CN115634692B - Fenton-like catalyst with double reaction centers and preparation method and application thereof - Google Patents
Fenton-like catalyst with double reaction centers and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a double-reaction center Fenton-like catalyst, a preparation method and application thereof, wherein the preparation method comprises the following steps: step S1, dissolving an organic complexing agent in water, adding a metal precursor, and uniformly mixing to obtain a blending solution; wherein the metal precursor comprises aluminum isopropoxide and inorganic metal salts, and the inorganic metal salts comprise Fe salts and Co salts; s2, regulating the pH value of the blending solution to be less than 7, and stirring to a gel state to obtain a gel state blend; and step S3, carrying out vacuum drying on the gel state blend, and carrying out high-temperature treatment at the temperature of not lower than 500 ℃ to obtain the double-reaction center Fenton-like catalyst.
Description
Technical Field
The invention belongs to the technical field of water treatment, and particularly relates to a double-reaction-center Fenton-like catalyst, and a preparation method and application thereof.
Background
In industrial wastewater of mining and metallurgy, electroplating, printing and dyeing, papermaking, electronic manufacturing and the like, complexation effect generated by coexistence of heavy metals and organic matters has a remarkable influence on conversion paths and removal mechanisms of various pollutants, so that effective removal of the pollutants is difficult to achieve through traditional chemical precipitation, adsorption, membrane separation and other means. The Fenton advanced oxidation technology is based on the fact that coordination bonds in a complex molecular structure are destroyed, degradation mineralization of an organic ligand and free release of heavy metals are synchronously realized, and the method is a common strategy for treating the current heavy metal-organic complex.
To fundamentally solve the inherent defects of homogeneous Fenton oxidation reaction, such as narrow pH response range, difficult recovery of active components and H 2 O 2 Low utilization rate, and the like, and a plurality of scholars try to construct a heterogeneous high-efficiency Fenton-like catalytic system with an electron dense region and an electron scarcity region from an electron polarization theory. For example, researchers have used Ti, cu and Al trimetallics to dope taraxacum-like SiO 2 The fiber ball synthesizes a double-reaction center Fenton-like catalyst d-TiCuAl-SiO 2 Ns, which can realize the oxidative degradation of bisphenol a, diphenhydramine, ciprofloxacin, phenytoin, 2-chlorophenol, 2, 4-dichlorophenoxyacetic acid and other organic matters in sewage in a wider pH range. Also, the literature discloses that Cu-Al is prepared synthetically by constructing cation-pi bond to further strengthen electron polarization distribution on the basis of metal doping 2 O 3 -g-C 3 N 4 Fenton-like catalyst, under the action of said catalyst, H 2 O 2 Can be used for degrading different organic pollutants such as bisphenol A, rhodamine B, methylene blue, 2, 4-dichlorophenoxyacetic acid, phenytoin and the like to the greatest extent. However, most of the existing studies construct a unique electron rich reaction center and a single or multiple electron deficient reaction centers around metal Cu, and catalytic degradation targets are all aromatic organic pollutants.
Theoretically, aromatic hydrocarbon pollutants have strong electron donating ability and are easy to combine with electron-deficient reaction centers, but for other types of pollutants with weak electron donating ability, the combination efficiency of the aromatic hydrocarbon pollutants and the electron-deficient reaction centers is relatively low, and if more electron-rich reaction centers are provided, the aromatic hydrocarbon pollutants are helpful to promote H 2 O 2 OH is formed, enhancing oxidative degradation of such contaminants. The OH free radical formation capacity is significantly different due to the different electron rich center conditions.Therefore, how to screen and construct a high-efficiency Fenton-like catalytic system containing a plurality of electron-rich reaction centers so as to meet the characteristic of heavy metal complex, the complex breaking and removal of pollutants still needs to be deeply explored.
Disclosure of Invention
Aiming at the technical problems, the invention discloses a double-reaction-center Fenton-like catalyst, a preparation method and application thereof, which overcomes the defects that the pH response range of the traditional homogeneous Fenton oxidation reaction is narrow, active components are difficult to recover and H is difficult to recover 2 O 2 Low utilization rate and other inherent defects.
