CN116371419A - Microbial carbon-supported manganese-cobalt catalyst and preparation method and application thereof - Google Patents

Microbial carbon-supported manganese-cobalt catalyst and preparation method and application thereof Download PDF

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CN116371419A
CN116371419A CN202310439811.0A CN202310439811A CN116371419A CN 116371419 A CN116371419 A CN 116371419A CN 202310439811 A CN202310439811 A CN 202310439811A CN 116371419 A CN116371419 A CN 116371419A
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manganese
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谢建平
康欣可
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Central South University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
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    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
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    • B01D53/8671—Removing components of defined structure not provided for in B01D53/8603 - B01D53/8668
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Abstract

The invention belongs to the technical field of catalysts. The invention provides a microbial carbon-supported manganese-cobalt catalyst, and a preparation method and application thereof. The method comprises the steps of adsorbing manganese chloride solution and cobalt chloride solution independently and microbial residues to obtain a manganese-loaded microbial precursor and a cobalt-loaded microbial precursor, roasting the manganese-loaded microbial precursor, the cobalt-loaded microbial precursor and an activator, granulating the obtained microbial charcoal-loaded manganese-cobalt powder and a binder, and then carrying out secondary roasting to obtain the microbial charcoal-loaded manganese-cobalt catalyst. According to the invention, the microbial slag is used as a carrier, metal manganese and cobalt are supported, catalytic active sites are not easy to fall off, and the granular microbial carbon supported manganese-cobalt catalyst is obtained through activation roasting and secondary roasting after granulation, so that the specific surface area of the catalyst is increased, the catalytic activity and stability of the catalyst are improved, the service life is prolonged, and the catalyst can be used for catalytically decomposing ozone, has high ozone decomposition rate and can treat ozone pollution.

Description

Microbial carbon-supported manganese-cobalt catalyst and preparation method and application thereof
Technical Field
The invention relates to the technical field of catalysts, in particular to a microbial carbon-supported manganese-cobalt catalyst, and a preparation method and application thereof.
Background
Ozone (O) 3 ) Is oxygenThe allotrope of the gas has an pungent smell at normal temperature and normal pressure, and can be smelled at extremely low concentration (0.01-0.05 ppm). Ozone protects the surface organisms in the stratosphere, but is an atmospheric pollutant in the stratosphere near the ground, which can lead to reduced crop yields, damage building facilities, and serious injury to the respiratory, immune and nervous systems of humans. However, due to the strong oxidizing property of ozone, it is widely used in several industries such as water purification, food sterilization, pulp processing, etc., and the waste gas oxidation treatment process still contains a large amount of residual ozone, the concentration of which is far beyond the allowable level. Ozone pollution is thus a problem that is commonly faced worldwide.
At present, the ozone removal method generally comprises a thermal decomposition method, a radiation decomposition method, a plasma decomposition method, an adsorption absorption method, a catalytic decomposition method and the like, the former four methods generally have the defects of high energy consumption, low efficiency, secondary pollution and the like, the catalytic decomposition method can realize the efficient decomposition of ozone at room temperature without generating any secondary pollution, and the method has the advantages of safety, economy, high efficiency and the like, and is the ozone removal technology with the most research value and application potential at present. The active components of the ozonolysis catalyst are mainly divided into noble metal active components and non-noble metal active components, the application is limited by the high price of noble metal, and the non-noble metal active components mainly comprise manganese active components. However, in the practical application process of the catalyst doped with the manganese active component, because of the existence of water vapor, competing adsorption exists between the water vapor and oxygen to compete for the active sites on the surface of the catalyst, so that the stability of the catalyst is reduced and the catalyst is deactivated.
Therefore, the research and development of the microbial carbon-supported manganese-cobalt catalyst with high stability and high activity can catalyze and decompose ozone at room temperature, solve the ozone pollution problem and have good prospect.
