空气纳米气泡的稳定性及理化特性

doi:10.16085/j.issn.1000-6613.2021-2388

摘要/Abstract

摘要：

空气纳米气泡（Air-NBs）的理化特性是其广泛应用的基础。本文利用纳米粒度-zeta电位分析仪研究了水力空化原理产生的Air-NBs的理化特性，即粒径分布和zeta电位，考察了装置运行压力、电解质浓度、pH和温度对Air-NBs理化特性的影响；同时考察了去离子水和CaCl₂溶液中Air-NBs稳定性。结果表明：纳米气泡发生器的压力越大，其产生的Air-NBs的小粒径比例更大，且电解质的加入有助于气泡粒径的缩小。随着溶液中电解质浓度、pH和温度的升高，溶液中Air-NBs的平均粒径逐渐减小，但气泡间的聚结作用会导致其粒径随时间逐渐增大；通过对两种溶液中Air-NBs粒径的实时监测发现其能在溶液中存在5天之久。胶体稳定（DLVO）理论和zeta电位效应可以合理阐释溶液中Air-NBs的稳定性。

关键词: 空气纳米气泡, 电解质, 粒径分布, zeta电位, 稳定性

Abstract:

The physicochemical properties of air nanobubbles (Air-NBs) are the basis of their wide application. In this study, the physicochemical properties of Air-NBs produced by the principle of hydrodynamic cavitation, including the particle size distribution and zeta potential, were studied on the nanoparticle size-zeta potential analyzer. The effects of operating pressure, electrolyte concentration, pH and temperature on the physicochemical properties of Air-NBs were investigated, as well as the stability of Air-NBs respectively in deionized water and CaCl₂ solution. The results showed that the higher the pressure of the nano bubble generator, the larger the proportion of small particle size of Air-NBs, and the addition of electrolyte helped to reduce the particle size of bubbles. The average particle size distribution of Air-NBs decreased with the increase of electrolyte concentration, pH and temperature. However, the coalescence between bubbles was ascribed to the gradual increase of the particle size with time going. The Air-NBs particle size in the two solutions was monitored online. It was found that the Air-NBs could exist in the solutions for 5 days. The stability of Air-NBs in solution can be explained reasonably through DLVO theory and zeta potential effect.

Key words: air nanobubbles, electrolytes, particle size distribution, zeta potential, stability

中图分类号:

X703.1

陈二军, 张玉玲, 路少磊, 段海洋, 靳文章. 空气纳米气泡的稳定性及理化特性[J]. 化工进展, 2022, 41(9): 4673-4681.

CHEN Erjun, ZHANG Yuling, LU Shaolei, DUAN Haiyang, JIN Wenzhang. Stability and physicochemical properties of air nanobubbles[J]. Chemical Industry and Engineering Progress, 2022, 41(9): 4673-4681.

图/表 8

图1 实验装置流程

表1 纳米气泡发生器型号参数

参数	数值	参数	数值
型号	LF-1500	液体管或气体管/mm	ϕ6×2
电压/V	220（AC）	最大使用压力/MPa	0.8
功率/W	90	自吸高度/m	0.8
温度范围/℃	0~75	工况流量/mL·min^-1	1500

