WO2018166238A1 - 一种零价铁柱撑蒙脱石修复材料及其制备方法与应用 - Google Patents

一种零价铁柱撑蒙脱石修复材料及其制备方法与应用 Download PDF

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WO2018166238A1
WO2018166238A1 PCT/CN2017/112450 CN2017112450W WO2018166238A1 WO 2018166238 A1 WO2018166238 A1 WO 2018166238A1 CN 2017112450 W CN2017112450 W CN 2017112450W WO 2018166238 A1 WO2018166238 A1 WO 2018166238A1
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montmorillonite
zero
valent iron
pillared montmorillonite
solution
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French (fr)
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吴平霄
杨珊珊
朱能武
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South China University of Technology SCUT
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South China University of Technology SCUT
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    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/745—Iron
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/16—Clays or other mineral silicates
    • 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
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/04—Mixing
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/16—Reducing
    • 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
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
    • 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
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • 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
    • C02F2101/30—Organic compounds
    • C02F2101/36—Organic compounds containing halogen
    • 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
    • C02F2101/30—Organic compounds
    • C02F2101/40—Organic compounds containing sulfur

Definitions

  • the invention belongs to the field of environmental functional materials, and particularly relates to a zero-valent iron pillared montmorillonite repairing material and a preparation method and application thereof.
  • Brominated flame retardants As the most widely consumed organic flame retardant in the world, it is widely used in flammable materials such as plastics, textiles, and circuit boards to reduce its flammability. Brominated flame retardants mainly include tetrabromobisphenol A ( TBBPA ), polybrominated diphenyl ethers (PBDEs), polybrominated biphenyls (PBBs) and hexabromocyclododecane (HBDCD). Of which, TBBPA It has good flame retardant performance and simple synthesis process. It is the most widely used brominated flame retardant, accounting for 59% of the world's use and 76% in Asia.
  • TBBPA tetrabromobisphenol A
  • PBDEs polybrominated diphenyl ethers
  • PBBs polybrominated biphenyls
  • HDCD hexabromocyclododecane
  • TBBPA It has the characteristics of lipophilicity, bioaccumulation, persistence, and long-range atmospheric mobility. It has been detected in the atmosphere, water, soil, aquatic organisms, human blood and breast milk, even in polar bears far from the place of production and use. detected TBBPA. TBBPA It has a similar structure to thyroxine, has immunotoxicity, thyroid interference effect, estrogen interference effect, etc. It is a potential endocrine disruptor, and its negative impact on people's living environment and physical health has aroused widespread concern around the world.
  • TBBPA According to the principle of degradation of TBBPA, TBBPA
  • the degradation technologies mainly include microbial degradation technology, physical methods and chemical degradation technologies.
  • the oxidative degradation technology of TBBPA is mainly divided into classes.
  • Peroxymonosulfate is mainly present in the form of a 2KHSO 5 ⁇ KHSO 4 ⁇ K 2 SO 4 tri-salt compound, commercially available under the trade name Oxone, and is a versatile and environmentally friendly acid peroxide oxidizing agent.
  • Montmorillonite is a kind of 2:1 A layered silicate mineral whose stereostructure is a silicon tetrahedral skeleton.
  • Natural montmorillonite is mainly in the form of sodium montmorillonite and calcium-based montmorillonite. Montmorillonite is formed in nature, mainly composed of basic igneous tuff in the natural environment, the material produced by the decomposition of volcanic ash, and the three minerals of porphyrite, bentonite and bleaching earth. Most of them are montmorillonite. Montmorillonite is rich in resources, large in reserves and widely distributed in China. It is a kind of mineral that is very cheap and easy to obtain. It is widely used in metallurgy, machinery, chemical, petroleum, environmental protection and other fields.
  • Nano-zero-valent iron refers to Fe 0 particles with a particle size ranging from 1 to 100 nm. As the particle size decreases, the specific surface area and surface activity of the nanoparticles also increase rapidly.
  • the nano-zero-valent iron is chemically active, has a relatively high electronegativity, and has an electrode potential of -0.44 V. It has a strong reducing ability and can reduce many types of heavy metal contaminants; it has electrochemical properties, and nano-zero-valent iron also has micro-electrolysis; It will form flocculent precipitates (iron hydroxide and ferrous hydroxide, etc.) during oxidation, and nano-zero-valent iron also has coagulation adsorption. As a fast, efficient and low-cost repair material, nano-zero-valent iron has been widely used in drinking water treatment, polluted soil and groundwater remediation, and can handle a variety of organic pollutants and heavy metal pollution.
  • zero-valent iron modified montmorillonite was used to prepare zero-valent iron particles by chemical reduction method (sodium borohydride), thereby broadening the application of montmorillonite in the field of environmental pollution repair.
  • chemical reduction method sodium borohydride
  • the application of zero-valent iron modified montmorillonite is mainly focused on the adsorption of heavy metal contaminated wastewater and the reduction of organic pollutants.
  • persulfate persulfate
  • the zero-valent iron-pillared montmorillonite composite can be used as a high-efficiency catalyst to activate persulfate to generate sulfate radicals, which is difficult to achieve simultaneous reduction and oxidative degradation.
  • the purpose of degrading organic pollutants The development and application of zero-valent iron pillared montmorillonite technology has great practical significance for the treatment of refractory organic pollutant wastewater.
  • Another object of the present invention is to provide a zero-valent iron pillared montmorillonite repairing material prepared by the above preparation method and its highly efficient activated persulfate (PMS) is a method for removing refractory organics.
