CN113289626B - Preparation method and application of 3D printing monolithic catalyst applied to Fenton/persulfate-like system - Google Patents

Preparation method and application of 3D printing monolithic catalyst applied to Fenton/persulfate-like system Download PDF

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CN113289626B
CN113289626B CN202110770300.8A CN202110770300A CN113289626B CN 113289626 B CN113289626 B CN 113289626B CN 202110770300 A CN202110770300 A CN 202110770300A CN 113289626 B CN113289626 B CN 113289626B
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persulfate
catalyst
fenton
nano material
printing
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CN113289626A (en
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于杨
谢宇星
黄菲
孙一斐
何志琴
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Nanjing Normal University
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Abstract

The invention discloses a preparation method and application of a 3D printing monolithic catalyst applied to a Fenton/persulfate-like system. The active metal oxide nano material is in an irregular polyhedral shape, the surface of the active metal oxide nano material is provided with a large number of gully-shaped cracks, and the surface defects effectively increase the roughness and the specific surface area of the active metal oxide nano material and provide more active components. The catalyst can rapidly and efficiently remove refractory organic matters in the wastewater. The prepared monolithic catalyst has the advantages of high catalytic activity, good stability, controllable structure, easy recovery and the like in Fenton/persulfate-like systems, and can be applied to the fields of sewage treatment and the like.

Description

Preparation method and application of 3D printing monolithic catalyst applied to Fenton/persulfate-like system
Technical Field
The invention relates to a preparation method and application of a catalyst, in particular to a preparation method and application of a 3D printing monolithic catalyst applied to a Fenton/persulfate-like system.
Background
In recent years, with the rapid development of the medical industry, the wide application of antibiotics causes a large amount of antibiotic residues to be discharged into water bodies around the world, and water environment pollution is caused. The presence of antibiotics in the environment may lead to the production of Antibiotic Resistance Genes (ARGs) and to the acquired resistance of microbial pathogens, thus leading to the production of antibiotic-resistant bacteria or multi-antibiotic-resistant bacteria, which pose a significant threat to human health and the ecosystem. In general, antibiotics are hardly metabolized by humans and animals, and thus it is extremely important to seek efficient sewage treatment technology.
Advanced oxidation technologies (AOPs) utilize technologies such as light, electricity, catalysis and the like, and catalyze to generate a large amount of strong oxidative free radicals through physical and chemical processes, so as to attack organic pollutants which are difficult to degrade in wastewater, degrade the organic macromolecular pollutants into low-toxicity or nontoxic inorganic micromolecular substances, and even mineralize the organic macromolecular pollutants completely. In recent years, new advanced oxidation technologies typified by Fenton-like oxidation technology and persulfate oxidation technology have been increasingly developed, mainly utilizing OH radicals and 5O 4 - The free radicals react directly with the contaminants to oxidize the organic contaminants to CO 2 、H 2 O and small molecular inorganic matters, and has low energy consumption and no secondary pollution. Because of strong oxidizing ability, no selectivity, economy, environmental protection and quick reactionThe Fenton-like oxidation technology and the persulfate oxidation technology have been widely applied to the wastewater treatment industry.
The activated hydrogen peroxide/persulfate process includes both homogeneous and heterogeneous reactions. For a homogeneous catalytic system, dissolved metal ions in the reaction system can freely activate hydrogen peroxide/persulfate, so mass transfer is not a major factor limiting the hydrogen peroxide/persulfate homogeneous activation process. However, homogeneous catalytic systems have significant limitations. First, metal ions are difficult to recycle in the reaction system. Second, when high-concentration antibiotic wastewater is effectively removed, the metal ion demand is greatly increased, which results in a large amount of metal ions remaining in the reaction system, resulting in secondary pollution. Thirdly, the existence form of metal ions in water is greatly influenced by pH and other coexisting substances, and precipitation phenomenon of metal ions can occur under alkaline conditions, and hydrated species can be formed under acidic conditions, so that the activation performance of metal ions is reduced.
Thus, heterogeneous activation processes of Fenton-like/persulfate systems have received great attention. In view of the above problems, it has been found that a transition metal oxide can fix metal ions without losing activity, and becomes a new generation of catalysts for efficiently activating persulfates. The heterogeneous metal oxide combines one or more metal ions, can adjust the crystal structure and morphological characteristics of the heterogeneous metal oxide and the interaction among the ions, so that the catalytic performance of the heterogeneous metal oxide is improved, and the heterogeneous metal oxide has more efficient excitation effect on hydrogen peroxide/persulfate. However, the number of times of recycling of the nano-particle catalyst is limited, the nano-particle catalyst is difficult to separate from a system, and the nano-particle catalyst is required to be separated and recovered by post-treatment means such as filtration, centrifugation, flocculation and the like, so that the application of the nano-particle catalyst is limited.
And the 3D printing technology provides a new method for preparing the catalyst. Currently, the mainstream 3D printing technology mainly includes: stereolithography rapid prototyping (SLA), selective Laser Sintering (SLS), fused Deposition (FDM), stereoinkjet printing (3 DP), and the like. The 3D Stereolithography (SLA) is the most mature and most commonly used rapid prototyping method, and the principle is that liquid photosensitive resin is used as a raw material, and ultraviolet light with specific wavelength and intensity is utilized to scan the photosensitive resin to perform crosslinking reaction and solidification, and the liquid photosensitive resin is formed by printing layer by layer from top to bottom. Compared with other 3D printing technologies, the SLA can be used for manufacturing various parts with complex shapes and fine structures, the formed part has higher structural precision and complexity, the surface is smooth, the degree of automation is high, the material utilization rate is high, and the whole manufacturing process is pollution-free.
