合成了一种氧化/还原型开关表面活性剂11-二茂铁十一烷酰基三甲基溴化铵(FcCOC10N),通过二茂铁基团氧化及还原态的转变来实现自身表面活性的“开”与“关”,以期在强化有机污染土壤淋洗修复的同时,实现表面活性剂的分离回收.FcCOC10N发生氧化/还原反应前后的理化性质差异表明其具有良好的氧化/还原可逆特性.FcCOC10N溶液与硝基苯易乳化成液滴小而均匀的乳液,向其中添加氧化剂随即破乳分离,且FcCOC10N反复开关5次后与硝基苯形成的乳液性质几乎无变化,破乳率在80%以上,二者之间具有良好的乳化破乳循环能力.对硝基苯污染土壤进行淋洗,以乳化的方式去除土壤中非水相污染物,乳化去除率最高为92.40%,通过破乳分离硝基苯,对FcCOC10N进行回收利用,进一步去除土壤中残余硝基苯,最终去除率达到94.70%.
Abstract
A redox-switchable surfactant, 11-ferrocene undecanoyl trimethylammonium bromide (FcCOC10N), was synthesized in this study, achieving the “on” and “off” of its surface activity through the oxidation and reduction state transition of the ferrocene groups. The aim was to facilitate the separation and recovery of the surfactant while improving the remediation of polluted soil by organic contaminates through soil flushing technique. The differences in physical and chemical properties of FcCOC10N before and after the redox reaction indicated its good redox-reversible characteristics. The FcCOC10N solution and nitrobenzene were easily emulsified into an emulsion with small and uniform droplets, which was immediately demulsified and separated with the addition of an oxidant. Moreover, no change was observed for the properties of the emulsion formed by FcCOC10N and nitrobenzene after repeated 5switches, with a demulsification efficiency of > 80%, demonstrating a good emulsification and demulsification cyclic capability between FcCOC10N and nitrobenzene. Flushing of nitrobenzene-contaminated soil was conducted to remove the non-aqueous phase pollutants from the soil via emulsification, with the highest emulsification removal efficiency of 92.40%. Residual nitrobenzene in the soil was further removed through demulsification and separation of nitrobenzene and recycling of FcCOC10N, with a final removal efficiency of 94.70%.
关键词
分离回收 /
乳化/破乳 /
污染土壤淋洗 /
硝基苯 /
氧化/还原型开关表面活性剂
Key words
contaminated soil flushing /
emulsification/demulsification /
nitrobenzene /
redox-switchable surfactant /
separation and recovery
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参考文献
[1] 齐美珠,邢亚男.土壤污染的主要影响因素与保护措施[J]. 皮革制作与环保科技, 2021,2(24):124-126. Qi M Z, Xing Y N. Main influencing factors and protective measures of soil pollution[J]. Leather Manufacture and Environmental Technology, 2021,2(24):124-126.
[2] 李隋.表面活性剂强化抽取处理修复DNAPL污染含水层的实验研究[D]. 长春:吉林大学, 2008. LI S. Research on surfactant enhanced pump and treat remediation of a DNAPL contaminated aquifer[D]. Changchun: Jilin University, 2008.
[3] Engelmann C, Handel F, Binder M, et al. The fate of DNAPL contaminants in non-consolidated subsurface systems-Discussion on the relevance of effective source zone geometries for plume propagation[J]. Journal of Hazardous Materials, 2019,375:233-240.
[4] Sakari M, Zakaria M P, Junos M B, et al. Spatial distribution of petroleum hydrocarbon in sediments of major rivers from east coast of peninsular Malaysia[J]. Coastal marine science, 2008,32(1):9-18.
[5] Sun Y, Yang Z, Tian P, et al. Oxidative degradation of nitrobenzene by a Fenton-like reaction with Fe-Cu bimetallic catalysts[J]. Applied Catalysis B: Environmental, 2019,244:1-10.
[6] Huo L, Liu G, Yang X, et al. Surfactant-enhanced aquifer remediation: Mechanisms, influences, limitations and the countermeasures[J]. Chemosphere, 2020,252:126620.
[7] 李英杰,田森林,宁平.开关表面活性剂及其应用研究进展[J]. 应用化工, 2008,37(4):438-441. Li Y J, Tian S L, Ning P. Progress in the application and research of switchable surfactants[J]. Applied Chemical Industry, 2008,37(4): 438-441.
[8] 龙坚.多环芳烃污染土壤的光化学可逆增溶修复研究[D]. 昆明:昆明理工大学, 2015. Long J. Photochemical reversible surfactant enhanced remediation of polycyclic aromatic hydrocarbon contaminated soils[D]. Kunming: Kunming University of Science and Technology, 2015.
[9] Li Y, Liu L, Liu X, et al. Reversibly responsive microemulsion triggered by redox reactions[J]. Journal of Colloid and Interface Science, 2019,540:51-58.
[10] Kuddushi M, Patel N K, Rajput S, et al. Thermo-switchable de novo ionic liquid-based gelators with dye-absorbing and drug- encapsulating characteristics[J]. ACS Omega, 2018,3(9):12068-12078.
