WO2018045790A1 - 一种介孔铁酸锰类芬顿催化剂及其制备方法和应用 - Google Patents

一种介孔铁酸锰类芬顿催化剂及其制备方法和应用 Download PDF

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WO2018045790A1
WO2018045790A1 PCT/CN2017/089467 CN2017089467W WO2018045790A1 WO 2018045790 A1 WO2018045790 A1 WO 2018045790A1 CN 2017089467 W CN2017089467 W CN 2017089467W WO 2018045790 A1 WO2018045790 A1 WO 2018045790A1
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mesoporous
fenton
catalyst
ferromanganese
catalytic material
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French (fr)
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王津南
徐苏倩
邵宁
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Nanjing University
Nanjing Tech University
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Nanjing Tech University
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Definitions

  • the invention relates to a Fenton-like catalyst, in particular to a mesoporous ferromanganese-based Fenton catalyst material, a preparation method and application thereof, and a mesoporous molecular sieve KIT-6 (porous silicon Porous Si) as a hard template by impregnation method Synthesis of mesoporous MnFe 2 O 4 type Fenton catalyst.
  • a Fenton-like catalyst in particular to a mesoporous ferromanganese-based Fenton catalyst material, a preparation method and application thereof, and a mesoporous molecular sieve KIT-6 (porous silicon Porous Si) as a hard template by impregnation method Synthesis of mesoporous MnFe 2 O 4 type Fenton catalyst.
  • Fenton-like technology is an advanced oxidation water treatment technology that has been studied in recent years.
  • the hydroxyl radicals generated in the reaction system are oxidized next to oxyfluoride in water, have high activity and no selectivity, and can be effectively degraded.
  • a variety of biologically difficult to degrade organic pollutants Many researchers have carried out extensive research on Fe-based metal oxides as Fenton-like catalysts, and have made great progress.
  • existing research and application of iron-based metal oxides as Fenton-like catalysts have the following drawbacks:
  • the bimetal oxide Fenton reagent prepared by the existing synthesis method has a small morphology and a small specific surface area, and the above morphology is not favorable for the improvement of catalytic efficiency;
  • Comparative Publication No. 1 Preparation of an iron-cobalt-based Fenton catalyst and its products and applications.
  • the patent uses FeCl 2 ⁇ 4H 2 O, CoCl 2 ⁇ 6H 2 O as the reaction precursor, KBH 4 is the reaction reducing agent, PVP is the surface protective agent, which is prepared by liquid phase reduction method, and finally is aged, filtered, washed. , vacuum drying products.
  • the iron-cobalt Fenton catalyst prepared by the modified method can reduce the COD cr of the industrial wastewater containing acrylic fiber by more than 60% in a short period of time, the removal rate of COD cr in the self-dispensed dye wastewater is as high as 70% or more.
  • the patent has the following drawbacks: (1) The pH of the reaction is strictly controlled during the preparation of the catalyst, and the operating conditions are complicated. (2) The dosage of hydrogen peroxide is higher during the reaction, and the running cost is higher; (3) The pH control range of the reaction process in the patent is about 2.0 ⁇ 0.5, and the precipitation of iron and cobalt ions is more under this pH condition, resulting in the reaction. A large amount of iron sludge is precipitated in the process, which reduces the active ions of the catalyst and thus affects the reusability of the catalyst.
  • Comparative Publication No. 2 Preparation of a Mesoporous Material Doped with MnO 2 and Cu and Its Application in Advanced Oxidation Technology of Fenton Water Treatment. Application number: 201510234344.3.
  • the patent provides a preparation method of a MnO 2 -doped Cu mesoporous material in the form of a powder, which is prepared by using CuMn doped with KMnO 4 , CuSO 4 ⁇ 5H 2 O and maleic acid as main materials. MnO 2 mesoporous material and applied to the treatment of degradation of benzotriazole wastewater.
  • the doped mesoporous material synthesized in this patent requires the dropwise addition of maleic acid (cis-butadienoic acid) to the precursor solution to reduce the manganese element in the potassium permanganate as a reducing agent, followed by subsequent washing, drying and calcination. And got it.
  • maleic acid cis-butadienoic acid
  • the above preparation process has two obvious defects: (1) the precursor is simply mixed in the form of a salt solution, and it is difficult to form a uniform uniform mesoporous structure through subsequent steps of stirring, aging, calcination, etc., and it is difficult to make the doping Cu very Good distribution in the pores, and the supported Cu may occupy the original adsorption catalytic activity of MnO 2 , thereby affecting the catalytic degradation effect; (2) the prepared catalyst has a relatively high dosage during the catalytic degradation reaction. The processing cost is high, which is not conducive to practical engineering applications.
  • Comparative Publication No. 3 A method for preparing a Fe-Co bimetallic multiphase Fenton catalyst supported by modified sepiolite.
  • the sepiolite powder is acidified and activated to obtain modified sepiolite, and then the mixed solution of ferric nitrate and cobalt nitrate is added to the urea and mixed with the modified sepiolite.
  • the mixture is reacted under heating in a water bath to form a precipitate by cooling. Things.
  • calcination completes the synthesis of the catalyst.
  • the synthesized catalyst degraded the reactive brilliant blue with an initial concentration of 50 ng/L.
  • the removal rate of reactive brilliant blue reached about 86.9% after 1 hour of reaction under the condition of hydrogen peroxide addition of 0.2 mL and stirring speed of 150 r/min.