The metal nano material is uniformly dispersed in the 3D printing raw material through the configuration of the 3D printing premix, and the SLA technology can be used for directly preparing the catalyst carrier with a complex structure by combining the design of a three-dimensional model, and the preparation of the catalyst is completed through the loading of the active components. After the catalyst is molded, the nano particles are effectively prevented from leaching and falling off in a liquid phase catalytic system, and the activity and stability of the catalyst are effectively improved in the reaction process. In addition, SLA technique can provide bigger catalyst structural design degree of freedom, directly orders the catalyst that has complicated structure, and is quick stable, integrated into one piece, need not the secondary equipment. Compared with the traditional mould processing and manufacturing mode, the fine manufacturing can be realized. Through the design of the internal channel of the 3D printing integral catalyst, the geometric structure is optimized, the geometric surface area of the whole catalyst is improved, so that the active site of the catalyst is further exposed, the contact area between the reactant and the catalyst is increased while the material transmission pressure is reduced, and the effective utilization of the catalyst is improved.
In conclusion, the 3D printing technology is utilized to prepare the integral catalyst with adjustable structure, high catalytic activity and high stability loaded by the active metal oxide, and the integral catalyst is applied to the oxidative degradation of organic wastewater by a Fenton-like/persulfate system and has better application potential in the aspect of wastewater treatment.
Disclosure of Invention
The invention aims to: the invention aims to provide an active metal oxide supported monolithic catalyst with structure controllability, high catalytic activity and high stability. And the metal type and the load are controlled to obtain the monolithic catalyst of the load metal. Under the condition of hydrogen peroxide/potassium persulfate, the catalytic efficiency is improved by controlling the reaction atmosphere, the reaction temperature, the catalyst addition amount and the catalyst structure. The high-efficiency activated hydrogen peroxide/persulfate 3D printing monolithic catalyst can efficiently and rapidly remove organic pollutants in water, and is a catalyst with excellent performance and suitable for Fenton-like/persulfate oxidation systems.
The technical scheme is as follows: the invention provides a preparation method of a 3D printing integral catalyst applied to a Fenton/persulfate-like system, which comprises the steps of adopting a chemical reduction method, taking metal salt as a precursor, preparing a transition metal nano material by reduction, and then loading the transition metal nano material on a 3D printing carrier to obtain the integral catalyst applicable to the Fenton/persulfate-like system.
Preferably, the metal salt is one or more of copper acetate, ferric chloride, cobalt chloride and cerium chloride.
Preferably, the reducing agent is one or more than two of hydrazine hydrate, sodium borohydride, sodium citrate, sodium tartrate, ascorbic acid and sodium (secondary) phosphite.
Preferably, the method comprises the following steps:
(1) Preparation of metal nano materials:
weighing soluble metal salt, putting the soluble metal salt into pure water to obtain transparent and clear metal salt solution with the concentration of 0.1-0.8M (preferably 0.2-0.5M), dripping 5-50 mL (preferably 5-20 mL) of reducing agent with the concentration of 0.1-0.8 mol/L, and stirring. Then, carrying out precipitation centrifugal separation, washing for a plurality of times by using pure water and absolute ethyl alcohol, and drying in an oven for a plurality of hours to obtain the corresponding metal nano material;
(2) The metal nanomaterial is supported on a 3D printing carrier:
mixing Ultraviolet (UV) curing resin, a surfactant and a metal nano material proportionally and uniformly stirring, controlling metal loading capacity to obtain a premix, pouring the premix into a resin tank of a three-dimensional light curing molding (SLA) 3D printer, loading an STL file with a required 3D structure into slicing software, printing according to a set model, immediately cleaning uncured resin on the surface of a finished product printed product by using ethanol and pure water, drying to constant weight, and performing high-temperature sintering treatment to obtain the 3D printing integral catalyst.
Preferably, in the step (2), the surfactant is one or more of polyoxyethylene ether and isopropanol.
Preferably, in the step (2), the premix solution comprises the following components: 70-80 wt% of UV curing resin, 0-20 wt% of surfactant and 0-10 wt% of metal nano material.
Preferably, in the step (2), the high-temperature sintering condition is: using N 2 As protective gas, roasting for 1-8 h at 200-900 ℃ and then adding N 2 Cooling to room temperature under the protection of (2) to obtain the 3D printing monolithic catalyst.
Preferably, in the step (1), the soluble metal salt is weighed and put into pure water to obtain transparent and clear metal salt solution with the concentration of 0.2-0.5M, and 5-20 mL of reducing agent with the concentration of 0.1-0.8 mol/L is dripped and stirred.
The prepared 3D printing monolithic catalyst applied to the Fenton/persulfate-like system is applied to the oxidation treatment of organic wastewater by activating hydrogen peroxide/persulfate.