[11] Alava C, Saunders B R. Temperature-responsive emulsions: The effect of added surfactant[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2005,270-271:18-25.
[12] 詹树娇,田森林,龙坚,等.阳离子型可逆表面活性剂在膨润土上的吸附行为[J]. 中国环境科学, 2014,34(7):1831-1837. Zhan S J, Tian S L, Long J, et al. Sorption behavior of reversible cationic surfactant on bentonite[J]. China Environmental Science, 2014,34(7):1831-1837.
[13] Orihara Y, Matsumura A, Saito Y, et al. Reversible release control of an oily substance using photoresponsive micelles[J]. Langmuir, 2001,17(20):6072-6076.
[14] Takahashi Y, Koizumi N, Kondo Y. Active demulsification of photoresponsive emulsions using cationic-anionic surfactant mixtures[J]. Langmuir, 2016,32(3):683-688.
[15] Johnsson M, Wagenaar A, Engberts J B. Sugar-based gemini surfactant with a vesicle-to-micelle transition at acidic pH and a reversible vesicle flocculation near neutral pH[J]. Journal of the American Chemical Society, 2003,125(3):757-760.
[16] Liu H, Wang C, Zou S, et al. Simple, reversible emulsion system switched by pH on the basis of chitosan without any hydrophobic modification[J]. Langmuir, 2012,28(30):11017-11024.
[17] 田森林,牛艳华,李光,等.典型多环芳烃电化学可逆增溶作用研究[J]. 上海师范大学学报(自然科学版), 2011,40(6):557-561. Tian S L, Niu Y H, LI G, et al. Electrochemically reversible solubilization of typical polycyclic aromatic hydrocarbons by a ferrocenyl surfacanat and its application[J]. Journal of Shanghai Normal University (Natural Sciences), 2011,40(6):557-561.
[18] Takei T, Sakai H, Kondo Y, et al. Electrochemical control of solubilization using a ferrocene-modified nonionic surfactant[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2001,183-185:757-765.
[19] Tsuchiya K, Orihara Y, Kondo Y, et al. Control of viscoelasticity using redox reaction[J]. Journal of the American Chemical Society, 2004,126(39):12282-12283.
[20] Li Y, Hu J, Liu H, et al. Electrochemically reversible foam enhanced flushing for PAHs-contaminated soil: Stability of surfactant foam, effects of soil factors, and surfactant reversible recovery[J]. Chemosphere, 2020,260:127645.
[21] 赵艳涛,孔伟伟,陈志强,等.氧化-还原响应型表面活性剂的研究进展[J]. 中国洗涤用品工业, 2020,5:49-59. Zhao Y T, Kong W W, Chen Z Q, et al. Research development in redox-responsive surfactants[J]. China Cleaning Industry, 2020,5: 49-59.
[22] Gallardo B S, Metcalfe K L, Abbott N L. Ferrocenyl surfactants at the surface of water: Principles for active control of interfacial properties[J]. Langmuir, 1996,12(17):4116-4124.
[23] Saji T, Hoshino K, Aoyagui S. Reversible formation and disruption of micelles by control of the redox state of the head group[J]. Journal of the American Chemical Society, 1985,107(24):6865-6868.
[24] Zhang H, Wu J, Jiang J, et al. Redox-responsive oil-in-dispersion emulsions stabilized by similarly charged ferrocene surfactants and alumina nanoparticles[J]. Langmuir, 2020,36(48):14589-14596.
[25] Saji T, Hoshino K, Ishii Y, et al. Formation of organic thin films by electrolysis of surfactants with the ferrocenyl moiety[J]. Journal of the American Chemical Society, 2002,113(2):450-456.
[26] 张云浩,翟兰兰,等.硅烷偶联剂KH-570表面改性纳米SiO2[J]. 材料科学与工程学报, 2012,30(5):752-756. Zhang Y H, Zhai L L, et al. Surface modification of nano-SiO2 by silane coupling agent 3- (methacryloyloxy)propyltrimethoxysilane[J]. Journal of Materials Science and Engineering, 2012,30(5):752-756.
[27] 柳鹏.低温时间分辨红外光谱电化学方法及二茂铁衍生物电子转移机理研究[D]. 合肥:安徽大学, 2007. Liu P. Low temperature time-resolved FTIR spectroelectrochemistry technique and the studies on electron transfer mechanisms of ferrocenyl derivatives[D]. Hefei: Anhui University, 2007.
[28] 郭辉,庄玉伟,庞海岩,等.合成季铵盐阳离子双子表面活性剂反应机理的红外光谱研究[J]. 光谱学与光谱分析, 2018,38(S1):3-4. Guo H, Zhuang Y W, Pang H Y, et al. Studies on the reaction mechanism of cationic quaternary ammonium gemini surfactant by IR spectroscopy[J]. Spectroscopy and Spectral Analysis, 2018,38(S1):3-4.
[29] Takahashi Y, Koizumi N, Kondo Y. Demulsification of redox-active emulsions by chemical oxidation[J]. Langmuir, 2016,32(30):7556-7563.
基金
国家自然科学基金面上项目(42177049)
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