WO2024012391A1 - 一种高效去除水体中全氟化合物的界面吸附方法 - Google Patents

一种高效去除水体中全氟化合物的界面吸附方法 Download PDF

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WO2024012391A1
WO2024012391A1 PCT/CN2023/106500 CN2023106500W WO2024012391A1 WO 2024012391 A1 WO2024012391 A1 WO 2024012391A1 CN 2023106500 W CN2023106500 W CN 2023106500W WO 2024012391 A1 WO2024012391 A1 WO 2024012391A1
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water
oil
perfluorinated compounds
adsorption method
efficiently removing
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PCT/CN2023/106500
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English (en)
French (fr)
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谷成
陈张浩
黄柳青
滕影
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南京大学
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/26—Treatment of water, waste water, or sewage by extraction
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/12—Halogens or halogen-containing compounds
    • C02F2101/14—Fluorine or fluorine-containing compounds

Definitions

  • the invention relates to wastewater treatment technology, and in particular to an interfacial adsorption method for efficiently removing perfluorinated compounds in water.
  • PFASs Perfluorinated compounds
  • PFASs are a class of synthetic aliphatic chain compounds. Their superior hydrophobic and lipophobic properties, high temperature resistance and oxidation resistance have been used in all aspects of human life.
  • the production, use and disposal process of perfluorinated compounds has currently caused global water pollution (Fang S, Chen X, Zhao S, et al. Trophic Magnification and Isomer Fractionation of Perfluoroalkyl Substances in the Food Web of Taihu Lake, China.
  • perfluorinated compounds are mainly divided into four categories, including perfluoroalkyl acids (PFAAs), perfluoroalkyl ether derivatives (PFPEs), perfluoroalkyl acid fluorides (PASFs) and fluorotelomers (PFAIs), research has found that these four types of perfluorinated compounds can be quickly converted into persistent perfluoroalkylcarboxylic acids and sulfonic acids under chemical oxidation or microbial action, (Li L, Zhai Z, Liu J, et al .Estimating industrial and domestic environmental releases of perfluorooctanoic acid and its salts in China from 2004to 2012.Chemosphere,2015,129:100-109.Buck R C,Franklin J,Berger U,et al.Perfluoroalkyl and Polyfluoroalkyl Substances in the Environment:Terminology ,Classification,and Origins.Integrated Environmental Assessment and Management,2011,7(4)
  • the present invention provides an interfacial adsorption method for removing perfluorinated compounds in water with high efficiency, strong applicability, no secondary pollution, and high removal rate.
  • the interfacial adsorption method for efficiently removing perfluorinated compounds in water includes the following steps: adding polluted water containing perfluorinated compounds, long carbon chain cationic surfactants and water-immiscible oil substances Mix to obtain an oil-water mixture containing a water phase and an oil phase containing perfluorinated compounds and long carbon chain cationic surfactants. Let the oil-water mixture stand and wait for adsorption equilibrium.
  • the above method is to introduce a long carbon chain cationic surfactant at the oil-water interface, so that the long carbon chain cationic surfactant and the anionic perfluorinated compound are closely combined through hydrogen bonding or electrostatic interaction, thereby constructing an absorbent material.
  • the active interface with electronic capabilities realizes the efficient enrichment and removal of perfluorinated compounds on the interface.
  • the number of linear carbon atoms in the long carbon chain cationic surfactant is 12 or more.
  • the number of linear carbon atoms of the long carbon chain cationic surfactant is 16, and the long carbon chain cationic surfactant is cetyl trimethyl ammonium bromide, cetyl tert.
  • cetyl trimethyl ammonium bromide cetyl tert.
  • amine and hexadecylamine are preferably 16 or more of amine and hexadecylamine.
  • the long carbon chain cationic surfactant is one or more of long carbon chain alkyl trimethyl ammonium bromide, long carbon chain alkyl tertiary amine, and long carbon chain amine.
  • the concentration of the long carbon chain cationic surfactant is 0.02-1mM.
  • the oil substance is n-hexane, n-octane, n-heptane or vegetable oil, and more preferably, the oil substance is n-hexane.
  • the volume ratio of the water phase to the oil phase is 1:0.125-1.125.
  • the perfluorinated compound includes perfluoropentanoic acid, perfluoroheptanoic acid, perfluorooctanoic acid, perfluorononanoic acid, perfluorooctane sulfonic acid, perfluorosuberic acid or hexafluoropropylene oxide trimer carboxylic acid;
  • concentration of perfluorinated compounds is 0.0073 ⁇ 0.2mM.
  • the pH value of the oil-water mixture is adjusted to 2-10, more preferably 4.
  • the adsorption temperature is 25°C, and the adsorption equilibrium time is 1 hour.
  • the present invention has the following advantages:
  • the method of the present invention discloses for the first time the introduction of a long carbon chain cationic surfactant into the oil-water system, so that the long carbon chain of the cationic surfactant is distributed in the oil phase, and the cationic head is distributed in the water phase, thereby forming a layer with absorbent properties.
  • the electronic effect of the oil-water interface enables efficient adsorption of PFASs; the cationic surfactant used in the present invention can be combined with PFASs molecules through hydrogen bonding and electrostatic interactions, thereby directly improving the oil-water interface's adsorption of PFASs under standing conditions.
  • the adsorption efficiency can effectively remove PFASs in the water phase;
  • the method of the present invention solves the problem of processes such as exogenous heavy metal ions or continuous aeration that are often introduced in traditional interface enrichment technology. It is simple to operate, green and economical; and the system can achieve efficient removal of PFASs even under complex environmental background values, and has Better application prospects; at the same time, this invention is also the first time to propose using this physical method to remove other anionic PFASs other than PFOS and PFOA, providing a treatment solution for actual composite PFASs polluting water bodies.
