多尺度研究油水乳状液稳定性的技术进展

doi:10.16085/j.issn.1000-6613.2016.01.004

摘要/Abstract

摘要： 油水乳状液在石油化工、食品、医药等领域有广泛的应用,其中乳状液的稳定性一直是人们研究的热点。本文回顾了近年来乳状液稳定性的研究方法,从宏观相分离、介观液滴粒度及微观界面膜稳定性3个不同尺度对油水乳状液稳定性研究技术的进展进行综述,并简要比较了同尺度不同研究方法的优劣。宏观尺度上,稳定性分析仪和低场核磁共振的引入使得乳状液相分离过程的表征更加准确便捷;介观尺度上,通过对分散相表征结果的拟合计算实现对乳状液液滴粒度的原位表征;微观尺度上,微量吸液管技术、显微观测等表征技术的发展和引入使得界面膜的机械强度、厚度及形态结构三方面的研究更加深入,从而更加直接准确地表征界面膜的稳定性。此外,本文还重点对综合运用不同尺度研究方法全面深入探究乳状液稳定机制进行了论述,并指出原位表征技术是乳状液稳定性研究方法的重要发展方向。

关键词: 乳液, 稳定性, 多尺度, 相分离, 液滴, 界面膜

Abstract: Oil-water emulsions have wide range of applications in the field of petrochemicals, food, medicine and others. The stability of emulsion has been a research hotspot. This paper reviewed research methods of emulsion stability in recent years, summarized the progress of research techniques from three aspects and made brief comparison of the advantages and disadvantages of different methods of the same scale. On the macro-scale, emulsion stability analyzers and low-field NMR are used to characterize the phase separation process, which simplifies the test operation and renders a more accurate result. On mesoscopic scale, the in situ characterization of emulsion droplet size can be achieved by fitting calculation of the optical and NMR results. On the micro-scale, the accurate characterization of interfacial film stability is realized by the development and introduction of micropipette, microscopic observation technologies and others, which includes the research of mechanical strength, thickness and morphology of interfacial film. In addition, this article also identified the integrated use of different methods in in-depth inquiring the stability mechanism, analyzed trends of research methods in oil-water emulsion stability, and noted that in situ characterization technology is the development direction of emulsion stability research.

Key words: emulsions, stability, multiscale, phase separation, droplet, interfacial film

中图分类号:

O648

黄翔峰, 王旭慧, 陆丽君, 刘佳, 彭开铭. 多尺度研究油水乳状液稳定性的技术进展[J]. 化工进展, 2016, 35(01): 26-33.

HUANG Xiangfeng, WANG Xuhui, LU Lijun, LIU Jia, PENG Kaiming. Technical progress of multiscale study on oil-water emulsion stability[J]. Chemical Industry and Engineering Progree, 2016, 35(01): 26-33.

