静态条件下表面活性剂OP-13促进HCFC-141b水合物生成

doi:10.16085/j.issn.1000-6613.2022-1428

摘要/Abstract

摘要：

为了促进静态条件下HCFC-141b水合物的生成，选择辛基酚与环氧乙烷的缩合物表面活性剂OP-13来研究其对HCFC-141b水合物生成效果的影响。OP-13促进HCFC-141b分散在水中，形成稳定的乳液。研究结果表明，添加适量的OP-13可大幅度缩短HCFC-141b水合物形成的诱导时间。添加质量分数1%的OP-13，HCFC-141b水合物生成的平均诱导时间最短，约为96min。OP-13的添加会影响HCFC-141b水合物的蓄冷量，当添加0.5%和1%的OP-13时，HCFC-141b水合物的蓄冷量较大，分别为247.57kJ/kg和248.42kJ/kg。综合水合物生成的诱导时间和蓄冷量，1%的OP-13为最佳添加量。研究结果也表明HCFC-141b水合物成核具有随机性，OP-13的添加稳定了水合物成核；表面活性剂OP-13促进水合物形成主要是由于其形成的胶束。水合物形成/分解循环实验过程中由于“记忆”效应，水合物可快速稳定形成。

关键词: 水合物, 诱导时间, HCFC-141b, 蓄冷, 循环稳定性, 表面活性剂, 乳液

Abstract:

In order to promote the formation of HCFC-141b hydrate under static conditions, the condensate surfactant OP-13 of octylphenol and ethylene oxide was chosen to study its effect on the formation of HCFC-141b hydrate. Stable HCFC-141b-water emulsion can be prepared by adding OP-13. The experimental results showed that adding of OP-13 can significantly shorten the induction time of HCFC-141b hydrate formation. When OP-13 with mass fraction of 1% was added, the average induction time of HCFC-141b hydrate formation was the shortest, about 96min. The mass fraction of OP-13 affected the cold storage capacity of HCFC-141b hydrate. When 0.5% or 1% OP-13 was added, the cold storage capacity of HCFC-141b hydrate was bigger, which was 247.57kJ/kg and 248.42kJ/kg, respectively. Considering the induction time and cold storage capacity of hydrate formation, 1% OP-13 was the best addition. The experimental results also showed that HCFC-141b hydrate nucleation was random, and the addition of OP-13 stabilized hydrate nucleation. The surfactant OP-13 promoted hydrate formation mainly due to its micelles. Hydrate can form rapidly and stably due to the "memory" effect during hydrate formation/dissociation.

Key words: hydrate, induction time, HCFC-141b, cold storage, cyclic stability, surfactants, emulsions

中图分类号:

TK02

杨扬, 孙志高, 李翠敏, 李娟, 黄海峰. 静态条件下表面活性剂OP-13促进HCFC-141b水合物生成[J]. 化工进展, 2023, 42(6): 2854-2859.

YANG Yang, SUN Zhigao, LI Cuimin, LI Juan, HUANG Haifeng. Promotion on the formation of HCFC-141b hydrate under static conditions by surfactant OP-13[J]. Chemical Industry and Engineering Progress, 2023, 42(6): 2854-2859.