  • Figure 1 shows the adsorption amount of PFOA at the n-hexane-water interface in the presence of hexadecylamine, cetyl tertiary amine or cetyltrimethylammonium bromide in Example 1 of the present invention
  • Figure 2 is the adsorption isotherm of PFOA at the n-hexane-water interface under different linear chain lengths of cationic surfactants in Example 2 of the present invention
  • Figure 3 is the adsorption isotherm of PFOA at the n-hexane-water interface in the presence of three C16 cationic surfactants in Example 3 of the present invention
  • Figure 4 is the adsorption isotherm of PFOA by the cetyltrimethylammonium bromide system under different n-hexane volumes in Example 4 of the present invention
  • Figure 5 is a schematic diagram of the adsorption of PFOA at the active n-hexane-water interface in the presence of cetyltrimethylammonium bromide;
  • Figure 6 is the adsorption isotherm of PFOA adsorbed at the active n-hexane-water interface under different concentrations of cetyltrimethylammonium bromide in Example 5 of the present invention
  • Figure 7 is the adsorption isotherm of PFOA adsorbed at the active n-hexane-water interface composed of cetyltrimethylammonium bromide under different pH conditions in Example 6 of the present invention
  • Figure 8 is the adsorption isotherm of PFOA adsorbed at the active n-hexane-water interface composed of cetyltrimethylammonium bromide in the presence of humus in Example 7 of the present invention
  • Figure 9 is the adsorption isotherm of different PFASs adsorbed on the active n-hexane-water interface composed of cetyltrimethylammonium bromide in Example 8 of the present invention.
  • Figure 10 shows the adsorption thermodynamics of PFOA at the oil-water interface constructed by n-heptane, n-octane and cetyltrimethylammonium bromide in Example 9 of the present invention
  • Figure 11 shows the adsorption thermodynamics of PFOA at the oil-water interface constructed between edible oil and cetyltrimethylammonium bromide in Example 10 of the present invention.
  • the interfacial adsorption method for efficiently removing perfluorinated compounds in water bodies of the present invention includes the following steps:
  • the concentration of the perfluorinated compound solution is mixed in equal volumes to obtain a mixed solution with a cationic surfactant concentration of 0.05mM and a perfluorinated compound concentration of 0.00001 ⁇ 0.2mM; and use 5mM ⁇ 1M HCl and NaOH to adjust the pH value of the mixture to 2 -10, preferably 4.
  • the long carbon chain cationic surfactant is preferably cetyltrimethylammonium bromide, cetyl tertiary amine and hexadecylamine, and its own hydrocarbon chain is oriented towards n-hexane. distribution trend, and the aminated groups or amino groups in the structure tend to be distributed in the water phase, and can be closely combined with the negatively charged anionic PFASs in the water through electrostatic interaction or hydrogen bonding, achieving PFASs in n-hexane-water Efficient enrichment at the interface.
  • step S20 Place the threaded centrifuge tube obtained in step S10 into a constant temperature box and let it stand at a constant temperature of 25°C to enrich the perfluorinated compounds on the active n-hexane-water interface.
  • the adsorption equilibrium time is 1 hour.
  • the common cationic surfactant cetyltrimethylammonium bromide is directly used, which not only improves the adsorption efficiency of PFOA at the n-hexane-water interface , and the reaction conditions only require standing, which greatly reduces the difficulty of operation. At the same time, subsequent waste liquid treatment is convenient and will not cause secondary pollution to the environment.
  • This example mainly examines the effect of the presence of long carbon chain cationic surfactants on the adsorption and removal of PFOA at the oil-water interface composed of n-hexane and water.
  • the cationic surfactants include hexadecylamine, cetyl tertiary amine, Hexaalkyltrimethylammonium bromide, the specific steps are:
  • the concentration of hexamine or cetyl tertiary amine is 0.05mM, prepare an aqueous solution containing only 0.0725mM PFOA, and adjust the pH value of the PFOA aqueous solution to 4. Take 16mL of the aqueous solution and place it in a 50mL polypropylene threaded centrifuge tube. Quickly add 8mL of n-hexane containing surfactant and tighten the tube cap. ;
  • step S20 Use the oil-water mixture obtained in step S10 to stand in a constant temperature box at 25°C for 1 hour.
  • the cationic surfactants include primary amines, tertiary amines, bromine and bromine with linear carbon atoms of 6, 8, 12, 16 and 18.
  • the specific steps are;
  • aqueous solution containing only 0.00001 ⁇ 0.2mM PFOA. Adjust the pH value of the PFOA aqueous solution to 4. Take 16mL of the aqueous solution and place it in a 50mL polypropylene threaded centrifuge tube. Quickly add 8mL of cationic surfactant-containing surfactant. Hexane, and tighten the cap of the tube;
  • step S20 Use the oil-water mixture obtained in step S10 to stand in a constant temperature box at 25°C for 1 hour. Use LC-MS/MS to measure the remaining PFOA content in the water phase to calculate the adsorption removal of PFOA. The specific adsorption The isotherms are shown in Figure 2.
  • This example mainly examines the ability to adsorb PFOA on the oil-water interface constructed of three cationic surfactants and n-hexane.
  • the cationic surfactants include hexadecylamine, cetyl tertiary amine, and cetyl triamine.
  • Methyl ammonium bromide the specific steps are:
  • step S20 Use the oil-water mixture obtained in step S10 to stand in a constant temperature box at 25°C for 1 hour. Use LC-MS/MS to measure the remaining PFOA content in the water phase to calculate the adsorption removal of PFOA. The specific adsorption The isotherms are shown in Figure 3.