图2 Air-NBs的胶体性质及空气泵压力对其粒径分布的影响

图3 电解质浓度对Air-NBs理化特性的影响

图4 pH对Air-NBs理化特性的影响

图5 温度对Air-NBs理化特性的影响

图6 Air-NBs粒径随时间变化

图7 Air-NBs的稳定性

参考文献 64

1	QUINN J J, KRACHT W, GOMEZ C O, et al. Comparing the effect of salts and frother (MIBC) on gas dispersion and froth properties[J]. Minerals Engineering, 2007, 20(14): 1296-1302.
2	QUINN J J, SOVECHLES J M, FINCH J A, et al. Critical coalescence concentration of inorganic salt solutions[J]. Minerals Engineering, 2014, 58: 1-6.
3	DAYARATHNE H N P, JEONG S, JANG A. Chemical-free scale inhibition method for seawater reverse osmosis membrane process: air micro-nano bubbles[J]. Desalination, 2019, 461: 1-9.
4	马艳, 张鑫, 韩小蒙, 等. 臭氧微纳米气泡技术在水处理中的应用进展[J]. 净水技术, 2019, 38(8): 64-67.
	MA Yan, ZHANG Xin, HAN Xiaomeng, et al. Application of micro-nano ozone bubble technology in water treatment: a review[J]. Water Purification Technology, 2019, 38(8): 64-67.
5	LUKIANOVA-HLEB E Y, BELYANIN A, KASHINATH S, et al. Plasmonic nanobubble-enhanced endosomal escape processes for selective and guided intracellular delivery of chemotherapy to drug-resistant cancer cells[J]. Biomaterials, 2012, 33(6): 1821-1826.
6	WEN D S. Intracellular hyperthermia: nanobubbles and their biomedical applications[J]. International Journal of Hyperthermia, 2009, 25(7): 533-541.
7	GREENBERG M R, PIEROG J E. Evaluation of race and gender sensitivity in the American Heart Association materials for Advanced Cardiac Life Support[J]. Gender Medicine, 2009, 6(4): 604-613.
8	KHALED ABDELLA AHMED A, SUN C Z, HUA L K, et al. Colloidal properties of air, oxygen, and nitrogen nanobubbles in water: effects of ionic strength, natural organic matters, and surfactants[J]. Environmental Engineering Science, 2018, 35(7): 720-727.
9	AGARWAL A, NG W J, LIU Y. Principle and applications of microbubble and nanobubble technology for water treatment[J]. Chemosphere, 2011, 84(9): 1175-1180.
10	DAYARATHNE H N P, CHOI J, JANG A. Enhancement of cleaning-in-place (CIP) of a reverse osmosis desalination process with air micro-nano bubbles[J]. Desalination, 2017, 422: 1-4.
11	KHUNTIA S, MAJUMDER S K, GHOSH P. Microbubble-aided water and wastewater purification: a review[J]. Reviews in Chemical Engineering, 2012, 28(4/5/6): 191-221.
12	FUJITA T, KUROKAWA H, HAN Z Y, et al. Free radical degradation in aqueous solution by blowing hydrogen and carbon dioxide nanobubbles[J]. Scientific Reports, 2021, 11(1): 3068-3079.
13	DATTA S, PILLAI R, BORG M K, et al. Acoustothermal nucleation of surface nanobubbles[J]. Nano Letters, 2021, 21(3): 1267-1273.
14	杨丽, 廖传华, 朱跃钊, 等. 微纳米气泡特性及在环境污染控制中的应用[J]. 化工进展, 2012, 31(6): 1333-1337.
	YANG Li, LIAO Chuanhua, ZHU Yuezhao, et al. Characteristics of micro-bubble and nano-bubble and their application in environmental pollution control[J]. Chemical Industry and Engineering Progress, 2012, 31(6): 1333-1337.
15	张小波, 李琰君, 沈绍传, 等. 微泡吸收技术处理丙酮废气[J]. 化工进展, 2015, 34(7): 2075-2079.
	ZHANG Xiaobo, LI Yanjun, SHEN Shaochun, et al. Experimental investigation on the microbubble absorption of acetone in waste gases[J]. Chemical Industry and Engineering Progress, 2015, 34(7): 2075-2079.
16	AZEVEDO A, ETCHEPARE R, CALGAROTO S, et al. Aqueous dispersions of nanobubbles: generation, properties and features[J]. Minerals Engineering, 2016, 94: 29-37.
17	孙逊, 赵越, 玄晓旭, 等. 基于水力空化的化工过程强化研究进展[J]. 化工进展, 2022, 41(5): 2243-2255.
	SUN Xun, ZHAO Yue, XUAN Xiaoxu, et al. Advances in process intensification based on hydrodynamic cavitation[J]. Chemical Industry and Engineering Progress, 2022, 41(5): 2243-2255.
18	EKLUND F, SWENSON J. Stable air nanobubbles in water: the importance of organic contaminants[J]. Langmuir, 2018, 34(37): 11003-11009.
19	CHO S H, KIM J Y, CHUN J H, et al. Ultrasonic formation of nanobubbles and their zeta-potentials in aqueous electrolyte and surfactant solutions[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2005, 269(1/2/3): 28-34.
20	CHEN Q J, WIEDENROTH H S, GERMAN S R, et al. Electrochemical nucleation of stable N₂ nanobubbles at Pt nanoelectrodes[J]. Journal of the American Chemical Society, 2015, 137(37): 12064-12069.
