CN110921807A - Transition metal nano oxidase, preparation method, water treatment device and application - Google Patents

Transition metal nano oxidase, preparation method, water treatment device and application Download PDF

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CN110921807A
CN110921807A CN201911283080.5A CN201911283080A CN110921807A CN 110921807 A CN110921807 A CN 110921807A CN 201911283080 A CN201911283080 A CN 201911283080A CN 110921807 A CN110921807 A CN 110921807A
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oxidase
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water
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CN110921807B (en
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杨涵焜
俞文正
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Research Center for Eco Environmental Sciences of CAS
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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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures

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Abstract

The invention discloses a transition metal nano oxidase, a preparation method, a water treatment device and application, and relates to the field of nano catalysts, wherein the active site of the transition metal nano oxidase is expressed as M-N-C, M is one or more of Fe, Co, Cu, Mn, Zn, Ni, Ti, Zr and Mo; the oxidase has the property of a platinum-like catalyst, and directly catalyzes oxygen to oxidize organic matters. Transition metal nanometer oxidase is when being used for surface water pollution treatment in this application, compares in traditional water treatment catalyst, does not produce hydroxyl free radical in the reaction to need additionally to add oxidants such as ozone, hydrogen peroxide and persulfate, except that the required energy of aeration and water pump, do not need extra energy input, greatly reduced medicament and energy cost, reached the purpose of high-efficient processing surface aquatic natural organic pollutant.

Description

Transition metal nano oxidase, preparation method, water treatment device and application
Technical Field
The invention relates to the field of nano catalysts, in particular to a transition metal nano oxidase, a preparation method, a water treatment device and application.
Background
The nano enzyme is a nano catalyst with high catalytic activity, and has higher environmental tolerance and stability, and lower preparation, storage and use costs compared with natural enzyme; compared with the traditional catalyst, the nano enzyme has higher catalytic activity and can be catalyzed under mild conditions; meanwhile, the nano enzyme has the advantages of easiness in modification, easiness in loading, easiness in recovery and the like. Currently, many studies are made on nano peroxidase and nano oxidase, and the nano oxidase has attracted much attention in various fields because it can perform catalytic oxidation using naturally occurring oxygen as a substrate.
Natural organic pollutants in surface water are a class of pollutants widely existing in the field of water treatment, and can seriously affect the water quality. For example, the increase of natural organic pollutants in source water can increase the treatment cost of drinking water, mainly manifested by increasing the dosage of flocculation, accelerating to cause serious membrane pollution, generating a large amount of disinfection byproducts, and the like; for natural water, the increase of natural organic pollutants not only causes water quality problems such as malodor, color change, increase of microorganism content and the like, but also affects aquatic organisms, and finally causes ecological problems. Therefore, the removal of natural organic pollutants in water is of great significance. The natural organic matter consists of protein substances, polysaccharide and water-soluble humus, wherein the water-soluble humus accounts for more than 80 percent of the total mass, so that the removal of the humus content is an important factor for reducing the natural organic matter in the surface water.
The existing water treatment technology has a limited removal rate of water-soluble humus, and the existing nano oxidase and most oxidation technologies have acidic use conditions and are difficult to be directly used for surface water treatment. The above problems lead to the urgent need for a water-soluble humus removal technique that is both efficient and cost effective.
Disclosure of Invention
The invention aims to provide a transition metal nano oxidase, a preparation method, a water treatment device and application, so as to solve the problems in the prior art, when the transition metal nano oxidase is used for treating surface water pollution, compared with the traditional water treatment catalyst, the transition metal nano oxidase has stronger acid-base tolerance and environmental stability, hydroxyl free radicals are not generated in the reaction, and oxidants such as ozone, hydrogen peroxide and persulfate are not required to be additionally added, besides energy required by aeration and a water pump, extra energy input is not required, so that the medicament and energy cost is greatly reduced.
In order to achieve the purpose, the invention provides the following scheme:
one of the purposes of the invention is to provide a transition metal nano oxidase, the active site of which is expressed as M-N-C, M is one or more of Fe, Co, Cu, Mn, Zn, Ni, Ti, Zr and Mo;
the general formula of the active center of the transition metal nano-oxidase is M-N-C, and the representative structure is N.FeN4-Cn(ii) a In the transition metal nano-oxidase, an electronegative group can be formed on the surface of the nano-oxidase by using a substance containing O, P, S element in a precursor, so that an acidic microenvironment is formed.