  • cetyltrimethylammonium bromide, cetyltertiary amine and hexadecylamine can significantly promote the adsorption of PFOA at the oil-water interface. Among them, cetyltrimethylammonium bromide adsorbs best effect.
  • step S20 Use the oil-water mixture obtained in step S10 to stand in a constant temperature box at 25°C for 1 hour.
  • the specific adsorption The isotherms are shown in Figure 4. It can be seen from Figure 4 that the volume of n-hexane has basically no effect on the adsorption of cetyltrimethylammonium bromide system.
  • Figure 5 shows a schematic diagram of the adsorption of PFOA at the n-hexane-water interface with the participation of cetyltrimethylammonium bromide.
  • This example mainly examines the effect of cetyltrimethylammonium bromide concentration on n-hexane-water interface adsorption.
  • the specific steps are:
  • step S20 Use the oil-water mixture obtained in step S10 to stand in a constant temperature box at 25°C for 1 hour. Use LC-MS/MS to measure the remaining PFOA content in the water phase to calculate the adsorption removal of PFOA. The specific adsorption The isotherms are shown in Figure 6.
  • This example mainly examines the effect of pH on the adsorption of PFOA at the active n-hexane-water interface constructed with cetyltrimethylammonium bromide. The specific steps are:
  • step S20 Use the oil-water mixture obtained in step S10 to stand in a constant temperature box at 25°C for 1 hour. Use LC-MS/MS to measure the remaining PFOA content in the water phase to calculate the adsorption removal of PFOA. The specific adsorption The isotherms are shown in Figure 7.
  • This example mainly examines the effect of natural organic matter in water on the adsorption of PFOA at the active n-hexane-water interface constructed with cetyltrimethylammonium bromide. The specific steps are:
  • step S20 Use the oil-water mixture obtained in step S10 to stand in a constant temperature box at 25°C for 1 hour. Use LC-MS/MS to measure the remaining PFOA content in the water phase to calculate the adsorption removal of PFOA. The specific adsorption The isotherms are shown in Figure 8.
  • PFASs include perfluoropentanoic acid, perfluoroheptanoic acid, perfluorooctanoic acid, perfluorononanoic acid, and perfluorooctane Sulfonic acid, perfluorosuberic acid and hexafluoropropylene oxide trimer carboxylic acid
  • step S20 Use the oil-water mixture obtained in step S10 to stand in a constant temperature box at 25°C for 1 hour. Use LC-MS/MS to measure the remaining PFASs content in the water phase to calculate the adsorption removal of PFOA. The specific adsorption The isotherms are shown in Figure 9.
  • This example mainly examines the efficiency of adsorbing PFOA at the active oil-water interface constructed with n-heptane, n-octane and cetyltrimethylammonium bromide. The specific steps are:
