化工学报 ›› 2024, Vol. 75 ›› Issue (11): 4369-4377.DOI: 10.11949/0438-1157.20240574
梁爽1(), 李兴洵1(), 高龙燕1, 郭绪强2, 陈光进1, 孙长宇1
收稿日期:
2024-05-30
修回日期:
2024-08-09
出版日期:
2024-11-25
发布日期:
2024-12-26
通讯作者:
李兴洵
作者简介:
梁爽(1995—),男,博士研究生,2697972207@qq.com
基金资助:
Shuang LIANG1(), Xingxun LI1(), Longyan GAO1, Xuqiang GUO2, Guangjin CHEN1, Changyu SUN1
Received:
2024-05-30
Revised:
2024-08-09
Online:
2024-11-25
Published:
2024-12-26
Contact:
Xingxun LI
摘要:
在海底或寒冷地区原油的开采和运输过程中,当达到气体水合物形成的温度和压力条件后,水合物会在管道内形成和聚集,进而堵塞管道、阀门等,威胁油气运输安全。因此,研究水合物在油气输送管道中的形成问题一直是油气生产和运输部门关注的焦点。本实验应用高压可视水合物膜生长微观实验装置,采用悬滴法对悬垂在甲苯、甲苯与正庚烷混合油相(1∶1,体积比)、正庚烷中的微水滴表面甲烷水合物膜形貌与生长特性进行研究,测定了不同温度(274.15~277.15 K)和压力(5.37~7.26 MPa)下甲烷水合物膜生长动力学数据。实验结果表明,水合物膜生长速率随甲烷在不同油相中的溶解度增大而增大,膜生长速率(274.15 K,6 MPa)在正庚烷中(0.26 mm/s)>混合油中(0.23 mm/s)>甲苯中(0.21 mm/s)。水合物膜增厚生长过程中水通过膜向外转移,使得水合物膜上的褶皱间的“沟壑”逐渐被增厚生长的水合物填平,甲苯中形成的水合物表面粗糙增厚速率最快而正庚烷中形成的水合物膜表面光滑增厚速率最慢。温度的降低和压力的增加都使得水合物膜横向生长速率增加,其中压力的影响比温度更显著,且生长速率均呈现在甲苯中最慢正庚烷中最快。以压力差为驱动力的模型可很好地预测甲烷水合物膜生长动力学数据(AARD=6.12%)。
中图分类号:
梁爽, 李兴洵, 高龙燕, 郭绪强, 陈光进, 孙长宇. 油相中水滴表面甲烷水合物膜生长动力学研究[J]. 化工学报, 2024, 75(11): 4369-4377.
Shuang LIANG, Xingxun LI, Longyan GAO, Xuqiang GUO, Guangjin CHEN, Changyu SUN. Research on kinetics of methane hydrate film growth on water droplet in oil phase[J]. CIESC Journal, 2024, 75(11): 4369-4377.
图6 不同油相中生成的水合物膜增厚生长1 h前后形貌对比(a),(d)在甲苯中增厚生长前和生长后的水合物膜;(b),(e)在混合油中增厚生长前和生长后的水合物膜;(c),(f)在正庚烷中增厚生长前和生长后的水合物膜Fig.6 Morphology comparison of hydrate films before and after 1 h of thickening growth(a), (d) hydrate film before and after thickening growth in toluene; (b), (e) hydrate film before and after thickening growth in mixed oil; (c), (f) hydrate film before and after thickening growth in n-heptane
图7 图6中红框处同油相中生成的水合物膜增厚生长1 h前后形貌局部放大对比(a),(d)在甲苯中增厚生长前和生长后的水合物膜;(b),(e)在混合油中增厚生长前和生长后的水合物膜;(c),(f)在正庚烷中增厚生长前和生长后的水合物膜(a), (d) hydrate film before and after thickening growth in toluene; (b), (e) hydrate film before and after thickening growth in mixed oil; (c), (f) hydrate film before and after thickening growth in n-heptane
Fig.7 Morphology comparison of local magnification of the hydrate films before and after 1 h of thickening growth at the red box in Fig.6
图9 不同压力和油相中水滴表面水合物膜生长速率对比(274.15 K)
Fig.9 The comparison of hydrate film growth rates on water droplet surfaces in different pressure and oil (274.15 K)
油样 | 温度/ K | 压力/ MPa | ΔP/MPa | ψ | 实验值/ (mm/s) | 计算值/ (mm/s) | AARD/% |
---|---|---|---|---|---|---|---|
甲苯 | 274.15 | 5.37 | 2.48 | 0.0315 | 0.1730 | 0.1929 | 11.48 |
6.00 | 3.11 | 0.3167 | 0.3036 | 4.13 | |||
6.63 | 3.74 | 0.4394 | 0.4394 | 0.00 | |||
7.26 | 4.37 | 0.6301 | 0.6001 | 4.76 | |||
混合油 | 274.15 | 5.37 | 2.48 | 0.0339 | 0.1843 | 0.2076 | 12.67 |
6.00 | 3.11 | 0.3525 | 0.3268 | 7.31 | |||
6.63 | 3.74 | 0.4640 | 0.4728 | 1.90 | |||
7.26 | 4.37 | 0.6511 | 0.6458 | 0.80 | |||
正庚烷 | 274.15 | 5.37 | 2.48 | 0.0385 | 0.1950 | 0.2358 | 20.93 |
6.00 | 3.11 | 0.3961 | 0.3711 | 6.31 | |||
6.63 | 3.74 | 0.5256 | 0.5370 | 2.17 | |||
7.26 | 4.37 | 0.7415 | 0.7334 | 1.09 |
表1 不同条件下水合物膜生长速率预测结果
Table 1 The predicted growth rates of hydrate film under different conditions
油样 | 温度/ K | 压力/ MPa | ΔP/MPa | ψ | 实验值/ (mm/s) | 计算值/ (mm/s) | AARD/% |
---|---|---|---|---|---|---|---|
甲苯 | 274.15 | 5.37 | 2.48 | 0.0315 | 0.1730 | 0.1929 | 11.48 |
6.00 | 3.11 | 0.3167 | 0.3036 | 4.13 | |||
6.63 | 3.74 | 0.4394 | 0.4394 | 0.00 | |||
7.26 | 4.37 | 0.6301 | 0.6001 | 4.76 | |||
混合油 | 274.15 | 5.37 | 2.48 | 0.0339 | 0.1843 | 0.2076 | 12.67 |
6.00 | 3.11 | 0.3525 | 0.3268 | 7.31 | |||
6.63 | 3.74 | 0.4640 | 0.4728 | 1.90 | |||
7.26 | 4.37 | 0.6511 | 0.6458 | 0.80 | |||
正庚烷 | 274.15 | 5.37 | 2.48 | 0.0385 | 0.1950 | 0.2358 | 20.93 |
6.00 | 3.11 | 0.3961 | 0.3711 | 6.31 | |||
6.63 | 3.74 | 0.5256 | 0.5370 | 2.17 | |||
7.26 | 4.37 | 0.7415 | 0.7334 | 1.09 |
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