CN113289626A - Preparation method and application of 3D printing monolithic catalyst applied to Fenton-like/persulfate system - Google Patents
Preparation method and application of 3D printing monolithic catalyst applied to Fenton-like/persulfate system Download PDFInfo
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- CN113289626A CN113289626A CN202110770300.8A CN202110770300A CN113289626A CN 113289626 A CN113289626 A CN 113289626A CN 202110770300 A CN202110770300 A CN 202110770300A CN 113289626 A CN113289626 A CN 113289626A
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- GSDSWSVVBLHKDQ-UHFFFAOYSA-N 9-fluoro-3-methyl-10-(4-methylpiperazin-1-yl)-7-oxo-2,3-dihydro-7H-[1,4]oxazino[2,3,4-ij]quinoline-6-carboxylic acid Chemical compound FC1=CC(C(C(C(O)=O)=C2)=O)=C3N2C(C)COC3=C1N1CCN(C)CC1 GSDSWSVVBLHKDQ-UHFFFAOYSA-N 0.000 claims description 51
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- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 2
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- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 2
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- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 2
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- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 2
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/069—Hybrid organic-inorganic polymers, e.g. silica derivatized with organic groups
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
- B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y80/00—Products made by additive manufacturing
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/74—Treatment of water, waste water, or sewage by oxidation with air
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/026—Fenton's reagent
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
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Abstract
The invention discloses a preparation method and application of a 3D printing monolithic catalyst applied to a Fenton-like/persulfate system. The active metal oxide nano material is in an irregular polyhedral shape, a large number of gully-shaped cracks are formed on the surface, and the roughness and the specific surface area of the active metal oxide nano material are effectively increased by surface defects, so that more active components are provided. The catalyst can quickly and efficiently remove refractory organic matters in wastewater. The prepared monolithic catalyst has the advantages of high catalytic activity, good stability, controllable structure, benefit for recovery and the like in a Fenton-like/persulfate system, and can be applied to the fields of sewage treatment and the like.
Description
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, thereby causing water environment pollution. The presence of antibiotics in the environment may lead to the production of Antibiotic Resistance Genes (ARGs) and confer resistance to microbial pathogens, leading to the production of antibiotic-resistant or multi-antibiotic resistant bacteria, constituting a significant threat to human health and ecosystem. Generally, antibiotics belong to refractory organic matters and are difficult to be metabolized by human beings and animals, so that the search for efficient sewage treatment technology is extremely important.
Advanced oxidation technologies (AOPs) utilize technologies such as light, electricity and catalysis, and generate a large amount of strong oxidative free radicals through processes such as physical chemistry and the like to attack organic pollutants which are difficult to degrade in wastewater, so that organic macromolecular pollutants are degraded into inorganic micromolecular substances with low toxicity or no toxicity, and even the inorganic micromolecular substances are finally mineralized. In recent years, new advanced oxidation technologies represented by fenton-like oxidation technology and persulfate oxidation technology have been developed, mainly using OH radicals and 5O4 -Free radicals reacting directly with the pollutants to oxidise the organic pollutants to CO2、H2O and small molecular inorganic substances, low energy consumption and no secondary pollution. Because of the advantages of strong oxidizing ability, no selectivity, economy, environmental protection, high reaction rate, simple operation and the like, the Fenton-like oxidation technology and the persulfate oxidation technology are widely applied to the wastewater treatment industry.
The activated hydrogen peroxide/persulfate process includes both homogeneous and heterogeneous reactions. For homogeneous catalysis systems, the dissolved metal ions in the reaction system can freely activate the hydrogen peroxide/persulfate, so the mass transfer effect is not a main factor limiting the homogeneous activation process of the hydrogen peroxide/persulfate. However, homogeneous catalytic systems have significant limitations. First, metal ions are difficult to recycle in the reaction system. Secondly, when the antibiotic wastewater with high concentration is effectively removed, the demand of metal ions is greatly increased, which causes the residue of a large amount of metal ions in the reaction system and causes secondary pollution. Thirdly, the existing form of the metal ions in water is greatly influenced by pH and other coexisting substances, the metal ions may be precipitated under an alkaline condition, and hydrated species can be formed under an acidic condition, so that the activation performance of the metal ions is reduced.
Therefore, heterogeneous activation processes of fenton/persulfate-like systems have received much attention. In view of the above problems, it has been found that transition metal oxides can immobilize metal ions without deactivation, and thus they are 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 the morphological characteristics of the heterogeneous metal oxide and the interaction among the ions, improves the catalytic performance of the heterogeneous metal oxide, and has a more efficient excitation effect on hydrogen peroxide/persulfate. However, these nanoparticulate catalysts have a limited number of recycling times, are difficult to separate from the system, and must be separated and recovered by post-treatment means such as filtration, centrifugation, flocculation, etc., thus limiting their applications.