参考文献

[1] GAO S,MORAN K,XU Z,et al. Role of bitumen components in stabilizing water-in-diluted oil emulsions[J]. Energy & Fuels,2009, 23:2606-2612.
[2] GAFONOVA O V,YARRANTON H W. The stabilization of water-in-hydrocarbon emulsions by asphaltenes and resins[J]. Journal of Colloid and Interface Science,2001,241(2):469-478.
[3] LIU J,HUANG X,LU L,et al. Turbiscan Lab (R) Expert analysis of the biological demulsification of a water-in-oil emulsion by two biodemulsifiers[J]. Journal of Hazardous Materials,2011,190(1-3):214-221.
[4] WEN Y,CHENG H,LU L J,et al. Analysis of biological demulsification process of water-in-oil emulsion by Alcaligenes sp S-XJ-1[J]. Bioresource Technology,2010,101(21):8315-8322.
[5] KIRAN S K,NG S,ACOSTA E J. Impact of asphaltenes and naphthenic amphiphiles on the phase behavior of solvent-bitumen-water systems[J]. Energy & Fuels,2011,25(5):2223-2231.
[6] MOSCHAKIS T,MURRAY B S,DIC and Interface Science,2005, 284(2):714-728.
[7] YOUAN B B C,JACKSON T L,DICKENS L,et al. Protein release profiles and morphology of biodegradable microcapsules containing an oily core[J]. Journal of Controlled Release,2001,76(3):313-326.
[8] TCHOLAKOVA S,DENKOV N D,SIDZHAKOVA D,et al. Interrelation between drop size and protein adsorption at various emulsification conditions[J]. Langmuir,2003,19(14):5640-5649.
[9] 黄翔峰,程航,陆丽君,等. 利用稳定性分析仪研究化学破乳过程[J]. 化工进展,2010,29(5):825-830.
[10] VAN DER TUUK OPEDAL N,SØRLAND G,SJÖBLOM J. Methods for droplet size distribution determination of water-in-oil emulsions using low-field NMR[J]. Diffusion fundamentals,2009,7:1-29.
[11] OPEDAL N V D T,KRALOVA I,LESAINT C,et al. Enhanced sedimentation and coalescence by chemicals on real crude oil systems[J]. Energy & Fuels,2011,25(12):5718-5728.
[12] DENKOVA P S,TCHOLAKOVA S,DENKOV N D,et al. Evaluation of the precision of drop-size determination in oil/water emulsions by low-resolution NMR spectroscopy[J]. Langmuir,2004,20(26):11402-11413.
[13] HARBOTTLE D,CHEN Q,MOORTHY K,et al. Problematic stabilizing films in petroleum emulsions:shear rheological response of viscoelastic asphaltene films and the effect on drop coalescence[J]. Langmuir,2014,30(23):6730-6738.
[14] YARRANTON H W,URRUTIA P,SZTUKOWSKI D M. Effect of interfacial rheology on model emulsion coalescence——Ⅱ. Emulsion coalescence[J]. Journal of Colloid and Interface Science,2007,310(1):253-259.
[15] YEUNG A,DABROS T,MASLIYAH J,et al. Micropipette:a new technique in emulsion research[J]. Colloids and Surfaces A(Physicochemical and Engineering Aspects),2000,174(1-2):169-181.
[16] 刘龙伟,郭睿,解传梅,等. 支链聚醚原油破乳剂的合成与表征[J]. 精细化工,2014(7):898-902.
[17] BURON H, MENGUAL O, MEUNIER G, et al. Optical characterization of concentrated dispersions:applications to laboratory analyses and on-line process monitoring and control[J]. Polymer International,2004,53(9):1205-1209.
[18] MENGUAL O,MEUNIER G,CAYRE I,et al. TURBISCAN MA 2000:multiple light scattering measurement for concentrated emulsion and suspension instability analysis[J]. Talanta,1999,50(2):445-456.
[19] 彭开铭. 生物破乳菌Alicaligenes sp. S-XJ-1表面物质、性质特征及其对乳状液作用规律的研究[D].上海:同济大学,2014.
[20] KANG W L,XU B,WANG Y J,et al. Stability mechanism of W/O crude oil emulsion stabilized by polymer and surfactant[J]. Colloids and Surfaces A(Physicochemical and Engineering Aspects),2011,384(1-3):555-560.
[21] SIMON S,PIERRARD X,SJOBLOM J,et al. Separation profile of model water-in-oil emulsions followed by nuclear magnetic resonance (NMR) measurements:application range and comparison with a multiple-light scattering based apparatus[J]. Journal of Colloid and Interface Science,2011,356(1):352-361.
[22] CARNEIRO G F,SILVA R C,BARBOSA L L,et al. Characterisation and selection of demulsifiers for water-in-crude oil emulsions using low-field ¹H NMR and ESI-FT-ICR MS[J]. Fuel,2015,140:762-769.
[23] MORGAN V G,BARBOSA L L,LACERDA V,et al. Evaluation of the physicochemical properties of the postsalt crude oil for low-field NMR[J]. Industrial & Engineering Chemistry Research,2014,53(21):8881-8889.