  • the patent has the following deficiencies in the actual use process: (1) The synthesis method essentially deposits the active metal oxide into the inner surface of the sepiolite channel by the impregnation method, and the Fe-Co oxide is easy to proceed with the catalytic degradation reaction. Peeling off from the sepiolite channel leads to poor catalyst stability; (2) The hardness of the sepiolite becomes soft after water absorption, and the hardness is restored after drying, and the Fe-Co oxide is supported. The structure is easy to change before and after the reaction, and the dispersibility is reduced, which accelerates the deactivation of the catalyst to some extent.
  • Comparative Publication No. 4 A preparation method and application of a ferric ion molecular sieve type Fenton catalyst.
  • 3A molecular sieve is used as the carrier, and ferrous sulfate is used as the precursor.
  • the 3A-Fe molecular sieve is prepared by controlling the high temperature calcination temperature of 3A molecular sieve, the reaction amount of Na 2 CO 3 and FeSO 4 , and the like.
  • the phase-like Fenton system catalyzes the degradation of nitrobenzene wastewater.
  • the patent has the following defects: (1) In the actual degradation process, the dosage of hydrogen peroxide is relatively large, which is not conducive to practical application.
  • Comparative Patent Publication 5 A heterogeneous catalyst and its use, Patent Application No.: 201410546489.2.
  • the patent relates to a surface-loaded hematite heterogeneous Fenton catalyst on a graphene modified-mesoporous molecular sieve (MCM-41) composite, which is doped into mesoporous molecular sieve by in situ synthesis thermal reduction method.
  • MCM-411 graphene modified-mesoporous molecular sieve
  • the modification is carried out to form a graphene-mesoporitic graphene-mesoporous MCM-41 composite, and then the surface is loaded with ferric iron by the immersion method, the high temperature calcination is protected by a nitrogen atmosphere, and the ferric iron salt is produced by the ferric iron salt ( ⁇ - The Fe 2 O 3 ) crystal form forms a graphene-MCM-41 composite supported iron oxide.
  • the heterogeneous catalyst synthesized in this patent effectively reduces the dissolution of iron ions during the reaction, the reaction conditions for degrading quinoline and phenol need to be carried out in a system with a pH of about 3, and there is no possibility that the actual wastewater is close to neutral.
  • the present invention provides a mesoporous.
  • the surface of the inner channel of the molecular sieve is loaded, and the metal oxide is formed by high-temperature calcination.
  • the template agent KIT-6 is stirred and dissolved in the strong alkali solution to realize the pore formation of the catalyst ferrite.
  • the catalyst prepared by the invention and the preparation method thereof enable the catalyst particles after perforation to expose a high specific surface area, provide more adsorption sites and catalytic sites, and reduce the mass transfer resistance at the solid-liquid phase interface;
  • the iron ions and manganese ions in the manganese manganate can participate in promoting the double oxidation to generate hydroxyl radicals and accelerate the reaction process; the amount of hydrogen peroxide and the amount of catalyst to be added in the reaction process are less.
  • the preparation method of mesoporous ferromanganese-based Fenton catalyst comprises the following steps:
  • Step (1) Dissolving molecular sieve KIT-6 with iron salt and manganese salt in an alcohol solution, refluxing under magnetic stirring for 12-24 hours, cooling the solution, and filtering and drying.
  • the molar ratio of iron salt to manganese salt is from 0.5 to 1:2.
  • the alcohol solution is one, two or three combinations of methanol, ethanol or ethylene glycol, and the magnetic stirring temperature is 70 °C.
  • Figure 3 shows the KIT-6 scanning electron micrograph, which is enlarged by 20,000 times.
  • Step (2) The above product is placed in a tube furnace, incubated at 150-300 ° C for 3-5 h, and then incubated at 450-600 ° C for 3-5 h.
  • the heating rate in the tube furnace is 5 to 10 ° C / min.
  • Step (3) After calcination, the product is stirred in a NaOH solution for 12-24 hours to remove the KIT-6 templating agent, and the mixture is stirred, washed with water, washed until the pH of the supernatant is neutral, and the precipitate is freeze-dried.
  • the molar concentration of NaOH is 1-3 mol/L.
  • the invention prepares a mesoporous manganese ferrite-based Fenton catalyst, which has the following advantages compared with the conventional Fenton-like catalyst:
  • the prepared mesoporous ferromanganese-based Fenton catalyst has a large specific surface area and a mesoporous structure. This structural feature allows the catalyst material itself to expose more effective catalytic reaction contact surfaces, thereby providing more adsorption sites and catalytic active sites for the catalytic reaction; in addition, the mesoporous structure can effectively reduce the solidity during the reaction process - Mass transfer resistance at the liquid phase to accelerate the progress of the catalytic reaction;
  • the prepared iron ions in the mesoporous ferrite-type Fenton catalyst work together with manganese ions to generate hydroxyl radicals to accelerate the reaction process; the multivalent state transition between iron and manganese elements accelerates the interface electrons. The migration between the two effectively reduces the dissolution of heavy metal ions during the reaction.
  • 1 is a schematic diagram showing the principle of catalytic degradation of methylene blue by mesoporous Fenton catalyst manganese ferrite MnFe 2 O 4 ;
  • Example 2 is a N 2 adsorption-desorption curve and a pore size distribution diagram of a mesoporous Fenton catalyst manganese ferrite MnFe 2 O 4 synthesized in Example 3.