21	NIRMALKAR N, PACEK A W, BARIGOU M. On the existence and stability of bulk nanobubbles[J]. Langmuir, 2018, 34(37): 10964-10973.
22	SOVECHLES J M, LEPAGE M R, JOHNSON B, et al. Effect of gas rate and impeller speed on bubble size in frother-electrolyte solutions[J]. Minerals Engineering, 2016, 99: 133-141.
23	CHERCHIL C, KESAANO M, BADRUZZAMAN M, et al. Municipal reclaimed water for multi-purpose applications in the power sector: a review[J]. Journal of Environmental Management, 2019, 236: 561-570.
24	CHAUSSEMIER M, POURMOHTASHAM E, GELUS D, et al. State of art of natural inhibitors of calcium carbonate scaling[J]. Desalination, 2015, 356: 47-55.
25	OKUDA T, MATSUI K, HASHIMOTO K, et al. Effect of ultrafine bubble onto accumulation and structure of urinary calculus[J]. Japanese Journal of Multiphase Flow, 2018, 32(1): 12-18.
26	YABE A, MORIMATSU T. Cleaning effect of small particle contaminated plate by utilizing nano-bubbles contained water[J]. Journal of the Heat Transfar Society of Japan, 2004, 43(183): 16-18.
27	ISHIZAKI T, MATSUDA Y, MORITA T, et al. Cleaning effect by fine bubbles generated with gas-liquid share method[J]. Journal of Chemical Engineering of Japan, 2018, 51(2): 170-174.
28	LIU G M, CRAIG V S J. Improved cleaning of hydrophilic protein-coated surfaces using the combination of nanobubbles and SDS[J]. ACS Applied Materials & Interfaces, 2009, 1(2): 481-487.
29	WU Z H, CHEN H B, DONG Y M, et al. Cleaning using nanobubbles: defouling by electrochemical generation of bubbles[J]. Journal of Colloid and Interface Science, 2008, 328(1): 10-14.
30	FANG Z, WANG L, WANG X Y, et al. Formation and stability of surface/bulk nanobubbles produced by decompression at lower gas concentration[J]. The Journal of Physical Chemistry C, 2018, 122(39): 22418-22423.
31	TUZIUTI T, YASUI K, KANEMATSU W. Influence of increase in static pressure on bulk nanobubbles[J]. Ultrasonics Sonochemistry, 2017, 38: 347-350.
32	TIAN Y L, XIAO Y F, ZHU H X, et al. Interfacial tensions between water and non-polar fluids at high pressures and high temperatures[J]. Acta Physico-Chimica Sinica, 1997, 13(1): 89-95.
33	YOO D H, TERASAKA K, TSUGE H. Behavior of bubble formation at elevated pressure[J]. Journal of Chemical Engineering of Japan, 1998, 31(1): 76-82.
34	O’CONNOR C T, RANDALL E W, GOODALL C M. Measurement of the effects of physical and chemical variables on bubble size[J]. International Journal of Mineral Processing, 1990, 28(1/2): 139-149.
35	SOVECHLES J M, WATERS K E. Effect of ionic strength on bubble coalescence in inorganic salt and seawater solutions[J]. AIChE Journal, 2015, 61(8): 2489-2496.
36	HENRY C L, DALTON C N, SCRUTON L, et al. Ion-specific coalescence of bubbles in mixed electrolyte solutions[J]. The Journal of Physical Chemistry C, 2007, 111(2): 1015-1023.
37	YE Y B, YU S L, HOU L A, et al. Microbubble aeration enhances performance of vacuum membrane distillation desalination by alleviating membrane scaling[J]. Water Research, 2019, 149: 588-595.
38	TAKAHASHI M. Zeta potential of microbubbles in aqueous solutions: electrical properties of the gas-water interface[J]. The Journal of Physical Chemistry B, 2005, 109(46): 21858-21864.
39	WU C D, NESSET K, MASLIYAH J, et al. Generation and characterization of submicron size bubbles[J]. Advances in Colloid and Interface Science, 2012, 179/180/181/182: 123-132.
40	CALGAROTO S, WILBERG K Q, RUBIO J. On the nanobubbles interfacial properties and future applications in flotation[J]. Minerals Engineering, 2014, 60: 33-40.
41	NAJAFI A S, DRELICH J, YEUNG A, et al. A novel method of measuring electrophoretic mobility of gas bubbles[J]. Journal of Colloid and Interface Science, 2007, 308(2): 344-350.
42	KIM J Y, SONG M G, KIM J D. Zeta potential of nanobubbles generated by ultrasonication in aqueous alkyl polyglycoside solutions[J]. Journal of Colloid and Interface Science, 2000, 223(2): 285-291.
43	SCHÄFER R, MERTEN C, EIGENBERGER G. Bubble size distributions in a bubble column reactor under industrial conditions[J]. Experimental Thermal and Fluid Science, 2002, 26(6/7): 595-604.