  • PMS highly efficient activated persulfate
  • a method for preparing a zero-valent iron pillared montmorillonite repairing material comprising the following steps:
  • Steps (3) The obtained hydroxy iron pillared montmorillonite is reduced at a high temperature in a mixed atmosphere of hydrogen and nitrogen to obtain a zero-valent iron pillared montmorillonite repairing material.
  • the montmorillonite in the step (1) is purified calcium montmorillonite; the concentration of the NaCl solution is 0.05-0.15M Further, it is preferably 0.1 M; the temperature of the constant temperature water bath is 50 ° C to 70 ° C; and the number of repetitions is 2 to 4 times.
  • the molar ratio of Na 2 CO 3 to FeCl 3 in the step (2) is from 0.5:1 to 1.5:1; further preferably 1:1.
  • the ratio of hydroxy iron/sodium montmorillonite in step (3) is from 5 mmol/g to 10 mmol/g. Further preferably, it is 10 mmol/g.
  • the stirring time in steps (2) and (3) is 1 ⁇ 3 h, and the aging time is 12 ⁇ 48 h.
  • the volume ratio of hydrogen to nitrogen in the mixed atmosphere in the step (4) is 10: 90 ⁇ 90: 7
  • the high temperature reduction condition is heated from room temperature to a heating rate of 5 to 10 min/°C to 200 ° C to 1000 ° C for 2 to 4 hours.
  • a zero-valent iron pillared montmorillonite repairing material prepared by the above preparation method.
  • the above-mentioned zero-valent iron pillared montmorillonite repairing material is applied to the activated persulfate to remove refractory organic pollutants, and the application comprises the following steps:
  • the organic pollutant solution described in the step (1) is a tetrabromobisphenol A solution (TBBPA).
  • the dosage of zero-valent iron pillared montmorillonite in step (2) is 0.02 g/L ⁇ 0.5 g/L; the dosage of peroxymonosulfate is 0.05 mM ⁇ 0.5 mM.
  • a method and application for preparing a zero-valent iron pillared montmorillonite repairing material comprises the following steps:
  • the first step - sodium sulphate smectite Disperse calcium montmorillonite in 0.1M NaCl solution, stir well in a constant temperature water bath at 60 °C 1 ⁇ 3h, then let stand for 1 ⁇ 3h, repeat three times, centrifuge the sodiumation product in a centrifuge, discard the clear solution, wash it with distilled water for 4 ⁇ 6 times, and finally heat the sodium product at 50 ⁇ 70°C. Dry down, then grind 200 mesh sieve to obtain sodium montmorillonite;
  • the second step - preparation of polyhydroxy iron column liquid under high speed stirring, according to a certain ratio of Na 2 CO 3 /FeCl 3 molar ratio (0.5:1 ⁇ 1.5:1), 0.05 M ⁇ 0.15 M na 2 CO 3 solution was slowly added dropwise through a constant pressure funnel 0.05 M ⁇ FeCl 3 solution 0.15 M, the resulting red-brown translucent liquid pillared stirring was continued for 1 ⁇ 3 h, then aged 12 ⁇ 48 h, to obtain poly a hydroxy iron column solution, wherein a preferred ratio of Na 2 CO 3 /FeCl 3 molar ratio is 1:1;
  • the third step - the preparation of hydroxy iron pillared montmorillonite according to the ratio of certain hydroxy iron / montmorillonite under high speed stirring ( 5mmol/g ⁇ 10 mmol/g), the sodium montmorillonite prepared in the first step is formulated into a mass fraction of 0.5% to 1%.
  • the slurry is slowly dripped into the slurry in the second step.
  • stirring is continued for 1 ⁇ 3 h, and then aged for 12 ⁇ 48 h.
  • the columnar product is centrifuged in a centrifuge, the supernatant is discarded, and washed with distilled water for 4-6 times.
  • the pillared product is dried at 50-70 °C, and then ground. Mesh sieve to obtain hydroxy iron pillared montmorillonite;
  • the fourth step--the preparation of zero-valent iron pillared montmorillonite the product obtained in the third step is in a mixed atmosphere of hydrogen and nitrogen in different proportions (the ratio of hydrogen to nitrogen is 10 : 90 ⁇ 70:30 ) High temperature reduction at 200 ⁇ 1000 °C, the product after calcination is ground and sieved to obtain zero-valent iron pillared montmorillonite;
  • Step 5 Zero-valent iron-pillared montmorillonite activation
  • PMS removes refractory organic (TBBPA) and adds a certain amount (0.02g/L ⁇ 0.5g/L) to a certain concentration (5 mg/L ⁇ 30 mg/L) TBBPA solution.
  • the zero-valent iron-pillared montmorillonite and a certain amount (0.05 mM to 0.5 mM) of oxidant (PMS) are reacted for a period of time to remove the refractory TBBPA in the solution.
  • the present invention has the following advantages and technical effects:
  • the zero-valent iron pillared montmorillonite prepared by the invention can be applied to remove refractory organic pollutants, and the organic matter is degraded into small molecular organic substances by monosulfate.