  • Figure 3 is a KIT-6 scanning electron micrograph, magnified 20000 times;
  • Example 4 is a scanning electron micrograph of mesoporous ferromanganese synthesized in Example 1, enlarged by 20,000 times;
  • Example 5 is a scanning electron micrograph of mesoporous ferromanganese synthesized in Example 2, which is enlarged by 60000 times;
  • Example 6 is a scanning electron micrograph of mesoporous ferromanganese synthesized in Example 3, which is enlarged by 60000 times;
  • Figure 7 is a graph showing the electronic energy spectrum of mesoporous ferromanganese synthesized in Example 3.
  • Fig. 8 is a Mn2p spectrum in the electronic energy spectrum of mesoporous ferromanganese synthesized in Example 3.
  • Figure 9 is a graph showing the Fe2p spectrum in the electronic energy spectrum of mesoporous ferromanganese synthesized in Example 3.
  • Figure 10 is an XRD pattern of mesoporous ferromanganese MnFe 2 O 4 synthesized in Examples 1, 2, and 3;
  • Figure 11 is a graph showing the catalytic degradation of methylene blue by the intermediate pores of ferromanganese MnFe 2 O 4 in Examples 1, 2, 3, 4, 5, 6, and 7.
  • a method for preparing a mesoporous ferromanganese-based Fenton catalyst the steps of which are:
  • the molecular sieve KIT-6 was dissolved in an alcohol solution with ferric chloride hexahydrate and manganese chloride tetrahydrate, and refluxed under magnetic stirring for 12 hours. The solution was cooled, filtered and dried.
  • the molar ratio of iron salt to manganese salt is: 0.5:2
  • the alcohol solution is methanol
  • the magnetic stirring temperature is 70 ° C
  • the scanning electron micrograph of molecular sieve KIT-6 is shown in FIG. 3 .
  • FIG. 9 was synthesized in Example 1.
  • Figure 1 is a schematic diagram of the catalytic degradation of methylene blue by mesoporous Fenton catalyst ferromanganese MnFe 2 O 4 in Example 1: hydrogen peroxide and Mn, Fe on the surface of manganese ferrite undergo oxidation-reduction reaction to produce ⁇ OH, free radicals in iron
  • the diffusion layer on the surface of the oxide or near surface degrades methylene blue into an intermediate such as an organic acid, and finally degrades into carbon dioxide and water.
  • the treatment results are shown in Fig. 11. Under the acidic pH condition, the material synthesized in Example 1 had a degradation rate of methylene blue of about 55% in 60 min.
  • the molecular sieve KIT-6 was dissolved in an alcohol solution with iron nitrate nonahydrate and manganese nitrate tetrahydrate, and refluxed under magnetic stirring for 16 hours. The solution was cooled, filtered and dried. Wherein, the molar ratio of iron salt to manganese salt is: 0.75:2, the alcohol solution is methanol, and the magnetic stirring temperature is 80 °C.
  • the Fenton-like catalytic degradation of methylene blue was carried out by disposing 20 mL of a 20 mg/L methylene blue solution in an Erlenmeyer flask, the initial pH was adjusted to 4, and 0.1 g of mesoporous ferromanganate was added. Placed in a shaker at 150 ° C and rotating at 150 rpm for 30 min, then remove and add 45 mmol/L of hydrogen peroxide for each quantitative time. The concentration of methylene blue was measured and the results are shown in Fig. 11. Under the acidic pH condition, the material synthesized in Example 2 had a degradation rate of methylene blue of about 80% within 60 min.
  • Fig. 6 is a scanning electron micrograph of mesoporous ferromanganese synthesized under the example.
  • Figure 7 is an XPS spectrum of the synthesized mesoporous ferromanganese MnFe 2 O 4 .
  • Figure 10 is an XRD pattern of mesoporous Fenton catalyst ferromanganese MnFe 2 O 4 synthesized in Example 3, with 2 ⁇ angles corresponding to manganese ferrite at 29.65°, 34.92°, 42.43°, 52.61°, and 61.56° ( 220), (311), (400), (422), (511), (440) crystal faces.
  • 2 is a graph showing the N 2 adsorption and desorption curve and pore size distribution of the product synthesized in this example. Under the BJH model calculation model, the mesoporous ferromanganese has a specific surface area of 109.99 m 2 g and an average pore diameter of 3.564 nm.
  • Figure VIII and Figure 9 respectively show the Mn 2p and Fe 2p electron binding energy spectra of mesoporous ferromanganese, respectively.
  • the two peaks at 640.5eV and 652.5eV in the Mn 2p map correspond to Mn 2p 3/2 and Mn 2p. 1/2 .
  • Two peaks at 724.6 eV and 710.8 eV in the Fe 2p map correspond to Fe 2p 3/2 and Fe 2p 1/2 .
  • the Fenton-like catalytic degradation of methylene blue was carried out by disposing 20 mL of a 20 mg/L methylene blue solution in an Erlenmeyer flask, the initial pH was adjusted to 4, and 0.1 g of mesoporous ferromanganate was added. The mixture was placed in a shaker at 25 ° C and rotating at 150 rpm for 30 min. Then, 45 mmol/L of hydrogen peroxide was taken out, and the concentration of methylene blue was measured at each quantitative time. The results are shown in Fig. 11. It can be seen from the figure that in alkaline conditions. Under the condition, the manganese ferrite can degrade the methylene blue to more than 90 in 60 min.