And 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), stereolithography (3DP), etc. The principle of the method is that liquid photosensitive resin is used as a raw material, a beam of ultraviolet light with specific wavelength and intensity is used for scanning the photosensitive resin to enable the photosensitive resin to generate a crosslinking reaction and be cured, and the photosensitive resin is printed and formed 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 automation degree is high, the material utilization rate is high, and the whole manufacturing process is pollution-free.
The preparation method comprises the steps of uniformly dispersing the metal nano material in the 3D printing raw material through the preparation of the 3D printing premix, combining the design of a three-dimensional model, and completing the preparation of the catalyst through the loading of active ingredients, wherein the SLA technology can be used for directly preparing a catalyst carrier with a complex structure. After the catalyst is formed, the leaching and falling of the nano particles in a liquid phase catalysis system are effectively avoided, and the performance of the activity and the stability of the catalyst in the reaction process is effectively improved. In addition, SLA technology can provide bigger catalyst structural design degree of freedom, directly customizes the catalyst that has complicated structure, and is fast and stable, and integrated into one piece need not secondary assembly. 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 monolithic catalyst, the geometric structure of the monolithic catalyst is optimized, and the overall geometric surface area of the catalyst is improved, so that the active sites of the catalyst are further exposed, the contact area of reactants 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 monolithic catalyst loaded with the active metal oxide, which has the advantages of structure controllability, high catalytic activity and high stability, is applied to the oxidative degradation of organic wastewater by a Fenton/persulfate-like system, and has good application potential in the aspect of wastewater treatment.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to provide an active metal oxide supported monolithic catalyst with structure controllability, high catalytic activity and high stability. And controlling the metal type and the loading amount to obtain the metal-loaded monolithic catalyst. Under the condition that hydrogen peroxide/potassium persulfate exist, the catalytic efficiency is improved by controlling the reaction atmosphere, the reaction temperature, the catalyst adding amount and the catalyst structure. The efficient activated hydrogen peroxide/persulfate 3D printing monolithic catalyst can efficiently and quickly remove organic pollutants in a water body, and is an excellent catalyst suitable for a Fenton-like/persulfate oxidation system.
The technical scheme is as follows: the invention provides a preparation method of a 3D printing monolithic catalyst applied to a Fenton-like/persulfate 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 of hydrazine hydrate, sodium borohydride, sodium citrate, sodium tartrate, ascorbic acid and sodium (hypophosphite) phosphate.
Preferably, the method comprises the following steps:
(1) preparing a metal nano material:
weighing soluble metal salt, putting the soluble metal salt into pure water to obtain a transparent and clear metal salt solution, dripping 5-50 mL (preferably 5-20 mL) of reducing agent with the concentration of 0.1-0.8M (preferably 0.2-0.5M), and stirring. Then carrying out centrifugal separation on the precipitate, washing the precipitate for several times by using pure water and absolute ethyl alcohol, and drying the precipitate in an oven for several hours to obtain a corresponding metal nano material;
(2) the metal nano material is loaded on a 3D printing carrier:
mixing Ultraviolet (UV) curing resin, a surfactant and a metal nano material in proportion, uniformly stirring, controlling metal loading amount to obtain premixed liquid, pouring the premixed liquid into a resin tank of a three-dimensional Stereolithography (SLA)3D printer, loading an STL file of a required 3D structure into slice 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 monolithic catalyst.
Preferably, in the step (2), the surfactant is one or more of polyoxyethylene ether and isopropanol.
Preferably, in the step (2), the composition of the premix is as follows: 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 conditions are as follows: using N2As protective gas, roasting at 200-900 ℃ for 1-8 h, and adding N2Cooling to room temperature under the protection of (1) to obtain the 3D printing monolithic catalyst.
Preferably, in the step (1), soluble metal salt is weighed and put into pure water to obtain a transparent and clear metal salt solution, the concentration of the transparent and clear metal salt solution is 0.2-0.5M, 5-20 mL of reducing agent with the concentration of 0.1-0.8 mol/L is dripped into the solution, and the solution is stirred.
The prepared 3D printing monolithic catalyst applied to a Fenton/persulfate-like system is applied to the oxidation treatment of organic wastewater by activating hydrogen peroxide/persulfate.
Preferably, the reaction conditions of the catalyst for treating the organic wastewater by the Fenton-like/persulfate are as follows: normal pressure, reaction atmosphere: one of air, oxygen and nitrogen, the reaction temperature is 10-80 ℃, the adding amount of hydrogen peroxide/potassium persulfate is 1-20 times of the content of ofloxacin, and the catalyst: the catalyst loading amount is 0.05-10%, and the catalyst structure is one or more than two of a solid small wafer, a cylinder containing parallel straight channels, an ordered reticular hollow cylinder, a honeycomb prism and a stirring paddle; the organic wastewater is refractory organic wastewater.