In this regard, the invention adopts the following technical scheme:
a preparation method of a double-reaction-center Fenton-like catalyst comprises the following steps:
step S1, dissolving an organic complexing agent in water, adding a metal precursor, and uniformly mixing to obtain a blending solution; wherein the metal precursor comprises aluminum isopropoxide and inorganic metal salts, and the inorganic metal salts comprise Fe salts and Co salts;
s2, regulating the pH value of the blending solution to be less than 7, and stirring to a gel state to obtain a gel state blend;
and step S3, carrying out vacuum drying on the gel state blend, and carrying out high-temperature treatment at the temperature of not lower than 500 ℃ to obtain the double-reaction center Fenton-like catalyst.
In step S1, aluminum isopropoxide is a synthetic metal oxide Al 2 O 3 The main raw materials of (a) are Fe salt and Co salt which are auxiliary raw materials for realizing crystal phase doping. Further, the Fe salt is FeCl 3 The Co salt is CoCl 2 。
By adopting the technical scheme, aluminum isopropoxide, inorganic ferric salt, cobalt salt and the like are used as metal precursors, and a novel efficient Fenton-like catalytic system with Fe and Co double-rich electron reaction centers is constructed through temperature rising induction and high-temperature heat treatment processes, so that the catalyst can overcome the defects of narrow pH response range, difficult recovery of active components and H in the traditional homogeneous Fenton reaction 2 O 2 Low utilization rate and other inherent defects.
As a further improvement of the present invention, the organic ligand is at least one of glucose and gelatin.
As a further improvement of the invention, the gelatin is derived from pigskin, bovine bone, tanning offal or biomass waste of aquatic animals.
As a further improvement of the invention, the mass ratio of the inorganic metal salt to the aluminum isopropoxide is 1:4-14. Further, the mass ratio of the inorganic metal salt to the aluminum isopropoxide is 1:6-12.
As a further improvement of the invention, the Fe salt is FeCl 3 ·6H 2 O, the Co salt is CoCl 2 ·6H 2 And O, wherein the mass ratio of the Fe salt to the Co salt is 1:3-3:1.
As a further improvement of the invention, in the step S2, the pH value of the blending solution is regulated to 5-6, and the blending solution is stirred to gel state at 45-55 ℃. Further, the pH of the blend solution was adjusted to 5. In step S2, ammonia may be added to adjust the pH of the blend solution.
As a further improvement of the invention, in the step S3, the temperature of the high-temperature treatment is 600-800 ℃. Further preferably, the temperature of the high temperature treatment is 700 ℃.
As a further improvement of the present invention, the preparation method of the dual reaction center Fenton-like catalyst further comprises: and S4, grinding and sieving the treated product in the step S3, washing and drying to constant weight.
The invention also discloses a double-reaction-center Fenton-like catalyst, which is prepared by adopting the preparation method of the double-reaction-center Fenton-like catalyst.
The invention discloses application of a double-reaction-center Fenton-like catalyst, which is used for breaking the complex of a heavy metal-organic complex.
Specifically, the method comprises the following steps: the pH value of the wastewater containing the heavy metal-organic complex is adjusted to 3-8, the double-reaction center Fenton-like catalyst is added into the wastewater for stirring, and then H is added dropwise 2 O 2 And (3) reacting the solution for 60-120 min, and finally adding NaOH to form precipitate and removing free heavy metals.
The heavy metal-organic complex as described above is mainly a complex formed by coordination of heavy metal with an organic complex, such as Ni-ethylenediamine tetraacetic acid (EDTA), cu-ethylenediamine tetraacetic acid (EDTA), ni-Citric Acid (CA), cu-Citric Acid (CA); the electron donating ability of the complex is reduced compared to a single organic complex.
As a further improvement of the invention, the addition amount of the double-reaction center Fenton-like catalyst is 0.001-0.005 g/mL.
