液氨-成品油混合体系相平衡及减压相变规律研究

doi:10.11949/0438-1157.20240680

摘要/Abstract

摘要：

氨作为高效的储氢载体，具有替代化石燃料能源的巨大潜力。利用成品油管道增输液氨，可充分利用管道运能，节约输送成本。液氨-成品油混合体系的相平衡问题对于管输工艺具有重要意义，此外减压过程会引起更为复杂的相变问题。针对液氨-成品油混合体系进行实验研究，初步阐述了氨/油（体积比）和含水率对液氨-成品油混合体系相平衡和减压相变的影响规律，得到了液氨-成品油混合体系的相平衡压力，揭示了液氨-成品油混合体系减压过程的相变现象。研究发现，在0~30℃，氨-油混合体系的平衡蒸气压小于两种纯组分的饱和蒸气压，而在-2~0℃大于纯液氨的饱和蒸气压，并在氨/油（体积比）为70∶30时达到最大值。同时水分的存在会降低氨-油混合体系的平衡蒸气压。氨-油无水混合体系在减压过程中会产生气泡，压力越低气泡增多，发泡行为越剧烈。含水液氨-成品油混合体系在减压过程中会产生液滴群，并慢慢变大且聚并，在减压结束后聚并形成大液滴留在底部。上述研究成果对成品油管道增输液氨技术发展和应用具有重要的理论指导意义。

关键词: 液氨, 成品油, 相平衡, 相变

Abstract:

Ammonia, as an efficient hydrogen storage carrier, has great potential to replace fossil fuel energy. The use of refined oil pipelines to increase the infusion of liquid ammonia can make full use of the pipeline capacity and save transportation costs. The phase equilibrium problem of the liquid ammonia-refined oil blend system is of great significance to the pipeline transportation process, and the decompression process will cause more complex phase change problems. In this paper, the effects of ammonia/oil ratio and moisture content on the phase equilibrium and decompression phase change of the liquid ammonia-refined oil mixed system were clarified, the phase equilibrium pressure of the liquid ammonia-refined oil mixed system was obtained, and the phase change mechanism of the liquid ammonia-refined oil mixed system was revealed. It is found that the equilibrium vapor pressure of the ammonia-oil mixed system is less than the saturation vapor pressure of the two pure components in 0—30℃, and is greater than the saturation vapor pressure of pure liquid ammonia in -2—0℃, and reaches the maximum value when the oil volume ratio is 0.3. At the same time, the presence of moisture reduces the equilibrium vapor pressure of the ammonia-oil mixture. The ammonia-oil anhydrous mixed system will produce bubbles during the decompression process. The lower the pressure, the more bubbles there are, and the more intense the foaming behavior. The aqueous liquid ammonia-oil mixing system generates droplet clusters during decompression, which slowly become larger and aggregate, and form large droplets that remain at the bottom at the end of decompression. The above research results have important theoretical guiding significance for the development and application of ammonia infusion technology in refined oil pipelines.

Key words: liquid ammonia, refined oil, phase equilibrium, phase transition

中图分类号:

TE 832

黄鑫, 李逸龙, 李卫东, 施鸿翔, 尹鹏博, 李臻超, 滕霖, 江莉龙. 液氨-成品油混合体系相平衡及减压相变规律研究[J]. 化工学报, 2025, 76(1): 71-80.

Xin HUANG, Yilong LI, Weidong LI, Hongxiang SHI, Pengbo YIN, Zhenchao LI, Lin TENG, Lilong JIANG. Research on the phase equilibrium and depressurization phase transition characteristics of liquid ammonia-refined oil mixed system[J]. CIESC Journal, 2025, 76(1): 71-80.

图/表 16

图1 高压可视化反应测试系统1—液氨瓶;2—气瓶(氮气);3—压力表;4—阀门;5—反应釜进气阀;6—恒温水浴;7—数据采集系统;8—摄像机;9—废液槽;10—反应釜;11—压力传感器;12—温度传感器;13—反应釜排气阀

Fig.1 High-pressure visual reaction test system1—liquid ammonia bottle; 2—gas cylinder (nitrogen); 3—pressure gauge; 4—valve; 5—reactor inlet valve; 6—constant temperature water bath; 7—data acquisition system; 8—camera; 9—waste liquid tank; 10—reactor; 11—pressure sensor; 12—temperature sensor; 13—reactor exhaust valve

表1 92#汽油和0#柴油的基础物性

Table 1 Physical parameters of 92# gasoline and 0# diesel

物性	92#汽油	0#柴油
密度/(g/cm³)	0.752	0.834
黏度（20℃）/(mPa·s)	0.72	4.74
饱和蒸气压（20℃）/MPa	0.047	0.001

图2 不同氨/油比下液氨-汽油混合体系的P-T曲线

Fig.2 P-T curves of liquid ammonia-gasoline blended system under different ammonia/oil ratios

表2 纯液氨饱和蒸气压实验值与文献［28］实验值误差分析

Table 2 Deviation between the experimental value of pure liquid ammonia saturation vapor pressure and the experimental value of Ref.［28］

温度/℃	实验值/MPa	实验值^[28]		相对误差/%
温度/℃	实验值/MPa	压力/mmHg	压力/MPa	相对误差/%
0	0.44	3220.5	0.43	2.33
5	0.52	3864.3	0.51	1.96
10	0.62	4615.4	0.61	1.64
15	0.74	5463.3	0.73	1.37
20	0.85	6432.5	0.86	-1.16
25	1.02	7525.1	1.00	2.00
30	1.18	8749.8	1.16	1.72

图3 不同氨/油比下液氨-汽油混合体系的气液平衡压力

Fig.3 Gas-liquid equilibrium pressure of liquid ammonia-gasoline mixture system under different ammonia/oil ratios

图4 含水液氨-汽油混合体系P-T曲线

Fig.4 P-T curves of aqueous liquid ammonia-gasoline blended system

图5 不同氨/油比下液氨-柴油混合体系的气液平衡压力

Fig.5 Gas-liquid equilibrium pressure of liquid ammonia-diesel mixture system under different ammonia/oil ratios

图6 含水液氨-柴油混合体系P-T曲线

Fig.6 P-T curves of aqueous liquid ammonia-diesel blended system

图7 液氨-汽油混合体系的减压过程

Fig.7 Decompression process of liquid ammonia-gasoline hybrid system

图8 液氨-汽油混合体系减压过程的P-T曲线

Fig.8 P-T curves of the decompression process of the liquid ammonia-gasoline hybrid system

图9 液氨-柴油混合体系的减压过程

Fig.9 Decompression process of liquid ammonia-diesel hybrid system

图10 液氨-柴油混合体系减压过程的P-T曲线

Fig.10 P-T curves of the decompression process of the liquid ammonia-diesel hybrid system

图11 含水液氨-汽油混合体系的减压过程

Fig.11 Decompression process of aqueous liquid ammonia-gasoline hybrid system

图12 含水液氨-汽油混合体系减压过程的P-T曲线

Fig.12 P-T curves of the decompression process of aqueous liquid ammonia-gasoline hybrid system

图13 含水液氨-柴油混合体系的减压过程

Fig.13 Decompression process of aqueous liquid ammonia-diesel hybrid system

图14 含水液氨-柴油混合体系减压过程的P-T曲线

Fig.14 P-T curves of the decompression process of aqueous liquid ammonia-diesel hybrid system

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