  • the Fenton-like catalytic degradation of methylene blue was carried out by disposing 20 mL of a 20 mg/L methylene blue solution in an Erlenmeyer flask, the initial pH was adjusted to 4, and 0.1 g of mesoporous ferromanganate was added. The mixture was placed in a shaker at 25 ° C and a rotation speed of 150 rpm for 30 min. Then, 45 mmol/L of hydrogen peroxide was taken out, and the concentration of methylene blue was measured at each quantitative time. The results are shown in Fig. 11. The manganese ferrite synthesized under the conditions of Example 4 had a degradation rate of about 90% for methylene blue in about 60 minutes.

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Abstract

一种介孔铁酸锰类芬顿催化剂及其制备方法和应用，利用KIT-6作为硬模板剂来合成介孔状铁酸锰催化剂。所制备的介孔铁酸锰与过氧化氢构成类芬顿体系氧化废水处理体系，对废水中的有机污染物进行高效去除与矿化。所制备的类芬顿催化剂具备介孔结构，较高的比表面积，能够提供较多的吸附位点和催化位点，可在较宽pH范围酸性、中性乃至碱性，高效降解污染物，解决了传统芬顿反应只能在酸性条件下反应与反应过程中产生大量铁泥易造成二次污染的问题，且催化剂可循环使用，使用后易于与水溶液分离回收。

Description

一种介孔铁酸锰类芬顿催化剂及其制备方法和应用 技术领域：
本发明涉及类芬顿催化剂，具体涉及到一种介孔铁酸锰类芬顿催化剂材料及其制备方法和应用，利用介孔分子筛KIT-6(多孔硅Porous Si)作为硬模板，通过浸渍法合成介孔MnFe2O4类芬顿催化剂。
背景技术：
类芬顿技术是近年来研究较多的一种高级氧化水处理技术，反应体系中产生的羟基自由基是水体中氧化性仅次于氟氧化物，具有高活性和无选择性，能够有效降解多种生物难降解的有机污染物。很多学者对Fe系金属氧化物作为类芬顿催化剂开展大量的研究，取得了较大的进展。但是现有研究和应用的铁系金属氧化物作为类芬顿催化剂存在着以下缺陷：
(1)已有的文献报道称铁矿石类类芬顿催化剂降解污染物的速率远小于相同条件下传统芬顿法处理污染物的速率。
(2)很多未改性的铁氧化物仍然只能在酸性pH范围下对有机物进行氧化降解，并不能适用于中性或碱性pH下的废水。
(3)部分铁氧化物具有磁性，易团聚从而减少了活性位点的暴露，不利于催化剂高效降解污染物。
近些年，有学者研究发现铁系金属氧化物中掺杂过渡金属能够发挥双金属协同作用，一定程度上提高催化剂的催化效率。但是在制备方法和实际使用中依然面临着以下的不足：
(1)现有合成方法制备出来的双金属氧化物类芬顿试剂的在形貌上表现为孔道较少，比表面积较小，上述形态不利于催化效率的提升；
(2)铁系氧化物掺杂某些过渡金属后，其对实际催化性能反而存有负影响，有文献报道称掺杂Ni(Ⅱ)、Ti(Ⅴ)在一定程度上抑制了羟基自由基的产生速率；
(3)多数掺杂后的双金属氧化物无法有效拓宽类芬顿催化反应的pH适用范围，仍然需要在酸性条件下使用。
现有相关专利如下：
对比公开专利1：一种铁钴类芬顿催化剂的制备及其产品和应用。专利申请号：20130533050.1。该专利以FeCl2·4H2O、CoCl2·6H2O为反应前驱物，KBH4 为反应还原剂，PVP为表面保护剂，利用液相还原法制备，最后经过陈化、抽滤、洗涤、真空干燥得产品。改方法制得的铁钴类芬顿催化剂虽然能够在较短的时间内将含腈纶的工业废水CODcr降低60％以上，对自配的染料废水中的CODcr的去除率高达70％以上。但是该专利存在以下缺陷：(1)催化剂制备过程中要严格控制反应的pH值，操作条件较为复杂。(2)反应过程中双氧水投加量较高，运行成本较高；(3)该专利中反应过程pH控制范围在2.0±0.5左右，此pH条件下铁、钴离子析出量较多，致使反应过程中会产生大量的铁泥析出，减少了催化剂的活性离子，进而影响催化剂的重复使用性。