  • Example 1 is an XRD pattern of montmorillonite, hydroxy iron pillared montmorillonite, and a zero-valent iron pillared montmorillonite repairing material prepared in Example 1;
  • Example 2 is an SEM image of a zero-valent iron pillared montmorillonite repairing material prepared in Example 1;
  • Example 3 is a TEM image of the zero-valent iron pillared montmorillonite repairing material prepared in Example 1;
  • Example 4 is an XPS diagram of a zero-valent iron pillared montmorillonite repairing material prepared in Example 1;
  • Example 5 is a UV-vis spectrum of a PMS-degrading TBBPA activated by a zero-valent iron pillared montmorillonite repairing material in different times in Example 2;
  • Example 6 is a UV-vis spectrum of a low-valent iron pillared montmorillonite activated PMS degrading TBBPA under different zero-valent iron pillared montmorillonite repair materials in Example 2;
  • Example 7 is a UV-vis spectrum of degraded TBBPA by zero-valent iron pillared montmorillonite activated PMS under different PMS dosages in Example 2;
  • Example 8 is an XRD pattern of a zero-valent iron pillared montmorillonite repairing material prepared in different calcination temperatures in Example 3;
  • Example 10 is an XRD pattern of a zero-valent iron pillared montmorillonite repairing material prepared in different hydrogen/nitrogen ratios in Example 4;
  • Figure 11 is a UV-vis spectrum of PMS-degrading TBBPA activated by zero-valent iron-pillared montmorillonite repair material prepared in different hydrogen/nitrogen ratios in Example 4.
  • a method for preparing a zero-valent iron pillared montmorillonite repairing material comprising the steps of:
  • Step 1 Weigh 10 g of calcium-based montmorillonite and disperse it in 200 ml of 0.1 M NaCl solution, stir well in a constant temperature water bath at 60 °C. h, after standing for 2 h, the sodium product was centrifuged in a centrifuge, the supernatant was discarded, 100 ml of 0.1 M NaCl solution was added, and the mixture was stirred for 2 h in a constant temperature water bath at 60 ° C for 2 h. After h, the sodium product is centrifuged in a centrifuge, the supernatant is discarded, and 50 ml of 0.1 M NaCl solution is added, and the mixture is stirred at 60 ° C in a constant temperature water bath.
  • Step 2 Under high-speed stirring at 4000 rpm, according to Na 2 CO 3 /FeCl 3 molar ratio of 1:1, 200 mL of 0.1 M Na 2 CO 3 solution was dropped into 200 mL of 0.1 M FeCl 3 solution through a constant pressure funnel. The obtained reddish-brown translucent column liquid was further stirred for 2 h, and then aged for 24 h to obtain 400 mL of a polyhydroxy iron column solution;
  • the third step According to the optimal ratio of hydroxy iron / montmorillonite is 10 mmol / g, accurately weigh 2g
  • the sodium montmorillonite prepared in the first step is added to 100 mL of deionized water to prepare a slurry with a mass fraction of 1%, and the columnar agent prepared in the second step is dropped into the slurry, and stirring is continued after the titration. 2 h After aging for 24 h, the columnar product was centrifuged in a centrifuge, the supernatant was discarded, and washed with distilled water for 5 times. Finally, the pillared product was dried at 60 ° C and then ground. Mesh sieve to obtain hydroxy iron pillared montmorillonite;
  • Step 4 The product obtained in the third step is heated to 700 °C at a heating rate of 5 min/°C in a mixed atmosphere of hydrogen and nitrogen at a volume ratio of 50:50 (total aeration flow rate of 100 cm 3 /min). 3h, the product after thermal reduction was ground and sieved to obtain a zero-valent iron pillared montmorillonite repairing material.
  • the X-ray diffraction pattern (XRD) of the zero-valent iron-pillared montmorillonite repair material (Fe 0 -Mt ) prepared in this example is shown in Figure 1, compared to montmorillonite (Mt) and hydroxy iron pillars.
  • the deuterated stone (FeOOH-Mt) showed obvious characteristic peaks of zero-valent iron (110) and (200);
  • the SEM image of zero-valent iron-pillared montmorillonite repairing material (Fe 0 -Mt ) is shown in Fig. 2.
  • the ellipsoidal zero-valent iron particles are clearly seen between the layers of montmorillonite.
  • the TEM image of the zero-valent iron-pillared montmorillonite repairing material (Fe 0 -Mt ) (Fig. 3) also fully illustrates this conclusion.
  • the high-resolution XPS diagram of the iron pillared montmorillonite repair material (Fe 0 -Mt ) Fe 2p is shown in Figure 4.
  • the peak at the binding energy of 706.35 eV again illustrates the presence of zero-valent iron particles in the final product.
  • a zero-valent iron pillared montmorillonite repairing material prepared by the embodiment 1 is used to remove refractory organic matter by using high-efficiency activated persulfate (PMS), including the following steps:
  • Step 1 Accurately weigh 0.4 g NaOH and 0.4 g TBBPA in 100 ml Add 4 g/L of TBBPA stock solution to the volumetric flask, and accurately measure 5 mL of 4 g/L TBBPA stock solution and dilute it to 10 mL in a 2000 mL volumetric flask. Mg/L of TBBPA solution;
  • Step 2 Prepare 250 mL of 10 mg/L TBBPA solution in a 500 mL beaker, and then accurately weigh 0.0154 g of PMS and 0.0125 g of Fe 0 -Mt in a 500 mL beaker, using a syringe every 5 min.