The invention also aims to provide a preparation method of the transition metal nano oxidase, which comprises the following steps:
(1) heating the transition metal nano oxidase precursor in a protective atmosphere, raising the temperature at 2-10 ℃/min, preserving the temperature at 600-800 ℃ for 3-6h, and naturally cooling;
(2) and (2) washing the product obtained in the step (1) with acid, then washing with water to be neutral, and drying.
Further, the transition metal nano oxidase precursor is a metal organic framework material precursor, a soluble metal salt and an organic amine or natural material mixture precursor;
the metal-organic framework material precursor comprises one or more transition metals as described in claim 1, and comprises one or more of C, N element and O, S, P element;
the soluble metal salts comprise one or more transition metals as defined in claim 1;
the organic amine precursor is obtained by mixing and dissolving organic amine and soluble metal salt in a mass ratio of 2:1-20:1 in methanol, and evaporating to dryness after ethanol or water;
the organic amine is one of melamine, cyanamide or dicyandiamide;
the natural material precursor is obtained by mixing a plant or animal biological material and a soluble metal salt according to the mass ratio of 2:1-20:1, adding methanol, ethanol or water, and evaporating to dryness;
the plant or animal biological material is wood chips, straws, shrimp shells, hair and the like.
Furthermore, the precursor of the transition metal nano-oxidase contains non-metallic elements of carbon and nitrogen, and 0-3 of oxygen, sulfur and phosphorus, and one or more of transition metal elements of iron, cobalt, nickel, copper, zinc, manganese, titanium, zirconium and molybdenum.
Furthermore, the mass fraction of the metal elements in the transition metal nano oxidase precursor is 0.1-20%, and the mass fraction of the nonmetal elements is 80-99.9%.
Further, when the transition metal nano-oxidase precursor is in the heat treatment process, the protective atmosphere is a mixed atmosphere of 0.00% -0.02% of oxygen and nitrogen;
the gas flow rate/precursor mass in the protective atmosphere was 100-400mL/min g.
Further, the pickling solution in the step (2) is one or more of sulfuric acid, phosphoric acid, hydrochloric acid or nitric acid, and the mass fraction of the total acid is 0.5-15%.
The invention also aims to provide a water treatment device of the transition metal nano oxidase, which comprises a pre-sedimentation tank, an aeration tank, a packed column reactor and an aeration system;
the pre-sedimentation tank is provided with a water inlet and a sludge discharge port, and the top of the pre-sedimentation tank is communicated with the top of the aeration tank through a pipeline; the aeration system is positioned at the bottom end of the aeration tank; the aeration tank is communicated with the bottom of the packed column reactor;
the packed column reactor is filled with the transition metal nano oxidase.
The fourth purpose of the invention is to provide a water treatment method of transition metal nano oxidase, which uses the water treatment device.
Loading the transition metal nano oxidase on a carrier or filling the carrier or the carrier into a packed column reactor of the water treatment device after granulation;
introducing surface water into the sedimentation tank to remove particles;
the effluent of the pre-sedimentation tank enters the aeration tank, and the oxygen content in the water is improved through an aeration system;
the effluent of the aeration tank enters the packed bed reactor loaded with the transition metal nano oxidase to carry out catalytic oxidation reaction;
the treatment process uses no less than 1 grade of aeration tank and packed bed reactor;
the transition metal nano oxidase carrier is silicon dioxide or ceramic hollow/porous balls, and the loading method is a one-pot method or a secondary sintering method.
The invention discloses the following technical effects:
the invention firstly utilizes chemical reagents and natural materials to prepare a transition metal nano oxidase precursor, and then the transition metal nano oxidase is obtained after acid washing and water washing to neutrality. The oxidase contains transition metal elements and non-metal elements from chemical reagents and natural materials, wherein the M-N-C structure is the main active site of the nano-oxidase, and oxygen molecules dissolved in water are adsorbed on the active site on the surface of the enzyme to form an O-O.M-N-C/+ HO-O.M-N-C-activated structure which can perform nucleophilic reaction or electrophilic reaction with natural organic matters in water and oxidize the natural organic matters. At the same time, -COOH, -SO formed in the nano oxidase3or-PO4The groups can also form an acidic microenvironment in a neutral or weakly alkaline environment, and can reduce the bond energy of O-O bonds or O.M bonds in the activated structure, thereby improving the reactivity of the activated structure.