图/表 11

参考文献 27

1	陈光进, 孙长宇, 马庆兰. 气体水合物科学与技术[M]. 北京: 化学工业出版社, 2008.
	CHEN Guangjin, SUN Changyu, MA Qinglan. Gas hydrate science and technology[M]. Beijing: Chemical Industry Press, 2008.
2	SUN Shicai, LI Yanmin, GU Linlin, et al. Experimental study on carbon dioxide hydrate formation in the presence of static magnetic field[J]. The Journal of Chemical Thermodynamics, 2022, 170: 106764.
3	方书起, 张欣悦, 李思齐, 等. 撞击流式反应器内水合物法分离沼气中CO₂研究[J]. 化工学报, 2020, 71(5): 2099-2108, 2457.
	FANG Shuqi, ZHANG Xinyue, LI Siqi, et al. Investigation on separation of CO₂from biogas by hydrate method in impinging stream reactor[J]. CIESC Journal, 2020, 71(5):2099-2108, 2457.
4	宋光春, 施政灼, 李玉星, 等. 油水体系内水合物的生成: 温度、压力和搅拌速率影响[J]. 化工进展, 2019, 38(3): 1338-1345.
	SONG Guangchun, SHI Zhengzhuo, LI Yuxing, et al. Hydrate formation in oil-water systems: investigations of the influences of temperature, pressure and rotation rate[J]. Chemical Industry and Engineering Progress, 2019, 38(3): 1338-1345.
5	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.
6	LI Airong, JIANG Lele, TANG Siyao. An experimental study on carbon dioxide hydrate formation using a gas-inducing agitated reactor[J]. Energy, 2017, 134: 629-637.
7	申小冬, 任俊杰, 梁德青. 微型鼓泡器中甲烷水合物的生成特性[J]. 石油化工, 2018, 47(5): 431-436.
	SHEN Xiaodong, REN Junjie, LIANG Deqing. Formation characteristics of methane hydrate in a micro-bubbler[J]. Petrochemical Technology, 2018, 47(5): 431-436.
8	Eduardo ANDRES-GARCIA, DIKHTIARENKO Alla, FAUTH Francois, et al. Methane hydrates: Nucleation in microporous materials[J]. Chemical Engineering Journal, 2019, 360: 569-576.
9	HEYDARI Atousa, PEYVANDI Kiana. Study of biosurfactant effects on methane recovery from gas hydrate by CO₂ replacement and depressurization[J]. Fuel, 2020, 272: 117681.
10	ASADI F, METAXAS P J, LIM V W, et al. Cyclodextrins as eco-friendly nucleation promoters for methane hydrate[J]. Chemical Engineering Journal, 2021, 417: 127932.
11	门文欣, 彭庆收, 桂霞. 不同季铵盐作用下的CO₂水合物相平衡[J]. 化工学报, 2022, 73(4): 1472-1482.
	Wenxin MEN, PENG Qingshou, GUI Xia. Phase equilibrium of CO₂ hydrate in the presence of four different quaternary ammonium salts[J]. CIESC Journal, 2022, 73(4): 1472-1482.
12	王英梅, 董世强, 展静, 等. 石英砂粒径大小对甲烷水合物形成及分布的影响[J]. 化工进展, 2020, 39(8): 3049-3056.
	WANG Yingmei, DONG Shiqiang, ZHAN Jing, et al. Effect of quartz sand particle size on the formation and distribution of methane hydrate[J]. Chemical Industry and Engineering Progress, 2020, 39(8): 3049-3056.
13	SAID S, GOVINDARAJ V, HERRI J M, et al. A study on the influence of nanofluids on gas hydrate formation kinetics and their potential: Application to the CO₂ capture process[J]. Journal of Natural Gas Science and Engineering, 2016, 32: 95-108.
14	李文昭, 潘振, 马贵阳, 等. 表面活性剂吸附对促进甲烷水合物生成效果的影响[J]. 化工学报, 2017, 68(4): 1542-1549.
	LI Wenzhao, PAN Zhen, MA Guiyang, et al. Promotion effects of surfactant adsorption on formation of methane hydrates[J].CIESC Journal, 2017, 68(4): 1542-1549.
15	RAJABI F S, BONYADI M. A comparative study on the effects of Fe₃O₄ nanofluid, SDS and CTAB aqueous solutions on the CO₂ hydrate formation[J]. Journal of Molecular Liquids, 2020, 300: 112251.
16	周麟晨, 孙志高, 陆玲, 等. 静态条件下表面活性剂促进HCFC-141b水合物生成[J]. 高校化学工程学报, 2020, 34(2): 402-410.
	ZHOU Linchen, SUN Zhigao, LU Ling, et al. Enhancement of HCFC-141b hydrate formation with surfactants in a static system[J]. Journal of Chemical Engineering of Chinese Universities, 2020, 34(2): 402-410.
17	张学民, 李洋, 姚泽, 等. 表面活性剂对气体水合物生成过程的定量影响[J]. 过程工程学报, 2018, 18(2): 356-360.
	ZHANG Xuemin, LI Yang, YAO Ze, et al. Quantitative influence of surfactant on the formation process for gas hydrate[J]. The Chinese Journal of Process Engineering, 2018, 18(2): 356-360.
18	李荣, 孙志高, 宋佳. 氨基酸侧链对HCFC-141b水合物形成的影响[J]. 储能科学与技术, 2022, 11(7): 2126-2132.
	LI Rong, SUN Zhigao, SONG Jia. Effect of amino acid side chains on HCFC-141b hydrate formation[J]. Energy Storage Science and Technology, 2022, 11(7): 2126-2132.
19	张龙明, 李璞, 李娜, 等. 混合量热法测定水合物浆体蓄冷密度[J]. 制冷学报, 2014, 35(6): 47-52.
	ZHANG Longming, LI Pu, LI Na, et al. Determination of hydrate slurry’s cool-storage density with mixing calorimetry method[J]. Journal of Refrigeration, 2014, 35(6): 47-52.
20	敬加强, 杨航, 张帅, 等. 水合物生成诱导期研究进展[J]. 天然气化工（C1化学与化工）, 2021, 46(6): 24-32.
	JING Jiaqiang, YANG Hang, ZHANG Shuai, et al. Research progress of hydrate formation induction period[J]. Natural Gas Chemical Industry, 2021, 46(6): 24-32.
21	KACHCHIEV Dimo. Nucleation-basic theory with applications[M]. Oxford: Butterworth Heinemann, 2001.
22	马鸿凯, 孙志高, 蔡伟, 等. HCFC-141b水合物静态生成促进技术的试验研究[J]. 流体机械, 2016, 44(1): 66-70.
	MA Hongkai, SUN Zhigao, CAI Wei, et al. Experimental study on promot technology of HCFC-141b hydration formation in quiescent system[J]. Fluid Machinery, 2016, 44(1): 66-70.
23	闫明月, 王岳, 刘嘉琪, 等. 表面活性剂对甲烷水合物生成影响研究进展[J]. 应用化工, 2021, 50(8): 2317-2325.
	YAN Mingyue, WANG Yue, LIU Jiaqi, et al. Research progress on influence factors of methane hydrate formation in surfactant solution[J]. Applied Chemical Industry, 2021, 50(8): 2317-2325.
24	ANDO N, KUWABARA Y, MORI Y H. Surfactant effects on hydrate formation in an unstirred gas/liquid system: An experimental study using methane and micelle-forming surfactants[J]. Chemical Engineering Science, 2012, 73(1): 79-85.
25	WANG Fei, GUO Gang, LIU Guoqiang, et al. Effects of surfactant micelles and surfactant-coated nanospheres on methane hydrate growth pattern[J]. Chemical Engineering Science, 2016, 144(1): 108-115.
26	NGUYEN N N, NGUYEM A V. Hydrophobic effect on gas hydrate formation in the presence of additives[J]. Energy and Fuels, 2017, 31(9): 10311-10323.
27	闫乐乐, 梁生康, 宋丹丹, 等. 鼠李糖脂生物表面活性剂胶束性质研究[J]. 中国海洋大学学报(自然科学版), 2016, 46(12): 68-72.
	YAN Lele, LIANG Shengkang, SONG Dandan, et al. Studies on some micelle properties of rhamnolipid biosurfactant[J]. Periodical of Ocean University of China, 2016, 46(12): 68-72.