对比公开专利2：一种MnO2掺杂Cu的介孔材料的制备及其在类芬顿水处理高级氧化技术中的应用。申请号：201510234344.3。该专利提供了一种MnO2掺杂Cu的介孔材料的制备方法，材料形状为粉末状，以KMnO4、CuSO4·5H2O和马来酸作为主要材料，制备成含有Cu掺杂的MnO2介孔材料，并将其应用在处理对苯并三唑废水的降解中。该专利中合成的掺杂介孔材料需要向前驱体溶液滴入马来酸(顺丁二烯酸)，作为还原剂还原高锰酸钾中的锰元素，而后经过后续的洗涤、干燥和煅烧而得。然而上述制备过程存在两个明显的缺陷：(1)前驱物以盐溶液的形式简单混合，经过后续的搅拌、老化、煅烧等步骤难以形成均匀的均一的介孔结构，难以使得掺杂Cu很好的分布在孔道内，且负载的Cu可能占据了MnO2原有的吸附催化活性位，从而影响催化降解效果；(2)所制备的催化剂在催化降解反应过程中的投加量比较高，使得处理成本较高，不利于实际工程应用。
对比公开专利3：以改性海泡石为载体的Fe-Co双金属多相类芬顿催化剂的制备方法。专利申请号：201210264664.X。该专利中海泡石粉经过酸化、活化反应后得到改性海泡石，而后将硝酸铁与硝酸钴混合溶液加入尿素后与改性海泡石混合，混合液在水浴加热条件下反应，冷却得到沉淀物。再经历水洗和干燥后煅烧完成催化剂的合成。合成的催化剂降解初始浓度为50ng/L的活性艳蓝，在双氧水投加量0.2mL，搅拌速度为150r/min条件下反应1小时后活性艳蓝的去除率到达86.9％左右。该专利在实际使用过程中存在以下不足：(1)该合成方法实质是通过浸渍法将活性金属氧化物沉淀到海泡石孔道内表面，随着催化降解反应的进行，Fe-Co氧化物易从海泡石孔道内脱落下来，导致催化剂稳定性能不佳；(2)由于海泡石吸水后硬度降低，变得柔软，干燥后硬度恢复，负载的Fe-Co氧化物 在反应前后结构易发生改变，分散性降低，一定程度上加速了催化剂的失活。
对比公开专利4:一种载铁分子筛型类芬顿催化剂的制备方法及应用。专利申请号：201310036533.0。该专利中以3A分子筛为载体，以硫酸亚铁为前驱体，通过控制3A分子筛高温焙烧温度、Na2CO3和FeSO4的反应加入量等参数制得3A-Fe型分子筛，并构成非均相类芬顿体系催化降解硝基苯废水。该专利在存在着以下的缺陷：(1)实际降解过程中，过氧化氢的投加量相对较大，不利于实际工程中的应用。(2)合成的Fe-Na氧化物负载在分子筛孔道内，随着反应的进行，存在着氧化物从分子筛表面和孔道内脱落的情况，降低了催化剂的稳定性。
对比公开专利5：一种非均相催化剂及其用途，专利申请号：201410546489.2。该专利涉及一种石墨烯改性-介孔分子筛(MCM-41)复合体表面负载赤铁矿非均相类芬顿催化剂，通过原位合成热还原法将石墨烯掺杂于介孔分子筛中进行改性，形成石墨烯-介孔石墨烯-介孔MCM-41复合体，然后通过浸置法表面负载三价铁，经过氮气氛围保护高温煅烧，三价铁盐生产赤铁矿(α-Fe2O3)晶型，形成石墨烯-MCM-41复合体负载氧化铁。该专利中合成的非均相催化剂虽然有效的降低了反应过程中铁离子的溶出，但是降解喹啉和苯酚的反应条件需要在pH值约为3的体系中进行，存在无法在实际废水接近中性pH值条件下发挥催化作用的缺陷，需要对水样进行调酸，增加了中性以及碱性废水处理的成本；此外，氧化石墨烯的制备过程较为复杂，成本较高。再者，随着反应的进行和催化剂的重复使用，负载在MCM-41孔道上的石墨烯存在脱落的情况，对赤铁矿的均匀分布造成影响，进而影响后期的催化效果。
发明内容:
1.发明要解决的技术问题
本发明针对目前类芬顿技术研究和应用面临着一些共性难题：
(1)由于芬顿反应是溶液中离子直接参与的均相反应，其传质过程速度较快，但是目前研究开发的类芬顿催化剂大多以固体形式存在，其反应实质是固相与液相的两相界面处发生的催化反应，这导致两相反应过程中传质阻力较大，极大的降低了反应速率；
(2)大多数铁系金属氧化物作为类芬顿催化剂进行催化反应时，需要在较低pH范围内进行，并不能很好的在实际废水接近中性pH值条件下发挥催化作用，增加了中性以及碱性废水处理的成本；
(3)催化剂本身的稳定性不高，不能够循环利用造成一定程度上的资源浪费。
目前，文献对双金属氧化物作为类芬顿试剂降解污染物的研究和制备方法比较成熟，但是对已有物质本身结构进行改性和调控的研究相对较少，本发明提供了一种介孔铁酸锰类芬顿催化剂及其制备方法和应用，通过水解法在酸性条件下使用三嵌段共聚物为结构导向剂合成介孔分子筛KIT-6，再通过高温浸渍法将铁盐和锰盐负载到分子筛的内孔道表面，经过高温煅烧后实现金属氧化物的成型，最后在强碱溶液中搅拌溶去模板剂KIT-6，实现催化剂铁酸锰的致孔。本发明所制备的催化剂及其制备方法实现了致孔后的催化剂颗粒能够暴露出较高的比表面积，提供更多吸附位点和催化位点，同时降低固-液相界面传质阻力；铁酸锰中的铁离子与锰离子能够协同参与促进双氧化产生羟基自由基，加速反应进程；反应过程需要加入的双氧水量与催化剂量较少。