The transition metal nano oxidase has the property of a platinum-like catalyst, has stronger acid-base tolerance and environmental stability compared with metal and metal oxide catalysts, has good catalytic effect in neutral condition and alkalescent condition, overcomes the technical problem that the nano oxidase and most oxidation technologies in the prior art are acidic in use condition, and has far lower preparation cost than noble metal catalysts.
When the transition metal nano oxidase is used for treating surface water pollution, compared with the traditional water treatment catalyst, the transition metal nano oxidase does not generate hydroxyl radicals in the reaction, does not need to additionally add oxidants such as ozone, hydrogen peroxide, persulfate and the like, does not need additional energy input except the energy required by aeration and a water pump, and greatly reduces the medicament and energy cost.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
FIG. 1 is a diagram of magnetic separation of a transition metal oxidase;
FIG. 2 is an XPS spectrum of a transition metal oxidase;
FIG. 3 is an infrared spectrum of a transition metal oxidase;
FIG. 4 is a schematic view of the structure of a unit of the surface water treatment apparatus;
note: the surface water treatment device comprises one or more circulating units;
wherein 1 is a water inlet; 2 is a pre-sedimentation tank; 3 is a sludge discharge port; 4 is an aeration tank; 5 is a packed column reactor; 6 is an aeration system; and 7 is a water outlet.
Detailed Description
Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but as a more detailed description of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Further, for numerical ranges in this disclosure, it is understood that each intervening value, between the upper and lower limit of that range, is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in a stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference herein for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present disclosure without departing from the scope or spirit of the disclosure. Other embodiments will be apparent to those skilled in the art from consideration of the specification. The specification and examples are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including, but not limited to.
Example 1
The preparation method comprises the following steps:
(1) heating Prussian blue in a tube furnace under the protection of nitrogen, controlling the gas flow rate/precursor mass to be 100 mL/min-g, heating at the speed of 2 ℃/min, keeping the temperature at 600 ℃ for 6h, and naturally cooling;
(2) washing with 0.5% sulfuric acid to remove unstable Fe, washing with water to neutrality, and oven drying to obtain transition metal nanometer oxidase.
The results of magnetic separation of the transition metal nano-oxidase are shown in fig. 1.
XPS characterization is carried out on the transition metal nano oxidase, and the result is shown in figure 2;
characteristic peaks of the-C-O/-C ═ O structure can be observed for XPS C1 s in fig. 2 (a);
the characteristic peak of the N-Fe structure can be observed in the N1s image in FIG. 2 (b);
characteristic peaks of feooh and feooh active structures are observed in the O1s image in fig. 2 (c).
The infrared spectrum detection of the transition metal nano oxidase is carried out, and the result is shown in figure 3, and the obvious peak rise of carboxyl and hydroxyl can be seen.
The Prussian blue precursor can be replaced by a metal organic framework material containing one or more of Fe, Co, Cu, Mn, Zn, Ni, Ti, Zr and Mo elements.
The oxygen in the groups is derived from inevitable impurities in nitrogen, namely oxygen and oxygen in a miscellaneous band in the processing process of raw materials of the oxygen, and oxygen molecules which are chemically adsorbed when the nano-oxidase is exposed to an oxygen-containing environment (air or an aqueous solution containing dissolved oxygen).
Example 2
(1) Heating Prussian blue in a tube furnace, using a mixed gas of oxygen and nitrogen with the oxygen content of 0.02% as a protective gas, controlling the gas flow rate/precursor mass to be 100 mL/min-g, heating at 2 ℃/min, keeping the temperature at 600 ℃ for 6h, and naturally cooling;
(2) washing with 0.5% sulfuric acid to remove unstable Fe, washing with water to neutrality, and oven drying to obtain transition metal nanometer oxidase.
The Prussian blue precursor can be replaced by a metal organic framework material containing one or more of Fe, Co, Cu, Mn, Zn, Ni, Ti, Zr and Mo elements.
