The dual action of N2 on morphology regulation and mass-transfer acceleration of CO2 hydrate film

doi:10.1016/j.cjche.2024.04.027

中国化学工程学报 ›› 2024, Vol. 73 ›› Issue (9): 120-129.DOI: 10.1016/j.cjche.2024.04.027

The dual action of N₂ on morphology regulation and mass-transfer acceleration of CO₂ hydrate film

Jinrong Zhong¹, Yu Tian¹, Yifei Sun², Li Wan¹, Yan Xie³, Yujie Zhu², Changyu Sun², Guangjin Chen², Yuefei Zhang¹

1. School of Chemistry and Chemical Engineering, Changsha University of Science and Technology, Changsha 410114, China;
2. State Key Laboratory of Heavy Oil Processing, China University of Petroleum, Beijing 102249, China;
3. Institute of Environmental and Ecological Engineering, Guangdong University of Technology, Guangzhou 510006, China

收稿日期:2023-11-14 修回日期:2024-04-21 接受日期:2024-04-24 出版日期:2024-11-21 发布日期:2024-06-29
通讯作者: Yuefei Zhang,E-mail:zhangyuefei@csust.edu.cn
基金资助:
This work was financially supported by the National Natural Science Foundation of China (52106002, 22378424), Natural Science Foundation of Hunan Province (2023JJ40026), Hunan Provincial Department of Education Scientific Research Project (22B0310), Natural Science Foundation of Guangdong Province (2021A1515010578, 2020A1515110693) and Shanghai Key Laboratory of Multiphase Materials Chemical Engineering (MMCE2023001).

The dual action of N₂ on morphology regulation and mass-transfer acceleration of CO₂ hydrate film

Jinrong Zhong¹, Yu Tian¹, Yifei Sun², Li Wan¹, Yan Xie³, Yujie Zhu², Changyu Sun², Guangjin Chen², Yuefei Zhang¹

1. School of Chemistry and Chemical Engineering, Changsha University of Science and Technology, Changsha 410114, China;
2. State Key Laboratory of Heavy Oil Processing, China University of Petroleum, Beijing 102249, China;
3. Institute of Environmental and Ecological Engineering, Guangdong University of Technology, Guangzhou 510006, China

Received:2023-11-14 Revised:2024-04-21 Accepted:2024-04-24 Online:2024-11-21 Published:2024-06-29
Contact: Yuefei Zhang,E-mail:zhangyuefei@csust.edu.cn
Supported by:
This work was financially supported by the National Natural Science Foundation of China (52106002, 22378424), Natural Science Foundation of Hunan Province (2023JJ40026), Hunan Provincial Department of Education Scientific Research Project (22B0310), Natural Science Foundation of Guangdong Province (2021A1515010578, 2020A1515110693) and Shanghai Key Laboratory of Multiphase Materials Chemical Engineering (MMCE2023001).

摘要/Abstract

摘要： The morphology characteristics of CH₄, CO₂, and CO₂+N₂ hydrate film forming on the suspending gas bubbles are studied using microscopic visual method at supercooling conditions from 1.0 to 3.0 K. The hydrate film vertical growth rate and thickness along the planar gas-water interface are measured to study the hydrate formation kinetics and mass transfer process. Adding N₂ in the gas mixture plays the same role as lowering the supercooling conditions, both retarding the crystal nucleation and growth rates, which results in larger single crystal size and rough hydrate morphology. N₂ in the gas mixture helps to delay the secondary nucleation on the hydrate film, which is beneficial to maintain the pore-throat structure and enhance the mass transfer. The vertical growth rate of hydrate film mainly depends on the supercooling conditions and gas compositions but has weak dependence on the experimental temperature and pressure. Under the same gas composition condition, the final film thickness shows a linear relationship with the supercooling conditions. The mass transfer coefficient of CH₄ molecules in hydrates ranges from 4.54×10^-8 to 7.54×10^-8 mol·cm^-2·s^-1·MPa^-1. The maximum mass transfer coefficient for CO₂ + N₂ hydrate occurs at the composition of 60% CO₂ + 40% N₂, which is 3.98×10^-8 mol·cm^-2·s^-1·MPa^-1.

关键词: Gas hydrate, Morphology, Secondary nucleation, Formation kinetics, Mass transfer

Abstract: The morphology characteristics of CH₄, CO₂, and CO₂+N₂ hydrate film forming on the suspending gas bubbles are studied using microscopic visual method at supercooling conditions from 1.0 to 3.0 K. The hydrate film vertical growth rate and thickness along the planar gas-water interface are measured to study the hydrate formation kinetics and mass transfer process. Adding N₂ in the gas mixture plays the same role as lowering the supercooling conditions, both retarding the crystal nucleation and growth rates, which results in larger single crystal size and rough hydrate morphology. N₂ in the gas mixture helps to delay the secondary nucleation on the hydrate film, which is beneficial to maintain the pore-throat structure and enhance the mass transfer. The vertical growth rate of hydrate film mainly depends on the supercooling conditions and gas compositions but has weak dependence on the experimental temperature and pressure. Under the same gas composition condition, the final film thickness shows a linear relationship with the supercooling conditions. The mass transfer coefficient of CH₄ molecules in hydrates ranges from 4.54×10^-8 to 7.54×10^-8 mol·cm^-2·s^-1·MPa^-1. The maximum mass transfer coefficient for CO₂ + N₂ hydrate occurs at the composition of 60% CO₂ + 40% N₂, which is 3.98×10^-8 mol·cm^-2·s^-1·MPa^-1.

Key words: Gas hydrate, Morphology, Secondary nucleation, Formation kinetics, Mass transfer

Jinrong Zhong, Yu Tian, Yifei Sun, Li Wan, Yan Xie, Yujie Zhu, Changyu Sun, Guangjin Chen, Yuefei Zhang. The dual action of N₂ on morphology regulation and mass-transfer acceleration of CO₂ hydrate film[J]. 中国化学工程学报, 2024, 73(9): 120-129.

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The dual action of N₂ on morphology regulation and mass-transfer acceleration of CO₂ hydrate film

The dual action of N₂ on morphology regulation and mass-transfer acceleration of CO₂ hydrate film

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