WO2020186795A1 - 一种混合改性有机蒙脱土及其合成方法与应用 - Google Patents

一种混合改性有机蒙脱土及其合成方法与应用 Download PDF

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WO2020186795A1
WO2020186795A1 PCT/CN2019/118710 CN2019118710W WO2020186795A1 WO 2020186795 A1 WO2020186795 A1 WO 2020186795A1 CN 2019118710 W CN2019118710 W CN 2019118710W WO 2020186795 A1 WO2020186795 A1 WO 2020186795A1
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montmorillonite
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solution
modified
modified organic
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谷成
陈张浩
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Nanjing University
Nanjing Tech University
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Nanjing Tech University
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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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
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/02—Aerobic processes
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/28—Anaerobic digestion processes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02W10/10—Biological treatment of water, waste water, or sewage

Definitions

  • the invention belongs to the field of persistent pollutant degradation, and more specifically, relates to a mixed modified organic montmorillonite and its synthesis method and application.
  • perfluorooctanoic acid is the highest perfluorinated compound detected in the environment, and it has received widespread attention in recent years (Rahman, MF; Peldszus, S.; Anderson, WB, Behavior of perfluoroalkyl and polyfluoroalkylsubstances(PFASs)in drinking water treatment:a review.Water research 2014,50,318-40).
  • Previous scientific studies have confirmed that PFOA can cause slow growth of embryos.
  • studies have found that for adolescents and children aged 5 to 18, the concentration of PFOA in the blood is positively correlated with children's ADHD.
  • PFOA is a compound in which all hydrogen atoms on the carbon chain of caprylic acid are replaced by fluorine atoms. Due to the strong electronegativity of fluorine atoms, the carbon-fluorine bond is considered to be the strongest chemical bond (the carbon-fluorine bond energy is 485kJ/mol), and it also has a strong antioxidant capacity, which shows that compared to oxidative degradation technology, PFOA It is easier to be degraded by reduction.
  • the principle of the invention is to use cetyltrimethylammonium bromide ion (HDTMA + ion) to balance the negative charge between layers of montmorillonite to obtain organically modified montmorillonite, and to use the longer C chain of HDTMA + , Make organic montmorillonite hydrophobic, thereby increasing its adsorption of perfluorinated compounds and indole acetic acid. Under ultraviolet light, the indole acetic acid adsorbed between the layers undergoes photoionization and generates hydrated electrons, which can pass through Reductive defluorination degrades perfluorinated compounds. However, this technology has limited degradation efficiency of perfluorinated compounds. In order to improve the degradation efficiency, it is necessary to further improve the organically modified montmorillonite.
  • HDTMA + ion cetyltrimethylammonium bromide ion
  • the present invention provides a hybrid modified organic montmorillonite and its synthesis Method and application: The present invention first uses poly-4-vinylpyridinestyrene to organically modify montmorillonite, and then uses cetyltrimethylammonium bromide to modify poly-4-vinylpyridinestyrene The montmorillonite is organically modified to obtain mixed modified organic montmorillonite.
  • the mixed modified organic montmorillonite is used as a catalytic medium to degrade PFOA in an aqueous solution containing indole acetic acid under ultraviolet light.
  • the mixed modified organic montmorillonite has the advantages of increasing the adsorption of the hydrated electron precursor indole acetic acid and protecting the hydrated electrons, so that it can realize the rapid degradation and defluorination of PFOA under aerobic and acidic conditions.
  • the method for synthesizing mixed modified organic montmorillonite of the present invention includes the following steps:
  • PVPcoS poly-4-vinylpyridine styrene
  • MMT montmorillonite
  • PVPcoS-MMT poly-4-vinylpyridine styrene modified montmorillonite
  • HDTMA hexadecyltrimethylammonium bromide
  • the total amount of poly-4-vinylpyridine styrene in the step S1 is consistent with the total amount of cation exchange (CEC) of the montmorillonite.
  • CEC cation exchange
  • the total amount of cetyltrimethylammonium bromide in step S2 is less than the total amount of cation exchange of montmorillonite.
  • the total amount of cetyltrimethylammonium bromide in the step S2 is 0.6 to 0.8 times the total amount of cation exchange of the montmorillonite.
  • step S1 the specific steps of organically modifying montmorillonite in step S1 are:
  • step (1) Add acidified poly-4-vinylpyridine styrene solution to the montmorillonite dispersion solution of step (1), and stir;
  • step (3) Centrifuge after stirring in step (2), discard the supernatant to obtain a precipitate
  • step (3) Wash the precipitate obtained in step (3) with water to obtain poly-4-vinylpyridinestyrene modified montmorillonite.
  • step S2 the specific steps of organically modifying the poly-4-vinylpyridinestyrene modified montmorillonite in step S2 are:
  • step (3) Centrifuge after stirring in step (2), discard the supernatant to obtain a precipitate
  • step (3) Wash the precipitate obtained in step (3) with water to obtain a mixed modified organic montmorillonite.
  • the dispersion time in the specific step (1) of the organic modification of the montmorillonite in the step S1 is 8 hours.
  • the precipitate is washed 10 times with deionized water.
  • the mixed modified organic montmorillonite of the present invention is synthesized by the above-mentioned method of synthesizing mixed modified organic montmorillonite.
  • the method for efficiently degrading perfluorinated compounds by using mixed modified organic montmorillonite of the present invention includes the following steps:
  • step (ii) Dispersing the above-mentioned mixed modified organic montmorillonite into the mixed solution of step (i) to obtain a reaction solution;
  • step (iii) Use a mercury lamp to photoreact the reaction solution obtained in step (ii) to degrade the perfluoro compound.
  • the step (ii) further includes adjusting the pH value of the reaction solution to 4.0-10.0.
  • step (iii) are: the reaction solution obtained in step (ii) is stirred for 30 minutes and then transferred to a quartz reaction tube, and a mercury lamp is immersed in the reaction solution for degradation in an aerobic environment Reaction; Among them, the total reaction liquid volume is 300mL, the reaction temperature is controlled at 25 ⁇ 2°C, the mercury lamp is a 36W low-pressure mercury lamp, and the reaction time is 14 hours.
  • a method for synthesizing mixed modified organic montmorillonite of the present invention includes first organically modifying montmorillonite with poly-4-vinylpyridine styrene, and then using cetyltrimethyl bromide Organic modification of poly-4-vinylpyridine styrene modified montmorillonite with ammonia to obtain mixed modified organic montmorillonite.
  • the mixed modified organic montmorillonite can greatly increase the adsorption of indole acetic acid molecules. Efficiency, promote the generation of more hydrated electron precursors between the layers, thereby improving the utilization of hydrated electrons during the reaction, and promoting the degradation of PFOA. Therefore, poly-4-vinylpyridinestyrene is used for the first step of montmorillonite.
  • Sub-organic modification ;
  • a mixed modified organic montmorillonite of the present invention is obtained by successively modifying poly-4-vinylpyridine styrene and cetyltrimethylammonium bromide.
  • the mixed modified organic montmorillonite Poly-4-vinylpyridinestyrene and cetyltrimethylammonium bromide are simultaneously adsorbed between the layers, which increases the adsorption of indole acetic acid and protects a large number of photogenerated hydrated electrons from being quenched by oxygen and protons. , So that the degradation reaction can occur under aerobic and acidic conditions, and by controlling the amount of poly-4-vinylpyridinestyrene and cetyltrimethylammonium bromide used in the two modifications, the mixing can be changed.