[24] HUNG J,CASTILLO J. Proc. SPIE 6337,Advanced environmental, chemical,and biological sensing technologies Ⅳ[C]. Boston,MA, US. 2006.
[25] HUNG J, CASTILLO J, REYES A. Kinetics of asphaltene aggregation in toluene-heptane mixtures studied by confocal microscopy[J]. Energy & Fuels,2005,19(3):898-904.
[26] CLAUSSE D, GOMEZ F, PEZRON I, et al. Morphology characterization of emulsions by differential scanning calorimetry[J]. Advances in Colloid and Interface Science,2005,117(1/2/3):59-74.
[27] ASKE N,KALLEVIK H,SJOBLOM J. Water-in-crude oil emulsion stability studied by critical electric field measurements. Correlation to physico-chemical parameters and near-infrared spectroscopy[J]. Journal of Petroleum Science and Engineering,2002,36(1-2):1-17.
[28] BARRABINO A,KELEŞOĞLU S,SØRLAND G H,et al. Phase inversion in emulsions studied by low field NMR[J]. Colloids and Surfaces A(Physicochemical and Engineering Aspects),2014,443:368-376.
[29] SANDNES R,SIMON S,SJOBLOM J,et al. Optimization and validation of low field nuclear magnetic resonance sequences to determine low water contents and water profiles in W/O emulsions[J]. Colloids and Surfaces A(Physicochemical and Engineering Aspects), 2014,441:441-448.
[30] YU X,BURNHAM N A,TAO M. Surface microstructure of bitumen characterized by atomic force microscopy[J]. Advances in Colloid and Interface Science,2015,218:17-33.
[31] HOU J,FENG X H,MASLIYAH J,et al. Understanding interfacial behavior of ethylcellulose at the water-diluted bitumen interface[J]. Energy & Fuels,2012,26(3):1740-1745.
[32] 于娜娜,邓平,王笃政. 石油破乳技术进展[J]. 精细石油化工进展, 2011(6):17-22.
[33] PENSINI E,HARBOTTLE D,YANG F,et al. Demulsification mechanism of asphaltene-stabilized water-in-oil emulsions by a polymeric ethylene oxide propylene oxide demulsifier[J]. Energy & Fuels,2014,28(11):6760-6771.
[34] YANG X L, VERRUTO V J,KILPATRICK P K. Dynamic asphaltene-resin exchange at the oil/water interface:time-dependent W/O emulsion stability for asphaltene/resin model oils[J]. Energy & Fuels,2007,21(3):1343-1349.
[35] HUA Y J,ANGLE C W. Brewster angle microscopy of langmuir films of athabasca bitumens,n-C₅ asphaltenes,and SAGD bitumen during pressure-area hysteresis[J]. Langmuir,2013,29(1):244-263.
[36] MORAN K,CZARNECKI J. Competitive adsorption of sodium naphthenates and naturally occurring species at water-in-crude oil emulsion droplet surfaces[J]. Colloids and Surfaces A(Physicochemical and Engineering Aspects),2007,292(2-3):87-98.
[37] CZARNECKI J,TCHOUKOV P,DABROS T,et al. Role of asphaltenes in stabilisation of water in crude oil emulsions[J]. Canadian Journal of Chemical Engineering,2013,91(8):1365-1371.
[38] 曹绪龙,崔晓红,李秀兰,等. 扩张流变法研究表面活性剂在界面上的聚集行为[J]. 化学通报,2009(6):507-515.
[39] TAO J,SHI P,FANG S W,et al. Effect of rheology properties of oil/water interface on demulsification of crude oil emulsions[J]. Industrial & Engineering Chemistry Research,2015,54(17):4851-4860.
[40] LI Z F,HARBOTTLE D,PENSINI E,et al. Fundamental study of emulsions stabilized by soft and rigid particles[J]. Langmuir,2015, 31(23):6282-6288.
[41] FAN Y,SIMON S,SJOBLOM J. Interfacial shear rheology of asphaltenes at oil-water interface and its relation to emulsion stability:influence of concentration,solvent aromaticity and nonionic surfactant[J]. Colloids and Surfaces A(Physicochemical and Engineering Aspects),2010,366(1-3):120-128.
[42] ALVAREZ G,JESTIN J,ARGILLIER J F,et al. Small-angle neutron scattering study of crude oil emulsions:structure of the oil-water interfaces[J]. Langmuir,2009,25(7):3985-3990.
[43] ALVES D R,CARNEIRO J S A,OLIVEIRA I F,et al. Influence of the salinity on the interfacial properties of a Brazilian crude oil-brine systems[J]. Fuel,2014,118:21-26.
[44] 张磊,宫清涛,周朝辉,等. 旋转滴方法研究界面扩张流变性质[J]. 物理化学学报,2009(1):41-46.
