超声波悬浮TBAB溶液液滴表面半笼型水合物生长过程研究

doi:10.11949/0438-1157.20220953

摘要/Abstract

摘要：

利用超声波悬浮技术将四丁基溴化铵(TBAB)溶液液滴悬浮，观测了不同TBAB质量分数(15%、20%、25%)时的水合物生长过程，并与悬挂液滴进行了对比。实验发现，超声波悬浮的液滴处于快速旋转状态，液滴呈扁球状，水合物生长速率较快，但当液滴中含有气泡时生成水合物的诱导时间延长。总结出超声波悬浮状态下TBAB水合物生长方式可以分为两大类：由内而外，由外而内。由外而内又可以分为单平顶式、双平顶式和包裹式。建立悬浮液滴和悬挂液滴的传热模型，通过对比发现，超声波可以加快悬浮液滴的传热效率，加速水合物的生成和生长。该实验为观测水合物生长提供了一种新的方法。

关键词: 超声波悬浮, TBAB溶液, 水合物, 结晶, 传热

Abstract:

Tetrabutylammonium bromide (TBAB) aqueous solution droplets were suspended by ultrasonic levitation technique. The hydrate growth process at different TBAB mass fraction (15%, 20%, 25%) was observed and compared with the pendent droplets. Experiments show that the droplets suspended by ultrasonic are in a state of rapid rotation, the droplets are oblate spheroids, and the hydrate growth rate is faster, but when the droplets contain bubbles, the induction time of hydrate formation is prolonged. It is concluded that the growth mode of TBAB hydrate in ultrasonic suspension can be divided into two categories: from inside to outside and from outside to inside. From the outside to the inside, it can be divided into three types: single flat top, double flat top and wrapped. The heat transfer models of suspension droplets and pendent droplets are established. Through comparison, it is found that ultrasonic can improve the heat transfer efficiency of suspension droplets, accelerate the formation and growth of hydrate. This experiment provides a new method for observing hydrate formation.

Key words: ultrasonic levitation, TBAB solution, hydrate, crystallization, heat transfer

中图分类号:

TQ 026.5

敬鹏程, 陈立涛, 闫传梁, 姜传祥, 夏煜翔, 于常宏, 王昊天. 超声波悬浮TBAB溶液液滴表面半笼型水合物生长过程研究[J]. 化工学报, 2022, 73(11): 4893-4902.

Pengcheng JING, Litao CHEN, Chuanliang YAN, Chuanxiang JIANG, Yuxiang XIA, Changhong YU, Haotian WANG. Study on growth process of semiclathrate hydrate on the surface of TBAB solution droplets suspended by ultrasonic[J]. CIESC Journal, 2022, 73(11): 4893-4902.

图/表 19

图1 实验装置

Fig.1 Experimental apparatus

图2 悬挂于玻璃表面的TBAB溶液液滴上水合物的生长过程

Fig.2 Growth process of hydrate in TBAB solution droplet pendent on glass surface

图3 悬挂于不锈钢针头的TBAB溶液液滴上水合物的生长过程

Fig.3 Growth process of hydrate in TBAB solution droplet pendent on stainless steel needles

图4 超声波悬浮的TBAB溶液液滴上水合物的生长过程(TBAB质量分数15%，液滴初始直径0.88 mm)

Fig.4 Growth process of hydrate in TBAB solution droplet by ultrasonic levitation (TBAB mass fraction 15%, φ=0.88 mm)

图5 超声波悬浮的TBAB溶液液滴上水合物的生长过程(TBAB质量分数20%，液滴初始直径1.96 mm)

Fig.5 Growth process of hydrate in TBAB solution droplet by ultrasonic levitation(TBAB mass fraction 20%, φ=1.96 mm)

图6 超声波悬浮的TBAB溶液液滴上水合物的生长过程(TBAB质量分数20%，液滴初始直径1.13 mm)

Fig.6 Growth process of hydrate in TBAB solution droplet by ultrasonic levitation (TBAB mass fraction 20%, φ=1.13 mm)

图7 超声波悬浮的TBAB溶液液滴上水合物的生长过程(TBAB质量分数25%，液滴初始直径1.95 mm)

Fig.7 Growth process of hydrate in TBAB solution droplets by ultrasonic levitation (TBAB mass fraction 25%, φ=1.95 mm)

表1 TBAB悬浮液滴生成水合物前后几何参数变化

Table 1 Changes of geometric parameters of TBAB levitation droplets before and after hydrate formation