  • Organic montmorillonite has high degradation and defluorination efficiency for perfluorinated compounds;
  • the montmorillonite and indole acetic acid used in the present invention are both widely existed in nature and will not cause pollution to the environment.
  • the organic modifiers used are poly-4-vinylpyridinestyrene and hexadecane Trimethylammonium bromide can be well fixed and will not be released into the environment to cause secondary pollution, and it is green and environmentally friendly.
  • Figure 1 is a schematic diagram of the degradation of PFOA in mixed modified montmorillonite in the present invention
  • Figure 2 is a schematic diagram of the degradation mechanism of PFOA in the present invention.
  • Figure 3a is a thermodynamic curve diagram of the adsorption of IAA by different organically modified montmorillonites in the present invention
  • Figure 3b is a thermodynamic curve diagram of the adsorption of PFOA by different organically modified montmorillonite in the present invention
  • Figure 4 is a diagram showing the degradation of PFOA by different organically modified montmorillonite in the present invention.
  • 5a and 5b are the kinetic curves of PFOA degradation by hydrated electrons in different atmospheres in the present invention.
  • 5c and 5d are the kinetic curves of PFOA degradation by hydrated electrons under different pH conditions in the present invention.
  • Fig. 6 is a kinetic curve diagram of the intermediate product of PFOA degradation by hydrated electrons in the present invention.
  • Figure 7 is a kinetic curve diagram of PFOA degradation by hydration electrons in the presence of different anions in the present invention
  • Figure 8 is the electron paramagnetic resonance spectra of hydrated electrons in different montmorillonite systems in the present invention.
  • the method for synthesizing mixed modified organic montmorillonite of the present invention includes the following steps:
  • step S2 Disperse the poly-4-vinylpyridinestyrene-modified montmorillonite obtained in step S1 into water and stir for 1 hour; after stirring, add cetyltrimethyl bromide less than the total amount of cation exchange of the montmorillonite
  • the poly-4-vinylpyridinestyrene-modified montmorillonite is re-organized with ammonia, and the total amount of cetyltrimethylammonium bromide usually added is 0.6 of the total cation exchange of montmorillonite ⁇ 0.8 times, stirring for 24 hours, centrifuging and discarding the supernatant to obtain a precipitate, and washing the precipitate with deionized water 10 times to obtain a mixed modified organic montmorillonite.
  • step S1 acidified poly-4-vinylpyridine styrene is added in order to make the modification of poly-4-vinylpyridine styrene easier, and poly-4-vinylpyridine styrene is used to modify montmorillonite.
  • Organic modification enables montmorillonite to greatly increase the adsorption efficiency of indole acetic acid molecules, promote the generation of more hydrated electron precursors between layers, and promote the degradation of PFOA.
  • a mixed modified organic montmorillonite of the present invention is obtained by successively modifying poly-4-vinylpyridinestyrene and cetyltrimethylammonium bromide twice, and poly-4-
  • the total amount of vinylpyridine styrene is consistent with the total amount of cation exchange of montmorillonite, and the total amount of cetyltrimethylammonium bromide is 0.6 to 0.8 times of the total amount of cation exchange of montmorillonite.
  • the amount of poly-4-vinylpyridine styrene, cetyltrimethylammonium bromide and montmorillonite makes the mixed modified organic montmorillonite have a higher adsorption capacity for indole acetic acid and simultaneously absorb perfluoro
  • the compound has high degradation and defluorination efficiency.
  • the method for efficiently degrading perfluorinated compounds by using mixed modified organic montmorillonite of the present invention includes the following steps:
  • step (ii) Disperse the above-mentioned mixed modified organic montmorillonite into the mixed solution of step (i), and use NaOH or HCl to adjust the pH value of the reaction solution to 4.0 to 10.0 to obtain a reaction solution;
  • step (iii) Use magnetic stirring to stir the reaction solution obtained in step (ii) for 30 minutes. After the stirring, the reaction solution is transferred to the quartz reaction tube, and the mercury lamp is immersed in the reaction solution for degradation reaction in an aerobic environment; Among them, the total reaction liquid volume is 300 mL, the reaction temperature is controlled at 25 ⁇ 2° C., the mercury lamp is a 36W low-pressure mercury lamp, and the reaction time is 14 hours.
  • montmorillonite mineral is a mineral material with a layered structure with negative charges between the layers and can be organically modified with positive charges Agent modification.
  • the organic montmorillonite modified by cationic polymer (poly-4-vinylpyridine styrene) increases the adsorption of indole acetic acid, which is the precursor of hydrated electrons, and is modified by cetyltrimethylammonium bromide
  • the montmorillonite can protect the hydrated electrons from being quenched by oxygen and protons.
  • the mixed modified organic montmorillonite obtained by organic modification can not only increase the adsorption of indole acetic acid, the precursor of hydrated electrons, and increase the utilization rate of hydrated electrons, but also protect hydrated electrons from being quenched by oxygen and protons. Rapid degradation and defluorination of PFOA under aerobic and acidic conditions.
  • PFOA perfluorooctane carboxylic acid
  • IAA indole acetic acid
  • the organically modified montmorillonite greatly promotes the adsorption of IAA.
  • the modified montmorillonite With the increase of the content of poly-4-vinylpyridine styrene in the mixed modified montmorillonite, the modified montmorillonite will affect the IAA The adsorption capacity increases, as shown in Figure 3a.
  • the adsorption of PFOA on the mixed modified montmorillonite was reduced, as shown in Figure 3b.
  • PFOA is selected as the representative substance of the perfluorinated compound.
  • the above-mentioned different montmorillonites were dispersed into the mixed solution of IAA and PFOA to obtain reaction solutions with the contents of IAA, PFOA and montmorillonite of 2mM, 10mg/L and 2.2g/L, respectively. Then use 0.1mM NaOH and HCl to adjust the pH of the reaction solution to 7.0. Use magnetic stirring to stir the reaction solution for 30 minutes.
  • the reaction solution After stirring, transfer the reaction solution to a photoreactor equipped with a 500W high-pressure mercury lamp, and turn on the light for degradation
  • the total reaction volume is 30 mL
  • the reaction temperature is controlled at 25 ⁇ 2°C
  • the reaction time is 6 hours.
  • the sample was taken and tested. The sample was divided into two parts. One part was extracted with 2 times the volume of acetonitrile and the remaining PFOA content was measured by high performance liquid chromatography (HPLC), and the other part was filtered and measured by ion chromatography (IC). Calculate the degradation rate and defluorination rate of PFOA based on the content.
  • the specific degradation and defluorination curve is shown in Figure 4.
  • the reductive degradation reaction Before the reductive degradation reaction, first mix the IAA solution and the PFOA solution uniformly, and then disperse 0.6MOM-MMT into the mixed solution of IAA and PFOA, and obtain the contents of IAA, PFOA and montmorillonite respectively 2mM, 10mg/L And 2.2g/L reaction solution. Then use 0.1mM NaOH and HCl to adjust the pH of the reaction solution to 7.0. Use magnetic stirring to stir the reaction solution for 30 minutes. After stirring, transfer the reaction solution to a quartz reaction tube. The total reaction solution volume is 300ml. The mercury lamp is immersed in the reaction solution, and the lamp is turned on for degradation reaction. The reaction temperature was controlled at 25 ⁇ 2°C, and the reaction time was 14 hours.
  • the experiment was carried out in the environment of nitrogen aeration, no aeration, and air aeration, and the aeration rate was 4L/min.