Example 3
The preparation method comprises the following steps:
(1) mixing melamine: mixing ferric trichloride according to the mass ratio of 2:1, dissolving the ferric trichloride by using methanol, and evaporating the dissolved ferric trichloride to dryness to obtain a melamine precursor;
(2) heating the precursor in a tube furnace, controlling the gas flow rate/precursor mass to be 200 mL/min-g under the protection of nitrogen, heating at 5 ℃/min, keeping the temperature at 800 ℃ for 3h, and naturally cooling;
(3) and (3) washing out unstable Fe by using a mixed acid of nitric acid and phosphoric acid with the mass fraction of 5%, washing to be neutral by using water, and drying to obtain the transition metal nano oxidase.
The ferric trichloride can be replaced by any one or more soluble metal salts of Co, Cu, Mn, Zn, Ni, Ti, Zr and Mo, so as to obtain the nano-oxidase.
Example 4
The preparation method comprises the following steps:
(1) mixing melamine: mixing ferric trichloride according to the mass ratio of 20:1, dissolving the ferric trichloride by using methanol, and evaporating the dissolved ferric trichloride to dryness to obtain a melamine precursor;
(2) heating the precursor in a tubular furnace, taking a mixed gas of oxygen and nitrogen with the oxygen content of 0.02 percent as a protective gas, controlling the gas flow rate/the precursor mass to be 200 mL/min-g, heating at 5 ℃/min, keeping the temperature at 800 ℃ for 3h, and naturally cooling;
(3) and (3) washing out unstable Fe by using a mixed acid of nitric acid and phosphoric acid with the mass fraction of 5%, washing to be neutral by using water, and drying to obtain the transition metal nano oxidase.
The ferric trichloride can be replaced by any one or more soluble metal salts of Co, Cu, Mn, Zn, Ni, Ti, Zr and Mo, so as to obtain the nano-oxidase.
Example 5
The preparation method comprises the following steps:
(1) wood chips are processed by the following steps: mixing ferric trichloride according to the mass ratio of 2:1, adding water, and evaporating to dryness to obtain a natural material precursor;
(2) heating the precursor in a tubular furnace, using nitrogen as protective gas, controlling the flow rate of the gas/the mass of the precursor to be 100 mL/min-g, heating at 10 ℃/min, keeping the temperature at 600 ℃ for 6h, and naturally cooling;
(3) and (3) washing unstable Fe and organic matters by using a mixed acid of nitric acid and hydrochloric acid with the mass fraction of 15%, washing to be neutral by using water, and drying to obtain the transition metal nano oxidase.
The ferric trichloride can be replaced by any one or more soluble metal salts of Co, Cu, Mn, Zn, Ni, Ti, Zr and Mo, so as to obtain the nano-oxidase.
Example 6
The preparation method comprises the following steps:
(1) wood chips are processed by the following steps: mixing ferric trichloride according to the mass ratio of 20:1, adding water, and evaporating to dryness to obtain a natural material precursor;
(2) heating the precursor in a tubular furnace, taking a mixed gas of oxygen and nitrogen with the oxygen content of 0.02 percent as a protective gas, controlling the gas flow rate/the precursor mass to be 400 mL/min-g, heating at 10 ℃/min, keeping the temperature at 600 ℃ for 6h, and naturally cooling;
(3) and (3) washing unstable Fe and organic matters by using a mixed acid of nitric acid and hydrochloric acid with the mass fraction of 15%, washing to be neutral by using water, and drying to obtain the transition metal nano oxidase.
The ferric trichloride can be replaced by any one or more soluble metal salts of Co, Cu, Mn, Zn, Ni, Ti, Zr and Mo, so as to obtain the nano-oxidase.
Example 7
As shown in fig. 4, a water treatment device for controlling the concentration of natural organic pollutants in surface water comprises a pre-settling tank, an aeration tank, a packed column reactor and an aeration system;
the pre-sedimentation tank is provided with a water inlet and a sludge discharge port, and the top of the pre-sedimentation tank is communicated with the top of the aeration tank through a pipeline; the aeration system is positioned at the bottom end of the aeration tank; the aeration tank is communicated with the bottom of the packed column reactor;
and the packed column reactor is filled with transition metal nano oxidase.
The transition metal nano oxidase carrier is silicon dioxide or ceramic hollow/porous balls, and the loading method is a one-pot method or a secondary sintering method.