44	LIN T J, TSUCHIYA K, FAN L S. Bubble flow characteristics in bubble columns at elevated pressure and temperature[J]. AIChE Journal, 1998, 44(3): 545-560.
45	田震, 成有为, 王丽军, 等. 温度与压力对单孔气泡形成过程的影响[J]. 化工学报, 2019, 70(9): 3337-3345.
	TIAN Zheng, CHENG Youwei, WANG Lijun, et al. Effect of temperature and pressure on formation process of single-hole bubbles[J]. CIESC Journal, 2019, 70(9): 3337-3345.
46	李赟, 白博峰, 阎晓, 等. 微气泡形成过程及温度影响[J]. 工程热物理学报, 2008, 29(9): 1511-1514.
	LI Yun, BAI Bofeng, YAN Xiao, et al. Microbubble generation process and temperature influence[J]. Journal of Engineering Thermophysics, 2008, 29(9): 1511-1514.
47	USHIKUBO F Y, FURUKAWA T, NAKAGAWA R, et al. Evidence of the existence and the stability of nano-bubbles in water[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2010, 361(1/2/3): 31-37.
48	AHMADI R, KHODADADI D A, ABDOLLAHY M, et al. Nano-microbubble flotation of fine and ultrafine chalcopyrite particles[J]. International Journal of Mining Science and Technology, 2014, 24(4): 559-566.
49	SHIN D, PARK J B, KIM Y J, et al. Growth dynamics and gas transport mechanism of nanobubbles in graphene liquid cells[J]. Nature Communications, 2015, 6(2): 6068-6073.
50	廖世双, 欧乐明, 周伟光. 空化过程微纳米气泡性质及其对细粒矿物浮选的影响[J]. 中国有色金属学报, 2019, 29(7): 1567-1574.
	LIAO Shishuang, Leming OU, ZHOU Weiguang. Micro-nano bubbles properties induced by hydrodynamic cavitation and their influences on fine mineral flotation[J]. The Chinese Journal of Nonferrous Metals, 2019, 29(7): 1567-1574.
51	ZHANG X H, LI G, MAEDA N, et al. Removal of induced nanobubbles from water/graphite interfaces by partial degassing[J]. Langmuir, 2006, 22(22): 9238-9243.
52	ANTONIO CERRÓN-CALLE G, LUNA MAGDALENO A, GRAF J C, et al. Elucidating CO₂ nanobubble interfacial reactivity and impacts on water chemistry[J]. Journal of Colloid and Interface Science, 2022, 607: 720-728.
53	OH S H, KIM J M. Generation and stability of bulk nanobubbles[J]. Langmuir, 2017, 33(15): 3818-3823.
54	ALHESHIBRI M, CRAIG V S J. Differentiating between nanoparticles and nanobubbles by evaluation of the compressibility and density of nanoparticles[J]. The Journal of Physical Chemistry C, 2018, 122(38): 21998-22007.
55	LJUNGGREN S, ERIKSSON J C. The lifetime of a colloid-sized gas bubble in water and the cause of the hydrophobic attraction[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 1997, 129/130: 151-155.
56	LIU S, KAWAGOE Y, MAKINO Y, et al. Effects of nanobubbles on the physicochemical properties of water: the basis for peculiar properties of water containing nanobubbles[J]. Chemical Engineering Science, 2013, 93: 250-256.
57	ULATOWSKI K, SOBIESZUK P, MRÓZ A, et al. Stability of nanobubbles generated in water using porous membrane system[J]. Chemical Engineering and Processing： Process Intensification, 2019, 136: 62-71.
58	DAS S, SNOEIJER J H, LOHSE D. Effect of impurities in description of surface nanobubbles[J]. Physical Review E, 2010, 82(5): 056310.
59	BUNKIN N F, SUYAZOV N V, SHKIRIN A V, et al. Cluster structure of stable dissolved gas nanobubbles in highly purified water[J]. Journal of Experimental and Theoretical Physics, 2009, 108(5): 800-816.
60	PALUCH M. Electrical properties of free surface of water and aqueous solutions[J]. Advances in Colloid and Interface Science, 2000, 84(1/2/3): 27-45.
61	HAMPTON M A, NGUYEN A V. Nanobubbles and the nanobubble bridging capillary force[J]. Advances in Colloid and Interface Science, 2010, 154(1/2): 30-55.
62	HEWAGE S A, KEWALRAMANI J, MEEGODA J N. Stability of nanobubbles in different salts solutions[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2021, 609: 125669.
63	GUO Z T, WANG X Z, WANG H X, et al. Effects of nanobubble water on the growth of Lactobacillus acidophilus 1028 and its lactic acid production[J]. RSC Advances, 2019, 9(53): 30760-30767.
64	CHEN C S, LI J, ZHANG X R. The existence and stability of bulk nanobubbles: a long-standing dispute on the experimentally observed mesoscopic inhomogeneities in aqueous solutions[J]. Communications in Theoretical Physics, 2020, 72(3): 037601.