  • the sampling time is set to 0h, 0.5h, 1.5h, 2.5h, 3.5h, 4.5h, 6h, 8h, 11h, 14h.
  • the sample was divided into two parts. One part was extracted with 2 times the volume of acetonitrile and the remaining PFOA content was measured by high performance liquid chromatography (HPLC), and the other part was filtered and measured the F ion content generated by ion chromatography (IC) to calculate PFOA.
  • HPLC high performance liquid chromatography
  • IC ion chromatography
  • the mixed modified montmorillonite has good sealing properties, can protect hydrated electrons from being quenched by oxygen, and improve the utilization rate of hydrated electrons.
  • step (5) in the method for efficiently degrading perfluorocompounds in this example is to investigate the degradation of PFOA by hydrated electrons under different pH conditions.
  • the specific operation steps are:
  • the reductive degradation reaction Before the reductive degradation reaction, first mix the IAA solution and the PFOA solution uniformly, and then disperse 0.6MOM-MMT into the mixed solution of IAA and PFOA, and obtain the contents of IAA, PFOA and montmorillonite respectively 2mM, 10mg/L And 2.2g/L reaction solution. Then use 0.1 mM NaOH and HCl to adjust the pH of the reaction solution to 4.0, 7.0, and 10.0, respectively. Use magnetic stirring to stir the reaction solution for 30 minutes. After stirring, transfer the reaction solution to a quartz reaction tube. The total volume of the reaction solution is 300 ml. A 36W mercury lamp is immersed in the reaction solution and the lamp is turned on for degradation reaction.
  • the reaction temperature was controlled at 25 ⁇ 2°C, and the reaction time was 14 hours.
  • the sampling time is set to 0h, 0.5h, 1.5h, 2.5h, 3.5h, 4.5h, 6h, 8h, 11h, 14h.
  • the sample was divided into two parts. One part was extracted with 2 times the volume of acetonitrile and the remaining PFOA content was measured by high performance liquid chromatography (HPLC), and the other part was filtered and measured the F ion content generated by ion chromatography (IC) to calculate PFOA.
  • HPLC high performance liquid chromatography
  • IC ion chromatography
  • step (5) in the method for efficiently degrading perfluorocompounds of this embodiment is specifically:
  • the reductive degradation reaction Before the reductive degradation reaction, first mix the IAA solution and the PFOA solution uniformly, and then disperse 0.6MOM-MMT into the mixed solution of IAA and PFOA, and obtain the contents of IAA, PFOA and montmorillonite respectively 2mM, 10mg/L And 2.2g/L reaction solution. Then use 0.1mM NaOH and HCl to adjust the pH of the reaction solution to 7.0. Use magnetic stirring to stir the reaction solution for 30 minutes. After stirring, transfer the reaction solution to a quartz reaction tube. The total reaction solution volume is 300ml. The mercury lamp is immersed in the reaction solution, and the lamp is turned on for degradation reaction. The reaction temperature was controlled at 25 ⁇ 2°C, and the reaction time was 14 hours.
  • the sampling time is set to 0h, 0.5h, 1.5h, 2.5h, 3.5h, 4.5h, 6h, 8h, 11h, 14h.
  • the intermediate product is detected and quantified by LC/MS/MS.
  • the curve of the intermediate product with time is shown in Figure 6.
