油相中水滴表面甲烷水合物膜生长动力学研究

doi:10.11949/0438-1157.20240574

摘要/Abstract

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%）。

关键词: 油气混输, 甲烷水合物, 水合物膜, 动力学, 形态学

Abstract:

During the extraction and transportation of crude oil in subsea or cold regions, gas hydrates can form and accumulate within pipelines under low-temperature and high-pressure conditions. This can subsequently lead to blockage in pipelines and valves, causing a significant threat to the safety of oil and gas transportation. Therefore, studying the formation of hydrates in oil and gas pipelines has always been the focus of attention of the oil and gas production and transportation departments. In this work, we applied a high-pressure microscopic experimental device of visualizing hydrate film growth to study the morphology and growth characteristics of methane hydrate film on the surface of microdroplets suspended in toluene, mixed oil phase of toluene and n-heptane (1∶1, volume ratio), and n-heptane by using the pendant droplet method, and the kinetics of methane hydrate film growth at different temperatures (274.15—277.15 K) and pressures (5.37—7.26 MPa) were determined. The experimental results show that the growth rate of hydrate film increases with the increase of methane solubility in different oil phases, the film growth rate (at 274.15 K, 6 MPa) in toluene (0.26 mm/s)>in mixed oil (0.23 mm/s)>in n-hexane (0.21 mm/s). During thickening growth of hydrate, water is transferred outward through the hydrate film causing the “grooves” between wrinkles on the hydrate film surface gradually filled with hydrate crystals, and the rough hydrate formed in toluene allows for the fastest thickening rate, while the smooth hydrate film formed in n-heptane allows for the slowest thickening rate. The decrease in temperature and the increase in pressure both lead to an increase in the lateral growth rate of hydrate films. The pressure has a more significant effect than temperature, and the growth rate is the slowest in toluene and the fastest in n-hexane. A model driven by pressure difference effectively predicts the kinetic data for methane hydrate film growth (AARD=6.12%).

Key words: oil-gas transportation, methane hydrate, hydrate film, kinetics, morphology

中图分类号:

TE 31

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/表 11

图1 高压可视水合物膜生长装置

Fig.1 High-pressure visible hydrate film growth device

图2 油相中甲烷水合物膜生长实验过程

Fig.2 Experimental process of methane hydrate film growth in oil

图3 甲苯中水滴表面甲烷水合物膜生长过程

Fig.3 The growth process of methane hydrate film on water droplet surfaces in toluene

图4 混合油中水滴表面甲烷水合物膜生长过程

Fig.4 The growth process of methane hydrate film on water droplet surfaces in mixed oil

图5 正庚烷中水滴表面甲烷水合物膜生长过程

Fig.5 The growth process of methane hydrate film on water droplet surfaces in n-hexane

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8 不同温度和油相中水滴表面水合物膜生长速率对比（6 MPa）

Fig.8 The comparison of hydrate film growth rates on water droplet surfaces in different temperature and oil (6 MPa)

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)

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

图10 甲烷水合物膜生长速率

Fig.10 The growth rate of methane hydrate film

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