序号	悬浮液滴初始条件和描述	长半轴			短半轴
序号	悬浮液滴初始条件和描述	生成水合物前/mm	生成水合物后/mm	变化率/%	生成水合物前/mm	生成水合物后/mm	变化率/%
1	液滴初始直径0.88 mm，TBAB质量分数15%（图4）	0.440	0.523	+18.9	0.330	0.291	-11.8
2	液滴初始直径1.96 mm，TBAB质量分数20%（图5）	0.980	1.023	+4.4	0.619	0.567	-8.4
3	液滴初始直径1.13 mm，TBAB质量分数20%（图6）	0.565	0.636	+12.6	0.381	0.311	-18.4
4	液滴初始直径1.95 mm，TBAB质量分数25%（图7）	0.975	1.059	+8.6	0.639	0.572	-10.5

图8 TBAB液滴旋转示意图

Fig.8 Schematic diagram of TBAB droplet rotation

图9 TBAB液滴旋转坐标系

Fig.9 Coordinate system of TBAB droplet rotation

表2 不同生长方式下TBAB水合物晶体的生长速率

Table 2 Growth rate of TBAB hydrate crystal in different growth ways

液滴直径4.55 mm，

TBAB质量分数15%（图2）

悬挂

1.300

液滴直径0.88 mm，

TBAB质量分数15%（图4）

超声波悬浮

3.647

图10 不同生长方式下15%(质量分数)TBAB液滴切开前后对比

Fig.10 Comparison of 15% (mass) TBAB droplet before and after cutting with different growth ways

表3 不同生长方式诱导时间对比

Table 3 Comparison of induction time in different growth ways

序号	超声波悬浮		悬挂
序号	诱导时间/min	是否生成	诱导时间/min	是否生成
1	12	是	15（水合物晶种诱导）	是
2	15	是	30（水合物晶种诱导）	是
3	56	是	270	否
4	82	是	300	否
5	100	是	305	否
6	140	是	348	否
7	350	否	870	否
8	545	否	900	否

图11 液滴不同方式下形成水合物的传热示意图

Fig.11 Heat transfer schematic diagram of hydrate formation in different ways of droplets

图12 超声波强加速水合物生长原理示意图

Fig.12 Schematic diagram of the principle of ultrasonic strong acceleration of hydrate growth

图13 液滴的三种状态

Fig.13 Three states of droplets

图14 含有气泡的TBAB液滴水合物的生长过程

Fig.14 Growth process of hydrate in TBAB droplet contain bubble

表4 液滴是否有气泡的诱导时间对比

Table 4 Comparison of induction time of droplets with or without bubble

实验序号	TBAB质量分数/%	诱导时间/min	是否生成	是否有气泡
1	15	12	是	否
2	15	15	是	否
3	15	56	是	是
4	15	82	是	是
5	15	100	是	是
6	15	140	是	是
7	15	545	否	是

