CN113083289B - Preparation method of moisture-proof efficient ozone decomposer - Google Patents
Preparation method of moisture-proof efficient ozone decomposer Download PDFInfo
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Abstract
The invention relates to a preparation method of a moisture-resistant and efficient ozonolysis agent, which comprises the steps of synchronously carrying out transition metal ion doping and manganese dioxide high-activity crystalline phase conversion, in particular to a mesoporous manganese dioxide material with low particle diameter and high specific surface area obtained by adding a framework material in a process of synthesizing manganese dioxide by a hydrothermal method, carrying out post-treatment reaction to realize transition metal ion cocatalyst doping and conversion from the low-catalytic-activity crystalline phase to the high-catalytic-activity crystalline phase of manganese dioxide, and finally obtaining the mesoporous ozone destructor with high environmental humidity resistance by a conventional granulation process. The invention has the advantages of simple operation, no need of additional heating, low cost and high efficiency in degrading ozone tail gas, and can still maintain excellent catalytic performance in high humidity environment.
Description
Technical Field
The invention relates to the technical field of preparation of ozone decomposers, in particular to a preparation method of a moisture-proof efficient ozone decomposer.
Background
With the further emphasis of the state on ozone pollution control, more and more ozone pollution treatment methods are presented, and mainly include an adsorption method, a thermal decomposition method, a plasma decomposition method, a drug absorption method and a catalytic decomposition method.
The adsorption method is to utilize porous adsorbent and its modified matter, such as active carbon, to react with the efficient ozone adhesive to eliminate ozone pollution. This is because the activated carbon has a porous structure and a certain reducibility. However, this method is only suitable for treating ozone at low concentrations, and is not suitable for use at high concentrations. Activated carbon exposed to ozone for a long period of time is susceptible to passivation and therefore needs to be replaced frequently with the risk of fire and explosion. This is because the reaction of activated carbon with ozone is exothermic and activated carbon itself is a fuel;
the thermal decomposition method is to eliminate pollution by utilizing the characteristic of ozone thermal decomposition, for example, ozone is obviously decomposed from 30-50 ℃ and 70% of ozone can be decomposed within 1min at 200 ℃, and 100% of ozone can be decomposed at 300 ℃ or above for 1-2 s. Thermal decomposition is most widely used in industrial applications, but has the disadvantage of high energy consumption;
the chemical absorption method is to absorb sodium thiosulfate, sodium sulfite or potassium iodide solution which can react with ozone, the principle is simple, but the waste liquid causes secondary pollution;
the plasma decomposition method is to decompose ozone by plasma bombardment generated in the high-voltage discharge process, but the method has the defects of expensive equipment, high power consumption and the like;
among the methods, the catalyst method satisfies both safety and economical requirements and also satisfies most of the practical applications of the process with respect to the removal efficiency of ozone, and thus is widely considered by the industry as the most promising alternative to the above-mentioned methods. One of the cores of the technology is that the decomposer is required to be suitable for most working conditions, such as dust, moisture and the like, and can stably and efficiently decompose ozone for a long time.
In general, many active components of ozone decomposition catalysts are noble metals, complex metal oxides, photocatalysts, modified or unmodified carbon-based catalysts, and the like. Noble metal catalysts are costly; the photocatalyst is driven by the energy of a light source, so that the efficiency is generally lower, and the cost is relatively higher; the carbon-based catalyst has higher efficiency, but has the defects of low service life, potential safety hazard and the like. In contrast, composite metal oxide catalysts have both cost and efficiency advantages, but higher ambient humidity is prone to metal oxide failure, and only a few composite metal oxides can withstand high ambient humidity.
Noble metal catalysts are currently considered the most stable, but these catalysts are expensive to manufacture and are all patented by foreign enterprises, such as Engelhard's Pd-MnO 2 Catalysts, pd-Pt catalysts supported on alumina from UOP, etc., have been patented. Although a few researches on ozone decomposition catalysts are also carried out in China, the ozone decomposition catalysts still do not reach the degree of practical application in China, and are still mainly dependent on import at present. Therefore, there is a need to develop a domestic ozone decomposition catalyst with good catalytic stability in a humid environment.