Disclosure of Invention
The invention aims to provide a microbial carbon-supported manganese-cobalt catalyst, a preparation method and application thereof, aiming at the defects of the prior art.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a microbial carbon-supported manganese cobalt catalyst, which comprises the following steps:
1) Mixing the manganese chloride solution and the cobalt chloride solution with microbial residues independently, and adsorbing the mixed solution to obtain a manganese-loaded microbial precursor and a cobalt-loaded microbial precursor;
2) Roasting the manganese-loaded microorganism precursor, the cobalt-loaded microorganism precursor and the activating agent to obtain microbial carbon-loaded manganese-cobalt type powder;
3) And mixing the microbial carbon-loaded manganese-cobalt type powder with a binder, granulating, and performing secondary roasting on the obtained microbial carbon-loaded manganese-cobalt type particles to obtain the microbial carbon-loaded manganese-cobalt type catalyst.
Preferably, the microbial residue in the step 1) is one or more of pichia pastoris residue, saccharomyces cerevisiae residue, shiwanella residue, candida residue, bacillus subtilis residue, lactobacillus residue, pseudomonas residue and micrococcus residue.
Preferably, in the step 1), the concentration of the manganese chloride solution is 0.5-2 g/L, the concentration of the cobalt chloride solution is 0.5-2 g/L, the concentration of the microbial residues in the mixed solution is 2-10 g/L, and the adsorption time is 6-24 hours.
Preferably, in the step 2), the mass ratio of the manganese-loaded microorganism precursor to the cobalt-loaded microorganism precursor is 1-5: 1, the mass ratio of the activator to the total mass of the manganese-loaded microbial precursor and the cobalt-loaded microbial precursor is 0.5-1:1, and the activator is potassium hydroxide.
Preferably, the roasting in the step 2) is performed under a protective atmosphere, wherein the protective atmosphere is argon and/or nitrogen, the roasting temperature is 600-900 ℃, the heating rate from the temperature rise to the roasting temperature is 8-12 ℃/min, and the roasting time is 1-3 h.
Preferably, the binder in the step 3) is one or more of sodium carboxymethyl cellulose, cellulose ether, coal tar, phenolic resin, starch and water glass, and the mass ratio of the microbial carbon-loaded manganese cobalt powder to the binder is 1:0.1-1;
the particle size of the manganese-cobalt-loaded microbial carbon particles is 1-5 mm.
Preferably, the secondary roasting in the step 3) is performed under a protective atmosphere, wherein the protective atmosphere is argon and/or nitrogen, the temperature of the secondary roasting is 600-900 ℃, the temperature rising rate from the temperature rising to the temperature of the secondary roasting is 8-12 ℃/min, and the time of the secondary roasting is 1-3 h.
The invention also provides the microbial carbon-supported manganese cobalt catalyst prepared by the preparation method.
The invention also provides application of the microbial carbon-supported manganese-cobalt catalyst in catalytic decomposition of ozone, wherein the microbial carbon-supported manganese-cobalt catalyst is used for carrying out catalytic decomposition reaction on the ozone, the initial concentration of the ozone is 10-50 mg/L, and the flow rate of the ozone is 1-2L/min; in the catalytic decomposition reaction, the relative humidity is 10-90%, and the reaction space velocity is 30-1200L/(g.h).
The beneficial effects of the invention include the following points:
1) Compared with the traditional catalyst which uses inorganic materials as carriers, the catalyst uses the microbial residues as carriers, and is used for adsorbing metal ions, the binding force between the metal ions and the functional groups on the surfaces of the microbial residues is superior to that between the metal ions and the inorganic materials, and catalytic active sites are not easy to fall off, so that the stability of the catalyst is remarkably improved, and the service life of the catalyst is prolonged.
2) According to the invention, the specific surface area of the microbial carbon supported manganese cobalt catalyst is increased through activation and twice roasting, the catalytic activity and stability of the microbial carbon supported manganese cobalt catalyst are improved, and the granular catalyst is obtained through granulation, so that the situations of powder flying and catalyst loss in ozonolysis application are reduced, the ozone adsorption performance is enhanced, and the problem of high-concentration ozone pollution can be solved.