Preferably, the catalyst is used for Fenton-like/persulfate treatment of organic wastewater under the following reaction conditions: atmospheric pressure, reaction atmosphere: one of air, oxygen and nitrogen, the reaction temperature is 10-80 ℃, the addition amount of hydrogen peroxide/potassium persulfate is 1-20 times of the content of ofloxacin, and the catalyst is as follows: the catalyst loading is 0.05-10%, the catalyst structure is one or more than two of solid small discs, cylinders with parallel straight channels, ordered net-shaped multi-hollow cylinders, honeycomb prisms and stirring paddles; the organic wastewater is organic wastewater which is difficult to degrade.
The beneficial effects are that:
1. the preparation method of the active metal oxide nano material is simple, the technology is mature, and the activity is high; is in an irregular polyhedron shape, and has a plurality of gully-shaped cracks on the surface. The surface defects of the metal nano material effectively increase the roughness and specific surface area of the metal nano material, and are beneficial to providing more active components and enabling the active components to be uniformly dispersed.
2. The 3D printing catalyst premix liquid can be flexibly prepared according to the types and the contents of the metal nano materials;
3. the prepared 3D printing integral catalyst belongs to a supported transition metal catalyst, active components are uniformly dispersed and stable and firm, the catalyst is easy to recycle from a solution, and secondary pollution caused by water metal residues is avoided to a certain extent;
4. the prepared 3D printing integral catalyst does not need a die, is integrally formed, does not need secondary assembly, has high structure controllability, and effectively improves the integral catalytic activity through the design of a catalyst structure;
5. the novel high-efficiency catalytic effect of the integrated catalyst for the Fenton-like/persulfate system 3D printing is tested, and the catalyst can be used for rapidly and efficiently removing organic antibiotics in wastewater under the Fenton-like/persulfate oxidation system. The monolithic catalyst has the advantages of high catalytic activity, good stability, controllable structure, easy recovery and the like in Fenton/persulfate-like system, and can be applied to the fields of sewage treatment and the like.
Drawings
FIG. 1 is Cu prepared in example 1 2 O particle scanning electron microscope images;
FIG. 2 is a catalyst prepared in example 1 and comparative example 1;
FIG. 3 is a graph of the removal rate of ofloxacin over a period of time for the catalyst prepared in example 1.
Detailed Description
Example 1:
(1) 0.1g of anhydrous copper acetate was poured into 50mL of pure water to obtain a transparent clear solution. 8.0mL of 0.15mol/L N are added dropwise 2 H 4 ·H 2 O solution and stirring. And then carrying out centrifugal separation on the precipitate, washing the precipitate with pure water and absolute ethyl alcohol for a plurality of times, and drying the precipitate in an oven for a plurality of hours to obtain the metal nano material.
(2) 80 weight percent of UV curing resin, 18 weight percent of polyoxyethylene ether and 2 weight percent of metal nano material are mixed and evenly stirred, and the loading amount of the metal nano material is controlled to be 0.2 percent. Pouring the mixture into a resin tank of an SLA 3D printer, and loading STL file of ordered network porous cylinder structure intoAnd in the slicing software, printing is carried out according to the set model. Immediately cleaning uncured resin on the surface of the finished printed matter with ethanol and pure water, naturally airing, and using N 2 As a shielding gas, after 2h of calcination at 200℃in N 2 Cooling to room temperature under the protection of (a) to obtain the 3D printing integral catalyst with the ordered reticular porous cylinder structure.
(3) The intermittent reaction conditions of the catalyst for Fenton-like oxidation treatment of organic wastewater are as follows: the method is characterized in that the method comprises the steps of normal pressure, air atmosphere, reaction temperature of 55 ℃, initial concentration of ofloxacin of 100mg/L, addition of hydrogen peroxide of 10 times of the content of ofloxacin, and removal rate of ofloxacin after 90 minutes of reaction.
Example 2:
(1) 0.1g of anhydrous ferric chloride was added to 50mL of pure water to obtain a clear solution. 8.0mL of a 0.15mol/L sodium borohydride solution was added dropwise and stirred. And then carrying out centrifugal separation on the precipitate, washing the precipitate with pure water and absolute ethyl alcohol for a plurality of times, and drying the precipitate in an oven for a plurality of hours to obtain the metal nano material.
(2) 80wt% of UV curing resin, 18wt% of isopropanol and 2wt% of metal nano material are mixed and uniformly stirred, and the loading amount of the metal nano material is controlled to be 0.2%. Pouring the mixture into a resin tank of an SLA 3D printer, loading an STL file with an ordered mesh porous cylinder structure into slicing software, and printing according to a set model. Immediately cleaning uncured resin on the surface of the finished printed matter with ethanol and pure water, naturally airing, and using N 2 As a shielding gas, after 2h of calcination at 200℃in N 2 Cooling to room temperature under the protection of (a) to obtain the 3D printing integral catalyst with the ordered reticular porous cylinder structure.
(3) The intermittent reaction conditions of the catalyst for Fenton-like oxidation treatment of organic wastewater are as follows: the reaction temperature is 55 ℃ in the atmosphere of normal pressure, the initial concentration of ofloxacin is 100mg/L, the addition amount of hydrogen peroxide is 10 times of the content of ofloxacin, and the removal rate of ofloxacin is 97.2% after 90 minutes of reaction.
