纳米粒子作用下CO2水合物生成机理研究

doi:10.11949/0438-1157.20231357

摘要/Abstract

摘要：

气体水合物技术在海水淡化、水合物蓄冷、CO₂封存等领域有着广阔的应用前景，水合物快速生成是制约水合物技术应用的关键问题之一。利用自主搭建的CO₂水合物可视化生成实验装置进行了纳米流体中CO₂水合物生成特性的实验研究，分析了纳米粒子对CO₂水合物生成特性的影响。结果表明，与纯水相比，纳米流体体系中气体消耗量增加了2.17 mmol/mol，且诱导时间缩短了277.5 min。对不同种类的纳米流体中CO₂水合物生成特性的研究发现，氧化铜纳米流体中水合物生成的诱导时间最短，只有179 min。氧化铜纳米流体对CO₂水合物的促进存在一个最佳浓度，CO₂水合物耗气量随着氧化铜纳米流体质量分数的增加先增加后减少。不同种类的纳米流体中CO₂水合物生成过程中形态学图像存在较大差异。

关键词: CO₂水合物, 纳米流体, 传质, 动力学, 形态学

Abstract:

Gas hydrate technology has broad application prospects in the seawater desalination, hydrate cold storage, carbon dioxide storage, etc. The rapid hydrate formation is considered to be one of the key issues restricting the application of hydrate technology. The self-built CO₂ hydrate visual generation experimental device was used to conduct experimental research on the CO₂ hydrate generation characteristics in nanofluids, and the impact of nanoparticles on the CO₂ hydrate generation characteristics was analyzed. The results show that in the nanofluidic system, the gas consumption is increased by 2.17 mmol/mol but the induction time is shortened by 277.5 min, comparing with pure water. A study on the characteristics of CO₂ hydrate formation in different types of nanofluids found that the induction time of hydrate formation in copper oxide nanofluids was the shortest, only 179 min. There is an optimal concentration of CO₂ hydrate promotion with copper oxide nanofluids. The gas consumption of CO₂ hydrate increases firstly and then decreases with the increment in the mass fraction of copper oxide nanofluids. There are great differences in the morphological images of CO₂ hydrate formation in different nanofluids.

Key words: carbon dioxide hydrate, nanofluids, mass transfer, kinetics, morphology

中图分类号:

TQ 028.8

王佳琪, 魏皓琦, 苟阿静, 刘佳兴, 周昕霖, 葛坤. 纳米粒子作用下CO₂水合物生成机理研究[J]. 化工学报, 2024, 75(3): 956-966.

Jiaqi WANG, Haoqi WEI, Ajing GOU, Jiaxing LIU, Xinlin ZHOU, Kun GE. Study on the formation mechanism of CO₂ hydrate under the action of nanoparticles[J]. CIESC Journal, 2024, 75(3): 956-966.

图/表 17

图1 水合物生成装置示意图

Fig.1 Schematic diagram of the hydrate generation device

表1 配制各纳米流体所需实验材料用量

Table 1 Experimental materials dosage required for each nanofluid preparation

纳米流体体系	去离子水体积/ml	纳米粒子种类	纳米粒子质量/g
0.10%石墨纳米流体	50	石墨纳米粒子	0.05
0.08%石墨纳米流体	50	石墨纳米粒子	0.04
0.08%铜纳米流体	50	铜纳米粒子	0.04
0.08%氧化铜纳米流体	50	氧化铜纳米粒子	0.04
0.04%氧化铜纳米流体	50	氧化铜纳米粒子	0.02
0.06%氧化铜纳米流体	50	氧化铜纳米粒子	0.03
0.10%氧化铜纳米流体	50	氧化铜纳米粒子	0.05

图 2 石墨纳米流体沉降图像

Fig.2 Graphite nanofluid sedimentation images

图3 纯水和0.10%石墨纳米流体中水合物生成的压力、温度变化曲线

Fig.3 Pressure and temperature curve of hydrate formation in water and 0.10% graphite nanofluid

图4 水合物平均生成速率和耗气量随时间变化曲线

Fig.4 Average rate of hydrate formation and gas consumption curves over time

图5 纳米粒子对液体表面张力的影响

Fig.5 Schematic diagram of the effect of nanoparticles on the liquid surface tension

图6 不同种类纳米粒子对水合物生成过程温度、压力变化曲线的影响

Fig.6 Effect of different types of nanoparticles on the temperature and pressure curves of hydrate formation

图7 不同种类纳米粒子对水合物生成过程耗气量变化曲线的影响

Fig.7 Effect of different types of nanoparticles on the variation curve of gas consumption in the hydrate generation process

图8 纳米流体中分子示意图

Fig.8 Schematic diagram of molecules in nanofluids

图9 不同种类0.08%纳米流体对水合物生成实验结果的影响

Fig.9 Effect of different types of nanoparticles （0.08% nanofluids) on the experimental results of hydrate formation

图10 不同质量分数氧化铜纳米流体中水合物生成过程压力、温度变化曲线

Fig.10 Pressure and temperature curve of hydrate formation in copper oxide nanofluids with different mass fractions

图11 不同质量分数氧化铜纳米流体中水合物生成实验结果

Fig.11 Experimental results of hydrate formation in copper oxide nanofluids with different mass fractions

图12 0.1%石墨纳米流体中CO2水合物生成压力、温度的变化

Fig.12 Pressure and temperature variation of CO2 hydrate formation in 0.1% graphite nanofluid

图13 0.10%石墨纳米流体中CO2水合物生成过程形态学图像

Fig.13 Morphological image of CO2 hydrate formation process in 0.10% graphite nanofluid

图14 石墨纳米流体与纯水中CO2水合物生成过程形态学图像

Fig.14 Morphological image of CO2 hydrate formation process in graphite nanofluid and water

图15 0.10%铜纳米流体中CO2水合物生成过程形态学图像

Fig.15 Morphological image of CO2 hydrate formation process in 0.10% copper nanofluid

图16 0.10%氧化铜纳米流体中CO2水合物生成过程形态学图像

Fig.16 Morphological image of CO2 hydrate formation process in 0.10% copper oxide nanofluid

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纳米粒子作用下CO₂水合物生成机理研究

Study on the formation mechanism of CO₂ hydrate under the action of nanoparticles

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