Filling the carrier loaded with the transition metal nano oxidase or granules formed by granulating the transition metal nano oxidase into a packed column reactor of the water treatment device; introducing surface water into the sedimentation tank to remove particles; the effluent of the pre-sedimentation tank enters the aeration tank, and the oxygen content in the water is improved through an aeration system; the effluent of the aeration tank enters the packed bed reactor loaded with the transition metal nano oxidase to carry out catalytic oxidation reaction;
the treatment process uses no less than 1 stage of aeration tank and packed bed reactor.
Example 8
The removal rate R was calculated by measuring the TOC values of the sodium humate solutions before and after the reaction using the transition metal nano-oxidase prepared in example 1 as a catalyst and 10mL/L of the sodium humate solution as a sample.
The method comprises the following specific steps:
(1) a10 mg/L sodium humate solution containing 5mmol/L sodium carbonate was prepared, and the TOC value thereof was measured (T0).
(2) The pH value of the sodium humate solution is adjusted to 5.
(3) 10mg of transition metal nano oxidase is loaded on a silicon dioxide carrier by a one-pot method and is added into a packed column reactor.
(4) Adding the sodium humate solution into a pre-sedimentation tank, and aerating by an air pump and an air stone, wherein the aeration flow rate is controlled at 400 mL/min.
(5) The treated sample solution was taken at the outlet, the transition metal nano-oxidase was filtered using a microfiltration membrane, and the TOC value (Te) of the filtrate was measured.
(6) The removal rate R is (T0-Te)/T0.
The removal rate of sodium humate measured by the TOC method was 57.7%.
Example 9
The removal rate R was calculated by measuring the TOC values of the sodium humate solutions before and after the reaction using the transition metal nano-oxidase prepared in example 3 as a catalyst and a 20mL/L sodium humate solution as a sample.
The method comprises the following specific steps:
(1) a20 mg/L sodium humate solution containing 5mmol/L sodium carbonate was prepared, and the TOC value thereof was measured (T0).
(2) The pH of the sodium humate solution is adjusted to 7.
(3) 15mg of transition metal nano oxidase is loaded on the ceramic hollow sphere carrier by a secondary sintering method and added into a packed column reactor.
(4) Adding the sodium humate solution into a pre-sedimentation tank, and aerating by an air pump and an air stone, wherein the aeration flow rate is controlled at 600 mL/min.
(5) The treated sample solution was taken at the outlet, the transition metal nano-oxidase was filtered using a microfiltration membrane, and the TOC value (Te) of the filtrate was measured.
(6) The removal rate R is (T0-Te)/T0.
The removal rate of sodium humate measured by the TOC method was 47.7%.
Example 10
The removal rate R was calculated by measuring the TOC values of the sodium humate solutions before and after the reaction using the transition metal nano-oxidase prepared in example 5 as a catalyst and a 25mg/L sodium humate solution as a sample.
The method comprises the following specific steps:
(1) a25 mg/L sodium humate solution containing 7mmol/L sodium carbonate was prepared, and the TOC value thereof was measured (T0).
(2) The pH of the sodium humate solution is adjusted to 9.
(3) And (3) loading 20mg of transition metal nano oxidase on a ceramic porous ball carrier by a one-pot method, and adding the carrier into a packed column reactor.
(4) Adding the sodium humate solution into a pre-sedimentation tank, and aerating by an air pump and an air stone, wherein the aeration flow rate is controlled at 500 mL/min.
(5) The treated sample solution was taken at the outlet, the transition metal nano-oxidase was filtered using a microfiltration membrane, and the TOC value (Te) of the filtrate was measured.
(6) The removal rate R is (T0-Te)/T0.
The removal rate of sodium humate measured by the TOC method was 50.23%.
Comparative example 1
The procedure of example 8 was repeated except that the transition metal nano-oxidase of example 8 was replaced with a platinum catalyst, and the removal rate of sodium humate by the platinum catalyst, as measured by the TOC method, was 49.35%.
Comparative example 2
The steps of the method are the same as those of example 8 except that the transition metal nano oxidase in example 9 is replaced by the palladium catalyst, and the removal rate of sodium humate by the palladium catalyst is 52.26% as determined by the TOC method.