  • the degradation intermediates of PFOA in this system mainly include perfluorocarboxylic acids with different chain lengths and methane acetate.
  • step (5) in the method for efficiently degrading perfluorinated compounds in this example is to investigate the degradation of PFOA by hydrated electrons in the presence of different anions.
  • the specific operation steps are:
  • a 36W mercury lamp is immersed in the reaction solution and the lamp is turned on for degradation reaction.
  • the reaction temperature was controlled at 25 ⁇ 2°C, and the reaction time was 14 hours.
  • the sampling time is set to 0h, 0.5h, 1.5h, 2.5h, 3.5h, 4.5h, 6h, 8h, 11h, 14h.
  • the sample was divided into two parts. One part was extracted with 2 times the volume of acetonitrile and the remaining PFOA content was measured by high performance liquid chromatography (HPLC), and the other part was filtered and measured the F ion content generated by ion chromatography (IC) to calculate PFOA.
  • HPLC high performance liquid chromatography
  • IC ion chromatography
  • a method for efficiently degrading perfluorinated compounds the steps are:

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Abstract

一种混合改性有机蒙脱土及其合成方法以及在高效降解全氟化合物中的应用，使用聚-4-乙烯基吡啶苯乙烯对蒙脱土进行有机改性，再使用十六烷基三甲基溴化铵对聚-4-乙烯基吡啶苯乙烯改性蒙脱土进行有机改性，得到的混合改性有机蒙脱土能够增加对水合电子前驱物吲哚乙酸的吸附并保护水合电子，实现对PFOA的快速降解和脱氟，且不受溶液pH、NO 3 -、SO 4 2-以及溶解氧的影响。

Description

一种混合改性有机蒙脱土及其合成方法与应用 技术领域
本发明属于持久性污染物降解领域，更具体地说，涉及一种混合改性有机蒙脱土及其合成方法与应用。
背景技术
自上世纪五十年代以来，全氟化合物由于具有极好的物理和化学稳定性，被广泛应用于工业生产的不同领域，如涂料、防火材料、聚合物合成以及抛光剂(Renner,R.,Evidence of toxic effects and environmental impacts has sent researchers scrambling to obtain more data.Environmental science&technology 2001,35,(7),154A-160A.Schultz,M.M.；Barofsky,D.F.；Field,J.A.,Fluorinated alkyl surfactants.Environmental Engineering Science 2003,20,(5),487-501.Giesy,J.P.；Kannan,K.,Perfluorochemical surfactants in the environment.Environmental science&technology 2002,36,(7),146A-152A)。在一系列的全氟化合物中，全氟辛酸是被检测到的环境中含量最高的全氟化合物，最近几年受到广泛关注(Rahman,M.F.；Peldszus,S.；Anderson,W.B.,Behaviour and fate of perfluoroalkyl and polyfluoroalkyl substances(PFASs)in drinking water treatment:a review.Water research 2014,50,318-40)。之前的科学研究证实全氟辛酸能够引起胚胎的生长发育缓慢。除此之外，还有研究发现对于5到18岁的青少年儿童，全氟辛酸在血液中的浓度与儿童的多动症呈现正相关关系。(Koustas,E.；Lam,J.；Sutton,P.；Johnson,P.I.；Atchley,D.S.；Sen,S.；Robinson,K.A.；Axelrad,D.A.；Woodruff,T.J.,The Navigation Guide-evidence-based medicine meets environmental health:systematic review of nonhuman evidence for PFOA effects on fetal growth.Environmental health perspectives 2014,122,(10),1015-27.Stein,C.R.；Savitz,D.A.,Serum Perfluorinated Compound Concentration and Attention Deficit/Hyperactivity Disorder in Children 5-18 Years of Age.Environmental health perspectives 2011,119,(10),1466-1471)。
PFOA是一种辛酸碳链上所有的氢原子全部被氟原子取代的化合物。由于氟原子强的电负性，碳氟键被认为是最强的化学键(碳氟键键能485kJ/mol)，而且还有很强的抗氧化能力，这表明相比于氧化降解技术，PFOA更容易被还原降解。(Rahman,M.F.；Peldszus,S.；Anderson,W.B.,Behaviour and fate of perfluoroalkyl and polyfluoroalkyl substances(PFASs)in drinking water treatment:a review.Water research 2014,50,318-40.Arvaniti,O.S.；Stasinakis,A.S.,Review on the occurrence,fate and removal of perfluorinated compounds during wastewater treatment.The Science of the total environment 2015,524-525,81-92.Park,H.；Vecitis,C.D.； Cheng,J.；Choi,W.；Mader,B.T.；Hoffmann,M.R.,Reductive Defluorination of Aqueous Perfluorinated Alkyl Surfactants:Effects of Ionic Headgroup and Chain Length.Journal of Physical Chemistry A 2009,113,(4),690-696)。