  • step S20 Use the oil-water mixture obtained in step S10 to stand in a constant temperature box at 25°C for 1 hour. Use LC-MS/MS to measure the remaining PFASs content in the water phase to calculate the adsorption removal of PFOA. The specific adsorption The isotherms are shown in Figure 9.
  • the active oil-water interface technology constructed with cetyltrimethylammonium bromide using other highly hydrophobic oil substances is universally applicable to the treatment of common PFASs in water bodies.
  • This example mainly examines the efficiency of adsorbing PFOA at the active oil-water interface constructed with edible oil. The specific steps are:
  • step S20 Use the oil-water mixture obtained in step S10 to stand in a constant temperature box at 25°C for 1 hour. Use LC-MS/MS to measure the remaining PFASs content in the water phase to calculate the adsorption removal of PFOA. The specific adsorption The isotherms are shown in Figure 9.
  • the active oil-water interface technology constructed from edible oil and cetyltrimethylammonium bromide is also effective in treating PFASs commonly found in water bodies.

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Abstract

一种高效富集水体中全氟化合物的界面吸附方法，步骤为：将含有全氟化合物的污染水体、长碳链阳离子型表面活性剂和不溶于水的油类物质混合，得到含全氟化合物和阳离子型表面活性剂的水相与油相的油-水混合物，油-水混合物静置吸附。通过在油-水界面上引入长碳链阳离子型表面活性剂，使阳离子型表面活性剂与阴离子型全氟化合物通过静电作用紧密结合，从而构建一个具有吸电子能力的活性界面，实现全氟化合物在界面上的高效富集去除。

Description

一种高效去除水体中全氟化合物的界面吸附方法 技术领域
本发明涉及废水处理技术，特别涉及一种高效去除水体中全氟化合物的界面吸附方法。
背景技术
全氟化合物(PFASs)是一类人工合成的脂肪链状化合物，其优越的疏水疏脂性、耐高温性与耐氧化性，目前已被应用到人类生活的方方面面。全氟化合物的生产、使用和废弃过程目前已造成全球水体污染(Fang S,Chen X,Zhao S,et al.Trophic Magnification and Isomer Fractionation of Perfluoroalkyl Substances in the Food Web of Taihu Lake,China.Environmental Science&Technology,2014,48(4):2173-2182.Guo-Hui Lu,Gai Nan,Zhang Peng,et al.Perfluoroalkyl acids in surface waters and tapwater in the Qiantang River watershed—Influences from paper,textile,and leather industries.Chemosphere,2017,185610-617.Mei Sun,Arevalo Elisa,Strynar Mark,et al.Legacy and Emerging Perfluoroalkyl Substances Are Important Drinking Water Contaminants in the Cape Fear River Watershed of North Carolina.Environmental Science&Technology Letters,2016,3(12):415-419.Liu Y,Zhang Y,Li J,et al.Distribution,partitioning behavior and positive matrix factorization-based source analysis of legacy and emerging polyfluorinated alkyl substances in the dissolved phase,surface sediment and suspended particulate matter around coastal areas of Bohai Bay,China.Environmental Pollution,2019,246:34-44.)。从结构上分，全氟化合物主要分为四类，包括全氟烷基酸(PFAAs)、全氟烷基醚类衍生物(PFPEs)、全氟烷基酰氟(PASFs)和氟调聚物(PFAIs)，研究发现，在化学氧化或者微生物作用下这四类全氟化合物均能快速转化为持久性的全氟烷基羧酸和磺酸，(Li L,Zhai Z,Liu J,et al.Estimating industrial and domestic environmental releases of perfluorooctanoic acid and its salts in China from 2004to 2012.Chemosphere,2015,129:100-109.Buck R C,Franklin J,Berger U,et al.Perfluoroalkyl and Polyfluoroalkyl Substances in the Environment:Terminology,Classification,and Origins.Integrated Environmental Assessment and