Has the advantages that:
1. the preparation method of the active metal oxide nano material is simple, the technology is mature, and the activity is high; the surface of the material is in an irregular polyhedral shape and is provided with a large number of gully-shaped cracks. The surface defects of the metal nano material effectively increase the roughness and the specific surface area of the metal nano material, and are beneficial to providing more active components and uniformly dispersing the active components.
2. The components of the 3D printing catalyst premix can be flexibly prepared according to the type and the content of the metal nano material;
3. the prepared 3D printing monolithic catalyst belongs to a supported transition metal catalyst, the active components are uniformly dispersed, stable and firm, the catalyst is easy to recycle from the solution, and secondary pollution caused by metal residue in a water body is avoided to a certain extent;
4. the prepared 3D printing monolithic catalyst is integrally formed without a die and secondary assembly, has high structure controllability, and effectively improves the integral catalytic activity by designing the catalyst structure;
5. the catalytic effect of the novel efficient application of the catalyst disclosed by the invention to a Fenton/persulfate-like system 3D printing monolithic catalyst is examined, and the catalyst disclosed by the invention can be used for quickly and efficiently removing organic antibiotics in wastewater under a Fenton/persulfate-like oxidation system. The monolithic catalyst has the advantages of high catalytic activity, good stability, controllable structure, benefit for recovery and the like in a Fenton/persulfate-like system, and can be applied to the fields of sewage treatment and the like.
Drawings
FIG. 1 shows Cu prepared in example 12Scanning electron microscope images of O particles;
FIG. 2 shows catalysts prepared in example 1 and comparative example 1;
FIG. 3 is a graph of ofloxacin removal versus time for the catalyst prepared in example 1.
Detailed Description
Example 1:
(1) 0.1g of anhydrous copper acetate was added to 50mL of purified water to obtain a clear and clear solution. 8.0mL of 0.15mol/L N was added dropwise2H4·H2O solution and stirring. And then carrying out centrifugal separation on the precipitate, washing the precipitate for a plurality of times by using pure water and absolute ethyl alcohol, and drying the precipitate for a plurality of hours in an oven to obtain the metal nano material.
(2) 80 wt% of UV curing resin, 18 wt% of polyoxyethylene ether and 2 wt% of metal nano material are mixed and uniformly stirred, and the load of the metal nano material is controlled to be 0.2%. And pouring the mixture into a resin tank of an SLA 3D printer, loading the STL file with the ordered reticular porous cylinder structure into slicing software, and printing according to a set model. Cleaning the uncured resin on the surface of the finished printed matter with ethanol and pure water, naturally drying, and then using N2As shielding gas, roasting at 200 deg.C for 2 hr, and adding N2Cooling to room temperature under the protection of the catalyst to obtain the ordered mesh porous cylindrical structure 3D printing monolithic catalyst.
(3) The catalyst is used for the Fenton-like oxidation treatment of the organic wastewater under the intermittent reaction conditions that: the reaction temperature is 55 ℃, the initial concentration of the ofloxacin is 100mg/L, the adding amount of the hydrogen peroxide is 10 times of the content of the ofloxacin, and the removal rate of the ofloxacin is 98.4 percent after 90min of reaction.
Example 2:
(1) 0.1g of anhydrous ferric chloride was added to 50mL of purified water to obtain a clear solution. 8.0mL of a 0.15mol/L sodium borohydride solution was added dropwise thereto, followed by stirring. And then carrying out centrifugal separation on the precipitate, washing the precipitate for a plurality of times by using pure water and absolute ethyl alcohol, and drying the precipitate for a plurality of hours in an oven to obtain the metal nano material.
(2) 80 wt% of UV curing resin, 18 wt% of isopropanol and 2 wt% of metal nano material are mixed and uniformly stirred, and 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, and loading an STL file of an ordered mesh porous cylinder structure into slicing software,printing according to the set model. Cleaning the uncured resin on the surface of the finished printed matter with ethanol and pure water, naturally drying, and then using N2As shielding gas, roasting at 200 deg.C for 2 hr, and adding N2Cooling to room temperature under the protection of the catalyst to obtain the ordered mesh porous cylindrical structure 3D printing monolithic catalyst.
(3) The catalyst is used for the Fenton-like oxidation treatment of the organic wastewater under the intermittent reaction conditions that: the reaction temperature is 55 ℃, the initial concentration of the ofloxacin is 100mg/L, the adding amount of the hydrogen peroxide is 10 times of the content of the ofloxacin, and the removal rate of the ofloxacin is 97.2 percent after 90min of reaction.
Example 3:
(1) 0.1g of anhydrous cobalt chloride was added to 40mL of pure water to obtain a clear solution. 8.0mL of a 0.1mol/L sodium citrate solution was added dropwise thereto, followed by stirring. And then carrying out centrifugal separation on the precipitate, washing the precipitate for a plurality of times by using pure water and absolute ethyl alcohol, and drying the precipitate for a plurality of hours in an oven to obtain the metal nano material.