在最近的研究中，很多还原PFOA的方法被报道，包括直接紫外光照、紫外/亚硫酸盐、紫外/碘化钾、紫外/光催化剂等技术方法(Lyu,X.J.；Li,W.W.；Lam,P.K.；Yu,H.Q.,Insights into perfluorooctane sulfonate photodegradation in a catalyst-free aqueous solution.Scientific reports 2015,5,9353.Gu,Y.；Dong,W.；Luo,C.；Liu,T.,Efficient Reductive Decomposition of Perfluorooctanesulfonate in a High Photon Flux UV/Sulfite System.Environmental science&technology 2016,50,(19),10554-10561.Qu,Y.；Zhang,C.；Li,F.；Chen,J.；Zhou,Q.,Photo-reductive defluorination of perfluorooctanoic acid in water.Water research 2010,44,(9),2939-47.Lin,H.；Niu,J.；Xu,J.；Huang,H.；Li,D.；Yue,Z.；Feng,C.,Highly efficient and mild electrochemical mineralization of long-chain perfluorocarboxylic acids(C9-C10)by Ti/SnO2-Sb-Ce,Ti/SnO2-Sb/Ce-PbO2,and Ti/BDD electrodes.Environmental science&technology 2013,47,(22),13039-46.Li,X.；Zhang,P.；Jin,L.；Shao,T.；Li,Z.；Cao,J.,Efficient photocatalytic decomposition of perfluorooctanoic acid by indium oxide and its mechanism.Environmental science&technology 2012,46,(10),5528-34.Tang,H.；Xiang,Q.；Lei,M.；Yan,J.；Zhu,L.；Zou,J.,Efficient degradation of perfluorooctanoic acid by UV–Fenton process.Chemical Engineering Journal 2012,184,156-162.Liu,Y.；Chen,S.；Quan,X.；Yu,H.；Zhao,H.；Zhang,Y.,Efficient Mineralization of Perfluorooctanoate by Electro-Fenton with H2O2 Electro-generated on Hierarchically Porous Carbon.Environmental science&technology 2015,49,(22),13528-33)。在这些方法中，还原活性物种比如水合电子、二氧化碳负离子自由基以及光生电子起到了主要作用。除此之外，这些研究也表明相比二氧化碳负离子自由基和光生电子，水合电子的强还原能力能够将PFOA完全脱氟，因此这种方法具有较高的应用前景。但是水合电子在还原降解PFOA的过程中需要较为苛刻的反应条件(如厌氧环境、高pH)，苛刻的反应条件增加了这种方法在实际应用中的不可应用性。因此，一种低能耗，降解效率高，可应用性强的方法亟待被研发。
经检索发现，中国专利申请号201510981853.2，申请公布日为2016年5月4日的专利申请文件公开了一种高效降解全氟化合物的方法，使用254nm紫外光照射吲哚乙酸(IAA)溶液产生水合电子，在好氧条件下还原降解PFCs，通过加入十六烷基三甲基溴化铵有机改性的蒙脱土来提供反应微区，大大提高了水合电子对PFCs的降解和脱氟效果，并且该方法不受溶液pH和溶解氧的影响，基本克服了已有水合电子还原降解PFCs方法的缺陷。该发明的原理为使用十六烷基三甲基溴化铵离子(HDTMA +离子)平衡蒙脱土的层间负电荷，得到有机 改性蒙脱土，并且利用HDTMA +的较长C链，使有机蒙脱土具有疏水性，从而增加其对全氟化合物和吲哚乙酸的吸附，在紫外光照下，吸附到层间的吲哚乙酸发生光致电离并产生水合电子，这些水合电子可通过还原脱氟的方式将全氟化合物降解。但是，该技术对全氟化合物的降解效率有限，为提高降解效率，需要对有机改性蒙脱土进一步改进。
发明内容
1.要解决的问题
针对现有的水合电子还原降解全氟化合物技术存在反应条件苛刻、可应用性差、水合电子利用率和降解效率有待进一步提高的问题，本发明提供了一种混合改性有机蒙脱土及其合成方法与应用；本发明先使用聚-4-乙烯基吡啶苯乙烯对蒙脱土进行有机改性，再使用十六烷基三甲基溴化氨对聚-4-乙烯基吡啶苯乙烯改性蒙脱土进行有机改性，得到混合改性有机蒙脱土。以该混合改性有机蒙脱土作为催化介质，在含有吲哚乙酸的水溶液中，紫外光照下降解PFOA。该混合改性有机蒙脱土具有增加对水合电子前驱物吲哚乙酸的吸附和保护水合电子的优点，从而能够实现了在好氧和酸性条件下对PFOA的快速降解和脱氟。
2.技术方案
为了解决上述问题，本发明所采用的技术方案如下：
本发明的一种合成混合改性有机蒙脱土的方法，包括以下步骤：
S1、使用聚-4-乙烯基吡啶苯乙烯(PVPcoS)对蒙脱土(MMT)进行有机改性，得到聚-4-乙烯基吡啶苯乙烯改性蒙脱土(PVPcoS-MMT)；
S2、使用十六烷基三甲基溴化氨(HDTMA)对步骤S1中得到的聚-4-乙烯基吡啶苯乙烯改性蒙脱土进行再有机改性，得到混合改性有机蒙脱土(MOM-MMT)。
优选地，所述步骤S1中的聚-4-乙烯基吡啶苯乙烯的总量与蒙脱土的阳离子交换(CEC)总量一致。
优选地，所述步骤S2中的十六烷基三甲基溴化氨的总量小于蒙脱土的阳离子交换总量。
优选地，所述步骤S2中的十六烷基三甲基溴化氨的总量为蒙脱土的阳离子交换总量的0.6～0.8倍。
优选地，所述步骤S1中对蒙脱土进行有机改性的具体步骤为：
(1)将钠蒙脱土分散到水中，得到蒙脱土分散溶液；
(2)向步骤(1)的蒙脱土分散溶液中加入酸化的聚-4-乙烯基吡啶苯乙烯溶液，搅拌；
(3)步骤(2)中搅拌结束后离心，弃去上清液，得到沉淀物；
(4)用水清洗步骤(3)中得到的沉淀物，得到聚-4-乙烯基吡啶苯乙烯改性蒙脱土。
优选地，所述步骤S2中对聚-4-乙烯基吡啶苯乙烯改性蒙脱土进行再有机改性的具体步 骤为：
(1)将聚-4-乙烯基吡啶苯乙烯改性蒙脱土分散到水中，得到聚-4-乙烯基吡啶苯乙烯改性蒙脱土分散溶液；
(2)向步骤(1)的聚-4-乙烯基吡啶苯乙烯改性蒙脱土分散溶液中加入十六烷基三甲基溴化铵溶液，搅拌；
(3)步骤(2)中搅拌结束后离心，弃去上清液，得到沉淀物；
(4)用水清洗步骤(3)中得到的沉淀物，得到混合改性有机蒙脱土。
优选地，所述步骤S1中对蒙脱土进行有机改性的具体步骤(1)中分散时间为8小时。
优选地，所述步骤S1中对蒙脱土进行有机改性的具体步骤(4)中用去离子水清洗沉淀物10遍。
本发明的一种混合改性有机蒙脱土，采用上述的合成混合改性有机蒙脱土的方法合成得到。
本发明的一种采用混合改性有机蒙脱土高效降解全氟化合物的方法，包括以下步骤：
(i)将吲哚乙酸溶液和全氟化合物溶液均匀混合；
(ii)将上述的混合改性有机蒙脱土分散到步骤(i)的混合溶液中，得到反应溶液；
(iii)使用汞灯对步骤(ii)中得到的反应溶液进行光反应以降解全氟化合物。