  • the TBBPA solution in a 5 ml beaker was taken and the UV-vis spectrum of TBBPA in the solution was measured by an ultraviolet spectrophotometer; the relevant results are shown in Figure 5, and complete degradation of TBBPA can be achieved within 15 min;
  • Step 3 Prepare 4 portions of 250 mL 10 mg/L TBBPA solution in four 500 mL beakers. Accurately weigh 4 parts of 0.0154 g of PMS in 250 mL of TBBPA solution, and accurately weigh 0.005 g. 0.0125 g, 0.025 g, and 0.05 g of Fe 0 -Mt were respectively dissolved in 250 mL of TBBPA solution. After reacting for 10 min, 5 ml of TBBPA solution in each beaker was extracted with a syringe, and UV-spectrophotometer was used to measure the UV of TBBPA in the solution. The vis spectrum; the relevant results are shown in Fig. 6. It can be seen from Fig. 6 that the larger the Fe 0 -Mt dosage, the faster the degradation of TBBPA and the better the effect;
  • Step 4 Prepare 4 parts of 250mL 10 mg/L TBBPA solution in four 500mL beakers. Accurately weigh 4 parts of 0.0125g of Fe 0 -Mt in 250mL of TBBPA solution, and then accurately weigh 0.0077. g, 0.0115g, 0.0154g and 0.0231g PMS were respectively dissolved in 250mL of TBBPA solution, after 10min reaction, 5ml of TBBPA solution in each beaker was extracted by syringe, and the UV-vis spectrum of TBBPA in solution was measured by ultraviolet spectrophotometer; The results are shown in Fig. 7. As can be seen from Fig. 7, the larger the dosage of PMS, the faster the degradation of TBBPA and the better the effect.
  • the first step the other steps are the same as in the first embodiment except that in the fourth step, the hydroxy iron pillared montmorillonite is heated to 300 at a heating rate of 5 min/° C. in a mixed atmosphere of hydrogen and nitrogen volume ratio of 50:50.
  • the reduced product is ground and sieved to obtain the zero-valent iron pillared montmorillonite repair material obtained by thermal reduction at different temperatures; comparing the thermal reduction at different temperatures
  • the XRD pattern of the zero-valent iron-pillared montmorillonite repair material shows that the characteristic peaks (110) and (200) of zero-valent iron can be observed;
  • Step 2 Prepare 4 parts of 250 mL 10 mg/L TBBPA solution in four 500 In the mL beaker, accurately weigh 4 parts of 0.0154 g of PMS in 250 mL of TBBPA solution, and weigh 0.0125 accurately.
  • gFe0-Mt obtained by thermal reduction at different temperatures (300 ° C, 500 ° C, 700 ° C and 900 ° C) in 250 mL of TBBPA solution, reacted for 10 min and then pumped with a syringe 5
