CN114247477A - Fenton-like reaction catalyst and preparation method and application thereof - Google Patents
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- C02F1/00—Treatment of water, waste water, or sewage
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- C02F1/722—Oxidation by peroxides
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Abstract
The invention discloses a Fenton-like reaction catalyst, and a preparation method and application thereof, and belongs to the technical field of environmental protection. The method comprises the steps of firstly synthesizing a metal framework organic compound MIL-101(Fe) with the advantages of large specific surface area, easy functionalized surface structure, stable chemical property and the like as a carrier material, and then adding ferrous ions and a reducing agent to form MIL-101(Fe) and high-reactivity nano zero-valent iron (Fe)0) Bound Fe0The catalyst prepared by the method has good dispersibility, high activity and easy recycling, can realize the degradation of organic arsenic in arsenic-containing wastewater and the synchronous immobilization of arsenate, and has good application prospect in the pollution treatment of arsenic-containing wastewater.
Description
Technical Field
The invention belongs to the technical field of environmental protection, and particularly relates to a Fenton-like reaction catalyst, and a preparation method and application thereof.
Background
Arsenic pollution is an environmental problem which is more and more concerned by human beings, arsenic belongs to class A carcinogenic chemical substances, and various cancers, muscle atrophy and the like can be caused by long-term intake of drinking water containing arsenic. Aromatic organic arsenics, such as 4-aminophenylarsonic Acid (p-Arsanilic Acid, p-ASA) and 4-hydroxy-3-nitrophenylarsonic Acid (Roxarsone, ROX), are widely used as feed additives for broiler chickens to increase feed utilization, increase meat production, control parasite growth and improve animal appearance.
The organic arsenic hardly participates in metabolism conversion in livestock, and the arsenic content in the livestock manure is up to more than 40 mg/kg. The use of poultry waste as an organic fertilizer converts arsenic pollution from point source pollution to non-point source pollution and increases the risk of organic pollution to soil and groundwater. Organic arsenic is highly mobile and water soluble. Studies have shown that organic arsenic compounds can release dimethyl arsenate (DMA), monomethyl arsenate (MMA), or the more toxic inorganic arsenic compounds arsenate (as (v)) and arsenite (as (iii)) through bioconversion, photodegradation and birnessite oxidation. Although the organic arsenic feed additives are relatively low in toxicity, their risk to the environment increases significantly after degradation. Organic arsenic and its degradation products coexist in the environment and permeate into groundwater or accumulate in soil and plants. The investigation shows that the content of inorganic arsenic compounds in the water around the pig farm using the feed containing the organic arsenic is obviously higher than the maximum value allowed by the state. ROX was banned from the european union and the us market since 1999 and 2013, respectively. However, these feed additives are still sold in many developing countries, including china and india. Rocarsone as a feed additive, although it is inherently less toxic to animals, it can be metabolized by environmental microorganisms as animal waste enters the natural environment, producing inorganic arsenic compounds that are more toxic and more mobile, and other forms of organic arsenic compounds, which can adversely affect the environment. Therefore, there is a need to study the migration of organic arsenic in the environment and the transformation rules of different forms and the efficient removal mode thereof.
The removal of organic arsenic compounds from aqueous solutions has been investigated by chemical oxidation and adsorption. It was observed that p-ASA and ROX can achieve relatively fast degradation in photocatalytic, hydrothermal and photo-oxidative reactions. The organic arsenic compounds are always oxidized to As (III) and As (V) during the reaction, while the released reaction products As (III) and As (V) are not yet further removed. There have also been studies on the removal of p-ASA and ROX from aqueous solutions by direct adsorption, but with much lower adsorption strength than As (V).
Disclosure of Invention
1. Problems to be solved
Aiming at the problems that organic arsenic is difficult to degrade, degradation products arsenate need to be treated for the second time and the like in the prior art, the invention provides a Fenton-like reaction catalyst and a preparation method and application thereof. The method comprises the steps of firstly synthesizing a metal framework organic compound MIL-101(Fe) with the advantages of large specific surface area, easy functionalized surface structure, stable chemical property and the like as a carrier material, and then adding ferrous ions and a reducing agent to form MIL-101(Fe) and high-reactivity nano zero-valent iron (Fe)0) Bound Fe0The @ MIL-101(Fe) composite material provides a Fenton-like catalyst which is simple to synthesize, high in catalytic activity and easy to recycle, and the catalyst can be suitable for synchronously immobilizing organic arsenic and arsenate in degradation wastewater.