Management,2011,7(4):513-541.Wang N,Szostek B,Buck R C,et al.8:2 Fluorotelomer alcohol aerobic soil biodegradation:Pathways,metabolites,and metabolite yields.Chemosphere,2009,75:1089–1096)由于这两类全氟烷基酸PKa值极低，在水体中往往以阴离子形式存在，有研究发现，负电性的全氟羧酸和磺酸容易通过细胞膜磷脂层，从而进入生物体内，引发免疫系统损伤、甲状腺功能破坏、肝损伤等毒性效应(Knutsen H K,Alexander J,Barregard L,et al.Risk to human health related to the presence of perfluorooctane sulfonic acid and perfluorooctanoic acid in food.EFSA JOURNAL,2018,16(12).Grandjean P,Clapp R.Perfluorinated Alkyl Substances:Emerging Insights Into Health Risks.NEW SOLUTIONS-A JOURNAL OF ENVIRONMENTAL AND OCCUPATIONAL HEALTH POLICY,2015,25(2):147-163.Armitage J,Cousins I T,Buck R C,et al.Modeling global-scale fate and  transport of perfluorooctanoate emitted from direct sources.ENVIRONMENTAL SCIENCE&TECHNOLOGY,2006,40(22):6969-6975.Toft G,Jonsson B,Lindh C H,et al.Exposure to perfluorinated compounds and human semen quality in arctic and European populations.HUMAN REPRODUCTION,2012,27(8):2532-2540.)。为了有效控制PFASs污染，两类典型的PFASs(PFOS、PFOA)以及相关产品相继被列入《关于持久性有机污染物的斯德哥尔摩公约》，在全球范围内限制生产使用。2016年，美国环境保护署(EPA)设立了饮用水中PFOS和PFOA总浓度低于70ng·L-1的健康标准。尽管多方面已经采取了相关措施，但是PFASs的环境浓度仍然没有下降的趋势，加之新型PFASs替代物层出不穷业已造成了水体污染(Liu Y N,Pereira A D,Martin J W.Discovery of C-5-C-17Poly-and Perfluoroalkyl Substances in Water by In-Line SPE-HPLC-Orbitrap with In-Source Fragmentation Flagging.ANALYTICAL CHEMISTRY,2015,87(8):4260-4268.De Silva A O,Spencer C,Scott B F,et al.Detection of a Cyclic Perfluorinated Acid,Perfluoroethylcyclohexane Sulfonate,in the Great Lakes of North America.Environmental Science&Technology,2011,45(19):8060-8066.)。因此，目前仍有必要研究PFASs污染水体的高效处理技术。
C-F键的稳定性使PFASs对大多数传统的水处理方法和许多新开发的方法具有出色的耐受性。(Grabda M,Oleszek S,Matsumoto M.Per-and polyfluoroalkyl substances:problematic emerging pollutants of aquatic environment.ARCHIVES OF ENVIRONMENTAL PROTECTION,2020,46(3):3-21.Gagliano E,Sgroi M,Falciglia P P,et al.Removal of poly-and perfluoroalkyl substances(PFAS)from water by adsorption:Role of PFAS chain length,effect of organic matter and challenges in adsorbent regeneration.WATER RESEARCH,2020,171.Wanninayake D M.Comparison of currently available PFAS remediation technologies in water:A review.Journal of Environmental Management,2021,283:111977.Militao IM,Roddick FA,Bergamasco R,Fan L.Removing PFAS from aquatic systems using natural and renewable material-based adsorbents:A review.Journal of Environmental Chemical Engineering.2021；9(4):105271.Du Z,Deng S,Bei Y,Huang Q,Wang B,Huang J,Yu G.Adsorption behavior and mechanism of perfluorinated compounds on various adsorbents—A review.Journal of hazardous materials.2014；274:443-54.)传统的吸附技术可先将水中微量的全氟化合物高度富集以便后续处理，是针对大体量污染水体有效且可行的方法。近年来，利用阴离子全氟化合物的表面活性剂性质，研究人员开发了两种界面富集技术——气浮法和油水乳化层法。