3) The microbial carbon-supported manganese-cobalt catalyst has the advantages of simple preparation process, low production cost and resource utilization of microbial residues by taking the microbial residues as carriers, mild catalytic reaction conditions, safety, low energy consumption and wide application range, can be used for catalytically decomposing ozone at room temperature, and is suitable for industrial production.
Drawings
FIG. 1 is N of a microbial charcoal-supported manganese cobalt catalyst prepared in example 1 2 Adsorption-desorption isotherms and pore size distribution curves, wherein a is N 2 Adsorption-desorption isotherms, b is the pore size distribution curve;
FIG. 2 is an XRD spectrum of the microbial carbon-supported manganese cobalt type catalyst prepared in example 1, the microbial carbon-supported manganese type catalyst of comparative example 1, the microbial carbon-supported cobalt type catalyst of comparative example 2, and the microbial carbon catalyst of comparative example 3;
FIG. 3 is a flow chart showing an apparatus for evaluating ozone decomposition reaction activity;
FIG. 4 is a schematic diagram of an apparatus for evaluating ozone decomposition reaction activity;
FIG. 5 shows the ozonolysis rates of the microbial charcoal-supported manganese cobalt catalysts of examples 1 to 4, the catalysts of comparative examples 1 to 4, and commercial catalyst 1 (KXA) and commercial catalyst 2 (JXHH-1) after 6h ozonolysis.
Detailed Description
The invention provides a preparation method of a microbial carbon-supported manganese cobalt catalyst, which comprises the following steps:
1) Mixing the manganese chloride solution and the cobalt chloride solution with microbial residues independently, and adsorbing the mixed solution to obtain a manganese-loaded microbial precursor and a cobalt-loaded microbial precursor;
2) Roasting the manganese-loaded microorganism precursor, the cobalt-loaded microorganism precursor and the activating agent to obtain microbial carbon-loaded manganese-cobalt type powder;
3) And mixing the microbial carbon-loaded manganese-cobalt type powder with a binder, granulating, and performing secondary roasting on the obtained microbial carbon-loaded manganese-cobalt type particles to obtain the microbial carbon-loaded manganese-cobalt type catalyst.
The microbial residues in the step 1) are preferably one or more of pichia pastoris residues, saccharomyces cerevisiae residues, shewanella residues, candida residues, bacillus subtilis residues, lactobacillus residues, pseudomonas residues and micrococcus residues.
The concentration of the manganese chloride solution in the step 1) is preferably 0.5-2 g/L, more preferably 0.8-1.5 g/L, and even more preferably 1.0-1.2 g/L; the concentration of the cobalt chloride solution is preferably 0.5 to 2g/L, more preferably 0.8 to 1.5g/L, and still more preferably 1.0 to 1.2g/L; the concentration of the microbial residues in the mixed solution is preferably 2 to 10g/L, more preferably 3 to 8g/L, still more preferably 4 to 6g/L, and the adsorption time is preferably 6 to 24 hours, still more preferably 10 to 20 hours, still more preferably 12 to 15 hours.
The adsorption in the step 1) of the invention further comprises sequential centrifugation and drying, wherein the rotation speed of centrifugation is preferably 8000-12000 rpm, more preferably 9000-11000 rpm, more preferably 9500-10000 rpm, the centrifugation time is preferably 8-16 min, more preferably 10-14 min, more preferably 12-13 min; the drying temperature is preferably 40 to 80 ℃, more preferably 50 to 70 ℃, still more preferably 55 to 60 ℃; the drying time is preferably 8 to 24 hours, more preferably 10 to 20 hours, and still more preferably 12 to 16 hours.
The mass ratio of the manganese-loaded microorganism precursor to the cobalt-loaded microorganism precursor in the step 2) is preferably 1-5: 1, more preferably 2 to 4:1, more preferably 3:1, a step of; the mass ratio of the activator to the total mass of the manganese-loaded microbial precursor and the cobalt-loaded microbial precursor is preferably 0.5-1:1, more preferably 0.6-0.9:1, still more preferably 0.7-0.8:1, and the activator is preferably potassium hydroxide.