The invention discloses a method for breaking a complex of a heavy metal-organic complex, which comprises the following steps: the pH value of the wastewater containing the heavy metal-organic complex is adjusted to 3-8, the double-reaction center Fenton-like catalyst is added into the wastewater for stirring, and then H is added dropwise 2 O 2 And (3) reacting the solution for 60-120 min, and finally adding NaOH to form precipitate and removing free heavy metals.
Compared with the prior art, the invention has the beneficial effects that:
by adopting the technical scheme of the invention, the metal atom electronegativity difference is fully utilized, a novel efficient Fenton-like catalyst which takes Fe and Co as double electron-rich reaction centers and Al as the only electron-deficient reaction center is constructed, and the catalyst can be applied to catalytic oxidation and vein breaking treatment of heavy metal-organic complex pollutants in industrial wastewater. Unlike the traditional homogeneous Fenton oxidation reaction, the Fenton catalyst in the technical scheme of the invention can catalyze and decompose H in a relatively wide pH range 2 O 2 And with Al alone 2 O 3 Catalyst and single metal crystalline phase doped Al 2 O 3 Compared with the catalyst, the catalyst of the technical scheme of the invention can realize H 2 O 2 The oxidant is utilized efficiently, and the generation amount of hydroxyl radicals is increased by 100 percent; co-doping Al with Fe, cu 2 O 3 Compared with the catalyst, the channel breaking effect is improved by at least 20 percent.
Drawings
FIG. 1 shows example 1 and comparative example 2, comparative example 3, al 2 O 3 Heterogeneous Fenton-like catalysts (Al) 2 O 3 、Co-Al 2 O 3 、Fe-Al 2 O 3 And FeCo-Al 2 O 3 ) XPS spectrum contrast plot of (c).
FIG. 2 is a novel high efficiency Fenton-like catalyst H of example 1 2 O 2 The effect of removing heavy metal-organic complex by breaking the collaterals is shown.
FIG. 3 is a graph showing the signals of the different heterogeneous Fenton-like catalysts in example 1, comparative example 2 and comparative example 3 for generating hydroxyl radicals EPR.
Detailed Description
Preferred embodiments of the present invention are described in further detail below.
Example 1
Step S1, dissolving 3.6 g glucose (or 0.2-0.5 g gelatin) in 20 mL deionized water at 70deg.C, sequentially adding aluminum isopropoxide water 4.2g and FeCl under ultrasonic condition 3 ·6H 2 O 0.2625 g、CoCl 2 ·6H 2 O0.0875 g, ensuring no macroscopic solid particles, wherein the mass ratio of inorganic metal salt to aluminum isopropoxide is 1:12, feCl 3 ·6H 2 O and CoCl 2 ·6H 2 The mass ratio of O is 3:1.
S2, regulating the pH value of the blending solution to 5 by using ammonia water (2.5 mol/L), and stirring to a gel state at 50 ℃;
step S3, vacuum drying the gel state blend in the step S2 at 80 ℃, and placing the gel state blend in a muffle furnace to treat 6 h at a high temperature of 700 ℃;
step S4, grinding the high-temperature product in the step S3, sieving with a 100-mesh sieve, washing with deionized water, and drying to obtain the novel efficient Fenton-like catalyst FeCo-Al 2 O 3 。
The novel high-efficiency Fenton-like catalyst obtained by the preparation method mainly comprises Al, O, fe, co four elements, wherein the XPS chart is shown in figure 1, and the XPS chart comprises 50.62 wt percent, 44.95 wt percent, 3.28 wt percent and 1.15 wt percent of the XPS chart and is similar to the theoretical content value.