Disclosure of Invention
The invention aims to solve the problems of the prior ozonolysis agent, and provides a preparation method of the ozonolysis agent with high moisture resistance and efficiency, which has the advantages of simple process, easily available materials, low cost and high applicability, and the prepared ozonolysis agent has the advantages of environmental protection, high efficiency, high moisture resistance and good catalytic stability in a humid environment.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the preparation method of the moisture-proof efficient ozonolysis agent mainly comprises three steps, namely preparation of mesoporous manganese dioxide material, transition metal doping and phase transition reaction, and granulation based on composite manganese dioxide catalytic active material, and comprises the following specific steps:
(1) Preparing a mesoporous manganese dioxide material:
a. preparing a potassium permanganate aqueous solution with the concentration of 5-15 wt%;
b. slowly dripping the solution into a prepared structure directing agent solution with the concentration of 2.5-25wt%, wherein the molar ratio of potassium permanganate to the structure directing agent is 0.5-10;
c. the mixture is placed at the temperature of 20-80 ℃ for reaction for 2-4 hours under the condition of fully stirring;
d. and standing and aging the reacted mixture for 6-24 hours, filtering by suction filtration, and fully drying for 12-24 hours at the temperature of 100-150 ℃ to obtain the mesoporous manganese dioxide material.
(2) Transition metal doping and phase transition reactions:
a. dispersing mesoporous manganese dioxide accounting for 5-20wt% of a dispersion solvent in water under ultrasonic or high-speed stirring to prepare a suspension;
b. adding 0.5-4wt% of transition metal salt and 0.5-2wt% of carbon reducer into the suspension, and stirring by ultrasonic or high-speed to prepare a uniform solution;
c. transferring the uniform solution into a polytetrafluoroethylene high-pressure sealing reaction kettle, and performing hydrothermal reaction in a muffle furnace at 150-200 ℃ for 6-12 h;
d. and (3) after the reaction is finished, carrying out suction filtration to obtain a precipitate, drying at 60-80 ℃, and grinding to obtain the composite manganese dioxide catalytic active material rich in alpha-phase manganese dioxide.
(3) Granulation based on composite manganese dioxide catalytically active material:
a. preparing a mixture of the composite manganese dioxide catalytic active material, an ozone adsorbent, a refractory additive, an adhesive and water according to a proportion under mechanical stirring;
b. solidifying and granulating the solid particles by using rolling granulation, extrusion granulation, a tablet press and other granulation equipment, wherein the manufactured solid particles are spherical, cylindrical and polygonal flaky semi-finished products;
c. acidizing the semi-finished product for 1-2 hours by using 2-4 mol/L nitric acid solution, drying at 70-140 ℃, and roasting at 300-450 ℃ under the protection of inert gas to obtain the finished product.
Further, in the step (1), the structure-directing solvent is citric acid, polyethylene glycol, water-soluble chitosan or gelatin.
Further, in the step (2), b, the transition metal salt is Fe-containing 3+ 、Ce 2+ 、Ni 2+ 、Cu 2+ And Sn (Sn) 2+ One or two of sulfate, nitrate and chloride.
Further, in the step (2), the carbon reducing agent is one of activated carbon powder, graphite powder, reducing agent grade blue carbon, charcoal, reduced graphene oxide and carbon nanotubes.
Further, in the step (3), the composite manganese dioxide catalytic active material accounts for 55% -75% of the total mass of the mixture.
Further, in the step (3), the ozone adsorbent is sodium silicate, tetraethoxysilane or mesoporous silica powder, and the addition amount of the ozone adsorbent is 4-10% of the total mass of the mixture.
Further, in the step (3), the refractory additive is magnesia or aluminum oxide powder, and the addition amount of the refractory additive is 4-10% of the total mass of the mixture.
Further, in the step (3), the adhesive is an activated carbon adhesive, attapulgite or sodium bentonite, and the addition amount of the adhesive is 15-25% of the total mass of the mixture.
Further, in the step (3), the addition amount of the water accounts for 10-20% of the total mass of the mixture.
Further, in the step (3), the diameter of the spherical particles is 5-10 mm, the diameter of the cylindrical particles is 5-15 mm, the column length is 10-20 mm, and the side length of the polygonal sheet particles is 5-20 mm.