图15 气泡状态下TBAB溶液的生长过程

Fig.15 Growth process of hydrate in TBAB solution with bubble state

参考文献 30

1	Oyama H, Shimada W, Ebinuma T, et al. Phase diagram, latent heat, and specific heat of TBAB semiclathrate hydrate crystals[J]. Fluid Phase Equilibria, 2005, 234(1/2): 131-135.
2	Ma Z W, Zhang P, Wang R Z, et al. Forced flow and convective melting heat transfer of clathrate hydrate slurry in tubes[J]. International Journal of Heat and Mass Transfer, 2010, 53(19/20): 3745-3757.
3	Li M Y, Gao M, Zuo Q R, et al. Experimental and theoretical investigation on hydrate nucleation in TBAB droplets[J]. Fuel, 2022, 308: 121994.
4	Ohmura R, Shimada W, Uchida T, et al. Clathrate hydrate crystal growth in liquid water saturated with a hydrate-forming substance: variations in crystal morphology[J]. Philosophical Magazine, 2004, 84(1): 1-16.
5	Shi X J, Zhang P. Crystallization of tetra-n-butyl ammonium bromide clathrate hydrate slurry and the related heat transfer characteristics[J]. Energy Conversion and Management, 2014, 77: 89-97.
6	Saito K, Kishimoto M, Tanaka R, et al. Crystal growth of clathrate hydrate at the interface between hydrocarbon gas mixture and liquid water[J]. Crystal Growth & Design, 2011, 11(1): 295-301.
7	钱文强, 张鹏. 四丁基溴化铵水合物结晶过程的可视化研究[J]. 制冷学报, 2012, 33(3): 35-39.
	Qian W Q, Zhang P. Visualization study on growth process of tetra-n-butyl ammonium bromide hydrate[J]. Journal of Refrigeration, 2012, 33(3): 35-39.
8	叶楠, 张鹏. TBAB水合物晶体生长过程的实验研究[J]. 过程工程学报, 2011, 11(5): 823-827.
	Ye N, Zhang P. Investigation on the growth of TBAB clathrate hydrate crystals[J]. The Chinese Journal of Process Engineering, 2011, 11(5): 823-827.
9	李梦钖, 高明, 左启蓉, 等. 过冷壁面液滴中四丁基溴化铵水合物生成的可视化研究[J]. 化工学报, 2021, 72(4): 2094-2101.
	Li M Y, Gao M, Zuo Q R, et al. Visualization investigation of TBAB hydrate formation in droplets on supercooled wall surfaces[J]. CIESC Journal, 2021, 72(4): 2094-2101.
10	钟栋梁, 杨晨, 刘道平. 静止悬垂水滴形成甲烷水合物的生长动力学[J]. 化学反应工程与工艺, 2010, 26(1): 52-57.
	Zhong D L, Yang C, Liu D P. Kinetics of methane hydrate formation from static pendant water droplets[J]. Chemical Reaction Engineering and Technology, 2010, 26(1): 52-57.
11	Zang D Y, Yu Y K, Chen Z, et al. Acoustic levitation of liquid drops: dynamics, manipulation and phase transitions[J]. Advances in Colloid and Interface Science, 2017, 243: 77-85.
12	Park S S, Kim N J. Study on methane hydrate formation using ultrasonic waves[J]. Journal of Industrial and Engineering Chemistry, 2013, 19(5): 1668-1672.
13	孙始财, 刘玉峰, 吕爱钟, 等. 超声波与表面活性剂协同影响水合物诱导期[J]. 化工学报, 2006, 57(1): 160-162.
	Sun S C, Liu Y F, Lyu A Z, et al. Effect of ultrasonic and surfactant on induction time of natural gas hydrate[J]. Journal of Chemical Industry and Engineering (China), 2006, 57(1): 160-162.
14	孙始财, 杨震东, 谷林霖, 等. 超声波对CO₂水合物生成过程的影响[J]. 科学技术与工程, 2022, 22(2): 628-634.
	Sun S C, Yang Z D, Gu L L, et al. Effects of ultrasonic on CO₂ hydrate formation[J]. Science Technology and Engineering, 2022, 22(2): 628-634.
15	Hong H J, Ko C H, Song M H, et al. Effect of ultrasonic waves on dissociation kinetics of tetrafluoroethane (CH₂FCF₃) hydrate[J]. Journal of Industrial and Engineering Chemistry, 2016, 41: 183-189.
16	时濛. 有限空间内四丁基溴化铵水合物生长动力学研究[D]. 广州: 华南理工大学, 2017.
	Shi M. Kinetic investigation of tetra-n-butylammonium bromide hydrate formation in confined space[D]. Guangzhou: South China University of Technology, 2017.
17	孙长宇, 黄强, 陈光进. 气体水合物形成的热力学与动力学研究进展[J]. 化工学报, 2006, 57(5): 1031-1039.
	Sun C Y, Huang Q, Chen G J. Progress of thermodynamics and kinetics of gas hydrate formation[J]. Journal of Chemical Industry and Engineering (China), 2006, 57(5): 1031-1039.
18	Zhong D L, Yang C, Liu D P, et al. Experimental investigation of methane hydrate formation on suspended water droplets[J]. Journal of Crystal Growth, 2011, 327(1): 237-244.
19	黄玲艳, 刘中良, 勾昱君, 等. 壁面温度对疏水表面上水滴冻结的影响[J]. 工程热物理学报, 2012, 33(6): 1009-1012.
	Huang L Y, Liu Z L, Gou Y J, et al. Effect of cold plate temperature on water droplet freezing on hydrophobic surface[J]. Journal of Engineering Thermophysics, 2012, 33(6): 1009-1012.
20	管国锋, 赵汝溥. 化工原理[M]. 4版. 北京: 化学工业出版社, 2015.
	Guan G F, Zhao R P. Unit Operation[M]. 4th ed. Beijing: Chemical Industry Press, 2015.
21	苏亚欣. 传热学[M]. 武汉: 华中科技大学出版社, 2009.
	Su Y X. Heat Transfer[M]. Wuhan: Huazhong University of Science and Technology Press, 2009.
22	Legay M, Gondrexon N, le Person S, et al. Enhancement of heat transfer by ultrasound: review and recent advances[J]. International Journal of Chemical Engineering, 2011, 2011: 670108.
23	梁德青, 樊栓狮, 余国保. 用超声波生产水合物及水合物浆的装置与方法: 100341615C[P]. 2007-10-10.
	Liang D Q, Fan S S, Yu G B. Method and device for producing hydrate and hydrate slurry using supersonic wave: 100341615C[P]. 2007-10-10.
24	刘永红, 郭开华, 梁德青, 等. 超声波对HCFC-141b水合物结晶过程的影响[J]. 武汉理工大学学报, 2002, 24(12): 21-23.
	Liu Y H, Guo K H, Liang D Q, et al. Experimental study on crystallizing process of HCFC-141b hydrate by ultrasonic[J]. Journal of Wuhan University of Technology, 2002, 24(12): 21-23.
25	孙始财, 樊栓狮. 超声波作用下天然气水合物的形成[J]. 化学通报, 2005, 68(11): 867-870.
	Sun S C, Fan S S. The formation of natural gas hydrates with ultrasonic[J]. Chemistry, 2005, 68(11): 867-870.
26	Kashchiev D, Firoozabadi A. Induction time in crystallization of gas hydrates[J]. Journal of Crystal Growth, 2003, 250(3/4): 499-515.
27	丘泰球, 李月花, 陈树功. 声场对蔗糖溶液结晶成核过程的影响[J]. 声学技术, 1993, 12(1): 15-20.
	Qiu T Q, Li Y H, Chen S G. Effect of sound field on nucleation process of sucrose solution crystallization [J]. Technical Acoustics, 1993, 12(1): 15-20.
28	刘永红, 郭开华, 梁德青, 等. 超声波作用下的制冷剂水合物结晶过程研究[J]. 工程热物理学报, 2003, 24(3): 385-387.
	Liu Y H, Guo K H, Liang D Q, et al. Study on refrigerant hydrate crystallization process in the action of ultrasonic[J]. Journal of Engineering Thermophysics, 2003, 24(3): 385-387.
29	Mason T J. Power Ultrasound in Food Processing—the Way Forward[M]. Glasgow, UK: Blackie Academic and Professional, 1998.
30	Zang D Y, Li L, Di W L, et al. Inducing drop to bubble transformation via resonance in ultrasound[J]. Nature Communications, 2018, 9: 3546.