(2) 80 wt% of UV curing resin, 18 wt% of isopropanol and 2 wt% of metal nano material are mixed and uniformly stirred, and the load of the metal nano material is controlled to be 0.2%. And pouring the mixture into a resin tank of an SLA 3D printer, loading the STL file with the ordered reticular porous cylinder structure into slicing software, and printing according to a set model. Cleaning the uncured resin on the surface of the finished printed matter with ethanol and pure water, naturally drying, and then using N2As shielding gas, roasting at 200 deg.C for 2 hr, and adding N2Cooling to room temperature under the protection of the catalyst to obtain the ordered mesh porous cylindrical structure 3D printing monolithic catalyst.
(3) The catalyst is used for the Fenton-like oxidation treatment of the organic wastewater under the intermittent reaction conditions that: the reaction temperature is 55 ℃, the initial concentration of the ofloxacin is 100mg/L, the adding amount of the hydrogen peroxide is 10 times of the content of the ofloxacin, and the removal rate of the ofloxacin is 95.1 percent after 90min of reaction.
Example 4:
(1) 0.1g of anhydrous cerium chloride was added to 50mL of purified water to obtain a clear solution. 8.0mL of a 0.15mol/L sodium citrate solution was added dropwise thereto, followed by stirring. And then carrying out centrifugal separation on the precipitate, washing the precipitate for a plurality of times by using pure water and absolute ethyl alcohol, and drying the precipitate for a plurality of hours in an oven to obtain the metal nano material.
(2) 80 wt% of UV curing resin, 18 wt% of polyoxyethylene ether and 2 wt% of metal nano material are mixed and uniformly stirred, and the load of the metal nano material is controlled to be 0.2%. And pouring the mixture into a resin tank of an SLA 3D printer, loading the STL file with the ordered reticular porous cylinder structure into slicing software, and printing according to a set model. Cleaning the uncured resin on the surface of the finished printed matter with ethanol and pure water, naturally drying, and then using N2As shielding gas, roasting at 200 deg.C for 2 hr, and adding N2Cooling to room temperature under the protection of the catalyst to obtain the ordered mesh porous cylindrical structure 3D printing monolithic catalyst.
(3) The catalyst is used for the Fenton-like oxidation treatment of the organic wastewater under the intermittent reaction conditions that: the reaction temperature is 55 ℃, the initial concentration of the ofloxacin is 100mg/L, the adding amount of the hydrogen peroxide is 10 times of the content of the ofloxacin, and the removal rate of the ofloxacin is 94.2 percent after 90min of reaction.
Example 5:
(1) 0.1g of anhydrous copper acetate was added to 50mL of purified water to obtain a clear and clear solution. 8.0mL of a 0.15mol/L sodium tartrate solution was added dropwise thereto, followed by stirring. And then carrying out centrifugal separation on the precipitate, washing the precipitate for a plurality of times by using pure water and absolute ethyl alcohol, and drying the precipitate for a plurality of hours in an oven to obtain the metal nano material.
(2) 80 wt% of UV curing resin, 18 wt% of polyoxyethylene ether and 2 wt% of metal nano material are mixed and uniformly stirred, and the load of the metal nano material is controlled to be 0.2%. And pouring the mixture into a resin tank of an SLA 3D printer, loading the STL file with the ordered reticular porous cylinder structure into slicing software, and printing according to a set model. Cleaning the uncured resin on the surface of the finished printed matter with ethanol and pure water, naturally drying, and then using N2As shielding gas, roasting at 200 deg.C for 2 hr, and adding N2Cooling to room temperature under the protection of (1) to obtain the ordered reticular porous cylinderBulk structure 3D printing monolithic catalyst.
(3) The intermittent reaction conditions of the catalyst for persulfate oxidation treatment of organic wastewater are as follows: the reaction temperature is 55 ℃, the initial concentration of the ofloxacin is 100mg/L, the adding amount of the potassium persulfate is 10 times of the content of the ofloxacin, and the removal rate of the ofloxacin is 93.2 percent after 90min of reaction.
Example 6:
(1) 0.1g of anhydrous copper acetate was added to 50mL of purified water to obtain a clear and clear solution. 8.0mL of a 0.15mol/L ascorbic acid solution was added dropwise thereto, followed by stirring. And then carrying out centrifugal separation on the precipitate, washing the precipitate for a plurality of times by using pure water and absolute ethyl alcohol, and drying the precipitate for a plurality of hours in an oven to obtain the metal nano material.