  • the TBBPA solution in the ml beaker was measured by UV spectrophotometer for the UV-vis spectrum of TBBPA in the solution; the relevant results are shown in Figure 9.
  • the temperature is 900 °C, zero-valent iron pillared montmorillonite activates PMS to degrade TBBPA. best effect.
  • the other steps are the same as in Example 1, except that in the fourth step, the hydroxy iron pillared montmorillonite has a volume ratio of hydrogen to nitrogen of 10:90, 30:70, 50:50 and 70:30, respectively.
  • the total aeration flow rate is 100 cm 3 /min.
  • the temperature is raised to 700 ° C in a mixed atmosphere at a heating rate of 5 min / ° C for 3 h, and the reduced product is ground and sieved to obtain a zero-valent iron column obtained by thermal reduction under different mixed atmospheres.
  • the montmorillonite product was compared; the XRD pattern of the zero-valent iron pillared montmorillonite repairing material obtained by high temperature reduction under different mixed atmospheres (as shown in Fig. 10) was observed, and the characteristic peak of zero-valent iron was observed (110). And (200);
  • Step 2 Prepare 4 parts of 250 mL 10 mg/L TBBPA solution in four 500 mL beakers. Accurately weigh 4 parts of 0.0154 g of PMS in 250 mL of TBBPA solution, and weigh 0.0125 accurately.
  • g Fe 0 -Mt obtained by thermal reduction in different mixed atmospheres (10:90, 30:70, 50:50 and 70:30 of hydrogen and nitrogen, respectively) in 250 mL of TBBPA solution, after 10 min reaction
  • the TBBPA solution in a 5 ml beaker was extracted with a syringe, and the UV-vis spectrum of TBBPA in the solution was measured by an ultraviolet spectrophotometer; the relevant results are shown in Fig. 11, when the volume ratio of hydrogen to nitrogen in the mixed atmosphere was 10: 90, respectively.

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Abstract

一种零价铁柱撑蒙脱石修复材料，属于环境功能材料领域。其制备方法主要在氢气和氮气的混合气氛中通过高温还原羟基铁柱撑蒙脱石得到零价铁柱撑蒙脱石修复材料，主要包括：(1)钠基蒙脱石的制备；(2)聚羟基铁柱化液的制备；(3)羟基铁柱撑蒙脱石的制备：(4)在氢气和氮气的混合气氛中通过高温还原煅烧得到零价铁柱撑蒙脱石修复材料。该零价铁柱撑蒙脱石修复材料能应用于去除难降解的有机污染物，有机物被过一硫酸盐(PMS)降解为小分子有机物。

Description

一种零价铁柱撑蒙脱石修复材料及其制备方法与应用
技术领域
本发明属于环境功能材料领域，具体涉及一种零价铁柱撑蒙脱石修复材料及其制备方法与应用。
背景技术
溴代阻燃剂（ BFRs ）作为目前全球消耗量最大的有机阻燃剂，被广泛地应用于塑料、纺织品、电路板等易燃物中，降低其可燃性。溴代阻燃剂主要包括四溴双酚 A （ TBBPA ）、多溴联苯醚（ PBDEs ）、多溴联苯（ PBBs ）和六溴环十二烷（ HBCD ）。其中， TBBPA 阻燃性能好，合成工艺简单，是应用最广泛的溴代阻燃剂，使用量占全球的 59% ，在亚洲地区则高达 76% 。 TBBPA 具有亲油性、生物富集性、持久性、长程大气迁移性等特性，已在大气、水体、土壤、水生生物、人体血液及母乳中检测出来，甚至在远离产地和使用地的北极熊体内也能检测出 TBBPA 。 TBBPA 具有与甲状腺素相似的结构，具有免疫毒性、甲状腺干扰效应、雌激素干扰效应等，是一种潜在的内分泌干扰物，对人们的生存环境和身体健康的负面影响已引起了全球的广泛关注。
根据降解 TBBPA 的作用原理不同， TBBPA 的降解技术主要有微生物降解技术、物理方法和化学降解技术。关于 TBBPA 的氧化降解技术主要分为类