2.技术方案
介孔铁酸锰类芬顿催化剂制备方法包括以下步骤：
步骤(1):将分子筛KIT-6与铁盐、锰盐溶于醇溶液中，在磁力搅拌作用下回流12～24h，溶液冷却后过滤烘干。其中，铁盐与锰盐摩尔浓度比为0.5-1：2。醇溶液为甲醇、乙醇或乙二醇中的一种、两种或三种组合，磁力搅拌温度为70℃。如图3为KIT-6扫描电镜图，放大20000倍，
步骤(2):将上述产物置于管式炉中，150-300℃条件下保温3-5h，然后在450-600℃条件下保温3-5h。其中：管式炉中的升温速率为5～10℃/min。
步骤(3):煅烧后产物在NaOH溶液中搅拌12-24h，以去除KIT-6模板剂，搅拌混合液，离心后水洗至上清液pH值至中性，沉淀物冷冻干燥。其中NaOH的摩尔浓度为1-3mol/L。
3.有益效果
本发明制备了一种介孔铁酸锰类芬顿催化剂，和传统类芬顿催化剂相比有以下优势：
(1)制备的介孔铁酸锰类芬顿催化剂，比表面积较大，介孔结构明显。这一结构特点使得催化剂材料本身暴露出更多的有效催化反应接触面，从而为催化反应提供更多的吸附位点和催化活性位点；此外，介孔结构能够有效降低反应过程中的固-液相界面传质阻力，加速催化反应进程；
(2)利用浸渍法使得金属氧化物成型，之后再将模板剂溶解去除，是对催化 剂材料本身的致孔，整个过程制备过程没有引入其他载体物质。因此，在催化反应过程中有效克服催化剂与载体材料脱离、流失的缺陷；
(3)制备的介孔铁酸锰类芬顿催化剂能够在酸性、中性乃至碱性条件下(pH＝4～10)与双氧水作用产生羟基自由基，高效降解亚甲基蓝废水。从而有效解决了芬顿反应只能在酸性条件下发挥催化降解污染物作用的局限性这一共性难题；
(4)制备的介孔铁酸锰类芬顿催化剂中的铁离子与锰离子与双氧水共同作用产生羟基自由基，加速反应进程；铁锰元素之间的多价态转换，加速了界面电子之间的迁移，有效减少了反应过程中重金属离子的溶出。
(5)氧化水处理反应过程需要加入的双氧水量与催化剂量较少。
附图说明：
图1为介孔类芬顿催化剂铁酸锰MnFe2O4催化降解亚甲基蓝原理示意图；
图2为实施例3中合成的介孔类芬顿催化剂铁酸锰MnFe2O4的N2吸脱附曲线和孔径分布图。
图3为KIT-6扫描电镜图，放大20000倍；
图4为实施例1中合成的介孔铁酸锰扫描电镜图片，放大20000倍；
图5为实施例2中合成的介孔铁酸锰扫描电镜图片，放大60000倍；
图6为实施例3中合成的介孔铁酸锰扫描电镜图片，放大60000倍；
图7为实施例3中合成的介孔铁酸锰电子能谱图。
图8为实施例3中合成的介孔铁酸锰电子能谱图中Mn2p图谱。
图9为实施例3中合成的介孔铁酸锰电子能谱图中Fe2p图谱。
图10为实施例1、2、3中合成的介孔铁酸锰MnFe2O4的XRD图谱；
图11为实施例1、2、3、4、5、6、7中介孔铁酸锰MnFe2O4催化降解亚甲基蓝效果图。
具体实施方式:
实施例1
介孔铁酸锰类芬顿催化剂制备方法，其步骤为：
(1)将分子筛KIT-6与六水合氯化铁、四水合氯化锰溶于醇溶液中，在磁力搅拌作用下回流12h，溶液冷却后过滤烘干。其中，铁盐与锰盐摩尔浓度比：0.5:2，醇溶液为甲醇，磁力搅拌温度：70℃，分子筛KIT-6扫描电镜图如图3所示。
(2)将上述产物置于管式炉空气氛围下，200℃条件下加热保温3h，然后在550℃条件下加热保温3h。其中：管式炉中的升温速率：5℃/min。
(3)煅烧后产物在NaOH溶液中搅拌24h，以此来去除KIT-6模板剂，搅拌混合液离心水洗三次至上清液pH至中性，沉淀物冷冻干燥，图9为实施例1中合成的介孔类芬顿催化剂铁酸锰MnFe2O4(合成的介孔铁酸锰)的XRD图谱。其中：NaOH的摩尔浓度：2mol/L。图4为该实施例下合成的介孔铁酸锰的扫面电镜图片，图10为实施例1中合成的介孔铁酸锰MnFe2O4的XRD图谱。
类芬顿催化降解亚甲基蓝实验:
配置20mg/L的亚甲基蓝溶液200mL于锥形瓶中，初始pH调为4，加入所制得的介孔铁酸锰0.1g。放置在25℃、转速为150rpm的摇床中吸附平衡30min，之后取出加45mmol/L的双氧水，构成类芬顿体系用于氧化废水处理，每个定量的时间取出样测定亚甲基蓝浓度。如图1为实施例1介孔类芬顿催化剂铁酸锰MnFe2O4催化降解亚甲基蓝效果图:过氧化氢与铁酸锰表面的Mn、Fe发生氧化还原反应产生·OH，自由基在铁氧化物表面或近表面的扩散层将亚甲基蓝降解为有机酸等中间产物，最终降解为二氧化碳和水，处理结果见图11。在酸性pH值条件下，实施例1中合成的材料在60min内对亚甲基蓝降解率在55％左右。