[1]	王鑫, 王兵兵, 杨威, 徐志明. 金属表面PDA/PTFE超疏水涂层抑垢与耐腐蚀性能[J]. 化工进展, 2023, 42(8): 4315-4321.
[2]	陆洋, 周劲松, 周启昕, 王瑭, 刘壮, 李博昊, 周灵涛. CeO₂/TiO₂吸附剂煤气脱汞产物的浸出规律[J]. 化工进展, 2023, 42(7): 3875-3883.
[3]	吴展华, 盛敏. 绝热加速量热仪在反应安全风险评估应用中的常见问题[J]. 化工进展, 2023, 42(7): 3374-3382.
[4]	谢志伟, 吴张永, 朱启晨, 蒋佳骏, 梁天祥, 刘振阳. 植物油基Ni_0.5Zn_0.5Fe₂O₄磁流体的黏度特性及磁黏特性[J]. 化工进展, 2023, 42(7): 3623-3633.
[5]	杨竞莹, 施万胜, 黄振兴, 谢利娟, 赵明星, 阮文权. 改性纳米零价铁材料制备的研究进展[J]. 化工进展, 2023, 42(6): 2975-2986.
[6]	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.
[7]	李玲, 马超峰, 卢春山, 于万金, 石能富, 金佳敏, 张建君, 刘武灿, 李小年. 新型含氟替代品1,1,2-三氟乙烯的合成工艺与催化剂研究进展[J]. 化工进展, 2023, 42(4): 1822-1831.
[8]	殷铭, 郭晋, 庞纪峰, 吴鹏飞, 郑明远. 铜催化剂在涉氢反应中的失活机制和稳定策略[J]. 化工进展, 2023, 42(4): 1860-1868.
[9]	李云闯, 谢方明, 席亚男, 万新月, 孙玉虎, 赵永峰, 李根, 刘宏海, 高雄厚, 刘洪涛. 高水热稳定性介孔分子筛的低成本合成研究进展[J]. 化工进展, 2023, 42(4): 1877-1884.
[10]	王钰琢, 李刚. 硫、氮共掺杂三维石墨烯的全固态超级电容器[J]. 化工进展, 2023, 42(4): 1974-1982.
[11]	谭德新, 曾佳欣, 梁莉敏, 申思慧, 曾子倩, 王艳丽. 取代烷基变化对芳炔单体及其聚合物性能影响[J]. 化工进展, 2023, 42(4): 2031-2037.
[12]	宗悦, 张瑞君, 高珊珊, 田家宇. “特殊稳定型”压力驱动薄膜复合（TFC）脱盐膜的研究进展[J]. 化工进展, 2023, 42(4): 2058-2067.
[13]	李光文, 华渠成, 黄作鑫, 达志坚. 聚甲基丙烯酸酯类黏度指数改进剂的研究进展[J]. 化工进展, 2023, 42(3): 1562-1571.
[14]	张晨光, 封硕, 邢玉烨, 沈伯雄, 苏立超. 柴油车用NH₃-SCR铜基分子筛催化剂孤立态Cu²⁺研究进展[J]. 化工进展, 2023, 42(3): 1321-1331.
[15]	张艺璇, 胡伟, 刘梦瑶, 鞠敬鸽, 赵义侠, 康卫民. 聚合物电解质在锌离子电池中的研究进展[J]. 化工进展, 2023, 42(3): 1397-1410.