优选地，所述步骤(ii)还包括调节反应溶液的pH值至4.0～10.0。
优选地，所述步骤(iii)的具体步骤为：将步骤(ii)中得到的反应溶液搅拌30分钟后转移至石英反应管内，在好氧环境下，将汞灯浸没到反应溶液中进行降解反应；其中，总反应液体积为300mL，反应温度控制在25±2℃，汞灯为36W低压汞灯，反应时间为14小时。
3.有益效果
相比于现有技术，本发明的有益效果为：
(1)本发明的一种合成混合改性有机蒙脱土的方法，包括首先使用聚-4-乙烯基吡啶苯乙烯对蒙脱土进行有机改性，再使用十六烷基三甲基溴化氨对聚-4-乙烯基吡啶苯乙烯改性蒙脱土进行有机改性得到混合改性有机蒙脱土，惊讶的发现混合改性有机蒙脱土能够大大增加对吲哚乙酸分子的吸附效率，促进更多的水合电子前驱物质在层间产生，从而提高反应过程中对水合电子的利用率，促进PFOA的降解，因此采用聚-4-乙烯基吡啶苯乙烯对蒙脱土进行第一次有机改性；
(2)本发明的一种混合改性有机蒙脱土，先后通过聚-4-乙烯基吡啶苯乙烯、十六烷基三甲基溴化氨改性得到，该混合改性有机蒙脱土层间同时吸附有聚-4-乙烯基吡啶苯乙烯和十六烷基三甲基溴化氨，增加了对吲哚乙酸吸附的同时保护了大量产生的光生水合电子不被氧 气和质子猝灭，从而使降解反应可以在好氧和酸性条件下发生，并且通过控制两次改性所用的聚-4-乙烯基吡啶苯乙烯、十六烷基三甲基溴化氨的量，使混合改性有机蒙脱土对全氟化合物具有较高的降解和脱氟效率；
(3)本发明的一种采用混合改性有机蒙脱土高效降解全氟化合物的方法，使用上述的混合改性有机蒙脱土作为催化介质，该混合改性有机蒙脱土的存在起到了一个微反应器的作用，实现高效降解PFOA；
(4)本发明中使用的蒙脱土和吲哚乙酸都是自然界广泛存在的物质，不会对环境造成污染，所用到的有机改性剂聚-4-乙烯基吡啶苯乙烯和十六烷基三甲基溴化氨能够被很好地固定，不会释放到环境中造成二次污染，实现了绿色环境友好。
附图说明
图1为本发明中PFOA在混合改性蒙脱土中降解的示意图；
图2为本发明中PFOA降解机制的示意图；
图3a为本发明中不同有机改性蒙脱土对IAA的吸附热力学曲线图；
图3b为本发明中不同有机改性蒙脱土对PFOA的吸附热力学曲线图；
图4为本发明中不同有机改性蒙脱土对PFOA的降解图；
图5a和5b为本发明中不同气氛下水合电子对PFOA降解的动力学曲线图；
图5c和5d为本发明中不同pH条件下水合电子对PFOA降解的动力学曲线图；
图6为本发明中水合电子对PFOA降解的中间产物动力学曲线图；
图7为本发明中不同阴离子存在下水合电子对PFOA降解的动力学曲线图；
图8为本发明中不同蒙脱土体系中水合电子的电子顺磁共振谱图。
具体实施方式
下面结合具体实施例对本发明进一步进行描述。
下文对本发明的示例性实施例的详细描述参考了附图，尽管这些示例性实施例被充分详细地描述以使得本领域技术人员能够实施本发明，但应当理解可实现其他实施例且可在不脱离本发明的精神和范围的情况下对本发明作各种改变。下文对本发明的实施例的更详细的描述并不用于限制所要求的本发明的范围，而仅仅为了进行举例说明且不限制对本发明的特点和特征的描述，以提出执行本发明的最佳方式，并足以使得本领域技术人员能够实施本发明。因此，本发明的范围仅由所附权利要求来限定。
本发明的一种合成混合改性有机蒙脱土的方法，包括以下步骤：
S1、将钠蒙脱土分散到水中，搅拌8小时得到蒙脱土分散溶液；再向蒙脱土分散溶液中 加入酸化的聚-4-乙烯基吡啶苯乙烯对蒙脱土进行有机改性，加入的聚-4-乙烯基吡啶苯乙烯的总量与蒙脱土的阳离子交换总量一致，搅拌24小时，离心弃去上清液，得到沉淀物，并且用去离子水水清洗沉淀物10遍得到聚-4-乙烯基吡啶苯乙烯改性蒙脱土；
S2、将步骤S1中得到聚-4-乙烯基吡啶苯乙烯改性蒙脱土分散到水中，搅拌1小时；搅拌均匀后加入小于蒙脱土阳离子交换总量的十六烷基三甲基溴化氨对聚-4-乙烯基吡啶苯乙烯改性蒙脱土进行再有机改性，通常加入的十六烷基三甲基溴化氨的总量为蒙脱土的阳离子交换总量的0.6～0.8倍，搅拌24小时，离心弃去上清液，得到沉淀物，并且用去离子水水清洗沉淀物10遍得到混合改性有机蒙脱土。
值得说明的是，步骤S1中加入酸化的聚-4-乙烯基吡啶苯乙烯为了更容易进行聚-4-乙烯基吡啶苯乙烯改性，采用聚-4-乙烯基吡啶苯乙烯对蒙脱土进行有机改性使得蒙脱土能够大大增加对吲哚乙酸分子的吸附效率，促进更多的水合电子前驱物质在层间产生，促进PFOA的降解。
进一步说明的是，本发明的一种混合改性有机蒙脱土先后采用聚-4-乙烯基吡啶苯乙烯、十六烷基三甲基溴化氨进行两次改性得到，聚-4-乙烯基吡啶苯乙烯的总量在与蒙脱土的阳离子交换总量一致，十六烷基三甲基溴化氨的总量为蒙脱土的阳离子交换总量的0.6～0.8倍，通过控制聚-4-乙烯基吡啶苯乙烯、十六烷基三甲基溴化氨与蒙脱土的量，使得混合改性有机蒙脱土在具有较高的吲哚乙酸吸附能力的同时对全氟化合物具有较高的降解和脱氟效率。
本发明的一种采用混合改性有机蒙脱土高效降解全氟化合物的方法，包括以下步骤：
(i)将吲哚乙酸溶液和全氟化合物溶液均匀混合；
(ii)将上述的混合改性有机蒙脱土分散到步骤(i)的混合溶液中，使用NaOH或HCl调节反应溶液的pH值至4.0～10.0，得到反应溶液；
(iii)使用磁力搅拌将步骤(ii)中得到的反应溶液搅拌30分钟，搅拌结束后将反应溶液转移至石英反应管内，在好氧环境下，将汞灯浸没到反应溶液中进行降解反应；其中，总反应液体积为300mL，反应温度控制在25±2℃，汞灯为36W低压汞灯，反应时间为14小时。
本发明采用混合改性有机蒙脱土高效降解全氟化合物的原理为：蒙脱土矿物是一种层状结构的矿物材料，层间带有负电荷，能够被带有正电荷的有机改性剂改性。被阳离子聚合物(聚-4-乙烯基吡啶苯乙烯)改性后的有机蒙脱土增加了对水合电子前驱物吲哚乙酸的吸附，被十六烷基三甲基溴化氨改性后的蒙脱土能够保护水合电子不被氧气和质子猝灭。因此，通过首先使用聚-4-乙烯基吡啶苯乙烯对蒙脱土进行有机改性，再使用十六烷基三甲基溴化氨对聚-4-乙烯基吡啶苯乙烯改性蒙脱土进行有机改性得到的混合改性有机蒙脱土，这样不仅能够增加对水合电子前驱物吲哚乙酸吸附，提高水合电子利用率，而且能够保护水合电子，不被 氧气和质子猝灭，从而实现在好氧和酸性条件下对PFOA的快速降解和脱氟。
实施例1
本实施例测定不同有机改性蒙脱土对全氟辛烷羧酸(PFOA)和吲哚乙酸(IAA)的吸附速率，其步骤为：
(1)将200g蒙脱土(购自浙江丰虹蒙脱土化工有限公司)分散在4L水中，加入0.4mol固体NaCl饱和8h，离心弃去上清液，得到沉淀物；将沉淀物再分散在4L水中，如此重复操作6次。用去离子水清洗沉淀物，洗至以AgNO 3溶液检测无沉淀生成。冷冻干燥即得到饱和的Na +蒙脱土；
(2)将制备好的Na +蒙脱土置于水中搅拌8小时，使蒙脱土均匀分散。向分散好的蒙脱土溶液中加入电荷总量与溶液中蒙脱土的阳离子交换总量一致的聚-4-乙烯基吡啶苯乙烯(溶于5mol/L H 2SO 4)水溶液50mL，搅拌24小时，离心得到沉淀物，用水清洗沉淀物，得到聚-4-乙烯基吡啶苯乙烯蒙脱土(PVPcoS-MMT)；
(3)将聚-4-乙烯基吡啶苯乙烯改性的蒙脱土分散在水中，搅拌1小时。搅拌均匀后，向分散好的聚-4-乙烯基吡啶苯乙烯蒙脱土中分别加入0.2CEC、0.4CEC、0.6CEC、0.8CEC量的十六烷基三甲基溴化氨溶液，搅拌24小时，离心得到沉淀物，用水清洗沉淀物，得到混合改性有机蒙脱土(0.2MOM-MMT、0.4MOM-MMT、0.6MOM-MMT、0.8MOM-MMT)；
(4)将制备好的Na +蒙脱土置于水中搅拌8小时，使蒙脱土均匀分散。向分散好的蒙脱土溶液中加入1CEC的十六烷基三甲基溴化氨水溶液，搅拌24小时，离心得到沉淀物，用去离子水水清洗沉淀物，得到十六烷基三甲基溴化氨改性蒙脱土(HDTMA-MMT)；