[1]	张双星, 刘舫辰, 张义飞, 杜文静. R-134a脉动热管相变蓄放热实验研究[J]. 化工学报, 2023, 74(S1): 165-171.
[2]	张义飞, 刘舫辰, 张双星, 杜文静. 超临界二氧化碳用印刷电路板式换热器性能分析[J]. 化工学报, 2023, 74(S1): 183-190.
[3]	陈爱强, 代艳奇, 刘悦, 刘斌, 吴翰铭. 基板温度对HFE7100液滴蒸发过程的影响研究[J]. 化工学报, 2023, 74(S1): 191-197.
[4]	刘明栖, 吴延鹏. 导光管直径和长度对传热影响的模拟分析[J]. 化工学报, 2023, 74(S1): 206-212.
[5]	王志国, 薛孟, 董芋双, 张田震, 秦晓凯, 韩强. 基于裂隙粗糙性表征方法的地热岩体热流耦合数值模拟与分析[J]. 化工学报, 2023, 74(S1): 223-234.
[6]	于宏鑫, 邵双全. 水结晶过程的分子动力学模拟分析[J]. 化工学报, 2023, 74(S1): 250-258.
[7]	晁京伟, 许嘉兴, 李廷贤. 基于无管束蒸发换热强化策略的吸附热池的供热性能研究[J]. 化工学报, 2023, 74(S1): 302-310.
[8]	程成, 段钟弟, 孙浩然, 胡海涛, 薛鸿祥. 表面微结构对析晶沉积特性影响的格子Boltzmann模拟[J]. 化工学报, 2023, 74(S1): 74-86.
[9]	李艺彤, 郭航, 陈浩, 叶芳. 催化剂非均匀分布的质子交换膜燃料电池操作条件研究[J]. 化工学报, 2023, 74(9): 3831-3840.
[10]	王玉兵, 李杰, 詹宏波, 朱光亚, 张大林. R134a在菱形离散肋微小通道内的流动沸腾换热实验研究[J]. 化工学报, 2023, 74(9): 3797-3806.
[11]	齐聪, 丁子, 余杰, 汤茂清, 梁林. 基于选择吸收纳米薄膜的太阳能温差发电特性研究[J]. 化工学报, 2023, 74(9): 3921-3930.
[12]	李科, 文键, 忻碧平. 耦合蒸气冷却屏的真空多层绝热结构对液氢储罐自增压过程的影响机制研究[J]. 化工学报, 2023, 74(9): 3786-3796.
[13]	陈天华, 刘兆轩, 韩群, 张程宾, 李文明. 喷雾冷却换热强化研究进展及影响因素[J]. 化工学报, 2023, 74(8): 3149-3170.
[14]	杨越, 张丹, 郑巨淦, 涂茂萍, 杨庆忠. NaCl水溶液喷射闪蒸-掺混蒸发的实验研究[J]. 化工学报, 2023, 74(8): 3279-3291.
[15]	傅予, 刘兴翀, 王瀚雨, 李海敏, 倪亚飞, 邹文静, 雷月, 彭永姗. F₃EACl修饰层对钙钛矿太阳能电池性能提升的研究[J]. 化工学报, 2023, 74(8): 3554-3563.