In the technical scheme of the invention, the doping of transition metal ions and the process of converting low-activity crystalline phase manganese dioxide into high-activity crystalline phase are carried out simultaneously, specifically, mesoporous manganese dioxide precursor is reacted by a one-step hydrothermal method, thereby realizing the doping of transition metal ions and simultaneously promoting delta-MnO with low catalytic activity 2 Conversion to highly catalytically active alpha-MnO 2 The product has rich pores and alpha-MnO 2 The catalyst has rich content, and compared with single manganese dioxide, the catalyst has higher ozone-destroying efficiency compared with the composite of transition metal ions; the ozone destructor particles manufactured by using the manganese dioxide as an active ingredient and compounding the auxiliary agent with stronger ozone adsorption can be used in an ozone waste gas destructor for treating high concentration and humidity. The preparation method has the advantages of simple process, easily obtained materials, low cost, low pollution, easy industrial amplification and excellent catalytic performance in a high humidity environment.
Drawings
FIG. 1 is a schematic flow chart of a catalytic evaluation test of an ozonolysis agent prepared according to the invention;
FIG. 2 is a summary of data from an evaluation test of an ozonolysis agent in an example of the invention;
FIG. 3 is an evaluation of the life span of an ozonolysis agent in an example of the invention.
Detailed Description
Example 1
In order that the invention may be more clearly understood, a method for preparing a moisture-resistant and efficient ozonolysis agent according to the invention will be further described with reference to the accompanying drawings, wherein the specific examples are given for the purpose of illustration only and are not intended to limit the invention.
According to the invention, a structural template material is added in a process of synthesizing manganese dioxide by a hydrothermal method, a mesoporous manganese dioxide material with low particle size and high specific surface area is obtained firstly, then a mesoporous manganese dioxide substrate with high specific surface area is doped with transition metal ions through one-step post-treatment reaction, and meanwhile gamma-phase or delta-phase manganese dioxide with low catalytic activity crystalline phase is converted into alpha-phase manganese dioxide with high activity crystalline phase, so that transition metal ion cocatalyst doping and conversion of low catalytic activity crystalline phase into high catalytic activity crystalline phase manganese dioxide are realized, and the obtained ozone-destroying active component is finally obtained through a conventional granulating process.
In the first embodiment, the preparation method specifically includes the following steps:
(1) Preparing a mesoporous manganese dioxide material:
a. preparing a potassium permanganate aqueous solution with the concentration of 5-10wt%;
b. slowly dripping the solution into a prepared citric acid solution with the concentration of 3wt%, wherein the solvent is water;
c. the mixture is placed at the temperature of 30 ℃ to react for 2 hours under the condition of fully stirring;
d. standing and aging the reacted mixture for 6 hours, filtering by suction filtration, and fully drying for 12 hours at 60 ℃ to obtain the mesoporous manganese dioxide material.
(2) Transition metal doping and phase transition reactions:
a. dispersing mesoporous manganese dioxide accounting for 25wt% of a dispersion solvent in water under ultrasonic or high-speed stirring to prepare a suspension;
b. adding cerium nitrate accounting for 5wt% of a dispersion solvent and 1wt% of active carbon powder into the suspension, and preparing a uniform solution by ultrasonic stirring or high-speed stirring;
c. transferring the uniform solution into a polytetrafluoroethylene high-pressure sealing reaction kettle, and carrying out hydrothermal reaction for 12 hours in a muffle furnace at 150 ℃;
d. after the reaction is finished, the precipitate is obtained by suction filtration, dried for 6 hours at 80 ℃, and ground into 400-mesh powder.
(3) Granulation based on composite manganese dioxide catalytically active material:
a. mixing the 75% doped powder with 5% mesoporous silica, 20% sodium bentonite, and adding proper amount of water;
b. using an extrusion granulator to prepare 5mm or 10mm size particles;
c. acidizing the semi-finished product for 1h by using a nitric acid solution with the concentration of 1mol/L, and roasting for 2.5h at the temperature of 450 ℃ to obtain the finished product.
Example 2
The procedure was the same as in example 1, the parameters being as follows:
precursor preparation: 5-10wt% of potassium permanganate and 2.5wt% of polyethylene glycol; the solvent is water, and the mixture is stirred for 2 hours in 50 ℃ water heating and aged for 12 hours; drying at 60℃for 12h.
Doping and pulverizing: 20wt% of the precursor, 2.5wt% of copper sulfate, 1.5wt% of cobalt sulfate and 0.4wt% of graphite powder, wherein the dispersion is water, the reaction is carried out for 12 hours at 150 ℃, the suction filtration is carried out, the drying is carried out for 12 hours at 80 ℃, and the powder is ground into 400-mesh powder.