2. Technical scheme
In order to solve the problems, the technical scheme adopted by the invention is as follows:
the preparation method of the Fenton-like reaction catalyst comprises the following steps of:
s10, ultrasonically dissolving terephthalic acid and ferric trichloride hexahydrate in N, N-dimethylformamide, transferring the N, N-dimethylformamide into a high-pressure reaction kettle, heating the N, N-dimethylformamide at 100-120 ℃ for 15-25 hours, centrifugally recovering tawny solids, washing and drying to obtain MIL-101;
s20, dispersing the MIL-101 obtained in the step S10 in an organic solvent, adding an iron salt solution, stirring to generate a precipitate, and separating and drying the precipitate;
s30, re-dispersing the dried precipitate in an organic solvent, adding a reducing agent, stirring, separating and drying to obtainFe0@ MIL-101(Fe) composite catalyst.
Preferably, in step S20, the ferric salt solution is Fe2+And (3) solution.
Preferably, in step S20, the volume ratio between the ferric salt solution and the organic solvent is 1: (30-60).
Preferably, in step S30, the reducing agent is sodium borohydride.
Preferably, in step S30, the molar ratio between the ferric salt solution and the reducing agent is 1: (10-20).
Preferably, in step S20, the ferric salt solution is dropwise added within 25 to 35 minutes, and stirring is continuously performed for 18 to 24 hours;
preferably, in step S30, the reducing agent is dropwise added within 25-35 minutes, and stirring is continued for 1-1.5 hours.
The Fenton-like reaction catalyst comprises a metal organic framework material and an active metal, wherein the metal organic framework material is MIL-101, and the active metal is zero-valent iron.
The invention relates to application of a Fenton-like reaction catalyst in treating arsenic-containing wastewater, wherein the Fenton-like reaction catalyst is Fe prepared by the preparation method of the Fenton-like reaction catalyst0@ MIL-101(Fe) composite catalyst, or one of the above-mentioned Fenton-like reaction catalysts.
The application of the Fenton-like reaction catalyst in treating the arsenic-containing wastewater comprises the steps of adding the catalyst into the arsenic-containing wastewater, then adding an oxidant hydrogen peroxide, stirring for reaction, and synchronously removing organic arsenic and inorganic arsenic in the wastewater.
Preferably, the mass volume ratio between the catalyst and the arsenic-containing wastewater is 50 mg: 400mL, the concentration ratio between the catalyst and the hydrogen peroxide is 0.125 g/L: 0.5 mmol/L.
3. Advantageous effects
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention relates to a preparation method of a Fenton-like reaction catalyst,synthesizes metal frame organic compounds (MOFs) MIL-101(Fe) with the advantages of larger specific surface area, easy functionalized surface structure, stable chemical properties and the like and nano zero-valent iron (Fe) with high reaction activity0) Combined composite materials, Fe0The @ MIL-101(Fe) has high catalytic activity on organic arsenic and high adsorption capacity on arsenate, can be effectively applied to Fenton-like reaction for degrading organic arsenic-containing wastewater and synchronously immobilizing arsenate, basically realizes complete removal of arsenic in wastewater, and cannot generate secondary pollution;
(2) the Fenton-like reaction catalyst has the advantages of wide and easily available raw materials, low cost and magnetism, can be used for directly and magnetically separating inorganic arsenic adsorbed materials from wastewater, can be reused by alkali washing, and is low in recycling cost;
(3) the application of the Fenton-like reaction catalyst in treating arsenic-containing wastewater is to add Fe into the solution0The method has the advantages that the reaction condition is mild, the process flow is simple to operate, the catalyst preparation raw materials are easy to obtain, the solid phase catalyst after reaction can be quickly separated through magnetism, and the method has a good application prospect in the field of arsenic-containing wastewater pollution treatment.
Drawings
FIG. 1 is a schematic diagram of a synthetic route of a Fenton-like reaction catalyst according to the present invention;
FIG. 2 is a scanning electron microscope (TEM) photograph of a Fenton-like reaction catalyst according to the present invention;
FIG. 3 shows a Fenton-like reaction catalyst Fe according to the present invention0Graph of the degradation rate of @ MIL-101(Fe) for Roxarsone (ROX), arsonic acid (p-ASA) and dimethyl arsenic acid (DMA).
Detailed Description
The invention is further described with reference to specific examples.