OP-13质量分数/%	诱导时间/min	平均诱导时间/min	诱导时间方差	形成持续时间/min	平均持续时间/min
0.5	129,157,79,69,193	125	42.65	41,44,50,56,49	48
1.0	70,80,109,117,104	96	16.36	53,42,44,45,38	44
1.5	133,142,110,146,189	144	23.48	43,44,50,45,45	45
2.0	204,235,186,162,195	196	21.76	42,54,41,49,42	46
2.5	201,351,198,428,284	292	80.78	36,64,40,47,43	46

OP-13质量分数/%	诱导时间/min	平均诱导时间/min	诱导时间方差	形成持续时间/min	平均持续时间/min
0.5	129,157,79,69,193	125	42.65	41,44,50,56,49	48
1.0	70,80,109,117,104	96	16.36	53,42,44,45,38	44
1.5	133,142,110,146,189	144	23.48	43,44,50,45,45	45
2.0	204,235,186,162,195	196	21.76	42,54,41,49,42	46
2.5	201,351,198,428,284	292	80.78	36,64,40,47,43	46

项目	实验1	实验2	实验3
冰质量/g	9.98	10.02	10.01
冰融化前后的温度/℃	-4.9/21.3	-4.7/18.2	-4.7/16.6
温水质量/g	239.47	215.88	208.21
温水放热前/后的温度/℃	26.4/21.3	23.6/18.2	22.0/16.6
冰蓄冷密度/kJ·kg^-1	327.05	326.48	321.23
相对误差/%	-2.4	-2.5	-4.1

项目	实验1	实验2	实验3
冰质量/g	9.98	10.02	10.01
冰融化前后的温度/℃	-4.9/21.3	-4.7/18.2	-4.7/16.6
温水质量/g	239.47	215.88	208.21
温水放热前/后的温度/℃	26.4/21.3	23.6/18.2	22.0/16.6
冰蓄冷密度/kJ·kg^-1	327.05	326.48	321.23
相对误差/%	-2.4	-2.5	-4.1

OP-13质量分数/%	实验1	实验2	实验3	平均值
0.5	246.68	240.72	255.21	247.54
1.0	250.42	243.35	251.49	248.42
1.5	234.82	238.03	230.47	234.44
2.0	235.21	225.54	229.80	230.18
2.5	223.53	215.34	210.40	216.42