[45] YUAN J,ZHAI X,XU G,et al. Influence of inorganic salts on the demulsification of block polyether with seven branches for crude oil emulsion[J]. Chemical Journal of Chinese Universities,2014,35(2):325-331.
[46] YANG F,TCHOUKOV P,PENSINI E,et al. Asphaltene subfractions responsible for stabilizing water-in-crude oil emulsions. part 1:interfacial behaviors[J]. Energy & Fuels,2014,28(11):6897-6904.
[47] VERRUTO V J,LE R K,KILPATRICK P K. Adsorption and molecular rearrangement of amphoteric species at oil-water interfaces[J]. Journal of Physical Chemistry B,2009,113(42):13788-13799.
[48] BORGES B,RONDON M,SERENO O, et al. Breaking of water-in-crude-oil emulsions. 3. influence of salinity and water-oil ratio on demulsifier action[J]. Energy & Fuels,2009,23:1568-1574.
[49] TCHOUKOV P,YANG F,XU Z H,et al. Role of asphaltenes in stabilizing thin liquid emulsion films[J]. Langmuir,2014,30(11):3024-3033.
[50] VERRUTO V J,KILPATRICK P K. Water-in-model oil emulsions studied by small-angle neutron scattering:interfacial film thickness and composition[J]. Langmuir,2008,24(22):12807-12822.
[51] ABUDU A,GOUAL L. Adsorption of crude oil on surfaces using quartz crystal microbalance with dissipation (QCM-D) under flow conditions[J]. Energy & Fuels,2009,23:1237-1248.
[52] KANG W L,JING G L,ZHANG H Y,et al. Influence of demulsifier on interfacial film between oil and water[J]. Colloids and Surfaces A(Physicochemical and Engineering Aspects),2006,272(1-2):27-31.
[53] GOUAL L,HORVATH-SZABO G,MASLIYAH J H, et al. Adsorption of bituminous components at oil/water interfaces investigated by quartz crystal microbalance:implications to the stability of water-in-oil emulsions[J]. Langmuir,2005,21(18):8278-8289.
[54] TAVAKKOLI M,PANUGANTI S R,TAGHIKHANI V,et al. Asphaltene deposition in different depositing environments:part 2. Real oil[J]. Energy & Fuels,2014,28(6):3594-3603.
[55] TAVAKKOLI M,PANUGANTI S R,VARGAS F M, et al. Asphaltene deposition in different depositing environments:part 1. Model oil[J]. Energy & Fuels,2014,28(3):1617-1628.
[56] 夏庆中,陈波. 中子小角散射实验技术[J]. 中国核科技报告,2005(2):21-34.
[57] FAN Y,SIMON S,SJOEBLOM J. Influence of nonionic surfactants on the surface and interfacial film properties of asphaltenes investigated by Langmuir balance and Brewster angle microscopy[J]. Langmuir,2010,26(13):10497-10505.
[58] ALVAREZ L,DIAZ M E,MONTES F J,et al. Langmuir technique and Brewster angle microscope studies of the interfacial behavior of bitumen,asphaltenes and maltenes at the air-water interface. I. effect of different spreading solution volumes[J]. Fuel,2010,89(3):691-702.
[59] ESE M H,SJOBLOM J,DJUVE J,et al. An atomic force microscopy study of asphaltenes on mica surfaces. influence of added resins and demulsifiers[J]. Colloid and Polymer Science,2000,278(6):532-538.
[60] VUILLAUME K,GIASSON S. Interactions between mica surfaces across crude oil and asphaltene solutions[J]. Journal of Physical Chemistry C,2009,113(9):3660-3665.
[61] CHANDRA M S,XU Z,MASLIYAH J H. Interfacial films adsorbed from bitumen in toluene solution at a toluene-water interface:a Langmuir and Langmuir-Blodgett film approach[J]. Energy & Fuels, 2008,22(3):1784-1791.
[62] FENG X H,MUSSONE P,GAO S,et al. Mechanistic study on demulsification of water-in-diluted bitumen emulsions by ethylcellulose[J]. Langmuir,2010,26(5):3050-3057.
[63] NATARAJAN A, KUZNICKI N, HARBOTTLE D, et al. Understanding mechanisms of asphaltene adsorption from organic solvent on mica[J]. Langmuir,2014,30(31):9370-9377.
[64] 吴召洪,陈建,附青山,等. 原子力显微镜探针针尖修饰的研究进展[J]. 材料导报,2014(15):62-68.
[65] ZHANG L Y,XU Z H,MASLIYAH J H. Characterization of adsorbed athabasca asphaltene films at solvent-water interfaces using a Langmuir interfacial trough[J]. Industrial & Engineering Chemistry Research,2005,44(5):1160-1174.
[66] DOS SANTOS S,PARTL M N,POULIKAKOS L D. Newly observed effects of water on the microstructures of bitumen surface[J]. Construction and Building Materials,2014,71:618-627.