(Lyu Y,Brusseau M L,Chen W,et al.Adsorption of PFOA at the Air–Water Interface during Transport in Unsaturated Porous Media.Environmental Science&Technology,2018,52(14):7745-7753.Lee Y,Wang P,Lo S,et al.Recovery of perfluorooctane sulfonate(PFOS)and perfluorooctanoate(PFOA)from dilute water solution by foam flotation.Separation and Purification Technology,2017,173:280-285.McMurdo C J,Ellis D A,Webster E,et al.Aerosol Enrichment of the Surfactant PFO and Mediation of the Water-Air  Transport of Gaseous PFOA.Environmental Science&Technology,2008,42(11):3969-3974.Ebersbach I,Ludwig S M,Constapel M,et al.An alternative treatment method for fluorosurfactant-containing wastewater by aerosol-mediated separation.Water Research,2016,101:333-340.Lee Y,Wang P,Lo S,et al.Recovery of perfluorooctane sulfonate(PFOS)and perfluorooctanoate(PFOA)from dilute water solution by foam flotation.Separation and Purification Technology,2017,173:280-285.孟萍萍.全氟和多氟化合物气液界面富集特性及气泡强化去除研究.清华大学,2019.)其中，气浮技术需要多级曝气，能耗成本过高，难以普及，而金属盐协同的气泡富集技术，对pH有较为严苛的要求，同时产生的泡沫液中含有大量的金属杂质，不利于后续的PFASs分离与回收。最近的一项研究利用PFASs疏水疏脂的特点，进一步构建了油、水、气三相组成的乳化层实现了对全氟化合物的富集。但这一技术需不断曝气维持乳化层，且乳化层厚度较高，产生大量油水混合废液。因此，亟待寻找一种研发一种简单，高效，可应用性强，没有二次污染的技术，提高油水界面对PFASs的去除效率的同时，解决高乳化层带来的产废液量过大的问题。
发明内容
发明目的：为了解决现有技术存在的问题，本发明提供一种高效、可应用性强、没有二次污染、去除率高的去除水体中全氟化合物的界面吸附方法。
技术方案：本发明所述的高效去除水体中全氟化合物的界面吸附方法，包括以下步骤：将含有全氟化合物的污染水体、长碳链阳离子型表面活性剂和与水不互溶的油类物质混合，得到含全氟化合物和长碳链阳离子型表面活性剂的水相与油相的油-水混合物，将油-水混合物静置，等待吸附平衡。
上述方法是在油-水界面上引入长碳链阳离子型表面活性剂，使长碳链阳离子型表面活性剂与阴离子型全氟化合物通过氢键作用或静电作用紧密结合，从而构建了一个具有吸电子能力的活性界面，实现了全氟化合物在界面上的高效富集去除。
优选地，所述长碳链阳离子型表面活性剂的直链碳原子个数为12以上。
更优选的，所述长碳链阳离子型表面活性剂的直链碳原子个数为16，为长碳链阳离子型表面活性剂为十六烷基三甲基溴化铵、十六烷基叔胺、十六胺中的一种或多种。
优选的，所述长碳链阳离子型表面活性剂为长碳链烷基三甲基溴化铵、长碳链烷基叔胺、长碳链胺中的一种或多种。
优选地，所述长碳链阳离子型表面活性剂的浓度为0.02-1mM。
优选地，所述油类物质为正己烷、正辛烷、正庚烷或植物油，更优选的，油类物质为正己烷。
优选地，所述水相与油相的体积比为1：0.125-1.125。
优选地，所述全氟化合物包括全氟戊酸、全氟庚酸、全氟辛酸、全氟壬酸、全氟辛烷磺酸、全氟辛二酸或六氟环氧丙烷三聚体羧酸；全氟化合物的浓度为0.0073～0.2mM。
优选地，将所述油-水混合物的pH值调节至2-10，更优选4。
优选地，所述吸附的温度为25℃，吸附平衡时间为1h。
有益效果：本发明与相比于现有技术，具有如下优势：
1、本发明方法首次公开在油水体系中引入长碳链的阳离子表面活性剂，使阳离子表面活性剂的长碳链分布于油相，而阳离子头部分布于水相，从而形成一层具有吸电子效应的油水界面，实现对PFASs的高效吸附；本发明使用的阳离子表面活性剂可以通过氢键作用和静电作用与PFASs分子相结合，从而直接提高了在静置情况下油-水界面对PFASs的吸附效率，高效去除水相中的PFASs；
2、本发明方法解决了传统界面富集技术中常引入外源重金属离子或持续曝气等过程，操作简单，绿色经济；且该体系在复杂环境背景值下均能实现对PFASs的高效去除，具有较好的应用前景；同时，本发明也是首次提出以这种物理方法去除PFOS、PFOA以外的其他阴离子型PFASs，为实际复合PFASs污染水体提供处理方案。
附图说明
图1为本发明实施例1中十六胺、十六烷基叔胺或十六烷基三甲基溴化铵存在下，正己烷-水界面对PFOA的吸附量；
图2为本发明实施例2中不同阳离子型表面活性剂直链链长下正己烷-水界面对PFOA的吸附等温线；
图3为本发明实施例3中三种C16阳离子型表面活性剂存在下正己烷-水界面对PFOA的吸附等温线；
图4为本发明实施例4中不同正己烷体积下十六烷基三甲基溴化铵体系对PFOA的吸附等温线；
图5为十六烷基三甲基溴化铵存在下的活性正己烷-水界面吸附PFOA的示意图；
图6为本发明实施例5中不同十六烷基三甲基溴化铵浓度下活性正己烷-水界面吸附PFOA的吸附等温线；
图7为本发明实施例6中不同pH条件下十六烷基三甲基溴化铵构成的活性正己烷-水界面吸附PFOA的吸附等温线；
图8为本发明实施例7中腐殖质存在下十六烷基三甲基溴化铵构成的活性正己烷-水界面吸附PFOA的吸附等温线；
图9为本发明实施例8中十六烷基三甲基溴化铵构成的活性正己烷-水界面吸附不同PFASs的吸附等温线；
图10为本发明实施例9中正庚烷、正辛烷与十六烷基三甲基溴化铵构建的油水界面对PFOA的吸附热力学；
图11为本发明实施例10中食用油与十六烷基三甲基溴化铵构建的油水界面对PFOA的吸附热力学。
具体实施方式
本发明的高效去除水体中全氟化合物的界面吸附方法，包括以下步骤：