The roasting in the step 2) is carried out under a protective atmosphere, wherein the protective atmosphere is preferably argon and/or nitrogen, the roasting temperature is preferably 600-900 ℃, further preferably 650-800 ℃, and further preferably 700-750 ℃; the heating rate to the firing temperature is preferably 8 to 12℃per minute, more preferably 9 to 11℃per minute, and still more preferably 10℃per minute; the calcination time is preferably 1 to 3 hours, more preferably 1.5 to 2.5 hours, and still more preferably 2 hours.
The roasting step 2) of the invention further comprises the steps of washing and drying sequentially, wherein the washed reagent is preferably water, the washing times are preferably 5-8 times, more preferably 6-7 times, the time of single washing is preferably 3-8 min, more preferably 4-7 min, more preferably 5-6 min; the drying temperature is preferably 40 to 80 ℃, more preferably 50 to 70 ℃, still more preferably 55 to 60 ℃; the drying time is preferably 6 to 24 hours, more preferably 10 to 20 hours, and still more preferably 12 to 16 hours.
The binder in the step 3) is preferably one or more of sodium carboxymethyl cellulose, cellulose ether, coal tar, phenolic resin, starch and water glass, and the mass ratio of the microbial carbon-loaded manganese-cobalt powder to the binder is preferably 1:0.1-1, more preferably 1:0.2-0.8, and even more preferably 1:0.4-0.6;
the particle diameter of the microbial carbon-supported manganese cobalt particles is preferably 1 to 5mm, more preferably 2 to 4mm, and even more preferably 3mm.
The secondary roasting in the step 3) is carried out under a protective atmosphere, wherein the protective atmosphere is preferably argon and/or nitrogen, the temperature of the secondary roasting is preferably 600-900 ℃, further preferably 650-800 ℃, and further preferably 700-750 ℃; the temperature rising rate of the secondary baking temperature is preferably 8 to 12 ℃/min, more preferably 9 to 11 ℃/min, and even more preferably 10 ℃/min; the time for the secondary calcination is preferably 1 to 3 hours, more preferably 1.5 to 2.5 hours, and still more preferably 2 hours.
The invention also provides the microbial carbon-supported manganese cobalt catalyst prepared by the preparation method.
The invention also provides application of the microbial charcoal-supported manganese-cobalt catalyst in catalytic decomposition of ozone, wherein the microbial charcoal-supported manganese-cobalt catalyst is used for carrying out catalytic decomposition reaction on the ozone, and the initial concentration of the ozone is preferably 10-50 mg/L, more preferably 20-40 mg/L, and even more preferably 30mg/L; the flow rate of ozone is preferably 1 to 2L/min, more preferably 2L/min; in the catalytic decomposition reaction, the relative humidity is preferably 10 to 90%, more preferably 30 to 80%, and even more preferably 50 to 70%; the reaction space velocity is preferably 30 to 1200L/(g.h), more preferably 100 to 800L/(g.h), still more preferably 300 to 600L/(g.h).
The technical solutions provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
2L of manganese chloride solution with the concentration of 1.0g/L and 2L of cobalt chloride solution with the concentration of 1.0g/L are respectively mixed with 10g of pichia pastoris residues to obtain manganese chloride mixed solution containing 5g/L of pichia pastoris residues and cobalt chloride mixed solution containing 5g/L of pichia pastoris residues, the manganese chloride mixed solution and the cobalt chloride mixed solution are adsorbed for 8 hours, the mixture is centrifuged for 10 minutes at the rotating speed of 10000rpm, and the precipitate is dried at 60 ℃ for 12 hours to obtain a manganese-loaded microorganism precursor and a cobalt-loaded microorganism precursor; mixing a manganese-loaded microorganism precursor and a cobalt-loaded microorganism precursor according to a mass ratio of 2:1, and mixing potassium hydroxide and the mixed precursor according to a mass ratio of 0.5:1, heating to 700 ℃ at a speed of 10 ℃/min under high-purity argon atmosphere, roasting for 2 hours at 700 ℃, cooling to room temperature, taking out, washing with water for 5 times, washing for 5 minutes once, and drying for 12 hours at 60 ℃ to obtain the microbial carbon-loaded manganese cobalt powder; mixing the microbial charcoal-loaded manganese-cobalt type powder and sodium carboxymethylcellulose in a mass ratio of 1:0.3, granulating to obtain microbial charcoal-loaded manganese-cobalt type particles with a particle size of 2mm, heating to 700 ℃ at a speed of 10 ℃/min under high-purity argon atmosphere, and performing secondary roasting at 700 ℃ for 2 hours to obtain the microbial charcoal-loaded manganese-cobalt type catalyst.