(5)准备初始浓度从0到1000mg/L的PFOA水溶液各10mL，分别加入22mg Na +蒙脱土或有机改性蒙脱土，室温下震荡10h，离心取上清液测定PFOA的浓度，使用langmuir模型拟合对PFOA的吸附等温线，模型为Q e＝(K L×C max×C e)/(1+K L×C e)，得到PFOA在不同蒙脱土上的最大吸附量分别为Q e(mmol/kg)＝8.199，PFOA在HDTMA +蒙脱土上的最大吸附量Q e(mmol/kg)＝277.312。同理，准备初始浓度从17.52到525.6mg/L的IAA水溶液各10mL，分别加入22mg Na +蒙脱土或有机改性蒙脱土，室温下震荡4h，离心取上清液测定IAA的浓度，使用langmuir模型拟合对IAA的吸附等温线，模型为Q e＝(K L×C max×C e)/(1+K L×C e)，得到IAA在不同蒙脱土上的最大吸附量分别为Q e(mmol/kg)＝156，IAA在HDTMA +蒙脱土上的最大吸附量Q e(mmol/kg)＝277。
由此可以得出结论：有机改性蒙脱土大大促进了对IAA的吸附，随着混合改性蒙脱土中聚-4-乙烯基吡啶苯乙烯含量的增加，改性蒙脱土对IAA吸附量增加，如图3a所示。惊讶的发现与HDTMA-蒙脱土相比，混合改性蒙脱土对PFOA吸附量有所减少，如图3b所示。
实施例2
本实施例的一种高效降解全氟化合物的方法，其步骤为：
(1)将200g蒙脱土(购自浙江丰虹蒙脱土化工有限公司)分散在4L水中，加入0.4mol固体NaCl饱和8h，离心弃去上清液，得到沉淀物；将沉淀物再分散在4L水中，如此重复操作6次。用去离子水清洗沉淀物，洗至以AgNO 3溶液检测无沉淀生成。冷冻干燥即得到饱和的Na +蒙脱土；
(2)将制备好的Na +蒙脱土置于水中搅拌8小时，使蒙脱土均匀分散。向分散好的蒙脱土溶液中加入电荷总量与溶液中蒙脱土的阳离子交换总量一致的聚-4-乙烯基吡啶苯乙烯(溶于5mol/L H 2SO 4)水溶液50mL，搅拌24小时，离心得到沉淀物，用水清洗沉淀物，得到聚-4-乙烯基吡啶苯乙烯蒙脱土(PVPcoS-MMT)；
(3)将聚-4-乙烯基吡啶苯乙烯改性的蒙脱土分散在水中，搅拌1小时。搅拌均匀后，向分散好的聚-4-乙烯基吡啶苯乙烯蒙脱土中分别加入0.2CEC、0.4CEC、0.6CEC、0.8CEC量的十六烷基三甲基溴化氨溶液，搅拌24小时，离心得到沉淀物，用水清洗沉淀物，得到混合改性有机蒙脱土(0.2MOM-MMT、0.4MOM-MMT、0.6MOM-MMT、0.8MOM-MMT)；
(4)将制备好的Na +蒙脱土置于水中搅拌8小时，使蒙脱土均匀分散。向分散好的蒙脱土溶液中加入1CEC的十六烷基三甲基溴化氨水溶液，搅拌24小时，离心得到沉淀物，用去离子水水清洗沉淀物，得到十六烷基三甲基溴化氨改性蒙脱土(HDTMA-MMT)；
(5)进行还原降解反应前，首先将IAA溶液和PFOA溶液(选取PFOA作为全氟化合物的代表性物质)混合均匀。将上述的不同蒙脱土分散到IAA和PFOA的混合溶液中，得到IAA、PFOA和蒙脱土的含量分别为2mM、10mg/L和2.2g/L的反应溶液。然后使用0.1mM的NaOH和HCl调节反应溶液的pH到7.0，使用磁力搅拌对反应溶液搅拌30分钟，搅拌结束后将反应溶液转移至装配有500W高压汞灯的光反应仪中，开灯进行降解反应，总反应体积为30mL，反应温度控制在25±2℃，反应时间为6小时。6小时后取样测试，样品分成两份，一份用2倍体积的乙腈萃取后以高效液相色谱(HPLC)测量剩余PFOA含量，另一份过滤后用离子色谱(IC)测量生成的F离子含量，以此计算PFOA的降解率和脱氟率，具体的降解和脱氟曲线如图4所示。
由此可以得出结论，在添加了有机蒙脱土的情况下，PFOA的还原降解被大大促进了，其中0.6MOM-MMT混合改性有机蒙脱土表现出最高的脱氟和降解效率。
实施例3
本实施例的一种高效降解全氟化合物的方法，其步骤为：
(1)将200g蒙脱土(购自浙江丰虹蒙脱土化工有限公司)分散在4L水中，加入0.4mol 固体NaCl饱和8h，离心弃去上清液，得到沉淀物；将沉淀物再分散在4L水中，如此重复操作6次。用去离子水清洗沉淀物，洗至以AgNO 3溶液检测无沉淀生成。冷冻干燥即得到饱和的Na +蒙脱土；
(2)将制备好的Na +蒙脱土置于水中搅拌8小时，使蒙脱土均匀分散。向分散好的蒙脱土溶液中加入电荷总量与溶液中蒙脱土的阳离子交换总量一致的聚-4-乙烯基吡啶苯乙烯(溶于5mol/L H 2SO 4)水溶液50mL，搅拌24小时，离心得到沉淀物，用水清洗沉淀物，得到聚-4-乙烯基吡啶苯乙烯蒙脱土(PVPcoS-MMT)；
(3)将聚-4-乙烯基吡啶苯乙烯改性的蒙脱土分散在水中，搅拌1小时。搅拌均匀后，向分散好的聚-4-乙烯基吡啶苯乙烯蒙脱土中分别加入0.2CEC、0.4CEC、0.6CEC、0.8CEC量的十六烷基三甲基溴化氨溶液，搅拌24小时，离心得到沉淀物，用水清洗沉淀物，得到混合改性有机蒙脱土(0.2MOM-MMT、0.4MOM-MMT、0.6MOM-MMT、0.8MOM-MMT)；
(4)将制备好的Na +蒙脱土置于水中搅拌8小时，使蒙脱土均匀分散。向分散好的蒙脱土溶液中加入1CEC的十六烷基三甲基溴化氨水溶液，搅拌24小时，离心得到沉淀物，用去离子水水清洗沉淀物，得到十六烷基三甲基溴化氨改性蒙脱土(HDTMA-MMT)；
(5)考察不同气氛下水合电子对PFOA降解的情况：
在进行还原降解反应前，首先将IAA溶液和PFOA溶液混合均匀，再将0.6MOM-MMT分散到IAA和PFOA的混合溶液中，得到IAA、PFOA和蒙脱土的含量分别为2mM、10mg/L和2.2g/L的反应溶液。然后使用0.1mM的NaOH和HCl调节反应溶液的pH到7.0，使用磁力搅拌对反应溶液搅拌30分钟，搅拌结束后将反应溶液转移至石英反应管中，总反应液体积为300ml，将一盏36W汞灯浸没到反应溶液中，开灯进行降解反应。反应温度控制在25±2℃，反应时间为14小时。分别在曝氮气、不曝气、曝空气的环境中进行实验，曝气速度4L/min。取样时间分别设置为0h、0.5h、1.5h、2.5h、3.5h、4.5h、6h、8h、11h、14h。样品分成两份，一份用2倍体积的乙腈萃取后以高效液相色谱(HPLC)测量剩余PFOA含量，另一份过滤后用离子色谱(IC)测量生成的F离子含量，以此计算PFOA的降解率和脱氟率，具体降解和脱氟曲线如图5a和5b所示。
由此可以得出结论，在曝氮气和不曝气的实验条件下，脱氟速率和降解速率基本不变，曝空气的实验组降解速率提高，脱氟速率只有很少的降低，因此可以得出混合改性蒙脱土具有很好的封闭性，能够保护住水合电子不被氧气猝灭，提高了水合电子的利用率。
实施例4
本实施例的基本内容同实施例3，不同之处在于本实施例的高效降解全氟化合物方法中的步骤(5)为考察不同pH条件下水合电子对PFOA降解的情况，具体操作步骤为：
在进行还原降解反应前，首先将IAA溶液和PFOA溶液混合均匀，再将0.6MOM-MMT分散到IAA和PFOA的混合溶液中，得到IAA、PFOA和蒙脱土的含量分别为2mM、10mg/L和2.2g/L的反应溶液。然后使用0.1mM的NaOH和HCl调节反应溶液的pH分别到4.0、7.0、10.0。使用磁力搅拌对反应溶液搅拌30分钟，搅拌结束后将反应溶液转移至石英反应管中，总反应液体积为300ml，将一盏36W汞灯浸没到反应溶液中，开灯进行降解反应。反应温度控制在25±2℃，反应时间为14小时。取样时间分别设置为0h、0.5h、1.5h、2.5h、3.5h、4.5h、6h、8h、11h、14h。样品分成两份，一份用2倍体积的乙腈萃取后以高效液相色谱(HPLC)测量剩余PFOA含量，另一份过滤后用离子色谱(IC)测量生成的F离子含量，以此计算PFOA的降解率和脱氟率，具体降解和脱氟曲线如图5c和5d所示。
由此可以得出结论，反应中PFOA的降解和脱氟几乎不受溶液pH的影响。