Fenton 法氧化、光催化氧化、催化后的硫酸根自由基氧化、金属氧化物氧化以及它们之间相互组合的联合技术。目前，利用过硫酸盐活化产生的硫酸根自由基降解有机污染物正在成为一类新型的高级氧化技术。过硫酸盐比较稳定 , 在常温下反应速率较慢 , 对有机物的降解效果不好。但在热、光和过渡金属离子等条件下 , 过硫酸根离子活化分解产生强氧化性 SO4 - , 被广泛应用于废水、地下水及土壤中的有机污染物的治理。过一硫酸盐主要以 2KHSO5·KHSO4·K2SO4 三盐化合物的形式存在 , 商品名为 Oxone, 是一种用途广泛且环境友好的酸式过氧化物氧化剂。
蒙脱土是一种 2:1 型的层状硅酸盐矿物，它的立体结构是一个硅氧四面体骨架。天然蒙脱土主要钠基蒙脱土、钙基蒙脱土的形式存在。蒙脱土是在自然中形成的，主要由基性火成凝灰岩在自然环境中风化而成，火山灰被分解之后产生的物质，并且斑脱岩、皂土和漂白土这三种矿物其组成部分也大多是蒙脱土。蒙脱土在我国资源丰富，储量大，分布地广，属于非常廉价易得的一种矿物，在冶金、机械、化工、石油、环保等领域应用广泛。
纳米零价铁（ nZVI ）是指粒径大小在 1~100 nm 范围内的 Fe0 颗粒。随着颗粒粒径的减小，纳米颗粒的比表面积和表面活性也迅速增大。纳米零价铁化学性质活泼，电负性比较大，电极电位为 -0.44 V ，还原能力很强，能还原多类重金属污染物；其有电化学特性，纳米零价铁还具有微电解作用；其在氧化过程中会生成絮状沉淀（氢氧化铁和氢氧化亚铁等），纳米零价铁还具有混凝吸附作用。纳米零价铁作为一种快速、高效、低成本的修复材料，在饮用水处理、污染土壤及地下水修复等领域得到了广泛的应用，能处理多种有机污染物及重金属污染。
已有研究中利用零价铁修饰蒙脱石的方法多采用化学还原法（硼氢化钠）制备零价铁颗粒，从而拓宽蒙脱石在环境污染修复领域内的应用。同时零价铁修饰蒙脱石的应用主要集中在吸附处理重金属污染废水及还原降解有机污染物，而作为催化剂活化过硫酸盐去除难降解有机物的报道非常少。基于零价铁的强还原能力以及硫酸根自由基的强氧化能力，零价铁柱撑蒙脱石复合材料可以作为高效催化剂活化过一硫酸盐产生硫酸根自由基，实现同步还原及氧化降解难降解有机污染物的目的。零价铁柱撑蒙脱石技术的开发和应用对难降解有机污染物废水的处理具有重大的现实意义。
发明内容
本发明的目的在于提供一种零价铁柱撑蒙脱石 修复 材料的制备方法。
本发明的另一个目的在于提供一种由上述制备方法制备得到的零价铁柱撑蒙脱石 修复 材料及其高效活化过一硫酸盐（ PMS ）应用于去除难降解有机物的方法。
本发明的目的通过以下技术方案实现。
一种零价铁柱撑蒙脱石修复材料的制备方法，包括以下步骤：
（ 1 ）将蒙脱石分散在 NaCl 溶液中，恒温水浴搅拌、静置、离心；重复以上分散、水浴搅拌、静置、离心步骤，然后洗涤，干燥，得到钠基蒙脱石；
（ 2 ） 将 Na2CO3 溶液滴入 FeCl3 溶液中，将得到的红褐色半透明柱撑液继续搅拌、陈化，得聚羟基铁柱化液；
（ 3 ）将步骤（ 1 ）得到的 钠基蒙脱石加入水中配成钠基蒙脱石浆液，再将 聚羟基铁柱化液滴入 钠基蒙脱石浆液中，搅拌、陈化、离心、洗涤、干燥和过筛，得到 羟基铁柱撑蒙脱石：
（ 4 ）将步骤（ 3 ）得到的羟基铁柱撑蒙脱石在氢气和氮气的混合气氛中高温还原得到零价铁柱撑蒙脱石修复材料 。
优选的，步骤（ 1 ）所述蒙脱石为纯化的钙基蒙脱石；所述 NaCl 溶液的浓度为 0.05-0.15M ，进一步优选为 0.1M ；所述恒温水浴的温度为 50 ℃ ~70 ℃；所述重复的次数为 2~4 次。
优选的，步骤（ 2 ）中 Na2CO3 与 FeCl3 的摩尔比为 0.5:1~1.5:1 ；进一步优选为 1 ： 1 。
优选的，步骤（ 3 ）中羟基铁 / 钠基 蒙脱石的比例为 5mmol/g~10 mmol/g ；进一步优选为 10 mmol/g 。
优选的，步骤（ 2 ）和（ 3 ）中搅拌时间为 1~3 h ，陈化时间为 12~48 h 。
优选的，步骤（ 4 ）中混合气氛中氢气和氮气的体积比为 10 ： 90~90 ： 7 ；所述高温还原的条件是由室温按 5~10 min/ ℃的升温速率升温至 200 ℃ ~1000 ℃煅烧 2~4h 。
由以上所述的制备方法制备得到的 一种零价铁柱撑蒙脱石修复材料 。
以上所述的一种零价铁柱撑蒙脱石 修复 材料应用于活化过一硫酸盐去除难降解有机污染物中，该应用包括以下步骤：
（ 1 ）配制 10 mg/L~30 mg/L 的有机污染物溶液；
（ 2 ）向有机污染物溶液中依次加入零价铁柱撑蒙脱石修复材料和过一硫酸盐，零价铁柱撑蒙脱石活化过一硫酸盐去除难降解的有机污染物。
优选的，步骤（ 1 ）中所述的有机污染物溶液为四溴双酚 A 溶液（ TBBPA ）。
优选的，步骤（ 2 ）中零价铁柱撑蒙脱石的投加量为0.02 g/L~0.5 g/L；过一硫酸盐的投加量为0.05 mM~0.5 mM 。
优选的， 一种零价铁柱撑蒙脱石 修复 材料的制备方法与应用包括以下步骤：
第一步--钙基蒙脱石的钠化：将钙基蒙脱石分散在 0.1M 的NaCl 溶液中，60 ℃恒温水浴充分搅拌 1~3h ，然后静置 1~3h ，重复三次，将钠化产物置于离心机中离心分离，弃去清液，用蒸馏水洗4~6次，最后将钠化产物在50~70℃温度下烘干，然后研磨过 200目筛，得到钠基蒙脱石；
第二步--聚羟基铁柱化液的制备：在高速搅拌下，按一定的 Na2CO3/FeCl3 摩尔比的比例 (0.5:1~1.5:1) ，将 0.05 M~0.15 M 的 Na2CO3 溶液通过恒压漏斗缓慢滴入 0.05 M~0.15 M 的 FeCl3 溶液中，得到的红褐色半透明柱撑液继续搅拌 1~3 h ，之后陈化 12~48 h ，制得聚羟基铁柱化液，其中 Na2CO3/FeCl3 摩尔比的优选比例为 1 ： 1 ；
第三步--羟基铁柱撑蒙脱石的制备：在高速搅拌下，按照一定的 羟基铁 / 蒙脱石的比例（ 5mmol/g~10 mmol/g ）， 将第一步制备的钠基蒙脱石配成质量分数为 0.5%~1% 的浆液，再将第二步制备好的柱化剂缓慢滴入上述浆液中，滴定完后继续搅拌 1~3 h ，之后陈化 12~48 h ，将柱撑产物置于离心机中离心分离，弃去清液，用蒸馏水洗 4~6 次，最后将柱撑产物在 50~70 ℃温度下烘干，然后研磨过 200 目筛，得到羟基铁柱撑蒙脱石；