As shown in fig. 1, the preparation method of a fenton-like reaction catalyst of the present invention comprises the following specific steps:
s10, 1: 2, 2.48mmol of terephthalic acid (H)2BDC) and 4.9mmol FeCl3·6H2Dissolving O in 30mL of N, N-Dimethylformamide (DMF) by ultrasonic, transferring the mixture into a 55mL Teflon sealed high-pressure reaction kettle, and heating at 100-120 ℃ for 15-25 hours, preferably at 110 ℃ for 20 hours; obtaining a yellow brown solid by centrifugal recovery, washing the yellow brown solid with DMF for three times, and then purifying the yellow brown solid with ethanol twice at 60 ℃ for 6 hours; finally, washing with deionized water for multiple times, and grinding into powder after freeze drying to obtain MIL-101 for further experiment;
s20, taking the iron-based metal organic framework material MIL-101 obtained in the step S10 as a carrier, ultrasonically dispersing the carrier in an organic solvent (such as n-hexane), dropwise adding an iron salt solution into the mixed solution within 25-35 minutes, continuously stirring for 18-24 hours to generate a precipitate, separating the precipitate, and performing vacuum drying at 40-60 ℃ for 6-8 hours; typically, the iron salt solution added is Fe2+The volume ratio of the solution, such as ferrous sulfate solution, ferric salt solution and organic solvent is 1: (30-60).
S30, re-dispersing the dried precipitate in a fresh organic solvent (such as n-hexane), uniformly stirring, dropwise adding a reducing agent (such as sodium borohydride) within 25-35 minutes, continuously stirring for 1-1.5 hours, magnetically separating, washing with ethanol, and drying at 40-60 ℃ for 6-8 hours in vacuum to obtain Fe0@ MIL-101(Fe) composite catalyst; typically, the molar ratio between the solution of iron salt and the reducing agent added in step S20 is 1: (10-20).
The invention synthesizes metal frame organic compounds (MOFs) MIL-101(Fe) with the advantages of larger specific surface area, easy functionalized surface structure, stable chemical properties and the like and nano zero-valent iron (Fe) with high reaction activity0) The combined composite material can be used as a Fenton-like reaction catalyst and can be applied to arsenic-containing wastewater treatment.
Following the reactionProceeding with, Fe in the composite material0Fe (II) ions on the surface of @ MIL-101(Fe) can catalyze H2O2Active oxygen free radicals are generated to oxidize and degrade the organic arsenic, and the organic arsenic is continuously degraded into arsenate. The hydroxyl radical will tend to attack the sites of higher electron density in the molecular structure of organic arsenic, where As-O is an electron-rich chemical bond, so the hydroxyl radical will attack the As-O bond first, resulting in the production of O-nitrophenol and As (v). The nitro group on the benzene ring is a strong electron-withdrawing substituent group, and is easily attacked by hydroxyl free radicals to generate catechol. The catechol is further oxidized to quinone compounds or one hydroxyl group is removed to phenol, and finally ring opening reaction occurs to oxidize to some short chain carboxylic acids.
In addition, the MOFs material MIL-101(Fe) has high adsorption affinity to As (V) and large adsorption capacity, and can effectively adsorb inorganic arsenic. After the reaction is finished, the composite material can realize solid-liquid separation through magnetism, so that the degradation of organic arsenic in the arsenic-containing wastewater and the synchronous immobilization of arsenate are realized, and further the complete removal of total arsenic in the solution is realized.
Example 1
The preparation method of the fenton-like reaction catalyst of the embodiment includes the following specific steps:
s10, mixing 2.48mmol of terephthalic acid (H)2BDC) and 4.9mmol FeCl3·6H2Dissolving O in 30mL of N, N-Dimethylformamide (DMF) by ultrasonic, transferring the mixture into a 55mL Teflon sealed high-pressure reaction kettle, and heating at 110 ℃ for 20 hours; obtaining a yellow brown solid by centrifugal recovery, washing the yellow brown solid with DMF for three times, and then purifying the yellow brown solid with ethanol twice at 60 ℃ for 6 hours; finally, washing with deionized water for many times, and grinding into powder after freeze drying to obtain MIL-101;
s20, taking the iron-based metal organic framework material MIL-101 obtained in the step S10 as a carrier, ultrasonically dispersing 800mg of the iron-based metal organic framework material MIL-101 into 120ml of n-hexane, and dropwise adding 2ml of ferrous sulfate heptahydrate solution (with the concentration of 25g/l) into the mixed solution within 30 minutes, wherein the volume ratio of the ferrous sulfate solution to the n-hexane is 1: 60, stirring is continued for 24 hours to generate a precipitate, and then the precipitate is separated and dried in vacuum at 50 ℃ for 6 hours;
s30, re-dispersing the dried precipitate in fresh n-hexane, uniformly stirring, dropwise adding reducing agent sodium borohydride within 30 minutes, and continuously stirring for 1.5 hours, wherein the molar ratio of the added ferric salt solution to the sodium borohydride is 1: 10, then magnetic separation, washing with ethanol and drying under vacuum at 50 ℃ for 6 hours to obtain Fe0@ MIL-101(Fe) composite catalyst, as shown in FIG. 2.