Example 3:
(1) 0.1g of anhydrous cobalt chloride was poured into 40mL of pure water to obtain a clear transparent solution. 8.0mL of a 0.1mol/L sodium citrate solution was added dropwise and stirred. And then carrying out centrifugal separation on the precipitate, washing the precipitate with pure water and absolute ethyl alcohol for a plurality of times, and drying the precipitate in an oven for a plurality of hours to obtain the metal nano material.
(2) 80wt% of UV curing resin, 18wt% of isopropanol and 2wt% of metal nano material are mixed and uniformly stirred, and the loading amount of the metal nano material is controlled to be 0.2%. Pouring the mixture into a resin tank of an SLA 3D printer, loading an STL file with an ordered mesh porous cylinder structure into slicing software, and printing according to a set model. Immediately cleaning uncured resin on the surface of the finished printed matter with ethanol and pure water, naturally airing, and using N 2 As a shielding gas, after 2h of calcination at 200℃in N 2 Cooling to room temperature under the protection of (a) to obtain the 3D printing integral catalyst with the ordered reticular porous cylinder structure.
(3) The intermittent reaction conditions of the catalyst for Fenton-like oxidation treatment of organic wastewater are as follows: the reaction temperature is 55 ℃ in the atmosphere of normal pressure, the initial concentration of ofloxacin is 100mg/L, the addition amount of hydrogen peroxide is 10 times of the content of ofloxacin, and the removal rate of ofloxacin is 95.1% after 90 minutes of reaction.
Example 4:
(1) 0.1g of anhydrous cerium chloride was put into 50mL of pure water to obtain a transparent clear solution. 8.0mL of a 0.15mol/L sodium citrate solution was added dropwise and stirred. And then carrying out centrifugal separation on the precipitate, washing the precipitate with pure water and absolute ethyl alcohol for a plurality of times, and drying the precipitate in an oven for a plurality of hours to obtain the metal nano material.
(2) 80 weight percent of UV curing resin, 18 weight percent of polyoxyethylene ether and 2 weight percent of metal nano material are mixed and evenly stirred, and the loading amount of the metal nano material is controlled to be 0.2 percent. Pouring the mixture into a resin tank of an SLA 3D printer, loading an STL file with an ordered mesh porous cylinder structure into slicing software, and printing according to a set model. Immediately cleaning uncured resin on the surface of the finished printed matter with ethanol and pure water, naturally airing, and using N 2 As a shielding gas, after 2h of calcination at 200℃in N 2 Cooling to room temperature under the protection of (2) to obtain ordered networkPorous cylinder structure 3D printed monolithic catalyst.
(3) The intermittent reaction conditions of the catalyst for Fenton-like oxidation treatment of organic wastewater are as follows: the reaction temperature is 55 ℃ in the atmosphere of normal pressure, the initial concentration of ofloxacin is 100mg/L, the addition amount of hydrogen peroxide is 10 times of the content of ofloxacin, and the removal rate of ofloxacin is 94.2% after 90min of reaction.
Example 5:
(1) 0.1g of anhydrous copper acetate was poured into 50mL of pure water to obtain a transparent clear solution. 8.0mL of a 0.15mol/L sodium tartrate solution was added dropwise and stirred. And then carrying out centrifugal separation on the precipitate, washing the precipitate with pure water and absolute ethyl alcohol for a plurality of times, and drying the precipitate in an oven for a plurality of hours to obtain the metal nano material.
(2) 80 weight percent of UV curing resin, 18 weight percent of polyoxyethylene ether and 2 weight percent of metal nano material are mixed and evenly stirred, and the loading amount of the metal nano material is controlled to be 0.2 percent. Pouring the mixture into a resin tank of an SLA 3D printer, loading an STL file with an ordered mesh porous cylinder structure into slicing software, and printing according to a set model. Immediately cleaning uncured resin on the surface of the finished printed matter with ethanol and pure water, naturally airing, and using N 2 As a shielding gas, after 2h of calcination at 200℃in N 2 Cooling to room temperature under the protection of (a) to obtain the 3D printing integral catalyst with the ordered reticular porous cylinder structure.
(3) The intermittent reaction conditions of the catalyst for the persulfate oxidation treatment of the organic wastewater are as follows: the normal pressure and the air atmosphere are adopted, the reaction temperature is 55 ℃, the initial concentration of ofloxacin is 100mg/L, the adding amount of potassium persulfate is 10 times of the content of ofloxacin, and the removal rate of ofloxacin is 93.2% after 90 minutes of reaction.
Example 6:
(1) 0.1g of anhydrous copper acetate was poured into 50mL of pure water to obtain a transparent clear solution. 8.0mL of a 0.15mol/L ascorbic acid solution was added dropwise and stirred. And then carrying out centrifugal separation on the precipitate, washing the precipitate with pure water and absolute ethyl alcohol for a plurality of times, and drying the precipitate in an oven for a plurality of hours to obtain the metal nano material.
(2) 80wt% of UV curing resin and polyoxyethylene ether18wt% and 2wt% of metal nano material, and uniformly mixing and stirring, wherein the load of the metal nano material is controlled to be 0.2%. Pouring the mixture into a resin tank of an SLA 3D printer, loading an STL file with an ordered mesh porous cylinder structure into slicing software, and printing according to a set model. Immediately cleaning uncured resin on the surface of the finished printed matter with ethanol and pure water, naturally airing, and using N 2 As a shielding gas, after 2h of calcination at 200℃in N 2 Cooling to room temperature under the protection of (a) to obtain the 3D printing integral catalyst with the ordered reticular porous cylinder structure.