S10、将含有全氟化合物的污染水体与长碳链阳离子型表面活性剂混合，并加入一半体积的正己烷，得到含有全氟化合物与长碳链阳离子型表面活性剂的正己烷-水混合物。具体地说(1)针对易溶于水的表面活性剂，配置0.1mM的长碳链阳离子型表面活性剂与不同浓度的全氟化合物溶液；将上述长碳链阳离子型表面活性剂溶液和不同浓度全氟化合物溶液等体积混合，得到阳离子型表面活性剂浓度为0.05mM全氟化合物浓度为0.00001～0.2mM的混合溶液；并用5mM～1M的HCl和NaOH将所述混合物的pH值调节至2-10，优选4。取16mL混合溶液置于50mL聚丙烯螺纹离心管中，迅速加入8mL的正己烷，拧紧管盖，得到24mL(水相和正己烷相体积之比为2：1、水相中表面活性剂为0.5mM同时含有全氟化合物)的油-水混合物；(2)针对难溶于水或不溶于水的表面活性剂，将表面活性剂溶于正己烷相中，且正己烷相中表面活性剂浓度0.05mM；配置全氟化合物的浓度为0.00001～0.2mM溶液，并用5mM～1M的HCl和NaOH将所述混合物的pH值调节至2-10，优选4。取16mL含全氟化合物溶液置于50mL聚丙烯螺纹离心管中，迅速加入8mL的含表面活性剂的正己烷，拧紧管盖，得到24mL(水相和正己烷相体积之比为2：1、水相中含有全氟化合物，正己烷相中表面活性剂的浓度为0.5mM)的油-水混合物；
需要说明的是，所述长碳链阳离子型表面活性剂优选为十六烷基三甲基溴化铵、十六烷基叔胺和十六胺，其自身的碳氢链有向正己烷向分布的趋势，而结构中的胺化基团或氨基更倾向分布于水相，并且能与水体中带负电的阴离子型PFASs通过静电作用或氢键作用紧密结合，实现了PFASs在正己烷-水界面上的高效富集。
S20、将步骤S10得到的螺纹离心管至于恒温箱中，25℃恒温静置，使全氟化合物富集在活性正己烷-水界面上，吸附平衡时间1小时。
通过本发明的一种高效去除水体中全氟化合物的界面吸附方法，直接使用常见阳离子型表面活性剂十六烷基三甲基溴化铵，不仅提高了PFOA在正己烷-水界面的吸附效率，而且反应条件仅需静置，大大减少了操作难度，同时后续废液处理方便，不会对环境造成二次污染。
以下为具体的实施例：
实施例1
本实施例主要考察长碳链阳离子表面活性剂的存在对正己烷和水构成的油-水界面吸附去除PFOA的影响，其中阳离子型表面活性剂包括十六胺、十六烷基叔胺、十六烷基三甲基溴化铵，其具体步骤为：
S10、配制好含0.05mM十六烷基三甲基溴化铵和0.0725mM的PFOA的混合溶液，和只含有0.0725mM PFOA的对照组溶液，并将不同混合溶液和对照溶液调节pH值至4，取16mL混合溶液或对照溶液置于50mL聚丙烯螺纹离心管中，迅速加入8mL的正己烷，拧紧管盖；将十六胺或十六烷基叔胺溶于正己烷，正己烷相中十六胺或十六烷基叔胺浓度为 0.05mM，配置好只含有0.0725mM PFOA的水溶液，并将PFOA水溶液调节pH值至4，取16mL水溶液置于50mL聚丙烯螺纹离心管中，迅速加入8mL含表面活性剂的正己烷，拧紧管盖；
S20、使用步骤S10得到的油-水混合物在恒温箱中，25℃恒温静置1小时，分别用LC-MS/MS测量水相中剩余PFOA含量，以此计算PFOA的吸附去除，具体吸附率如图1所示。
由图1可知，正己烷对水中PFOA的吸附可以忽略不计，十六胺、十六烷基叔胺、十六烷基三甲基溴化铵这三种阳离子表面活性剂的加入均对由正己烷构建的油-水界面吸附PFOA的效果有显著促进。
实施例2
本实施例主要考察不同链长阳离子型表面活性剂对界面吸附的影响，其中阳离子型表面活性剂包括直链碳原子个数为6、8、12、16、18的伯胺、叔胺、溴化铵盐，其具体步骤为；
S10、配制好0.00001～0.2mM PFOA和0.05mM的易溶型阳离子表面活性剂混合溶液，和只含有0.00001～0.2mM PFOA的对照组溶液，并将不同混合溶液和对照溶液调节pH值至4，取16mL混合溶液或对照溶液置于50mL聚丙烯螺纹离心管中，迅速加入8mL的正己烷，拧紧管盖；将不溶或难溶性阳离子型表面活性剂溶于正己烷，正己烷相中阳离子型表面活性剂浓度为0.05mM，配置好只含有0.00001～0.2mM PFOA的水溶液，并将PFOA水溶液调节pH值至4，取16mL水溶液置于50mL聚丙烯螺纹离心管中，迅速加入8mL含阳离子型表面活性剂的正己烷，拧紧管盖；
S20、使用步骤S10得到的油-水混合物在恒温箱中，25℃恒温静置1小时，分别用LC-MS/MS测量水相中剩余PFOA含量，以此计算PFOA的吸附去除，其具体吸附等温线如图2所示。
由图2可知，随着阳离子型表面活性剂直链碳原子个数的增加，油-水界面对PFOA的吸附能力也呈现增强的趋势，且当直链碳原子个数为16及以上时，吸附量可达到较高水平，且吸附极快达到平衡，继续增加直链碳原子个数，吸附效果无明显增强。
实施例3
本实施例主要考察由三种阳离子型表面活性剂、正己烷构建的油-水界面吸附PFOA的能力，其中阳离子型表面活性剂包括十六胺、十六烷基叔胺、十六烷基三甲基溴化铵，其具体步骤为：
S10、配制好0.00001～0.2mM PFOA和0.05mM的十六烷基三甲基溴化铵混合溶液，和只含有0.00001～0.2mM PFOA的对照组溶液，并将不同混合溶液和对照溶液调节pH值至4，取16mL混合溶液或对照溶液置于50mL聚丙烯螺纹离心管中，迅速加入8mL的正己烷，拧紧管盖；将十六胺或十六烷基叔胺溶于正己烷，正己烷相中十六胺或十六烷基叔胺浓度为0.05mM，配置好只含有0.00001～0.2mM PFOA的水溶液，并将PFOA水溶液调节pH值至4， 取16mL水溶液置于50mL聚丙烯螺纹离心管中，迅速加入8mL含十六胺或十六烷基叔胺的正己烷，拧紧管盖；
S20、使用步骤S10得到的油-水混合物在恒温箱中，25℃恒温静置1小时，分别用LC-MS/MS测量水相中剩余PFOA含量，以此计算PFOA的吸附去除，其具体吸附等温线如图3所示。
由图3可知，十六烷基三甲基溴化铵、十六烷基叔胺和十六胺均能显著促进油水界面对PFOA的吸附，其中，十六烷基三甲基溴化铵吸附效果最好。
实施例4
本实施例主要考察正己烷体积对界面吸附的影响，其具体步骤为；
S10、配制好0.00001～0.2mM PFOA的PFOA和0.05mM的十六烷基三甲基溴化铵混合溶液，和只含有0.00001～0.2mM PFOA的对照组溶液，并将不同混合溶液和对照溶液调节pH值至4，取16mL混合溶液或对照溶液置于50mL聚丙烯螺纹离心管中，迅速加入2mL、4mL、8mL、16mL、20mL的正己烷，拧紧管盖；
S20、使用步骤S10得到的油-水混合物在恒温箱中，25℃恒温静置1小时，分别用LC-MS/MS测量水相中剩余PFOA含量，以此计算PFOA的吸附去除，其具体吸附等温线如图4所示。由图4可知，正己烷体积对十六烷基三甲基溴化铵体系吸附基本无影响。图5示出了十六烷基三甲基溴化铵参与下正己烷-水界面对PFOA的吸附示意图。
实施例5
本实施例主要考察十六烷基三甲基溴化铵浓度对正己烷-水界面吸附的影响，其具体步骤为：
S10、配制好0.00001～0.2mM的PFOA和0.02mM、0.05mM、0.2mM、0.5mM、1mM的十六烷基三甲基溴化铵混合溶液，和只含有0.00001～0.2mM的PFOA的对照组溶液，并将不同混合溶液和对照溶液调节pH值至4，取16mL混合溶液或对照溶液置于50mL聚丙烯螺纹离心管中，迅速加入8mL的正己烷，拧紧管盖；
S20、使用步骤S10得到的油-水混合物在恒温箱中，25℃恒温静置1小时，分别用LC-MS/MS测量水相中剩余PFOA含量，以此计算PFOA的吸附去除，其具体吸附等温线如图6所示。