Comparative example 3
The procedure of example 8 was repeated except that the transition metal nano-oxidase of example 10 was replaced with an iridium catalyst, and the removal rate of sodium humate by the iridium catalyst was 50.29% as determined by the TOC method.
The above-described embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solutions of the present invention can be made by those skilled in the art without departing from the spirit of the present invention, and the technical solutions of the present invention are within the scope of the present invention defined by the claims.

Claims (10)

1. The transition metal nano oxidase is characterized in that active sites of the transition metal nano oxidase are expressed as M-N-C, wherein M is one or more of Fe, Co, Cu, Mn, Zn, Ni, Ti, Zr and Mo.
2. A method for preparing the transition metal nano-oxidase of claim 1, comprising the steps of:
(1) heating the transition metal nano oxidase precursor in a protective atmosphere, raising the temperature at 2-10 ℃/min, preserving the temperature at 600-800 ℃ for 3-6h, and naturally cooling;
(2) and (2) washing the product obtained in the step (1) with acid, then washing with water to be neutral, and drying.
3. The method according to claim 2, wherein the transition metal nano-oxidase precursor is a metal organic framework material precursor, a soluble metal salt, an organic amine or a natural material mixture precursor;
the metal-organic framework material precursor comprises one or more transition metals as described in claim 1, and comprises one or more of C, N element and O, S, P element;
the soluble metal salts comprise one or more transition metals as defined in claim 1;
the organic amine precursor is obtained by mixing and dissolving organic amine and soluble metal salt in a mass ratio of 2:1-20:1 in methanol, ethanol or water and then evaporating to dryness;
the organic amine is one of melamine, cyanamide or dicyandiamide;
the natural material precursor is obtained by mixing a plant or animal biological material and soluble metal salt according to the mass ratio of 2:1-20:1, adding methanol, ethanol or water, and evaporating to dryness.
4. The method for preparing transition metal nano-oxidase of claim 3, wherein the transition metal nano-oxidase precursor contains non-metallic elements of carbon and nitrogen, and 0-3 of oxygen, sulfur and phosphorus, and one or more of transition metal elements of iron, cobalt, nickel, copper, zinc, manganese, titanium, zirconium and molybdenum.
5. The method for preparing transition metal nano oxidase according to claim 3, wherein the mass fraction of metal elements in the transition metal nano oxidase precursor is 0.1% -20%, and the mass fraction of non-metal elements is 80% -99.9%.
6. The method for producing a transition metal nano-oxidase according to claim 3,
when different precursors of the transition metal nano oxidase are in the heat treatment process, the protective atmosphere is a mixed atmosphere of 0.00-0.02% of oxygen and nitrogen;
the gas flow rate/precursor mass in the protective atmosphere was 100-400mL/min g.
7. The method for preparing transition metal nano oxidase according to claim 2, wherein the acid washing solution in step (2) is one or more of sulfuric acid, phosphoric acid, hydrochloric acid or nitric acid, and the mass fraction of total acid is 0.5% -15%.
8. A water treatment device is characterized by comprising a pre-sedimentation tank, an aeration tank, a packed column reactor and an aeration system;
the pre-sedimentation tank is provided with a water inlet and a sludge discharge port, and the top of the pre-sedimentation tank is communicated with the top of the aeration tank through a pipeline; the aeration system is positioned at the bottom end of the aeration tank; the aeration tank is communicated with the bottom of the packed column reactor;
the packed column reactor is filled with the transition metal nano oxidase of claim 1.
9. A water treatment method characterized by using the water treatment apparatus according to claim 8;
loading the transition metal nano oxidase on a carrier or filling the carrier or the carrier into a packed column reactor of the water treatment device after granulation;
introducing surface water into the sedimentation tank to remove particles;
the effluent of the pre-sedimentation tank enters the aeration tank, and the oxygen content in the water is improved through an aeration system;
the effluent of the aeration tank enters the packed bed reactor loaded with the transition metal nano oxidase to carry out catalytic oxidation reaction;
the treatment process uses no less than 1 stage of aeration tank and packed bed reactor.
10. The water treatment method according to claim 9, wherein the transition metal nano-oxidase carrier is silica or ceramic hollow/porous spheres, and the loading method is a one-pot method or a secondary sintering method.
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