BET specific surface area test of the microbial charcoal-supported manganese cobalt catalyst of this example, N 2 The adsorption-desorption isotherms and pore size distribution curves are shown in FIG. 1, wherein a is N 2 Adsorption-desorption isotherms, b is the pore size distribution curve. N of the catalyst 2 The adsorption-desorption isotherms all show an H3-type hysteresis loop IV-type isotherm, which indicates that the catalyst of the embodiment is a mesoporous material with uneven pore size distribution, and the specific surface area of the catalyst of the embodiment is 446.87m by adopting a BET method through a nitrogen adsorption isotherm 2 And/g, the larger specific surface area is favorable for adsorption and heterogeneous catalytic reaction. At P/P 0 0.99 by single point method to a total pore volume of 0.53cm 3 And/g. The average pore diameter of the catalyst of this example was 5.09nm by BJH method. When decomposing ozone in a humid environment, the larger average pore diameter can inhibit condensation of water vapor in pore channels in the catalyst, reduce air flow resistance, promote ozone diffusion and mass transfer rate, facilitate full contact of ozone and active sites of the catalyst, and improve the hydrophobicity of the catalyst。
Comparative example 1
The cobalt-loaded microorganism precursor of example 1 was omitted, and the manganese-loaded microorganism precursor and potassium hydroxide were mixed in a mass ratio of 1:0.5, and the other conditions were the same as in example 1, to obtain a microbial charcoal-supported manganese catalyst.
Comparative example 2
The manganese-loaded microorganism precursor of example 1 was omitted, and the cobalt-loaded microorganism precursor and potassium hydroxide were mixed in a mass ratio of 1:0.5, and the other conditions were the same as in example 1, to obtain a microbial carbon-supported cobalt catalyst.
Comparative example 3
The cobalt microorganism-loaded precursor and the manganese microorganism-loaded precursor of the example 1 are omitted, and pichia pastoris residues and potassium hydroxide are mixed according to the mass ratio of 1:0.5, and the other conditions were the same as in example 1, to obtain a microbial charcoal catalyst.
Comparative example 4
The firing temperature and the secondary firing temperature in example 1 were adjusted to 500℃and the other conditions were the same as in example 1.
Example 2
The mass ratio of the manganese-loaded microorganism precursor to the cobalt-loaded microorganism precursor in example 1 was adjusted to 1:1, and the other conditions were the same as in example 1.
Example 3
The mass ratio of the manganese-loaded microorganism precursor to the cobalt-loaded microorganism precursor in example 1 was adjusted to 3:1, and the other conditions were the same as in example 1.
Example 4
The firing temperature and the secondary firing temperature in example 1 were adjusted to 900℃and the other conditions were the same as in example 1.