The novel high-efficiency Fenton-like catalyst prepared by the method is applied to the field of industrial wastewater treatment, and comprises the following specific implementation steps:
by common heavy metals-organic substances in industrial waste waterThe complex Ni-EDTA is a target pollutant, the pH value of wastewater is preset to 3-8, and a novel high-efficiency Fenton-like catalyst of 0.1 and g is added into a 50 mL target solution; under the magnetic stirring condition, 0.25-2 mL of H is continuously added dropwise 2 O 2 (30 wt%) solution; after the reaction is carried out for 60 min, 1 mol/L NaOH is added until the pH value of the solution is 11.0, and free heavy metals in the solution are removed after the solution is fully precipitated. As shown in FIG. 2, after the treatment, the Ni-EDTA decomplexing efficiency and TOC removal efficiency in the wastewater can reach 94.4% and 54.7% respectively. The catalyst performance is stable during the reaction, and the leaching amount of Fe and Co is 0-0.2 mg/L and 0.3-0.7 mg/L respectively.
Example 2
Step S1, dissolving 3.6 g glucose (or 0.2-0.5 g gelatin) in 20 mL deionized water at 70deg.C, sequentially adding aluminum isopropoxide water 4.2g and FeCl under ultrasonic condition 3 ·6H 2 O 0.175g、CoCl 2 ·6H 2 O0.525 g, ensuring no macroscopic solid particles, wherein the mass ratio of inorganic metal salt to aluminum isopropoxide is 1:6, feCl 3 ·6H 2 O and CoCl 2 ·6H 2 The mass ratio of O is 1:3.
s2, regulating the pH value of the blending solution to 5 by using ammonia water (2.5 mol/L), and stirring to a gel state at 50 ℃;
step S3, vacuum drying the gel state blend in the step S2 at 80 ℃, and placing the gel state blend in a muffle furnace to treat 6 h at a high temperature of 700 ℃;
step S4, grinding the high-temperature product in the step S3, sieving with a 100-mesh sieve, washing with deionized water, and drying to obtain the novel efficient Fenton-like catalyst FeCo-Al 2 O 3 。
The novel high-efficiency Fenton-like catalyst prepared by the method is applied to the field of industrial wastewater treatment, and comprises the following specific implementation steps:
presetting the pH value of the wastewater to 3-8 by taking common heavy metal-organic complex Ni-EDTA in industrial wastewater as target pollutant, and adding a novel high-efficiency Fenton-like catalyst of 0.1 g into a 50 mL target solution; under the magnetic stirring condition, 0.25-2 mL of H is continuously added dropwise 2 O 2 (30 wt%) solution; fully react60 After min, 1 mol/L NaOH is added until the pH value of the solution is 11.0, and free heavy metals in the solution are removed after full precipitation. After the treatment, the Ni-EDTA decomplexation efficiency and TOC removal efficiency in the wastewater can reach 91.3% and 42.4% respectively. The catalyst performance during the reaction was stable, and the elution amounts of Fe and Co were 0.83 mg/L and 0.35 mg/L, respectively.
Comparative example 1
Step S1, dissolving 3.6 g glucose (or 0.2-0.5 g gelatin) in 20 mL deionized water at 70deg.C, and sequentially adding aluminum isopropoxide 4.2g and FeCl under ultrasonic conditions 3 ·6H 2 O 0.2625g、CuCl 2 ·2H 2 O0.0875 g, ensuring no macroscopic solid particles, wherein the mass ratio of inorganic metal salt to aluminum isopropoxide is 1:12, feCl 3 ·6H 2 O and CuCl 2 ·6H 2 The mass ratio of O is 3:1.
S2, regulating the pH value of the blending solution to 5 by using ammonia water (2.5 mol/L), and stirring to a gel state at 50 ℃;
step S3, vacuum drying the gel state blend in the step S2 at 80 ℃, and placing the gel state blend in a muffle furnace to treat 6 h at a high temperature of 700 ℃;
step S4, grinding the high-temperature product in the step S3, sieving with a 100-mesh sieve, washing with deionized water, and drying to obtain the Fenton-like catalyst; the Fenton-like catalyst obtained based on the preparation method mainly comprises Al, O, fe, cu elements.