实施例5
本实施例的基本内容同实施例3，不同之处在于本实施例的高效降解全氟化合物方法中的步骤(5)具体为：
在进行还原降解反应前，首先将IAA溶液和PFOA溶液混合均匀，再将0.6MOM-MMT分散到IAA和PFOA的混合溶液中，得到IAA、PFOA和蒙脱土的含量分别为2mM、10mg/L和2.2g/L的反应溶液。然后使用0.1mM的NaOH和HCl调节反应溶液的pH到7.0，使用磁力搅拌对反应溶液搅拌30分钟，搅拌结束后将反应溶液转移至石英反应管中，总反应液体积为300ml，将一盏36W汞灯浸没到反应溶液中，开灯进行降解反应。反应温度控制在25±2℃，反应时间为14小时。取样时间分别设置为0h、0.5h、1.5h、2.5h、3.5h、4.5h、6h、8h、11h、14h。样品通过SPE柱处理后利用LC/MS/MS检测并定量其中间产物，中间产物随时间变化曲线如图6所示。
由此可以得出结论，该体系中PFOA的降解中间产物主要包括不同链长的全氟羧酸以及乙酸甲烷。
实施例6
本实施例的基本内容同实施例3，不同之处在于本实施例的高效降解全氟化合物方法中的步骤(5)为考察不同阴离子存在下水合电子对PFOA降解的情况，具体操作步骤为：
在进行还原降解反应前，首先将IAA溶液和PFOA溶液混合均匀，再将0.6MOM-MMT分散到IAA和PFOA的混合溶液中，得到IAA、PFOA和蒙脱土的含量分别为2mM、10mg/L和2.2g/L的反应溶液。然后使用0.1mM的NaOH和HCl调节反应溶液的pH到7.0，分别在两组实验中加入1mM NO 3 -和SO 4 2-。使用磁力搅拌对反应溶液搅拌30分钟，搅拌结束后将反应溶液转移至石英反应管中，总反应液体积为300ml，将一盏36W汞灯浸没到反应溶液中， 开灯进行降解反应。反应温度控制在25±2℃，反应时间为14小时。取样时间分别设置为0h、0.5h、1.5h、2.5h、3.5h、4.5h、6h、8h、11h、14h。样品分成两份，一份用2倍体积的乙腈萃取后以高效液相色谱(HPLC)测量剩余PFOA含量，另一份过滤后用离子色谱(IC)测量生成的F离子含量，以此计算PFOA的降解率和脱氟率，具体降解和脱氟曲线如图7所示。
由此可以得出结论，水体硝酸根和硫酸根的存在几乎对该反应不产生影响。
实施例7
一种高效降解全氟化合物的方法，其步骤为：
(1)将200g蒙脱土(购自浙江丰虹蒙脱土化工有限公司)分散在4L水中，加入0.4mol固体NaCl饱和8h，离心弃去上清液，得到沉淀物；将沉淀物再分散在4L水中，如此重复操作6次。用去离子水清洗沉淀物，洗至以AgNO 3溶液检测无沉淀生成。冷冻干燥即得到饱和的Na +蒙脱土；
(2)将制备好的Na +蒙脱土置于水中搅拌8小时，使蒙脱土均匀分散。向分散好的蒙脱土溶液中加入电荷总量与溶液中蒙脱土的阳离子交换总量一致的聚-4-乙烯基吡啶苯乙烯(溶于5mol/L H 2SO 4)水溶液50mL，搅拌24小时，离心得到沉淀物，用水清洗沉淀物，得到聚-4-乙烯基吡啶苯乙烯蒙脱土(PVPcoS-MMT)；
(3)将聚-4-乙烯基吡啶苯乙烯改性的蒙脱土分散在水中，搅拌1小时。搅拌均匀后，向分散好的聚-4-乙烯基吡啶苯乙烯蒙脱土中分别加入0.2CEC、0.4CEC、0.6CEC、0.8CEC量的十六烷基三甲基溴化氨溶液，搅拌24小时，离心得到沉淀物，用水清洗沉淀物，得到混合改性有机蒙脱土(0.2MOM-MMT、0.4MOM-MMT、0.6MOM-MMT、0.8MOM-MMT)；
(4)将制备好的Na +蒙脱土置于水中搅拌8小时，使蒙脱土均匀分散。向分散好的蒙脱土溶液中加入1CEC的十六烷基三甲基溴化氨水溶液，搅拌24小时，离心得到沉淀物，用去离子水水清洗沉淀物，得到十六烷基三甲基溴化氨改性蒙脱土(HDTMA-MMT)；
(5)首先将配制好的吲哚乙酸溶液和蒙脱土混合后转移到20ml玻璃管中，使用0.1mM的NaOH和HCl调节溶液的pH到7.0，加入水合电子捕获剂二甲基吡啶N-氧化物(DMPO)。反应总体积为10mL，其中吲哚乙酸和DMPO的浓度分别为2mM和20mM，蒙脱土浓度为2.2g/L。180W汞灯照射3.5min后，取样20μL放入电子顺磁共振仪(EPR)中检测自由基信号，具体如图8所示。
由此可以得出结论，没有蒙脱土、钠蒙脱土存在时，溶液中的活性物种主要是羟基自由基，因此样品中检测不到水合电子的信号，在添加了有机蒙脱土后，样品中除检测到羟基自由基外，同时也检测到了水合电子的信号，在HDTMA改性的蒙脱土和0.6MOM混合改性的 蒙脱土中都检测到了较强的水和电子信号。在PVPcoS改性的蒙脱土中，检测到了羟基自由基信号以及较弱的水合电子信号。这说明HDTMA的存在保护了水合电子不被氧气猝灭，因此促进了水合电子对全氟化合物的降解和脱氟。

Claims (10)

  1. 一种合成混合改性有机蒙脱土的方法，包括以下步骤：
    S1、使用聚-4-乙烯基吡啶苯乙烯对蒙脱土进行有机改性，得到聚-4-乙烯基吡啶苯乙烯改性蒙脱土；
    S2、使用十六烷基三甲基溴化氨对步骤S1中得到的聚-4-乙烯基吡啶苯乙烯改性蒙脱土进行再有机改性，得到混合改性有机蒙脱土。
  2. 根据权利要求1所述的一种合成混合改性有机蒙脱土的方法，其特征在于：所述步骤S1中的聚-4-乙烯基吡啶苯乙烯的总量与蒙脱土的阳离子交换总量一致。
  3. 根据权利要求1所述的一种合成混合改性有机蒙脱土的方法，其特征在于：所述步骤S2中的十六烷基三甲基溴化氨的总量小于蒙脱土的阳离子交换总量。
  4. 根据权利要求1所述的一种合成混合改性有机蒙脱土的方法，其特征在于：所述步骤S2中的十六烷基三甲基溴化氨的总量为蒙脱土的阳离子交换总量的0.6～0.8倍。
  5. 根据权利要求1所述的一种合成混合改性有机蒙脱土的方法，其特征在于：所述步骤S1中对蒙脱土进行有机改性的具体步骤为：
    (1)将钠蒙脱土分散到水中，得到蒙脱土分散溶液；
    (2)向步骤(1)的蒙脱土分散溶液中加入酸化的聚-4-乙烯基吡啶苯乙烯溶液，搅拌；
    (3)步骤(2)中搅拌结束后离心，弃去上清液，得到沉淀物；
    (4)用水清洗步骤(3)中得到的沉淀物，得到聚-4-乙烯基吡啶苯乙烯改性蒙脱土。
  6. 根据权利要求1所述的一种合成混合改性有机蒙脱土的方法，其特征在于：所述步骤S2中对聚-4-乙烯基吡啶苯乙烯改性蒙脱土进行再有机改性的具体步骤为：
    (1)将聚-4-乙烯基吡啶苯乙烯改性蒙脱土分散到水中，得到聚-4-乙烯基吡啶苯乙烯改性蒙脱土分散溶液；
    (2)向步骤(1)的聚-4-乙烯基吡啶苯乙烯改性蒙脱土分散溶液中加入十六烷基三甲基溴化铵溶液，搅拌；
    (3)步骤(2)中搅拌结束后离心，弃去上清液，得到沉淀物；
    (4)用水清洗步骤(3)中得到的沉淀物，得到混合改性有机蒙脱土。
  7. 一种混合改性有机蒙脱土，其特征在于：采用权利要求1～6任意一项所述的合成混合改性有机蒙脱土的方法合成得到。
  8. 一种采用混合改性有机蒙脱土高效降解全氟化合物的方法，包括以下步骤：
    (i)将吲哚乙酸溶液和全氟化合物溶液均匀混合；
    (ii)将权利要求7所述的混合改性有机蒙脱土分散到步骤(i)的混合溶液中，得到反应溶液；
    (iii)使用汞灯对步骤(ii)中得到的反应溶液进行光反应以降解全氟化合物。
  9. 根据权利要求8所述的一种高效降解全氟化合物的方法，其特征在于：所述步骤(ii)还包括调节反应溶液的pH值至4.0～10.0。
  10. 根据权利要求8所述的一种高效降解全氟化合物的方法，其特征在于：所述步骤(iii)的具体步骤为：将步骤(ii)中得到的反应溶液搅拌30分钟后转移至石英反应管内，在好氧环境下，将汞灯浸没到反应溶液中进行降解反应，反应温度控制在25±2℃。
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