Example 5
2L of manganese chloride solution with the concentration of 2.0g/L and 2L of cobalt chloride solution with the concentration of 2.0g/L are respectively mixed with 4g of saccharomyces cerevisiae residues to obtain manganese chloride mixed solution containing 2g/L of saccharomyces cerevisiae residues and cobalt chloride mixed solution containing 2g/L of saccharomyces cerevisiae residues, the manganese chloride mixed solution and the cobalt chloride mixed solution are adsorbed for 12 hours, the mixture is centrifuged for 16 minutes at the rotating speed of 8000rpm, and the precipitate is dried at 80 ℃ for 8 hours to obtain a manganese-loaded microorganism precursor and a cobalt-loaded microorganism precursor; mixing a manganese-loaded microorganism precursor and a cobalt-loaded microorganism precursor according to a mass ratio of 3:1, and mixing potassium hydroxide and a mixed precursor according to a mass ratio of 0.8:1, heating to 600 ℃ at a speed of 8 ℃/min under high-purity argon atmosphere, roasting for 1h at 600 ℃, cooling to room temperature, taking out, washing with water for 6 times, washing for 5min once, and drying for 8h at 80 ℃ to obtain the microbial charcoal-loaded manganese cobalt type powder; mixing the microbial charcoal-loaded manganese-cobalt type powder and methyl cellulose ether in a mass ratio of 1:0.5, granulating to obtain microbial charcoal-loaded manganese-cobalt type particles with a particle size of 5mm, heating to 600 ℃ at a speed of 8 ℃/min under high-purity argon atmosphere, and performing secondary roasting at 600 ℃ for 1h to obtain the microbial charcoal-loaded manganese-cobalt type catalyst.
Example 6
The conditions were the same as in example 5 except that the Saccharomyces cerevisiae residue in example 5 was changed to Candida residue.
Example 7
The conditions were the same as in example 5 except that the Saccharomyces cerevisiae residue in example 5 was changed to Lactobacillus residue.
XRD characterization analysis was performed on the microbial charcoal-supported manganese cobalt type catalyst of example 1, the microbial charcoal-supported manganese type catalyst of comparative example 1, the microbial charcoal-supported cobalt type catalyst of comparative example 2, and the microbial charcoal catalyst of comparative example 3, and as a result, as shown in FIG. 3, the microbial charcoal-supported manganese cobalt type catalyst of example 1 had diffraction peaks at 2 theta angles of 40.23 deg., 43.92 deg., 51.94 deg., 58.18 deg., 76.23 deg., and was formed by a reaction with Mn 3 Co 7 Comparison of Standard Spectrum (PDF#18-0408) shows that the catalyst of example 1 is carbon-supported Mn 3 Co 7 A catalyst; the microbial charcoal-supported manganese catalyst of comparative example 1 has diffraction peaks at 2θ angles of 22.04 °, 36.31 °, 44.79 °, which correspond to (111), (220), and (222) crystal planes of Mn respectively by comparison with a Mn standard spectrum (PDF # 21-0547); diffraction peaks of the microbial charcoal-supported cobalt catalyst of comparative example 2 at angles of 2 theta of 44.22 degrees, 51.52 degrees and 75.85 degrees correspond to (111), (200) and (220) crystal faces respectively, and by comparison with a standard spectrum of Co (PDF#15-0806),the microbial charcoal-supported cobalt catalyst of comparative example 2 was found to have a diffraction peak similar to that of Co; the microbial charcoal catalyst of comparative example 3 did not exhibit a significant crystal diffraction peak.
The catalysts of examples 1 to 4 and comparative examples 1 to 4 and commercial catalyst 1 (model KXA) and commercial catalyst 2 (model JXHH-1) were subjected to catalytic decomposition ozone activity test by using an ozone decomposition activity evaluation device, the flow chart of the ozone decomposition activity evaluation device is shown in FIG. 3, the physical chart of the ozone decomposition activity evaluation device is shown in FIG. 4, ozone catalytic decomposition was performed in a reactor, and the reactor was a quartz tube having an inner diameter of 20mm and a length of 25 cm. And placing manganese cobalt catalyst particles loaded by microbial charcoal in the reactor, installing ozone detection instruments at two ends of an air inlet and an air outlet of the reactor, measuring the concentration of ozone at two ends of the reactor, and calculating to obtain the ozonolysis rate according to the ozone removal rate= (ozone inlet concentration-ozone outlet concentration)/ozone inlet concentration multiplied by 100 percent. The test conditions were as follows: the initial concentration of ozone is 10mg/L, the ozone gas flow is 1.5L/min, the relative humidity is 60%, the dosage of the manganese cobalt catalyst loaded by the microbial charcoal is 1g, the reaction airspeed is 90L/(g.h), and the test result is shown in figure 5. As can be seen from fig. 5, the microbial charcoal-supported manganese cobalt catalyst of example 1 has the highest catalytic activity, and the ozone decomposition rate after ozone decomposition for 6 hours can be maintained at about 70% and at a high level. Comparing examples 1-4 with comparative examples 1-4 shows that doping manganese cobalt can greatly improve the ozone decomposition rate and stability of the catalyst. The microbial charcoal-supported manganese cobalt catalyst prepared by the method has better performance, higher ozone decomposition rate and stronger stability through comparison with commercial ozone decomposition catalysts.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.