由图6可知，随着十六烷基三甲基溴化铵浓度上升，最大吸附量Qe呈现先上升后下降的趋势，在一定面积的正己烷-水界面上可构建的吸附位点有限。
实施例6
本实施例主要考察pH对十六烷基三甲基溴化铵构建的活性正己烷-水界面吸附PFOA的影响，其具体步骤为：
S10、配制好0.00001～0.2mM的PFOA和0.05mM的十六烷基三甲基溴化铵混合溶液，并将不同混合溶液调节pH值至2、3.5、5、6.5、7.5和10，取16mL混合溶液置于50mL聚 丙烯螺纹离心管中，迅速加入8mL的正己烷，拧紧管盖；
S20、使用步骤S10得到的油-水混合物在恒温箱中，25℃恒温静置1小时，分别用LC-MS/MS测量水相中剩余PFOA含量，以此计算PFOA的吸附去除，其具体吸附等温线如图7所示。
由图7可知，在pH＝2～10时，十六烷基三甲基溴化铵参与的活性正己烷-水界面对PFOA均有良好的吸附效果，pH在中性及碱性条件下的影响很小，对界面最大吸附量Qe的促进效果几乎可以忽略，而酸性条件对PFOA的吸附显著增强。
实施例7
本实施例主要考察水体中天然有机质对十六烷基三甲基溴化铵构建的活性正己烷-水界面吸附PFOA的影响，其具体步骤为：
S10、配制好0.00001～0.2mM的PFOA和0.05mM的十六烷基三甲基溴化铵，以及不同浓度的天然有机质(0.1～5mg L-1NOM)混合溶液，和只含有0.121mM的PFOA和0.05mM的十六烷基三甲基溴化铵的对照组溶液，并将不同混合溶液和对照溶液调节pH值至4，取16mL混合溶液或对照溶液置于50mL聚丙烯螺纹离心管中，迅速加入8mL的正己烷，拧紧管盖；
S20、使用步骤S10得到的油-水混合物在恒温箱中，25℃恒温静置1小时，分别用LC-MS/MS测量水相中剩余PFOA含量，以此计算PFOA的吸附去除，其具体吸附等温线如图8所示。
由图8可知，将水体中的天然有机质浓度提升至5ppm，活性油-水界面仍能高效吸附PFOA，首先，NOM中大量弱极性组分更易分配至正己烷相中，不会与全氟化合物竞争界面上有效吸附位点；其次，CTAB在该实验体系中构建的吸附位点足够PFOA与NOM极性组分同时吸附；而强极性的小分子有机酸组分，更易分布在水中，难以被CTAB吸附。所以，天然有机质NOM对CTAB构建的活性正己烷-水界面吸附PFOA几乎无影响，本发明构建的活性正己烷-水界面技术对含NOM的复杂水体中具有良好的适应性。
实施例8
本实施例主要十六烷基三甲基溴化铵构建的活性正己烷-水界面吸附不同PFASs的效率，其具体步骤为：
S10、配制好0.05mM的十六烷基三甲基溴化铵以及不同浓度的PFASs(3～80mg L-1)混合溶液，并将不同混合溶液和对照溶液调节pH值至4，取16mL混合溶液或对照溶液置于50mL聚丙烯螺纹离心管中，迅速加入8mL的正己烷，拧紧管盖；所述PFASs包括全氟戊酸、全氟庚酸、全氟辛酸、全氟壬酸、全氟辛烷磺酸、全氟辛二酸和六氟环氧丙烷三聚体羧酸
S20、使用步骤S10得到的油-水混合物在恒温箱中，25℃恒温静置1小时，分别用LC-MS/MS测量水相中剩余PFASs含量，以此计算PFOA的吸附去除，其具体吸附等温线如图9所示。
由图9可知，该十六烷基三甲基溴化铵构建的活性正己烷-水界面技术对处理水体中常见PFASs具有普适性。
实施例9
本实施例主要考察正庚烷、正辛烷和十六烷基三甲基溴化铵构建的活性油水界面吸附PFOA的效率，其具体步骤为：
S10、配制好0.05mM的十六烷基三甲基溴化铵以及不同浓度的PFOA(3～80mg L-1)混合溶液，并将不同混合溶液和对照溶液调节pH值至4，取16mL混合溶液或对照溶液置于50mL聚丙烯螺纹离心管中，迅速加入8mL的正庚烷/辛烷，拧紧管盖
S20、使用步骤S10得到的油-水混合物在恒温箱中，25℃恒温静置1小时，分别用LC-MS/MS测量水相中剩余PFASs含量，以此计算PFOA的吸附去除，其具体吸附等温线如图9所示。
由图10可知，其他具有强疏水性油类物质对十六烷基三甲基溴化铵构建的活性油-水界面技术对处理水体中常见PFASs具有普适性。
实施例10
本实施例主要考察食用油构建的活性油水界面吸附PFOA的效率，其具体步骤为：
S10、配制好0.05mM的十六烷基三甲基溴化铵以及不同浓度的PFOA(3～80mg L-1)混合溶液，并将不同混合溶液和对照溶液调节pH值至4，取16mL混合溶液或对照溶液置于50mL聚丙烯螺纹离心管中，迅速加入8mL的正庚烷/辛烷，拧紧管盖
S20、使用步骤S10得到的油-水混合物在恒温箱中，25℃恒温静置1小时，分别用LC-MS/MS测量水相中剩余PFASs含量，以此计算PFOA的吸附去除，其具体吸附等温线如图9所示。
由图11可知，食用油对十六烷基三甲基溴化铵构建的活性油-水界面技术对处理水体中常见PFASs也有效果。

Claims (10)

  1. 一种高效去除水体中全氟化合物的界面吸附方法，其特征在于：包括以下步骤：将含有全氟化合物的污染水体、长碳链阳离子型表面活性剂和与水不互溶的油类物质混合，得到含全氟化合物和长碳链阳离子型表面活性剂的水相与油相的油-水混合物，将油-水混合物进行静置吸附。
  2. 根据权利要求1所述的高效去除水体中全氟化合物的界面吸附方法，其特征在于：所述长碳链阳离子型表面活性剂的直链碳原子个数为12以上。
  3. 根据权利要求2所述的高效去除水体中全氟化合物的界面吸附方法，其特征在于：所述长碳链阳离子型表面活性剂的直链碳原子个数为16。
  4. 根据权利要求1所述的高效去除水体中全氟化合物的界面吸附方法，其特征在于：所述长碳链阳离子型表面活性剂为长碳链烷基三甲基溴化铵、长碳链烷基叔胺、长碳链胺中的一种或多种。
  5. 根据权利要求1所述的高效去除水体中全氟化合物的界面吸附方法，其特征在于：所述油类物质为正己烷、正辛烷、正庚烷或植物油。
  6. 根据权利要求1所述的高效去除水体中全氟化合物的界面吸附方法，其特征在于：所述全氟化合物包括全氟戊酸、全氟庚酸、全氟辛酸、全氟壬酸、全氟辛烷磺酸、全氟辛二酸或六氟环氧丙烷三聚体羧酸。
  7. 根据权利要求1所述的高效去除水体中全氟化合物的界面吸附方法，其特征在于：所述长碳链阳离子型表面活性剂的浓度为0.02-1mM。
  8. 根据权利要求1所述的高效去除水体中全氟化合物的界面吸附方法，其特征在于：所述水相与油相的体积比为1：0.125～1.125。
  9. 根据权利要求1所述的高效去除水体中全氟化合物的界面吸附方法，其特征在于：所述全氟化合物的浓度为0.00001～0.2mM。
  10. 根据权利要求1所述的高效去除水体中全氟化合物的界面吸附方法，其特征在于：将油-水混合物的pH值调节至2-10。
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