(3) The intermittent reaction conditions of the catalyst for the persulfate oxidation treatment of the organic wastewater are as follows: the normal pressure and the air atmosphere are adopted, the reaction temperature is 55 ℃, the initial concentration of ofloxacin is 100mg/L, the adding amount of potassium persulfate is 10 times of the content of ofloxacin, and the removal rate of ofloxacin is 92.7% after 90 minutes of reaction.
Example 7:
(1) 0.1g of anhydrous copper acetate was poured into 50mL of pure water to obtain a transparent clear solution. 8.0mL of a 0.15mol/L sodium hypophosphite solution was added dropwise and stirred. And then carrying out centrifugal separation on the precipitate, washing the precipitate with pure water and absolute ethyl alcohol for a plurality of times, and drying the precipitate in an oven for a plurality of hours to obtain the metal nano material.
(2) 80 weight percent of UV curing resin, 18 weight percent of polyoxyethylene ether and 2 weight percent of metal nano material are mixed and evenly stirred, and the loading amount of the metal nano material is controlled to be 0.2 percent. Pouring the mixture into a resin tank of an SLA 3D printer, loading an STL file with an ordered mesh porous cylinder structure into slicing software, and printing according to a set model. Immediately cleaning uncured resin on the surface of the finished printed matter with ethanol and pure water, naturally airing, and using N 2 As a shielding gas, after 2h of calcination at 200℃in N 2 Cooling to room temperature under the protection of (a) to obtain the 3D printing integral catalyst with the ordered reticular porous cylinder structure.
(3) The intermittent reaction conditions of the catalyst for the persulfate oxidation treatment of the organic wastewater are as follows: the normal pressure and the air atmosphere are adopted, the reaction temperature is 55 ℃, the initial concentration of ofloxacin is 100mg/L, the adding amount of potassium persulfate is 10 times of the content of ofloxacin, and the removal rate of ofloxacin is 92.5% after 90 minutes of reaction.
Example 8:
(1) 0.1g of anhydrous copper acetate was poured into 50mL of pure water to obtain a transparent clear solution. 8.0mL of a 0.15mol/L sodium phosphite solution was added dropwise thereto and stirred. And then carrying out centrifugal separation on the precipitate, washing the precipitate with pure water and absolute ethyl alcohol for a plurality of times, and drying the precipitate in an oven for a plurality of hours to obtain the metal nano material.
(2) 80 weight percent of UV curing resin, 18 weight percent of polyoxyethylene ether and 2 weight percent of metal nano material are mixed and evenly stirred, and the loading amount of the metal nano material is controlled to be 0.2 percent. Pouring the mixture into a resin tank of an SLA 3D printer, loading an STL file with an ordered mesh porous cylinder structure into slicing software, and printing according to a set model. Immediately cleaning uncured resin on the surface of the finished printed matter with ethanol and pure water, naturally airing, and using N 2 As a shielding gas, after 2h of calcination at 200℃in N 2 Cooling to room temperature under the protection of (a) to obtain the 3D printing integral catalyst with the ordered reticular porous cylinder structure.
(3) The intermittent reaction conditions of the catalyst for the persulfate oxidation treatment of the organic wastewater are as follows: the normal pressure and the air atmosphere are adopted, the reaction temperature is 55 ℃, the initial concentration of ofloxacin is 100mg/L, the adding amount of potassium persulfate is 10 times of the content of ofloxacin, and the removal rate of ofloxacin is 90.6% after the reaction is carried out for 90 min.
Comparative example 1:
(1) 0.1g of anhydrous copper acetate was poured into 50mL of pure water to obtain a transparent clear solution. 8.0mL of 0.15mol/LN was added dropwise 2 H 4 ·H 2 O solution and stirring. And then carrying out centrifugal separation on the precipitate, washing the precipitate with pure water and absolute ethyl alcohol for a plurality of times, and drying the precipitate in an oven for a plurality of hours to obtain the metal nano material.
(2) 80wt% of UV curing resin, 18wt% of isopropanol and 2wt% of metal nano material are mixed and uniformly stirred, and the loading amount of the metal nano material is controlled to be 0.2%. Pouring the mixture into a resin tank of an SLA 3D printer, loading an STL file with a solid small disc structure into slicing software, and settingIs printed on the model of (c). Immediately cleaning uncured resin on the surface of the finished printed matter with ethanol and pure water, naturally airing, and using N 2 As a shielding gas, after 2h of calcination at 200℃in N 2 Cooling to room temperature under the protection of the catalyst to obtain the 3D printing integral catalyst with the solid small disc structure.
(3) The intermittent reaction conditions of the catalyst for Fenton-like oxidation treatment of organic wastewater are as follows: the normal pressure and the air atmosphere are adopted, the reaction temperature is 55 ℃, the initial concentration of ofloxacin is 100mg/L, the adding amount of potassium persulfate is 10 times of the content of ofloxacin, and the removal rate of ofloxacin is 62.9% after 90 minutes of reaction.
Comparative example 2:
(1) 0.1g of anhydrous ferric chloride was added to 50mL of pure water to obtain a clear solution. 8.0mL of a 0.15mol/L sodium borohydride solution was added dropwise and stirred. And then carrying out centrifugal separation on the precipitate, washing the precipitate with pure water and absolute ethyl alcohol for a plurality of times, and drying the precipitate in an oven for a plurality of hours to obtain the metal nano material.