Granulating: 75% of the doped powder, 10% of mesoporous silica and 15% of attapulgite by weight are added with a proper amount of water to be uniformly mixed, 5 x 10 mm-sized particles are prepared by using an extrusion granulator, 2mol/L nitric acid solution is used for acidizing for 3 hours, and roasting is carried out at 350 ℃ for 2 hours, so that a finished product is obtained.
Example 3
The procedure was the same as in example 1, the parameters being as follows:
precursor preparation: 5-10wt% of potassium permanganate and 2wt% of citric acid; the solvent is water, and the mixture is stirred for 2 hours at 70 ℃ in a hydrothermal mode and aged for 6 hours; drying at 80℃for 12h.
Doping and pulverizing: 30wt% of the precursor, 5wt% of copper sulfate and 0.4wt% of carbon nano tubes, wherein the dispersion liquid is water, the reaction is carried out for 12 hours at 150 ℃, the suction filtration is carried out, the drying is carried out for 12 hours at 80 ℃, and the powder is ground into 400 meshes of powder.
Granulating: 60% of the doped powder, 10% of mesoporous silica, 10% of magnesia and 20% of attapulgite by weight, using a rolling granulation machine to prepare spheres, adding a proper amount of water to prepare spheres with the diameter of 2-4 mm, acidizing the spheres for 1h by using a 1mol/L nitric acid solution, and roasting the spheres at 350 ℃ for 3h to obtain a finished product.
Example 4
The procedure was the same as in example 1, the parameters being as follows:
precursor preparation: 5-10wt% of potassium permanganate and 1wt% of gelatin; the solvent is water, and the mixture is stirred for 2 hours at 70 ℃ in a hydrothermal mode and aged for 12 hours; drying at 60℃for 12h.
Doping and pulverizing: 20wt% of the precursor, 2.5wt% of copper sulfate, 1.5wt% of cobalt sulfate, 0.5wt% of nickel sulfate and 0.5wt% of active carbon powder, wherein the dispersion is water, the reaction is carried out for 12 hours at 180 ℃, the suction filtration is carried out, the drying is carried out for 12 hours at 80 ℃, and the powder is ground into 400-mesh powder.
Granulating: 70% of the doped powder, 10% of mesoporous silica and 20% of attapulgite by weight, using a rolling granulator to prepare spheres, adding a proper amount of water to prepare spheres with the diameter of 2-4 mm, acidizing for 1h by using a 1mol/L nitric acid solution, and roasting for 3h at 450 ℃ to obtain a finished product.
Referring to fig. 1 to 3, for a catalytic evaluation test of an ozonolysis agent prepared by the preparation method of the present invention, the test is mainly performed according to the following procedures:
the method comprises the steps of using a 10g/L pure oxygen source ozone generator to simulate an ozone waste gas source, firstly, passing through a gas washing bottle filled with deionized water, discharging gas, then introducing a communicating device filled with a humidity agent and an ozone degradation agent, operating the ozone generator for at least 30 minutes until the ozone concentration in the gas washing bottle is saturated and the ozone concentration of gas is stable before each measurement, reading the inlet gas humidity, measuring the ozone concentration of inlet gas and outlet gas respectively by adopting a HJ504-2009 sodium indigo disulfonate spectrophotometry or an iodometry, and calculating the ozone removal rate. The flow rate of the simulated ozone waste gas source is 0.4-1L/min, the ozone concentration is 60-140 mg/L, and the load of the ozone catalyst is 10cm 3 。
The preparation method is simple and low in cost, and meanwhile, the prepared decomposer can still maintain excellent catalytic performance in a high-humidity environment.
In addition to the embodiments described above, other embodiments of the invention are possible. All technical schemes formed by equivalent substitution or equivalent transformation fall within the protection scope of the invention.