Claims (9)

1. The preparation method of the microbial carbon supported manganese cobalt catalyst is characterized by comprising the following steps of:
1) Mixing the manganese chloride solution and the cobalt chloride solution with microbial residues independently, and adsorbing the mixed solution to obtain a manganese-loaded microbial precursor and a cobalt-loaded microbial precursor;
2) Roasting the manganese-loaded microorganism precursor, the cobalt-loaded microorganism precursor and the activating agent to obtain microbial carbon-loaded manganese-cobalt type powder;
3) And mixing the microbial carbon-loaded manganese-cobalt type powder with a binder, granulating, and performing secondary roasting on the obtained microbial carbon-loaded manganese-cobalt type particles to obtain the microbial carbon-loaded manganese-cobalt type catalyst.
2. The preparation method of claim 1, wherein the microbial residue in step 1) is one or more of pichia pastoris residue, saccharomyces cerevisiae residue, shiwanella residue, candida residue, bacillus subtilis residue, lactobacillus residue, pseudomonas residue and micrococcus residue.
3. The preparation method according to claim 1 or 2, wherein the concentration of the manganese chloride solution in the step 1) is 0.5-2 g/L, the concentration of the cobalt chloride solution is 0.5-2 g/L, and the concentration of the microbial residues in the mixed solution is 2-10 g/L; the adsorption time is 6-24 h.
4. The preparation method according to claim 3, wherein the mass ratio of the manganese-loaded microorganism precursor to the cobalt-loaded microorganism precursor in the step 2) is 1-5: 1, the mass ratio of the activator to the total mass of the manganese-loaded microbial precursor and the cobalt-loaded microbial precursor is 0.5-1:1, and the activator is potassium hydroxide.
5. The method according to claim 4, wherein the firing in step 2) is performed under a protective atmosphere of argon and/or nitrogen, the firing temperature is 600 to 900 ℃, the rate of temperature rise from the firing temperature to the firing temperature is 8 to 12 ℃/min, and the firing time is 1 to 3 hours.
6. The preparation method of the microbial carbon-loaded manganese cobalt powder is characterized in that the binder in the step 3) is one or more of sodium carboxymethyl cellulose, cellulose ether, coal tar, phenolic resin, starch and water glass, and the mass ratio of the microbial carbon-loaded manganese cobalt powder to the binder is 1:0.1-1;
the particle size of the manganese-cobalt-loaded microbial carbon particles is 1-5 mm.
7. The method according to claim 6, wherein the secondary baking in step 3) is performed under a protective atmosphere of argon and/or nitrogen, the temperature of the secondary baking is 600-900 ℃, the temperature rising rate from the temperature of the secondary baking is 8-12 ℃/min, and the time of the secondary baking is 1-3 h.
8. The microbial charcoal-supported manganese cobalt catalyst prepared by the preparation method of any one of claims 1 to 7.
9. The application of the microbial charcoal-supported manganese-cobalt catalyst in the aspect of catalytically decomposing ozone, which is characterized in that the microbial charcoal-supported manganese-cobalt catalyst is used for carrying out catalytic decomposition reaction on ozone, the initial concentration of the ozone is 10-50 mg/L, and the flow rate of the ozone is 1-2L/min; in the catalytic decomposition reaction, the relative humidity is 10-90%, and the reaction airspeed is 30-1200L/(g.h) 。
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