(2) 80 wt% of UV curing resin, 18 wt% of polyoxyethylene ether and 2 wt% of metal nano material are mixed and uniformly stirred, and the load of the metal nano material is controlled to be 0.2%. And pouring the mixture into a resin tank of an SLA 3D printer, loading the STL file with the ordered reticular porous cylinder structure into slicing software, and printing according to a set model. Cleaning the uncured resin on the surface of the finished printed matter with ethanol and pure water, naturally drying, and then using N2As shielding gas, roasting at 200 deg.C for 2 hr, and adding N2Cooling to room temperature under the protection of the catalyst to obtain the ordered mesh porous cylindrical structure 3D printing monolithic catalyst.
(3) The intermittent reaction conditions of the catalyst for persulfate oxidation treatment of organic wastewater are as follows: the reaction temperature is 55 ℃, the initial concentration of the ofloxacin is 100mg/L, the adding amount of the potassium persulfate is 10 times of the content of the ofloxacin, and the removal rate of the ofloxacin is 92.7 percent after 90min of reaction.
Example 7:
(1) 0.1g of anhydrous copper acetate was added to 50mL of purified water to obtain a clear and clear solution. 8.0mL of 0.15mol/L sodium hypophosphite solution was added dropwise and stirred. And then carrying out centrifugal separation on the precipitate, washing the precipitate for a plurality of times by using pure water and absolute ethyl alcohol, and drying the precipitate for a plurality of hours in an oven to obtain the metal nano material.
(2) 80 wt% of UV curing resin and 18 wt% of polyoxyethylene ether% and 2 wt% of metal nano material, mixing and uniformly stirring, and controlling the loading of the metal nano material to be 0.2%. And pouring the mixture into a resin tank of an SLA 3D printer, loading the STL file with the ordered reticular porous cylinder structure into slicing software, and printing according to a set model. Cleaning the uncured resin on the surface of the finished printed matter with ethanol and pure water, naturally drying, and then using N2As shielding gas, roasting at 200 deg.C for 2 hr, and adding N2Cooling to room temperature under the protection of the catalyst to obtain the ordered mesh porous cylindrical structure 3D printing monolithic catalyst.
(3) The intermittent reaction conditions of the catalyst for persulfate oxidation treatment of organic wastewater are as follows: the reaction temperature is 55 ℃, the initial concentration of the ofloxacin is 100mg/L, the adding amount of the potassium persulfate is 10 times of the content of the ofloxacin, and the removal rate of the ofloxacin is 92.5 percent after 90min of reaction.
Example 8:
(1) 0.1g of anhydrous copper acetate was added to 50mL of purified water to obtain a clear and clear solution. 8.0ml of 0.15mol/L sodium phosphite solution is added dropwise and stirred. And then carrying out centrifugal separation on the precipitate, washing the precipitate for a plurality of times by using pure water and absolute ethyl alcohol, and drying the precipitate for a plurality of hours in an oven to obtain the metal nano material.
(2) 80 wt% of UV curing resin, 18 wt% of polyoxyethylene ether and 2 wt% of metal nano material are mixed and uniformly stirred, and the load of the metal nano material is controlled to be 0.2%. And pouring the mixture into a resin tank of an SLA 3D printer, loading the STL file with the ordered reticular porous cylinder structure into slicing software, and printing according to a set model. Cleaning the uncured resin on the surface of the finished printed matter with ethanol and pure water, naturally drying, and then using N2As shielding gas, roasting at 200 deg.C for 2 hr, and adding N2Cooling to room temperature under the protection of the catalyst to obtain the ordered mesh porous cylindrical structure 3D printing monolithic catalyst.
(3) The intermittent reaction conditions of the catalyst for persulfate oxidation treatment of organic wastewater are as follows: the reaction temperature is 55 ℃, the initial concentration of the ofloxacin is 100mg/L, the adding amount of the potassium persulfate is 10 times of the content of the ofloxacin, and the removal rate of the ofloxacin is 90.6 percent after 90min of reaction.
Comparative example 1:
(1) 0.1g of anhydrous copper acetate was added to 50mL of purified water to obtain a clear and clear solution. 8.0mL of 0.15mol/LN was added dropwise2H4·H2O solution and stirring. And then carrying out centrifugal separation on the precipitate, washing the precipitate for a plurality of times by using pure water and absolute ethyl alcohol, and drying the precipitate for a plurality of hours in an oven to obtain the metal nano material.
(2) 80 wt% of UV curing resin, 18 wt% of isopropanol and 2 wt% of metal nano material are mixed and uniformly stirred, and the load of the metal nano material is controlled to be 0.2%. And pouring the mixture into a resin tank of an SLA 3D printer, loading the STL file with the solid small disc structure into the slicing software, and printing according to the set model. Cleaning the uncured resin on the surface of the finished printed matter with ethanol and pure water, naturally drying, and then using N2As shielding gas, roasting at 200 deg.C for 2 hr, and adding N2Cooling to room temperature under the protection of (1) to obtain the 3D printing monolithic catalyst with the solid small wafer structure.