Claims (10)
1. The preparation method of the moisture-proof efficient ozonolysis agent mainly comprises the steps of three stages, and is characterized by comprising the following steps:
(1) Preparing a mesoporous manganese dioxide material:
a. preparing a potassium permanganate aqueous solution with the concentration of 5-15 wt%;
b. slowly dripping the solution into a prepared structure directing agent solution with the concentration of 2.5-25wt%, wherein the molar ratio of potassium permanganate to the structure directing agent is 0.5-10;
c. the mixture is placed at the temperature of 20-80 ℃ for reaction for 2-4 hours under the condition of fully stirring;
d. standing and aging the reacted mixture for 6-24 hours, filtering by suction filtration, and fully drying for 12-24 hours at the temperature of 100-150 ℃ to obtain a mesoporous manganese dioxide material;
(2) Transition metal doping and phase transition reactions:
a. dispersing mesoporous manganese dioxide accounting for 5-20wt% of a dispersion solvent in water under ultrasonic or high-speed stirring to prepare a suspension;
b. adding 0.5-4wt% of transition metal salt and 0.5-2wt% of carbon reducer into the suspension, and stirring by ultrasonic or high-speed to prepare a uniform solution;
c. transferring the uniform solution into a polytetrafluoroethylene high-pressure sealing reaction kettle, and performing hydrothermal reaction in a muffle furnace at 150-200 ℃ for 6-12 h;
d. filtering after the reaction is finished to obtain a precipitate, drying at 60-80 ℃, and grinding to obtain a composite manganese dioxide catalytic active material rich in alpha-phase manganese dioxide;
(3) Granulation based on composite manganese dioxide catalytically active material:
a. preparing a mixture of the composite manganese dioxide catalytic active material, an ozone adsorbent, a refractory additive, an adhesive and water according to a proportion under mechanical stirring;
b. solidifying and granulating the solid particles by using rolling granulation, extrusion granulation, a tablet press and other granulation equipment, wherein the manufactured solid particles are spherical, cylindrical and polygonal flaky semi-finished products;
c. acidizing the semi-finished product for 1-2 hours by using 2-4 mol/L nitric acid solution, drying at 70-140 ℃, and roasting at 300-450 ℃ under the protection of inert gas to obtain the finished product.
2. The method for producing a moisture-resistant and efficient ozone decomposer as claimed in claim 1, characterized in that:
in the step (1), the structure directing agent is citric acid, polyethylene glycol, water-soluble chitosan or gelatin.
3. The method for producing a moisture-resistant and efficient ozonolysis agent according to claim 1 or 2, characterized in that:
in the step (2), b, the transition metal salt is Fe 3+ 、Ce 2+ 、Ni 2+ 、Cu 2+ And Sn (Sn) 2+ One or two of sulfate, nitrate and chloride.
4. The method for producing a moisture-resistant and efficient ozonolysis agent according to claim 1 or 2, characterized in that:
in the step (2), the carbon reducing agent is one of activated carbon powder, graphite powder, reducing agent grade blue carbon, charcoal, reduced graphene oxide and carbon nanotubes.
5. The method for producing a moisture-resistant and efficient ozonolysis agent according to claim 1 or 2, characterized in that:
in the step (3), the composite manganese dioxide catalytic active material accounts for 55% -75% of the total mass of the mixture.
6. The method for producing a moisture-resistant and efficient ozonolysis agent according to claim 1 or 2, characterized in that:
in the step (3), the ozone adsorbent is sodium silicate, tetraethoxysilane or mesoporous silica powder, and the addition amount of the ozone adsorbent accounts for 4-10% of the total mass of the mixture.
7. The method for producing a moisture-resistant and efficient ozonolysis agent according to claim 1 or 2, characterized in that:
in the step (3), the refractory additive is magnesia or aluminum oxide powder, and the addition amount of the refractory additive accounts for 4-10% of the total mass of the mixture.
8. The method for producing a moisture-resistant and efficient ozonolysis agent according to claim 1 or 2, characterized in that:
in the step (3), the adhesive is an activated carbon adhesive, attapulgite or sodium bentonite, and the addition amount of the adhesive is 15-25% of the total mass of the mixture.
9. The method for producing a moisture-resistant and efficient ozonolysis agent according to claim 1 or 2, characterized in that:
in the step (3), the addition amount of the water accounts for 10-20% of the total mass of the mixture.
10. The method for producing a moisture-resistant and efficient ozonolysis agent according to claim 1 or 2, characterized in that:
in the step (3), the diameter of the spherical particles is 5-10 mm, the diameter of the cylindrical particles is 5-15 mm, the column length is 10-20 mm, and the side length of the polygonal sheet particles is 5-20 mm.
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| RU2009106689A (en) * | 2009-02-26 | 2010-09-10 | Общество с ограниченной ответственностью "Научно-технический центр "ТИМИС" (RU) | CATALYTIC ACTIVITY MATERIAL FOR OZONE DECOMPOSITION AND METHOD FOR PRODUCING IT |
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