Study on growth process of semiclathrate hydrate on the surface of TBAB solution droplets suspended by ultrasonic

doi:10.11949/0438-1157.20220953

Abstract

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

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

CLC Number:

TQ 026.5

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.

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.

Figures/Tables 19

Fig.1 Experimental apparatus

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

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

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

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

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

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

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

Fig.8 Schematic diagram of TBAB droplet rotation

Fig.9 Coordinate system of TBAB droplet rotation

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

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

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

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

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

Fig.13 Three states of droplets

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

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

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

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