(2) 80wt% of UV curing resin, 18wt% of isopropanol and 2wt% of metal nano material are mixed and uniformly stirred, and the loading amount of the metal nano material is controlled to be 0.2%. Pouring the mixture into a resin tank of an SLA 3D printer, loading an STL file with a solid small disc structure into slicing software, and printing according to a set model. Immediately cleaning uncured resin on the surface of the finished printed matter with ethanol and pure water, naturally airing, and using N 2 As a shielding gas, after 2h of calcination at 200℃in N 2 Cooling to room temperature under the protection of the catalyst to obtain the 3D printing integral catalyst with the solid small disc structure.
(3) The intermittent reaction conditions of the catalyst for Fenton-like oxidation treatment of organic wastewater are as follows: the reaction temperature is 55 ℃ in the atmosphere of normal pressure, the initial concentration of ofloxacin is 100mg/L, the addition amount of hydrogen peroxide is 10 times of the content of ofloxacin, and the removal rate of ofloxacin is 60.4% after 90 minutes of reaction.
Comparative example 3:
(1) 0.1g of anhydrous cobalt chloride was poured into 40mL of pure water to obtain a clear transparent solution. 8.0mL of a 0.1mol/L sodium citrate solution was added dropwise and stirred. And then carrying out centrifugal separation on the precipitate, washing the precipitate with pure water and absolute ethyl alcohol for a plurality of times, and drying the precipitate in an oven for a plurality of hours to obtain the metal nano material.
(2) 80wt% of UV curing resin, 18wt% of isopropanol and 2wt% of metal nano material are mixed and uniformly stirred, and the loading amount of the metal nano material is controlled to be 0.2%. Pouring the mixture into a resin tank of an SLA 3D printer, loading an STL file with a solid small disc structure into slicing software, and printing according to a set model. Immediately cleaning uncured resin on the surface of the finished printed matter with ethanol and pure water, naturally airing, and using N 2 As a shielding gas, after 2h of calcination at 200℃in N 2 Cooling to room temperature under the protection of the catalyst to obtain the 3D printing integral catalyst with the solid small disc structure.
(3) The intermittent reaction conditions of the catalyst for Fenton-like oxidation treatment of organic wastewater are as follows: atmospheric pressure, air atmosphere, reaction temperature of 55 ℃, initial concentration of ofloxacin of 100mg/L, addition of hydrogen peroxide of 10 times of ofloxacin content, and removal rate of ofloxacin after 90min reaction.
Comparative example 4:
(1) 0.1g of anhydrous cerium chloride was put into 50mL of pure water to obtain a transparent clear solution. 8.0mL of a 0.15mol/L sodium citrate solution was added dropwise and stirred. And then carrying out centrifugal separation on the precipitate, washing the precipitate with pure water and absolute ethyl alcohol for a plurality of times, and drying the precipitate in an oven for a plurality of hours to obtain the metal nano material.
(2) 80 weight percent of UV curing resin, 18 weight percent of polyoxyethylene ether and 2 weight percent of metal nano material are mixed and evenly stirred, and the loading amount of the metal nano material is controlled to be 0.2 percent. Pouring the mixture into a resin tank of an SLA 3D printer, loading an STL file with a solid small disc structure into slicing software, and printing according to a set model. Immediately cleaning uncured resin on the surface of the finished printed matter with ethanol and pure water, naturally airing, and using N 2 As a shielding gas, after 2h of calcination at 200℃in N 2 Cooling to room temperature under the protection of the catalyst to obtain the 3D printing integral catalyst with the solid small disc structure.
(3) The intermittent reaction conditions of the catalyst for Fenton-like oxidation treatment of organic wastewater are as follows: the reaction temperature is 55 ℃ in the atmosphere of normal pressure, the initial concentration of ofloxacin is 100mg/L, the addition amount of hydrogen peroxide is 10 times of the content of ofloxacin, and the removal rate of ofloxacin is 57.6% after 90 minutes of reaction.
Comparative example 5:
(1) 0.1g of anhydrous copper acetate was poured into 50mL of pure water to obtain a transparent clear solution. 8.0mL of a 0.15mol/L sodium tartrate solution was added dropwise and stirred. And then carrying out centrifugal separation on the precipitate, washing the precipitate with pure water and absolute ethyl alcohol for a plurality of times, and drying the precipitate in an oven for a plurality of hours to obtain the metal nano material.
(2) 80 weight percent of UV curing resin, 18 weight percent of polyoxyethylene ether and 2 weight percent of metal nano material are mixed and evenly stirred, and the loading amount of the metal nano material is controlled to be 0.2 percent. Pouring the mixture into a resin tank of an SLA 3D printer, loading an STL file with a solid small disc structure into slicing software, and printing according to a set model. Immediately cleaning uncured resin on the surface of the finished printed matter with ethanol and pure water, naturally airing, and using N 2 As a shielding gas, after 2h of calcination at 200℃in N 2 Cooling to room temperature under the protection of the catalyst to obtain the 3D printing integral catalyst with the solid small disc structure.