实施例2
(1)将分子筛KIT-6与九水合硝酸铁、四水合硝酸锰溶于醇溶液中，在磁力搅拌作用下回流16h，溶液冷却后过滤烘干。其中，铁盐与锰盐摩尔浓度比：0.75:2，醇溶液为甲醇，磁力搅拌温度：80℃。
(2)将上述产物置于管式炉空气氛围下，300℃条件下保温4h，然后在600℃条件下保温4h。其中：管式炉中的升温速率：10℃/min。
(3)煅烧后产物在NaOH溶液中搅拌12h，以此来去除KIT-6模板剂，搅拌混合液离心水洗三次至上清液pH至中性，沉淀物冷冻干燥。其中：NaOH的摩尔浓度：3mol/L。图9为实施例2中合成的介孔类芬顿催化剂铁酸锰MnFe2O4的XRD图谱；图5为该实施例下合成的介孔铁酸锰的扫面电镜图片，图10为实施例2中合成的介孔铁酸锰MnFe2O4的XRD图谱。
(4)类芬顿催化降解亚甲基蓝实验，配置20mg/L的亚甲基蓝溶液200mL于锥形瓶中，初始pH调为4，加入介孔铁酸锰0.1g。放置在25℃、转速为150rpm的摇床中吸附平衡30min，之后取出加45mmol/L的双氧水，每个定量的时间取 出样测定亚甲基蓝浓度，结果见图11。在酸性pH值条件下，实施例2中合成的材料在60min内对亚甲基蓝降解率在80％左右。
实施例3
(1)将分子筛KIT与九水合硝酸铁、四水合硝酸锰溶于醇溶液中，在磁力搅拌作用下回流24h，溶液冷却后过滤烘干。其中，铁盐与锰盐摩尔浓度比：1:2，醇溶液为乙醇，磁力搅拌温度：70℃。
(2)将上述产物置于管式炉空气氛围下，200℃条件下保温5h，然后在550℃条件下保温5h。其中：管式炉中的升温速率：5℃/min。
(3)煅烧后产物在NaOH溶液中搅拌24h，以此来去除KIT-6模板剂，搅拌混合液离心水洗三次至上清液pH至中性，沉淀物冷冻干燥。其中：NaOH的摩尔浓度：2mol/L。图6为该实施例下合成的介孔铁酸锰的扫面电镜图片。图7为合成的介孔铁酸锰MnFe2O4的XPS图谱。图10为实施例3中合成的介孔类芬顿催化剂铁酸锰MnFe2O4的XRD图谱，2θ角在29.65°、34.92°、42.43°、52.61°、61.56°对应着铁酸锰的(220)，(311)，(400)，(422)，(511)，(440)晶面。图2为该实施例下合成的产物N2吸脱附曲线以及孔径分布图，BJH模型计算模型下，介孔铁酸锰的比表面积为109.99m2g，平均孔径为3.564nm。图8、图9分别合成的介孔铁酸锰的Mn 2p和Fe 2p电子结合能谱图，Mn 2p图谱中640.5eV处和652.5eV处的两个峰对应着Mn 2p3/2和Mn 2p1/2。Fe 2p图谱中724.6eV处和710.8eV处的两个峰对应着Fe 2p3/2和Fe 2p1/2。
表格1-实施案例3中合成的MnFe2O4的BET结果：
比表面积 109.99m2g
平均孔体积 0.209cm3/g
平均孔径 3.564nm
(4)类芬顿催化降解亚甲基蓝实验，配置20mg/L的亚甲基蓝溶液200mL于锥形瓶中，初始pH调为4，加入介孔铁酸锰0.1g。放置在25℃、转速为150rpm的摇床中吸附平衡30min，之后取出加45mmol/L的双氧水，每个定量的时间取出样测定亚甲基蓝浓度，结果见图11，从图中可知，在碱性条件下，铁酸锰能够在60min内对亚甲基蓝的降解率达到90以上。
实施例4
(1)将分子筛KIT-6与九水合硝酸铁、四水合硝酸锰溶于醇溶液中，在磁力搅拌作用下回流24h，溶液冷却后过滤烘干。其中，铁盐与锰盐摩尔浓度比：1:2，醇溶液为乙醇，磁力搅拌温度：50℃。
(2)将上述产物置于管式炉空气氛围下，150℃条件下保温5h，然后在450℃条件下保温5h。其中：管式炉中的升温速率：7℃/min。
(3)煅烧后产物在NaOH溶液中搅拌16h，以此来去除KIT-6模板剂，搅拌混合液离心水洗三次至上清液pH至中性，沉淀物冷冻干燥。其中：NaOH的摩尔浓度：1mol/L。
(4)类芬顿催化降解亚甲基蓝实验，配置20mg/L的亚甲基蓝溶液200mL于锥形瓶中，初始pH调为4，加入介孔铁酸锰0.1g。放置在25℃、转速为150rpm的摇床中吸附平衡30min，之后取出加45mmol/L的双氧水，每个定量的时间取出样测定亚甲基蓝浓度，结果见图11。在实施例4条件下合成的铁酸锰，在60min左右对亚甲基蓝的降解率达到90％左右。
实施例5
(1)将分子筛KIT-6与九水合硝酸铁、四水合硝酸锰溶于醇溶液中，在磁力搅拌作用下回流24h，溶液冷却后过滤烘干。其中，铁盐与锰盐摩尔浓度比：1:2，醇溶液为乙二醇，磁力搅拌温度：60℃。