(3) The catalyst is used for the Fenton-like oxidation treatment of the organic wastewater under the intermittent reaction conditions that: the reaction temperature is 55 ℃, the initial concentration of the ofloxacin is 100mg/L, the adding amount of the potassium persulfate is 10 times of the content of the ofloxacin, and the removal rate of the ofloxacin is 62.9 percent after 90min of reaction.
Comparative example 2:
(1) 0.1g of anhydrous ferric chloride was added to 50mL of purified water to obtain a clear solution. 8.0mL of a 0.15mol/L sodium borohydride solution was added dropwise thereto, followed by stirring. And then carrying out centrifugal separation on the precipitate, washing the precipitate for a plurality of times by using pure water and absolute ethyl alcohol, and drying the precipitate for a plurality of hours in an oven to obtain the metal nano material.
(2) 80 wt% of UV curing resin, 18 wt% of isopropanol and 2 wt% of metal nano material are mixed and uniformly stirred, and the load of the metal nano material is controlled to be 0.2%. And pouring the mixture into a resin tank of an SLA 3D printer, loading the STL file with the solid small disc structure into the slicing software, and printing according to the set model. Finished printed matterImmediately cleaning the uncured resin on the surface of the resin by using ethanol and pure water, naturally airing, and then using N2As shielding gas, roasting at 200 deg.C for 2 hr, and adding N2Cooling to room temperature under the protection of (1) to obtain the 3D printing monolithic catalyst with the solid small wafer structure.
(3) The catalyst is used for the Fenton-like oxidation treatment of the organic wastewater under the intermittent reaction conditions that: the reaction temperature is 55 ℃, the initial concentration of the ofloxacin is 100mg/L, the adding amount of the hydrogen peroxide is 10 times of the content of the ofloxacin, and the removal rate of the ofloxacin is 60.4 percent after 90min of reaction.
Comparative example 3:
(1) 0.1g of anhydrous cobalt chloride was added to 40mL of pure water to obtain a clear solution. 8.0mL of a 0.1mol/L sodium citrate solution was added dropwise thereto, followed by stirring. And then carrying out centrifugal separation on the precipitate, washing the precipitate for a plurality of times by using pure water and absolute ethyl alcohol, and drying the precipitate for a plurality of hours in an oven to obtain the metal nano material.
(2) 80 wt% of UV curing resin, 18 wt% of isopropanol and 2 wt% of metal nano material are mixed and uniformly stirred, and the load of the metal nano material is controlled to be 0.2%. And pouring the mixture into a resin tank of an SLA 3D printer, loading the STL file with the solid small disc structure into the slicing software, and printing according to the set model. Cleaning the uncured resin on the surface of the finished printed matter with ethanol and pure water, naturally drying, and then using N2As shielding gas, roasting at 200 deg.C for 2 hr, and adding N2Cooling to room temperature under the protection of (1) to obtain the 3D printing monolithic catalyst with the solid small wafer structure.
(3) The catalyst is used for the Fenton-like oxidation treatment of the organic wastewater under the intermittent reaction conditions that: the reaction temperature is 55 ℃, the initial concentration of the ofloxacin is 100mg/L, the adding amount of the hydrogen peroxide is 10 times of the content of the ofloxacin, and the removal rate of the ofloxacin is 58.1 percent after 90min of reaction.
Comparative example 4:
(1) 0.1g of anhydrous cerium chloride was added to 50mL of purified water to obtain a clear solution. 8.0mL of a 0.15mol/L sodium citrate solution was added dropwise thereto, followed by stirring. And then carrying out centrifugal separation on the precipitate, washing the precipitate for a plurality of times by using pure water and absolute ethyl alcohol, and drying the precipitate for a plurality of hours in an oven to obtain the metal nano material.
(2) 80 wt% of UV curing resin, 18 wt% of polyoxyethylene ether and 2 wt% of metal nano material are mixed and uniformly stirred, and the load of the metal nano material is controlled to be 0.2%. And pouring the mixture into a resin tank of an SLA 3D printer, loading the STL file with the solid small disc structure into the slicing software, and printing according to the set model. Cleaning the uncured resin on the surface of the finished printed matter with ethanol and pure water, naturally drying, and then using N2As shielding gas, roasting at 200 deg.C for 2 hr, and adding N2Cooling to room temperature under the protection of (1) to obtain the 3D printing monolithic catalyst with the solid small wafer structure.
(3) The catalyst is used for the Fenton-like oxidation treatment of the organic wastewater under the intermittent reaction conditions that: the reaction temperature is 55 ℃, the initial concentration of the ofloxacin is 100mg/L, the adding amount of the hydrogen peroxide is 10 times of the content of the ofloxacin, and the removal rate of the ofloxacin is 57.6 percent after 90min of reaction.