(3) The intermittent reaction conditions of the catalyst for the persulfate oxidation treatment of the organic wastewater are as follows: the normal pressure and the air atmosphere are adopted, the reaction temperature is 55 ℃, the initial concentration of ofloxacin is 100mg/L, the adding amount of potassium persulfate is 10 times of the content of ofloxacin, and the removal rate of ofloxacin is 55.2% after 90 minutes of reaction.
Comparative example 6:
(1) 0.1g of anhydrous copper acetate was poured into 50mL of pure water to obtain a transparent clear solution. 8.0mL of a 0.15mol/L ascorbic acid solution was added dropwise and stirred. And then carrying out centrifugal separation on the precipitate, washing the precipitate with pure water and absolute ethyl alcohol for a plurality of times, and drying the precipitate in an oven for a plurality of hours to obtain the metal nano material.
(2) 80 weight percent of UV curing resin, 18 weight percent of polyoxyethylene ether and 2 weight percent of metal nano material are mixed and evenly stirred, and the loading amount of the metal nano material is controlled to be 0.2 percent. Pouring the mixture into an SLA 3D printerAnd loading the STL file with the solid small disc structure into slicing software in a resin tank, and printing according to the set model. Immediately cleaning uncured resin on the surface of the finished printed matter with ethanol and pure water, naturally airing, and using N 2 As a shielding gas, after 2h of calcination at 200℃in N 2 Cooling to room temperature under the protection of the catalyst to obtain the 3D printing integral catalyst with the solid small disc structure.
(3) The intermittent reaction conditions of the catalyst for the persulfate oxidation treatment of the organic wastewater are as follows: the normal pressure and the air atmosphere are adopted, the reaction temperature is 55 ℃, the initial concentration of ofloxacin is 100mg/L, the adding amount of potassium persulfate is 10 times of the content of ofloxacin, and the removal rate of ofloxacin is 53.6% after 90 minutes of reaction.
Comparative example 7:
(1) 0.1g of anhydrous copper acetate was poured into 50mL of pure water to obtain a transparent clear solution. 8.0mL of a 0.15mol/L sodium hypophosphite solution was added dropwise and stirred. And then carrying out centrifugal separation on the precipitate, washing the precipitate with pure water and absolute ethyl alcohol for a plurality of times, and drying the precipitate in an oven for a plurality of hours to obtain the metal nano material.
(2) 80 weight percent of UV curing resin, 18 weight percent of polyoxyethylene ether and 2 weight percent of metal nano material are mixed and evenly stirred, and the loading amount of the metal nano material is controlled to be 0.2 percent. Pouring the mixture into a resin tank of an SLA 3D printer, loading an STL file with a solid small disc structure into slicing software, and printing according to a set model. Immediately cleaning uncured resin on the surface of the finished printed matter with ethanol and pure water, naturally airing, and using N 2 As a shielding gas, after 2h of calcination at 200℃in N 2 Cooling to room temperature under the protection of the catalyst to obtain the 3D printing integral catalyst with the solid small disc structure.
(3) The intermittent reaction conditions of the catalyst for the persulfate oxidation treatment of the organic wastewater are as follows: the normal pressure and the air atmosphere are adopted, the reaction temperature is 55 ℃, the initial concentration of ofloxacin is 100mg/L, the adding amount of potassium persulfate is 10 times of the content of ofloxacin, and the removal rate of ofloxacin is 52.5% after 90 minutes of reaction.
Comparative example 8:
(1) 0.1g of anhydrous copper acetate was poured into 50mL of pure water to obtain a transparent clear solution. 8.0mL of a 0.15mol/L sodium phosphite solution was added dropwise thereto and stirred. And then carrying out centrifugal separation on the precipitate, washing the precipitate with pure water and absolute ethyl alcohol for a plurality of times, and drying the precipitate in an oven for a plurality of hours to obtain the metal nano material.
(2) 80 weight percent of UV curing resin, 18 weight percent of polyoxyethylene ether and 2 weight percent of metal nano material are mixed and evenly stirred, and the loading amount of the metal nano material is controlled to be 0.2 percent. Pouring the mixture into a resin tank of an SLA 3D printer, loading an STL file with a solid small disc structure into slicing software, and printing according to a set model. Immediately cleaning uncured resin on the surface of the finished printed matter with ethanol and pure water, naturally airing, and using N 2 As a shielding gas, after 2h of calcination at 200℃in N 2 Cooling to room temperature under the protection of the catalyst to obtain the 3D printing integral catalyst with the solid small disc structure.
(3) The intermittent reaction conditions of the catalyst for the persulfate oxidation treatment of the organic wastewater are as follows: the normal pressure and the air atmosphere are adopted, the reaction temperature is 55 ℃, the initial concentration of ofloxacin is 100mg/L, the adding amount of potassium persulfate is 10 times of the content of ofloxacin, and the removal rate of ofloxacin is 50.6% after 90 minutes of reaction.