第四步--零价铁柱撑蒙脱石的制备：将第三步得到的产物在不同比例氢气和氮气的混合气氛中（氢气与氮气的体积比为 10 ： 90~70:30 ） 200~1000 ℃下高温还原，煅烧后的产物研磨过筛，得到零价铁柱撑蒙脱石；
第五步--零价铁柱撑蒙脱石活化 PMS 去除难降解有机物：将第四步得到的零价铁柱撑蒙脱石作为催化剂活化 PMS 去除难降解有机（ TBBPA ） , 在一定浓度 (5 mg/L~30 mg/L)TBBPA 溶液中加入一定量（ 0.02g/L~0.5g/L ）的零价铁柱撑蒙脱石和一定量（ 0.05mM~0.5mM ）氧化剂（ PMS ），反应一段时间达到去除溶液中难降解的 TBBPA 的目的。
与现有技术相比，本发明具有如下优点与技术效果：
本发明所制备的零价铁柱撑蒙脱石能应用于去除难降解的有机污染物，有机物被过一硫酸盐降解为小分子有机物。
附图说明
图1为蒙脱石、羟基铁柱撑蒙脱石以及实施例1制备的零价铁柱撑蒙脱石修复材料的XRD图；
图2为实施例1制备的零价铁柱撑蒙脱石修复材料的SEM图；
图3为实施例1制备的零价铁柱撑蒙脱石修复材料的TEM图；
图4为实施例1制备的零价铁柱撑蒙脱石修复材料的XPS图；
图5为实施例2中不同时间内零价铁柱撑蒙脱石修复材料活化PMS降解TBBPA的UV-vis图谱；
图6为实施例2中不同零价铁柱撑蒙脱石修复材料投加量下，零价铁柱撑蒙脱石活化PMS降解TBBPA的UV-vis图谱；
图7为实施例2中不同PMS投加量下，零价铁柱撑蒙脱石活化PMS降解TBBPA的UV-vis图谱；
图8为实施例3中不同煅烧温度下制备的零价铁柱撑蒙脱石修复材料的XRD图；
图9为实施例3中不同煅烧温度下制备的零价铁柱撑蒙脱石修复材料活化PMS降解TBBPA的UV-vis图谱；
图10为实施例4中不同氢气/氮气比例下制备的零价铁柱撑蒙脱石修复材料的XRD图；
图11为实施例4中不同氢气/氮气比例下制备的零价铁柱撑蒙脱石修复材料活化PMS降解TBBPA的UV-vis图谱。
具体实施方式
下面结合实施例和附图对本发明作进一步详细的描述，但本发明的实施方式不限于此。
实施例1
一种制备零价铁柱撑蒙脱石修复材料的方法，包括以下步骤：
第一步：称取10 g钙基蒙脱石分散在200 ml 的0.1M的NaCl溶液中，60℃恒温水浴充分搅拌2 h，静置2 h后，将钠化产物置于离心机中离心分离，弃去清液，加入100 ml 的0.1M的NaCl溶液，60℃恒温水浴充分搅拌2 h，静置2 h后，将钠化产物置于离心机中离心分离，弃去清液，再加入50 ml 的0.1M的NaCl溶液，60℃恒温水浴充分搅拌2 h，静置24h后，将钠化产物置于离心机中离心分离，弃去清液，用蒸馏水洗5次，最后将钠化产物在60℃温度下烘干，然后研磨过200目筛，得到钠基蒙脱石；
第二步：在 4000rpm 高速搅拌下，按 Na2CO3/FeCl3 摩尔比例为 1 ： 1 ，将 200mL 的 0.1M 的 Na2CO3 溶液通过恒压漏斗滴入 200 mL 0.1M 的 FeCl3 溶液中，得到的红褐色半透明柱撑液继续搅拌 2 h ，之后陈化 24 h ，得到 400 mL 的聚羟基铁柱化液；
第三步： 按最优羟基铁 / 蒙脱石的比例为 10 mmol/g ， 准确称取 2g 第一步制备的钠基蒙脱石加入到 100 mL 的去离子水中配成质量分数为 1% 的浆液，再将第二步制备好的柱化剂滴入上述浆液中，滴定完后继续搅拌 2 h ，之后陈化 24 h ，将柱撑产物置于离心机中离心分离，弃去清液，用蒸馏水洗 5 次，最后将柱撑产物在 60 ℃温度下烘干，然后研磨过 200 目筛，得到羟基铁柱撑蒙脱石；
第四步：将第三步得到的产物在氢气和氮气的体积比为 50 ： 50 （总的通气流量为 100 cm3/min ）混合气氛中以 5min/ ℃的升温速率升温至 700 ℃热还原 3h ，热还原后的产物研磨过筛，得到 零价铁柱撑蒙脱石修复材料 。
本实施例制备的零价铁柱撑蒙脱石修复材料 （ Fe0-Mt ）的 X 射线衍射图（ XRD ）如图 1 所示，相比于蒙脱石 (Mt) 和羟基铁柱撑蒙脱石 (FeOOH-Mt) 出现了明显的零价铁的特征峰（ 110 ）和（ 200 ）； 零价铁柱撑蒙脱石修复材料 （ Fe0-Mt ）的 SEM 图如图 2 所示，在蒙脱石的层间明显看到椭球状零价铁颗粒， 零价铁柱撑蒙脱石修复材料 （ Fe0-Mt ）的 TEM 图（如图 3 ）也充分说明这一结论， 零价铁柱撑蒙脱石修复材料 （ Fe0-Mt ） Fe 2p 的高分辨 XPS 图如图 4 所示，在结合能 706.35 eV 处的峰再次说明了最终产物中零价铁颗粒的存在。
实施例 2
一种由实施例1制备得到的零价铁柱撑蒙脱石修复材料高效活化过一硫酸盐（PMS）应用于去除难降解有机物，包括以下步骤：
第一步：依次准确称取 0.4 g NaOH 和 0.4 g TBBPA 于 100 ml 的容量瓶中加水配成 4 g/L 的 TBBPA 储备液，准确量取 5 mL4 g/L 的 TBBPA 储备液于 2000 mL 的容量瓶中稀释为 10 mg/L 的 TBBPA 溶液；
第二步：准备量取 250mL10 mg/L 的 TBBPA 溶液于 500mL 的烧杯中，再依次准确称取 0.0154 g 的 PMS 和 0.0125 g 的 Fe0-Mt 于 500 mL 的烧杯中，每隔 5 min 用注射器抽取 5 ml 烧杯中的 TBBPA 溶液，用紫外分光光度计测溶液中 TBBPA 的 UV-vis 图谱；相关结果如图 5 所示，在 15min 内就可以实现 TBBPA 的完全降解；
第三步：分别准备量取 4 份 250 mL10 mg/L 的 TBBPA 溶液于四个 500 mL 的烧杯中，准确称取 4 份 0.0154g 的 PMS 于 250mL 的 TBBPA 溶液中，再分别准确称取 0.005 g 、 0.0125 g 、 0.025 g 和 0.05 g 的 Fe0-Mt 分别于 250 mL 的 TBBPA 溶液中，反应 10min 后用注射器抽取 5ml 每个烧杯中的 TBBPA 溶液，用紫外分光光度计测溶液中 TBBPA 的 UV-vis 图谱；相关结果如图 6 所示，由图 6 可知， Fe0-Mt 的投加量越大， TBBPA 的降解越快，效果越好；