Example 2
Examination of Fe prepared in example 10The application of the @ MIL-101(Fe) composite catalyst in Fenton-like oxidation catalysis of pollutants such as organic arsenic in arsenic-containing wastewater.
Selecting Roxarsone (ROX), arsanilic acid (p-ASA) and dimethyl arsenic acid (DMA) as target harmful organic pollutants, wherein the concentrations of the pollutants are all 20mg/L, the volume of a reaction liquid is 0.4L, and at the temperature of 25 ℃, 0.05g of Fe0@ MIL-101(Fe) catalyst (mass concentration is 0.125g/L) is added into 0.4L of reaction liquid; then, hydrogen peroxide with the molar concentration of 0.5mmol/L is added, and after the mixture is stirred for 60min by a stirrer at the stirring speed of 250-350 rpm, the degradation rates of three pollutants of Roxarsone (ROX), arsonic acid (p-ASA) and dimethyl arsenic acid (DMA) respectively reach 96.59%, 81.27% and 53.16%, the total arsenic removal rates respectively reach 95.51%, 74.13% and 51.35%, and specific results are shown in FIG. 3.
The present invention and its embodiments have been described above schematically, the description is not restrictive, the data used are only one of the embodiments of the present invention, and the actual data combination is not limited to this. Therefore, if the person skilled in the art receives the teaching, the embodiments and examples similar to the above technical solutions shall not be designed in an inventive manner without departing from the spirit of the present invention, and shall fall within the protection scope of the present invention.
Claims (10)
1. A preparation method of a Fenton-like reaction catalyst is characterized by comprising the following steps of:
s10, ultrasonically dissolving terephthalic acid and ferric trichloride hexahydrate in N, N-dimethylformamide, transferring the N, N-dimethylformamide into a high-pressure reaction kettle, heating the N, N-dimethylformamide at 100-120 ℃ for 15-25 hours, centrifugally recovering tawny solids, washing and drying to obtain MIL-101;
s20, dispersing the MIL-101 obtained in the step S10 in an organic solvent, adding an iron salt solution, stirring to generate a precipitate, and separating and drying the precipitate;
s30, re-dispersing the dried precipitate in an organic solvent, adding a reducing agent, stirring, separating and drying to obtain Fe0@ MIL-101(Fe) composite catalyst.
2. The method for preparing a Fenton-like reaction catalyst according to claim 1, wherein: in step S20, the ferric salt solution is Fe2+And (3) solution.
3. The method for preparing a Fenton-like reaction catalyst according to claim 1, wherein: in step S20, the volume ratio between the ferric salt solution and the organic solvent is 1: (30-60).
4. The method for preparing a Fenton-like reaction catalyst according to claim 1, wherein: in step S30, the reducing agent is sodium borohydride.
5. The method for preparing a Fenton-like reaction catalyst according to claim 1, wherein: in step S30, the molar ratio between the ferric salt solution and the reducing agent is 1: (10-20).
6. The method for preparing a Fenton-like reaction catalyst according to claim 1, wherein: in the step S20, dropwise adding the ferric salt solution within 25-35 minutes, and continuously stirring for 18-24 hours; or in step S30, the reducing agent is dropwise added within 25-35 minutes, and stirring is continuously carried out for 1-1.5 hours.
7. A fenton-like reaction catalyst, characterized in that: the metal-organic composite material comprises a metal-organic framework material and an active metal, wherein the metal-organic framework material is MIL-101, and the active metal is zero-valent iron.
8. The application of the Fenton-like reaction catalyst in treating the arsenic-containing wastewater is characterized in that: the Fenton-like reaction catalyst is Fe prepared by the preparation method of the Fenton-like reaction catalyst according to any one of claims 1 to 60A @ MIL-101(Fe) composite catalyst, or a fenton-like reaction catalyst according to claim 7.
9. The use of a Fenton-like reaction catalyst according to claim 8 for treating arsenic-containing wastewater, wherein: the method comprises the steps of adding the catalyst into arsenic-containing wastewater, then adding an oxidant hydrogen peroxide, stirring for reaction, and synchronously removing organic arsenic and inorganic arsenic in the wastewater.
10. The use of a Fenton-like reaction catalyst according to claim 8 for treating arsenic-containing wastewater, wherein: the mass volume ratio of the catalyst to the arsenic-containing wastewater is 50 mg: 400mL, the concentration ratio between the catalyst and the hydrogen peroxide is 0.125 g/L: 0.5 mmol/L.
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| CN115254071A (en) * | 2022-08-04 | 2022-11-01 | 华侨大学 | Magnetic metal organic framework composite material and preparation method and application thereof |
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