关键词: 泡沫铜, 甲烷水合物, 生成, 动力学, 强化

Abstract:

Increasing hydrate formation rate and gas storage density is very important for the application of natural gas hydrate storage and transportation technology. Three pieces of copper foam (CF) with different pore density herein were immersed in sodium dodecyl sulfate (SDS) solution to build a gas storage enhancement system, and to study on the kinetic characteristics of the formation of methane hydrate by metal foam in a high-pressure static reactor. The research results showed that the copper foam framework can provide sufficient crystallization points for the formation of hydrates, at the same time, it can be used as a “highway” for hydration heat transfer during hydrate growth. Methane hydrate can be quickly formed in SDS/CF system, the maximum hydration gas storage rate is between 19.24—21.04 mmol·mol^-1·min^-1, the gas storage capacity of the SDS solution with 15 PPI copper foam was the highest (139 mmol·mol^-1), and it takes the shortest time to reach 90% of the maximum gas storage capacity (10.1 min). Under the pressure of 6.0—8.0 MPa, compared with SDS solution, the gas storage capacity of SDS solution with 15 PPI CF increased by 8.8%—35.6%, and the gas storage rates increased by 4.7%—40.4%. When the pressure is 5.0 MPa, the gas storage capacity of the pore density SDS/CF system is even increased by 13 times than that of the SDS solution, and the gas storage rate is increased by 16 times.

Key words: copper foam, methane hydrate, formation, kinetics, enhancement

中图分类号:

TE 89

裴俊华, 杨亮, 汪鑫, 胡晗, 刘道平. 泡沫铜强化甲烷水合物生成动力学实验研究[J]. 化工学报, 2021, 72(11): 5751-5760.

Junhua PEI, Liang YANG, Xin WANG, Han HU, Daoping LIU. Experimental study on kinetics of methane hydrate formation enhanced by copper foam[J]. CIESC Journal, 2021, 72(11): 5751-5760.

图/表 10

图1 不同孔密度泡沫铜样品

Fig.1 Copper foam samples with different pore densities

图2 水合储气实验装置

Fig.2 Experimental apparatus for gas storage in the hydrate

图3 SDS溶液填充泡沫铜体系水合储甲烷过程温压变化(P = 8.0 MPa, T = 274.15 K)

Fig.3 Variation of temperature and pressure during hydration and methane storage of copper foam system with different pore density filled with SDS solution

图4 SDS溶液及其填充泡沫铜体系储气过程中储气量和储气速率变化（P=8.0 MPa, T=274.15 K）

Fig.4 Changes in gas storage capacity and gas storage rate of SDS solution and its filled with copper foam system during gas storage

表1 所有水合储气实验结果

Table 1 Experimental results of all gas storage

Hydrate systems	P/MPa	t_in/min	C_s,max/(mmol·mol^-1)	R_s,max/(mmol·mol^-1·min^-1)	t₉₀/min
0.05% SDS + 5 PPI CF	8.0	52.1	129.1	19.24	61.4
0.05% SDS + 15 PPI CF	8.0	1.5	139.0	20.73	10.1
0.05% SDS + 30 PPI CF	8.0	68.8	131.8	21.04	77.5
0.05% SDS + 15 PPI CF	7.0	39.5	135.7	19.57	52.1
0.05% SDS + 15 PPI CF	6.0	49.4	133.2	15.00	74.6
0.05% SDS + 15 PPI CF	5.0	63.8	129.5	11.58	77.2
0.05% SDS	8.0	73.5	127.8	14.77	85.3
0.05% SDS	7.0	58.6	122.8	15.14	81.7
0.05% SDS	6.0	84.3	98.2	14.32	104.2
0.05% SDS	5.0	—	9.0	0.68	—

图5 甲烷水合物在SDS溶液及其填充泡沫铜体系中t90

Fig.5 t90 of methane hydrate in SDS solution and its filled copper foam system

图6 15 PPI泡沫铜扫描电镜图

Fig.6 Scanning electron microscope of copper foam (15 PPI)

图7 SDS溶液填充泡沫铜体系中水合物生成实物图

Fig.7 Physical images of hydrate growth in a copper foam system filled with SDS solution

图8 变压力下甲烷水合物在SDS/CF和SDS体系中生成动力学

Fig.8 Kinetics of methane hydrate formation in SDS/CF and SDS systems under variable pressure

图9 SDS/CF和SDS体系中水合物最大储气量(a)和最大储气速率(b)

Fig.9 Maximum gas storage capacity (a) and maximum gas storage rates (b) of hydrate in SDS/CF and SDS systems

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