Comparative example 5:
(1) 0.1g of anhydrous copper acetate was added to 50mL of purified water to obtain a clear and clear solution. 8.0mL of a 0.15mol/L sodium tartrate solution was added dropwise thereto, followed by stirring. And then carrying out centrifugal separation on the precipitate, washing the precipitate for a plurality of times by using pure water and absolute ethyl alcohol, and drying the precipitate for a plurality of hours in an oven to obtain the metal nano material.
(2) 80 wt% of UV curing resin, 18 wt% of polyoxyethylene ether and 2 wt% of metal nano material are mixed and uniformly stirred, and the load of the metal nano material is controlled to be 0.2%. And pouring the mixture into a resin tank of an SLA 3D printer, loading the STL file with the solid small disc structure into the slicing software, and printing according to the set model. Cleaning the uncured resin on the surface of the finished printed matter with ethanol and pure water, naturally drying, and then using N2As shielding gas, roasting at 200 deg.C for 2 hr, and adding N2Cooling to room temperature under the protection of (1) to obtain the 3D printing monolithic catalyst with the solid small wafer structure.
(3) The intermittent reaction conditions of the catalyst for persulfate oxidation treatment of organic wastewater are as follows: the reaction temperature is 55 ℃, the initial concentration of the ofloxacin is 100mg/L, the adding amount of the potassium persulfate is 10 times of the content of the ofloxacin, and the removal rate of the ofloxacin is 55.2 percent after 90min of reaction.
Comparative example 6:
(1) 0.1g of anhydrous copper acetate was added to 50mL of purified water to obtain a clear and clear solution. 8.0mL of a 0.15mol/L ascorbic acid solution was added dropwise thereto, followed by stirring. And then carrying out centrifugal separation on the precipitate, washing the precipitate for a plurality of times by using pure water and absolute ethyl alcohol, and drying the precipitate for a plurality of hours in an oven to obtain the metal nano material.
(2) 80 wt% of UV curing resin, 18 wt% of polyoxyethylene ether and 2 wt% of metal nano material are mixed and uniformly stirred, and the load of the metal nano material is controlled to be 0.2%. And pouring the mixture into a resin tank of an SLA 3D printer, loading the STL file with the solid small disc structure into slicing software, and printing according to a set model. Cleaning the uncured resin on the surface of the finished printed matter with ethanol and pure water, naturally drying, and then using N2As shielding gas, roasting at 200 deg.C for 2 hr, and adding N2Cooling to room temperature under the protection of (1) to obtain the 3D printing monolithic catalyst with the solid small wafer structure.
(3) The intermittent reaction conditions of the catalyst for persulfate oxidation treatment of organic wastewater are as follows: the reaction temperature is 55 ℃, the initial concentration of the ofloxacin is 100mg/L, the adding amount of the potassium persulfate is 10 times of the content of the ofloxacin, and the removal rate of the ofloxacin is 53.6 percent after 90min of reaction.
Comparative example 7:
(1) 0.1g of anhydrous copper acetate was added to 50mL of purified water to obtain a clear and clear solution. 8.0mL of 0.15mol/L sodium hypophosphite solution was added dropwise and stirred. And then carrying out centrifugal separation on the precipitate, washing the precipitate for a plurality of times by using pure water and absolute ethyl alcohol, and drying the precipitate for a plurality of hours in an oven to obtain the metal nano material.
(2) 80 wt% of UV curing resin, 18 wt% of polyoxyethylene ether and 2 wt% of metal nano material are mixed and uniformly stirred, and 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, and filling the pelletsAnd loading the disc-structured STL file into slicing software, and printing according to the set model. Cleaning the uncured resin on the surface of the finished printed matter with ethanol and pure water, naturally drying, and then using N2As shielding gas, roasting at 200 deg.C for 2 hr, and adding N2Cooling to room temperature under the protection of (1) to obtain the 3D printing monolithic catalyst with the solid small wafer structure.
(3) The intermittent reaction conditions of the catalyst for persulfate oxidation treatment of organic wastewater are as follows: the reaction temperature is 55 ℃, the initial concentration of the ofloxacin is 100mg/L, the adding amount of the potassium persulfate is 10 times of the content of the ofloxacin, and the removal rate of the ofloxacin is 52.5 percent after 90min of reaction.
Comparative example 8:
(1) 0.1g of anhydrous copper acetate was added to 50mL of purified water to obtain a clear and clear solution. 8.0mL of 0.15mol/L sodium phosphite solution was added dropwise thereto and stirred. And then carrying out centrifugal separation on the precipitate, washing the precipitate for a plurality of times by using pure water and absolute ethyl alcohol, and drying the precipitate for a plurality of hours in an oven to obtain the metal nano material.