The Fenton-like catalyst prepared by the method is used for carrying out the vein breaking treatment on the heavy metal-organic complex in industrial wastewater, and the specific implementation steps comprise:
presetting the pH value of the wastewater to 3-8 by taking common heavy metal-organic complex Ni-EDTA in the industrial wastewater as target pollutant, and adding 0.1 g Fenton catalyst into 50 mL target solution; under the magnetic stirring condition, 0.25-2 mL of H is continuously added dropwise 2 O 2 (30 wt%) solution; after the reaction is carried out for 60 min, 1 mol/L NaOH is added until the pH value of the solution is 11.0, and free heavy metals in the solution are removed after the solution is fully precipitated. After the treatment, the Ni-EDTA decomplexation efficiency and TOC removal efficiency in the wastewater are 70.9% and 52.6%.
Comparative example 2
Step S1, dissolving 3.6 g glucose (or 0.2-0.5 g gelatin) in 20 mL deionized water at 70deg.C, and sequentially adding aluminum isopropoxide (4.2 g/20 mL) and FeCl under ultrasonic conditions 3 ·6H 2 O (0.35 g/15 mL) ensuring that no macroscopic solid particles are present, wherein the mass ratio of inorganic metal salt to aluminum isopropoxide is 1:12;
s2, regulating the pH value of the blending solution to 5 by using ammonia water (2.5 mol/L), and stirring to a gel state at 50 ℃;
step S3, vacuum drying the gel state blend in the step S2 at 80 ℃, and placing the gel state blend in a muffle furnace to treat 6 h at a high temperature of 700 ℃;
step S4, grinding the high-temperature product in the step S3, sieving with a 100-mesh sieve, washing with deionized water, and drying to obtain the Fenton-like catalyst Fe-Al 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the As shown in FIG. 1, the Fenton-like catalyst obtained based on the preparation method mainly comprises three elements of Al, O and Fe.
The Fenton-like catalyst prepared by the method is used for carrying out the vein breaking treatment on the heavy metal-organic complex in industrial wastewater, and the specific implementation steps comprise:
presetting the pH value of the wastewater to 3-8 by taking common heavy metal-organic complex Ni-EDTA in the industrial wastewater as target pollutant, and adding 0.1 g Fenton catalyst into 50 mL target solution; under the magnetic stirring condition, 0.25-2 mL of H is continuously added dropwise 2 O 2 (30 wt%) solution; after the reaction is carried out for 60 min, 1 mol/L NaOH is added until the pH value of the solution is 11.0, and free heavy metals in the solution are removed after the solution is fully precipitated. After the treatment, the Ni-EDTA complex breaking efficiency and TOC removal efficiency in the wastewater are only 58.9% and 52.1%, which are obviously lower than the treatment effect in the embodiment 1.
Comparative example 3
Step S1, dissolving 3.6 g glucose (or 0.2-0.5 g gelatin) in 20 mL deionized water at 70deg.C, and sequentially adding aluminum isopropoxide (4.2 g/20 mL) and CoCl under ultrasonic conditions 2 ·6H 2 O (0.35 g/15 mL), ensuring that no macroscopic solid particles, in which the mineral gold is present, are presentThe mass ratio of the sodium salt to the aluminum isopropoxide is 1:12;
s2, regulating the pH value of the blending solution to 5 by using ammonia water (2.5 mol/L), and stirring to a gel state at 50 ℃;
step S3, vacuum drying the gel state blend in the step S2 at 80 ℃, and placing the gel state blend in a muffle furnace to treat 6 h at a high temperature of 700 ℃;
step S4, grinding the high-temperature product in the step S3, sieving with a 100-mesh sieve, washing with deionized water, and drying to obtain the Fenton-like catalyst Co-Al 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the The Fenton-like catalyst obtained based on the preparation method mainly comprises three elements of Al, O and Co.
The Fenton-like catalyst prepared by the method is used for carrying out the vein breaking treatment on the heavy metal-organic complex in industrial wastewater, and the specific implementation steps comprise:
presetting the pH value of the wastewater to 3-8 by taking common heavy metal-organic complex Ni-EDTA in the industrial wastewater as target pollutant, and adding 0.1 g Fenton catalyst into 50 mL target solution; under the magnetic stirring condition, 0.25-2 mL of H is continuously added dropwise 2 O 2 (30 wt%) solution; after the reaction is carried out for 60 min, 1 mol/L NaOH is added until the pH value of the solution is 11.0, and free heavy metals in the solution are removed after the solution is fully precipitated. After the treatment, the Ni-EDTA decomplexing efficiency and TOC removal efficiency in the wastewater are only 48.4% and 44.2%, which are obviously lower than the treatment effect in the embodiment 1.