第四步：分别准备量取 4 份 250mL10 mg/L 的 TBBPA 溶液于四个 500mL 的烧杯中，准确称取 4 份 0.0125g 的 Fe0-Mt 于 250mL 的 TBBPA 溶液中，再分别准确称取 0.0077g 、 0.0115g 、 0.0154g 和 0.0231g PMS 分别于 250mL 的 TBBPA 溶液中，反应 10min 后用注射器抽取 5ml 每个烧杯中的 TBBPA 溶液，用紫外分光光度计测溶液中 TBBPA 的 UV-vis 图谱；相关结果如图 7 所示，由图 7 可知， PMS 的投加量越大， TBBPA 的降解越快，效果越好。
实施例3
第一步：其它步骤同实施例1，只是在第四步中将羟基铁柱撑蒙脱石在氢气和氮气体积比为50：50的混合气氛中以5min/℃的升温速率分别升温至300℃、500℃、700℃和900℃热还原3h，还原后的产物研磨过筛，得到在不同温度下热还原得到的零价铁柱撑蒙脱石修复材料；比较不同温度下热还原得到的零价铁柱撑蒙脱石修复材料的XRD图谱（如图8所示），发现均可以观察到零价铁的特征峰（110）和（200）；
第二步：分别准备量取4份250 mL10 mg/L的TBBPA溶液于四个500 mL的烧杯中，准确称取4份0.0154 g的PMS分别于250 mL的TBBPA溶液中，再分别准确称取0.0125 g不同温度（300℃、500℃、700℃和900℃）下热还原得到的Fe0-Mt分别于250 mL的TBBPA溶液中，反应10 min后用注射器抽取5 ml烧杯中的TBBPA溶液，用紫外分光光度计测溶液中TBBPA的UV-vis图谱；相关结果如图9所示，当温度为900℃时，零价铁柱撑蒙脱石活化PMS降解TBBPA的效果最好。
实施例4
第一步：其它步骤同实施例1，只是在第四步中将羟基铁柱撑蒙脱石在氢气和氮气的体积比分别为10：90、30：70、50：50和70：30（总的通气流量为 100cm3/min ） 混合气氛中以5min/℃的升温速率升温至700℃热还原3h，还原后的产物研磨过筛，得到在不同混合气氛下热还原得到的零价铁柱撑蒙脱石产物；比较不同混合气氛下高温还原得到的零价铁柱撑蒙脱石修复材料的XRD图谱（如图10所示），发现均可以观察到零价铁的特征峰（110）和（200）；
第二步：分别准备量取4份250 mL10 mg/L的TBBPA溶液于四个500 mL的烧杯中，准确称取4份0.0154 g的PMS于250 mL的TBBPA溶液中，再分别准确称取0.0125 g不同混合气氛下（氢气和氮气的体积比分别为10：90、30：70、50：50和70：30）热还原得到的 Fe0-Mt 于 250 mL 的 TBBPA 溶液中，反应 10 min 后用注射器抽取 5 ml 烧杯中的 TBBPA 溶液，用紫外分光光度计测溶液中 TBBPA 的 UV-vis 图谱；相关结果如图 11 所示，当混合气氛中的氢气和氮气的体积比分别为 10 ： 90 时，零价铁柱撑蒙脱石活化 PMS 降解 TBBPA 的效果最好。
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受上述实施例的限制，其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化，均应为等效的置换方式，都包含在本发明的保护范围之内。

Claims (10)

  1. 一种零价铁柱撑蒙脱石修复材料的制备方法，其特征在于，包括以下步骤：
    （1）将蒙脱石分散在NaCl溶液中，恒温水浴搅拌、静置、离心；重复所述分散、水浴搅拌、静置、离心步骤，然后洗涤，干燥，得到钠基蒙脱石；
    （2）将Na2CO3溶液滴入FeCl3溶液中，将得到的红褐色半透明柱撑液继续搅拌、陈化，得聚羟基铁柱化液；
    （3）将步骤（1）得到的钠基蒙脱石加入水中配成钠基蒙脱石浆液，再将聚羟基铁柱化液滴入钠基蒙脱石浆液中，搅拌、陈化、离心、洗涤、干燥和过筛，得到羟基铁柱撑蒙脱石：
    （4）将步骤（3）得到的羟基铁柱撑蒙脱石在氢气和氮气的混合气氛中高温还原得到零价铁柱撑蒙脱石修复材料。
  2. 根据权利要求1所述的一种零价铁柱撑蒙脱石修复材料的制备方法，其特征在于：步骤（1）所述蒙脱石为纯化的钙基蒙脱石；所述NaCl溶液的浓度为0.05-0.15M；所述恒温水浴的温度为50℃~70℃；所述重复的次数为2~4次。
  3. 根据权利要求1所述的一种零价铁柱撑蒙脱石修复材料的制备方法，其特征在于：步骤（2）中Na2CO3与FeCl3的摩尔比为0.5:1~1.5:1。
  4. 根据权利要求1所述的一种零价铁柱撑蒙脱石修复材料的制备方法，其特征在于：步骤（3）中羟基铁/钠基蒙脱石的比例为5mmol/g~10 mmol/g。
  5. 根据权利要求1所述的一种零价铁柱撑蒙脱石修复材料的制备方法，其特征在于：步骤（2）和（3）中搅拌时间为1~3 h，陈化时间为12~48 h。
  6. 根据权利要求1所述的一种零价铁柱撑蒙脱石修复材料的制备方法，其特征在于：步骤（4）中混合气氛中氢气和氮气的体积比为10：90~90：7；所述高温还原的条件是由室温以5~10 min/℃的升温速率升温至200℃~1000℃煅烧2~4h。
  7. 由权利要求1-6任一项所述的制备方法制备得到的一种零价铁柱撑蒙脱石修复材料。
  8. 权利要求7所述的一种零价铁柱撑蒙脱石修复材料应用于活化过一硫酸盐去除难降解有机污染物中，其特征在于，包括以下步骤：
    （1）配制10 mg/L~30 mg/L的有机污染物溶液；
    （2）向有机污染物溶液中依次加入零价铁柱撑蒙脱石修复材料和过一硫酸盐，零价铁柱撑蒙脱石活化过一硫酸盐去除难降解的有机污染物。
  9. 根据权利要求8所述的应用，其特征在于：步骤（1）中所述的有机污染物溶液为四溴双酚A溶液。
  10. 根据权利要求8所述的应用，其特征在于：步骤（2）中零价铁柱撑蒙脱石修复材料的投加量为0.02 g/L~0.5 g/L；过一硫酸盐的投加量为0.05 mM~0.5 mM。
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