(2) 80 wt% of UV curing resin, 18 wt% of polyoxyethylene ether and 2 wt% of metal nano material are mixed and uniformly stirred, and the load of the metal nano material is controlled to be 0.2%. And pouring the mixture into a resin tank of an SLA 3D printer, loading the STL file with the solid small disc structure into the slicing software, and printing according to the set model. Cleaning the uncured resin on the surface of the finished printed matter with ethanol and pure water, naturally drying, and then using N2As shielding gas, roasting at 200 deg.C for 2 hr, and adding N2Cooling to room temperature under the protection of (1) to obtain the 3D printing monolithic catalyst with the solid small wafer structure.
(3) The intermittent reaction conditions of the catalyst for persulfate oxidation treatment of organic wastewater are as follows: the reaction temperature is 55 ℃, the initial concentration of the ofloxacin is 100mg/L, the adding amount of the potassium persulfate is 10 times of the content of the ofloxacin, and the removal rate of the ofloxacin is 50.6 percent after 90min of reaction.
Claims (10)
1. A preparation method of a 3D printing monolithic catalyst applied to a Fenton-like/persulfate system is characterized by comprising the following steps: firstly, a chemical reduction method is adopted, metal salt is used as a precursor, a transition metal nano material is prepared by reduction, and then the transition metal nano material is loaded on a 3D printing carrier, so that the monolithic catalyst suitable for a Fenton-like/persulfate system is obtained.
2. The preparation method of the 3D printing monolithic catalyst applied to Fenton/persulfate-like system according to claim 1, is characterized in that: the metal salt is one or more than two of copper acetate, ferric chloride, cobalt chloride and cerium chloride.
3. The preparation method of the 3D printing monolithic catalyst applied to Fenton/persulfate-like system according to claim 1, is characterized in that: the reducing agent is one or more than two of hydrazine hydrate, sodium borohydride, sodium citrate, sodium tartrate, ascorbic acid and sodium (hypophosphite).
4. The preparation method of the 3D printing monolithic catalyst applied to the fenton/persulfate-like system according to any one of claims 1 to 3, characterized by comprising the following steps:
(1) preparing a metal nano material:
weighing soluble metal salt, putting the soluble metal salt into pure water to obtain a transparent and clear metal salt solution, dripping 5-50 mL (preferably 5-20 mL) of reducing agent with the concentration of 0.1-0.8M (preferably 0.2-0.5M), and stirring. Then carrying out centrifugal separation on the precipitate, washing the precipitate for several times by using pure water and absolute ethyl alcohol, and drying the precipitate in an oven for several hours to obtain a corresponding metal nano material;
(2) the metal nano material is loaded on a 3D printing carrier:
mixing Ultraviolet (UV) curing resin, a surfactant and a metal nano material in proportion, uniformly stirring, controlling metal loading amount to obtain premixed liquid, pouring the premixed liquid into a resin tank of a three-dimensional Stereolithography (SLA)3D printer, loading an STL file of a required 3D structure into slice 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 monolithic catalyst.
5. The preparation method of the 3D printing monolithic catalyst applied to Fenton/persulfate-like system according to claim 4, is characterized in that: in the step (2), the surfactant is one or more of polyoxyethylene ether and isopropanol.
6. The preparation method of the 3D printing monolithic catalyst applied to Fenton/persulfate-like system according to claim 4, is characterized in that: 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.
7. The preparation method of the 3D printing monolithic catalyst applied to Fenton/persulfate-like system according to claim 4, is characterized in that: in the step (2), the high-temperature sintering conditions are as follows: using N2As protective gas, roasting at 200-900 ℃ for 1-8 h, and adding N2Cooling to room temperature under the protection of (1) to obtain the 3D printing monolithic catalyst.
8. The preparation method of the 3D printing monolithic catalyst applied to Fenton/persulfate-like system according to claim 4, is characterized in that: weighing soluble metal salt in the step (1), putting the soluble metal salt into pure water to obtain a transparent and clear metal salt solution with the concentration of 0.2-0.5M, dripping 5-20 mL of reducing agent with the concentration of 0.1-0.8 mol/L, and stirring.
9. Use of a 3D printing monolith catalyst for fenton/persulfate-like systems prepared according to any of claims 1-8 for the oxidative treatment of organic wastewater with activated hydrogen peroxide/persulfate.
10. Use according to claim 9, characterized in that: the reaction conditions of the catalyst for treating organic wastewater by Fenton-like/persulfate are as follows: normal pressure, reaction atmosphere: one of air, oxygen and nitrogen, the reaction temperature is 10-80 ℃, the adding amount of hydrogen peroxide/potassium persulfate is 1-20 times of the content of ofloxacin, and the catalyst: the catalyst loading amount is 0.05-10%, and the catalyst structure is one or more than two of a solid small wafer, a cylinder containing parallel straight channels, an ordered reticular hollow cylinder, a honeycomb prism and a stirring paddle; the organic wastewater is refractory organic wastewater.
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