Example 1 and comparative example 2, comparative example 3 and Al 2 O 3 These several different types of heterogeneous Fenton-like catalysts are used for H 2 O 2 Comparison of the catalytic effects, a comparison of the signals of the EPR signals of the hydroxyl radicals produced by the catalysts is shown in FIG. 3, which shows that example 1 and Al alone 2 O 3 Fe-Al of comparative example 2 2 O 3 Co-Al of comparative example 3 2 O 3 Compared with a catalytic system, under the Fe and Co Co-doped catalytic system, H 2 O 2 The strength of the generated hydroxyl radical is obviously improved, and the amplification is up to 100%.
As can be seen from a comparison of the above examples and comparative examples, the crystalline phase of the metal is doped with Al compared with that of the single metal 2 O 3 Catalyst and Fe, cu co-doped Al of comparative example 1 2 O 3 Catalyst, fe, co Co-doped Al of example 1 2 O 3 The catalyst has obvious advantages.
The foregoing is a further detailed description of the invention in connection with the preferred embodiments, and it is not intended that the invention be limited to the specific embodiments described. It will be apparent to those skilled in the art that several simple deductions or substitutions may be made without departing from the spirit of the invention, and these should be considered to be within the scope of the invention.
Claims (7)
1. Use of a double-reaction-center Fenton-like catalyst, comprising: the pH value of the wastewater containing the heavy metal-organic complex is adjusted to 3-8, the double-reaction center Fenton-like catalyst is added into the wastewater for stirring, and then H is added dropwise 2 O 2 Reacting the solution for 60-120 min, and finally adding NaOH to form precipitate to remove free heavy metals;
the preparation method of the double-reaction center Fenton-like catalyst comprises the following steps:
step S1, dissolving an organic complexing agent in water, adding a metal precursor, and uniformly mixing to obtain a blending solution; wherein the metal precursor comprises aluminum isopropoxide and inorganic metal salts, and the inorganic metal salts comprise Fe salts and Co salts; the organic complexing agent is at least one of glucose and gelatin;
s2, regulating the pH value of the blending solution to be less than 7, and stirring to a gel state to obtain a gel state blend;
and step S3, carrying out vacuum drying on the gel state blend, and carrying out high-temperature treatment at the temperature of not lower than 500 ℃ to obtain the double-reaction center Fenton-like catalyst.
2. Use of a double reaction center Fenton-like catalyst according to claim 1, characterized in that: the gelatin is derived from pigskin, ox bone or leather leftovers.
3. Use of a double reaction center Fenton-like catalyst according to claim 1, characterized in that: the mass ratio of the inorganic metal salt to the aluminum isopropoxide is 1:4-14.
4. Use of a double reaction center Fenton-like catalyst according to claim 3, characterized in that: the Fe salt is FeCl 3 ·6H 2 O, the Co salt is CoCl 2 ·6H 2 And O, wherein the mass ratio of the Fe salt to the Co salt is 1:3-3:1.
5. Use of a double reaction center Fenton-like catalyst according to claim 1, characterized in that: in the step S2, the pH value of the blending solution is regulated to 5-6, and the blending solution is stirred to a gel state at 45-55 ℃;
in the step S3, the temperature of the high-temperature treatment is 600-800 ℃.
6. The use of a dual center Fenton-like catalyst according to any one of claims 1-5, further comprising: and S4, grinding and sieving the treated product in the step S3, washing and drying to constant weight.
7. Use of a double reaction center Fenton-like catalyst according to claim 1, characterized in that: the addition amount of the Fenton-like catalyst in the double reaction center is 0.001-0.005 g/mL.
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