(2)将上述产物置于管式炉空气氛围下，200℃条件下保温5h，然后在550℃条件下保温5h。其中：管式炉中的升温速率：5℃/min。
(3)煅烧后产物在NaOH溶液中搅拌24h，以此来去除KIT-6模板剂，搅拌混合液离心水洗三次至上清液pH至中性，沉淀物冷冻干燥。其中：NaOH的摩尔浓度：2mol/L。
(4)类芬顿催化降解亚甲基蓝实验，配置20mg/L的亚甲基蓝溶液200mL于锥形瓶中，初始pH调为6，加入介孔铁酸锰0.1g。放置在25℃、转速为150rpm的摇床中吸附平衡30min，之后取出加45mmol/L的双氧水，每个定量的时间取出样测定亚甲基蓝浓度，结果见图11。从图中可知，在接近中性pH值的条件下，铁酸锰能够在60min内对亚甲基蓝的降解率达到90％以上。
实施例6
(1)将分子筛KIT-6与九水合硝酸铁、四水合硝酸锰溶于醇溶液中，在磁力搅拌作用下回流24h，溶液冷却后过滤烘干。其中，铁盐与锰盐摩尔浓度比：1:2， 醇溶液为乙醇，磁力搅拌温度：60℃。
(2)将上述产物置于管式炉空气氛围下，200℃条件下保温5h，然后在550℃条件下保温5h。其中：管式炉中的升温速率：5℃/min。
(3)煅烧后产物在NaOH溶液中搅拌24h，以此来去除KIT-6模板剂，搅拌混合液离心水洗三次至上清液pH至中性，沉淀物冷冻干燥。其中：NaOH的摩尔浓度：2mol/L。
(4)类芬顿催化降解亚甲基蓝实验，配置20mg/L的亚甲基蓝溶液200mL于锥形瓶中，初始pH调为8，加入介孔铁酸锰0.1g。放置在25℃、转速为150rpm的摇床中吸附平衡30min，之后取出加45mmol/L的双氧水，每个定量的时间取出样测定亚甲基蓝浓度，结果见图11。
实施例7
(1)将分子筛KIT-6与九水合硝酸铁、四水合硝酸锰溶于醇溶液中，在磁力搅拌作用下回流24h，溶液冷却后过滤烘干。其中，铁盐与锰盐摩尔浓度比：1:2，醇溶液为乙醇，磁力搅拌温度：60℃。
(2)将上述产物置于管式炉空气氛围下，200℃条件下保温5h，然后在550℃条件下保温5h。其中：管式炉中的升温速率：5℃/min。
(3)煅烧后产物在NaOH溶液中搅拌24h，以此来去除KIT-6模板剂，搅拌混合液离心水洗三次至上清液pH至中性，沉淀物冷冻干燥。其中：NaOH的摩尔浓度：2mol/L。
(4)类芬顿催化降解亚甲基蓝实验，配置20mg/L的亚甲基蓝溶液200mL于锥形瓶中，初始pH调为10，加入介孔铁酸锰0.1g。放置在25℃、转速为150rpm的摇床中吸附平衡30min，之后取出加45mmol/L的双氧水，每个定量的时间取出样测定亚甲基蓝浓度，结果见图11。从图中可知，在碱性条件下，铁酸锰能够在60min内对亚甲基蓝的降解率达到90％以上。

Claims (8)

  1. 一种介孔铁酸锰类芬顿催化材料制备方法，其步骤为：
    (1)将分子筛KIT-6与铁盐、锰盐以摩尔浓度比为0.5-1：2比例溶于醇溶液中，在磁力搅拌作用下加热回流12～24h，溶液冷却后过滤烘干；
    (2)将上述过滤所得到的产物置于管式炉中，150-300℃条件下加热保温3-5h，然后在450-600℃条件下加热保温3-5h；
    (3)将步骤(2)煅烧后产物在NaOH溶液中搅拌12-24h，去除KIT-6模板剂，搅拌混合液，离心后水洗至上清液pH至中性，沉淀物冷冻干燥。
  2. 根据所述权利要求1所述的介孔铁酸锰类芬顿催化材料制备方法，其特征在于，所述步骤(1)中的醇溶液为甲醇、乙醇或乙二醇，磁力搅拌作用下加热温度为50～80℃。
  3. 根据所述权利要求1所述的介孔铁酸锰类芬顿催化材料制备方法，其特征在于，所述步骤(2)中管式炉中的升温速率为5～10℃/min。
  4. 根据所述权利要求1所述的介孔铁酸锰类芬顿催化材料制备方法，其特征在于，所述步骤(3)中NaOH的摩尔浓度为1～3mol/L。
  5. 根据所述权利要求1所述的介孔铁酸锰类芬顿催化材料制备方法，其特征在于，所述步骤(1)中的铁盐为九水合硝酸铁或者六水合氯化铁、锰盐为四水合硝酸锰或者四水合氯化锰。
  6. 根据所述权利要求1-5所述的方法制备介孔铁酸锰类芬顿催化材料，其特征在于，其由MnFe2O4金属氧化物构成，表面形态为介孔结构。
  7. 根据所述权利要求6所述的介孔铁酸锰类芬顿催化材料，其特征在于，比表面积为109.99m2g，平均孔径为3.564nm，平均孔体积0.209cm3/g。
  8. 根据所述权利要求6所述的介孔铁酸锰类芬顿催化材料与过氧化氢构成类芬顿体系用于氧化废水处理。
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