Claims (9)

1. The preparation method of the 3D printing monolithic catalyst applied to the Fenton/persulfate-like system is characterized by comprising the following steps of: firstly, adopting a chemical reduction method, taking metal salt as a precursor, reducing and preparing a transition metal nano material, and then loading the transition metal nano material on a 3D printing carrier to obtain the integral catalyst applicable to a Fenton/persulfate-like system, wherein the preparation method comprises the following specific steps of:
(1) Preparation of metal nano materials:
weighing soluble metal salt, putting the soluble metal salt into pure water to obtain transparent and clear metal salt solution with the concentration of 0.1-0.8M, dripping 5-50 mL of reducing agent with the concentration of 0.1-0.8 mol/L into the solution, stirring the solution, precipitating and centrifugally separating the solution, washing the solution with pure water and absolute ethyl alcohol for a plurality of times, and drying the solution in an oven for a plurality of hours to obtain the corresponding metal nano material;
(2) The metal nanomaterial is supported on a 3D printing carrier:
mixing ultraviolet light curing resin, a surfactant and a metal nano material proportionally and uniformly stirring, controlling metal loading capacity to obtain a premix, pouring the premix into a resin tank of a three-dimensional light curing molding 3D printer, loading an STL file with a required 3D structure into slicing software, printing according to a set model, immediately cleaning uncured resin on the surface of a finished product printed product by using ethanol and pure water, drying to constant weight, and performing high-temperature sintering treatment to obtain the 3D printing integral catalyst.
2. The method for preparing the 3D printed monolithic catalyst applied to the Fenton/persulfate-like system according to claim 1, wherein the method comprises the following steps of: the metal salt is one or more than two of copper acetate, ferric chloride, cobalt chloride and cerium chloride.
3. The method for preparing the 3D printed monolithic catalyst applied to the Fenton/persulfate-like system according to claim 1, wherein the method comprises the following steps of: the reducing agent is one or more than two of hydrazine hydrate, sodium borohydride, sodium citrate, sodium tartrate, ascorbic acid, sodium phosphite and sodium hypophosphite.
4. The method for preparing the 3D printed monolithic catalyst applied to the Fenton/persulfate-like system according to claim 1, wherein the method comprises the following steps of: in the step (2), the surfactant is one or more than two of polyoxyethylene ether and isopropanol.
5. The method for preparing the 3D printed monolithic catalyst applied to the Fenton/persulfate-like system according to claim 1, wherein the method comprises the following steps of: in the step (2), the premix comprises the following components: 70-80 wt% of UV curing resin, 0-20 wt% of surfactant and 0-10 wt% of metal nano material.
6. The 3D printed monolithic catalyst for Fenton/persulfate-like systems according to claim 1The preparation method of the chemical agent is characterized by comprising the following steps: in the step (2), the high-temperature sintering conditions are as follows: using N 2 As a protective gas, 200 to 900 o Roasting under C1-8 h, then adding N 2 Cooling to room temperature under the protection of (2) to obtain the 3D printing monolithic catalyst.
7. The method for preparing the 3D printed monolithic catalyst applied to the Fenton/persulfate-like system according to claim 1, wherein the method comprises the following steps of: and (3) weighing soluble metal salt in the step (1), putting the soluble metal salt into pure water to obtain transparent and clear metal salt solution, dripping 5-20 mL reducing agent with the concentration of 0.1-0.8 mol/L into the solution, and stirring the solution.
8. Use of the 3D printed monolithic catalyst for Fenton/persulfate-like systems prepared by the process of any one of claims 1 to 7 for the activation of hydrogen peroxide/persulfate oxidation treatment of organic wastewater.
9. The use according to claim 8, characterized in that: the reaction conditions for Fenton-like/persulfate-like treatment of organic wastewater by the catalyst are as follows: atmospheric pressure, reaction atmosphere: one of air, oxygen and nitrogen, the reaction temperature is 10-80 o And C, the addition amount of hydrogen peroxide/potassium persulfate is 1-20 times of the content of ofloxacin, and the catalyst is as follows: the catalyst loading is 0.05-10%, the catalyst structure is one or more than two of a cylinder containing parallel straight channels, an ordered net-shaped multi-hollow cylinder, a honeycomb prism and a stirring paddle; the organic wastewater is organic wastewater which is difficult to degrade.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106076400A (en) * 2016-06-16 2016-11-09 吴子豹 A kind of adsorption potential and catalytic active site dislocation type catalyst and preparation method thereof
CN108057437A (en) * 2017-11-28 2018-05-22 辽宁科技大学 Active ingredient passes through SCR catalyst of 3D printing straight forming and preparation method thereof
CN110479331A (en) * 2019-08-05 2019-11-22 江苏大学 A kind of preparation method and its usage of 3D printing monolithic catalyst
CN111229231A (en) * 2020-03-11 2020-06-05 中国华能集团清洁能源技术研究院有限公司 3D printing monolithic alloy catalyst and preparation method and application thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106076400A (en) * 2016-06-16 2016-11-09 吴子豹 A kind of adsorption potential and catalytic active site dislocation type catalyst and preparation method thereof
CN108057437A (en) * 2017-11-28 2018-05-22 辽宁科技大学 Active ingredient passes through SCR catalyst of 3D printing straight forming and preparation method thereof
CN110479331A (en) * 2019-08-05 2019-11-22 江苏大学 A kind of preparation method and its usage of 3D printing monolithic catalyst
CN111229231A (en) * 2020-03-11 2020-06-05 中国华能集团清洁能源技术研究院有限公司 3D printing monolithic alloy catalyst and preparation method and application thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
"3D打印多级孔整体型催化剂的理性设计及其甲烷化研究";陈思静;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;第23页 *
吴功德著.1.《环境催化基础及应用》.2019, *

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