CN115555008A - Multiphase advanced oxidation catalytic filter material with low impedance and high porosity and application thereof - Google Patents

Multiphase advanced oxidation catalytic filter material with low impedance and high porosity and application thereof Download PDF

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CN115555008A
CN115555008A CN202211334303.8A CN202211334303A CN115555008A CN 115555008 A CN115555008 A CN 115555008A CN 202211334303 A CN202211334303 A CN 202211334303A CN 115555008 A CN115555008 A CN 115555008A
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oxide
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filter material
catalyst
advanced oxidation
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徐涵
姜智康
张可轩
顾卫平
张玉苗
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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
    • B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D39/00—Filtering material for liquid or gaseous fluids
    • B01D39/02—Loose filtering material, e.g. loose fibres
    • B01D39/06—Inorganic material, e.g. asbestos fibres, glass beads or fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • 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
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/08—Silica
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K17/00—Soil-conditioning materials or soil-stabilising materials
    • C09K17/02—Soil-conditioning materials or soil-stabilising materials containing inorganic compounds only
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K17/00—Soil-conditioning materials or soil-stabilising materials
    • C09K17/02—Soil-conditioning materials or soil-stabilising materials containing inorganic compounds only
    • C09K17/04—Soil-conditioning materials or soil-stabilising materials containing inorganic compounds only applied in a physical form other than a solution or a grout, e.g. as granules or gases
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K17/00—Soil-conditioning materials or soil-stabilising materials
    • C09K17/02—Soil-conditioning materials or soil-stabilising materials containing inorganic compounds only
    • C09K17/06—Calcium compounds, e.g. lime
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/20—Nature of the water, waste water, sewage or sludge to be treated from animal husbandry
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
    • C02F2103/36—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds
    • C02F2103/365—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds from petrochemical industry (e.g. refineries)
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/06—Controlling or monitoring parameters in water treatment pH
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/08—Chemical Oxygen Demand [COD]; Biological Oxygen Demand [BOD]
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/10—Solids, e.g. total solids [TS], total suspended solids [TSS] or volatile solids [VS]
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/16—Total nitrogen (tkN-N)
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/18—PO4-P

Abstract

The invention relates to a multiphase advanced oxidation catalysis filter material with low impedance and high porosity and application thereof. The components of the catalytic filter material comprise at least two of manganese oxide, iron oxide, silicon dioxide, calcium oxide, titanium dioxide, chromium sesquioxide, copper oxide, zinc oxide, magnesium oxide, aluminum oxide, rubidium oxide, strontium oxide, silver, nickel and phosphorus pentoxide. The invention also provides the application of the catalytic filter material as a catalyst in the waste gas and wastewater treatment or soil remediation process. The invention solves the problems of high impedance, low catalytic efficiency, high energy consumption and large using amount of the existing oxidation catalytic filter material, and simultaneously expands a multi-element formula so as to adapt the technology to the application and resource utilization of sludge and garbage undersize containing various elements and incinerated fly ash.

Description

Multiphase advanced oxidation catalytic filter material with low impedance and high porosity and application thereof
Technical Field
The invention relates to the technical field of composite materials, in particular to a multiphase advanced oxidation catalysis filter material with low impedance and high porosity and application thereof.
Background
In the fluid treatment process, the filled filter material provides an important place for the gas-liquid mass transfer process, a liquid phase forms a liquid film on the surface of the filter material, a gas phase continuously flows through a flow channel formed by gaps among filter material layers, and interacts with the continuously updated liquid film in the flowing process, and a catalyzed substance is interactively converted on the solid phase surfaces of the gas, the liquid and a filter material catalyst, so that heterogeneous catalysis is realized. For example, in the process of degrading pollutants, catalysts in gas phase, liquid phase and filter material can continuously make the pollutants obtain energy and increase the contact and reaction opportunities with free radicals, thereby realizing heterogeneous catalysis.
In the existing fluid treatment process, when gas passes through a catalytic filter material, fluid cannot quickly and effectively contact with a catalyst at high density, and a filter material layer catalysis dead angle exists, so that the defects of large resistance, high energy consumption and low catalysis efficiency are caused, and the filling, backwashing and regeneration of the filter material are relatively difficult. The problem of high filter material resistance also exists for liquids. For example, in the ozone-bio activated carbon process, there are problems of high ozone dissipation rate, low efficiency of advanced catalytic oxidation and high pressure of biofilm, and it is faced with double pressure of ozone impact or insufficient oxygen concentration. Particularly, under the condition that the water quality and the water temperature are unstable, the regulation and control space becomes narrow, so that the situation that the treatment cannot reach the standard often occurs. Meanwhile, the ozone at the end cannot be effectively utilized and must be removed by using an ozone destructor, thereby increasing the treatment cost and reducing the efficiency. Therefore, a heterogeneous high-flux catalytic filter is urgently needed to be researched.
In practical studies, it has also been found that the catalytic oxidation performance of a catalytic filter is related to the hydrodynamic properties of the filter. And the hydrodynamic properties are mainly determined by the framework material and the final morphological structure of the filter material. Wherein, the framework material determines the firmness, wear resistance and processability of the filter material; the morphological structure of the filter material is a core factor influencing the hydrodynamic property. In general fluid, the filter material in the reaction tower is accumulated tightly, and the smaller the specific surface area of the filter material is, the larger the resistance is. Therefore, increasing the specific surface area of the filter material and increasing the interstitial space of the filter material are key to reducing the fluid resistance. However, the excessive space between the filter material gaps can reduce the ratio of the total area of the filter material to the volume of the reaction tower, which results in the reduction of the catalytic area and the catalytic reaction efficiency. In addition, analysis is carried out on the aspect of the flow velocity of the fluid, under the condition of a certain flow velocity, eddy currents in the gaps of the filter material are important influencing factors of catalytic reaction, wherein deep space utilization can be promoted by the gaps of the filter material and micro-nano pore runoff on the surface and inside of the filter material, so that the catalytic reaction is enlarged, and the catalytic efficiency is improved. Therefore, the morphological structure and size of the filter material are also one of the key factors affecting the catalytic performance of the catalytic filter material.
In the environmental protection field, the recycling of sludge formed by waste gas treatment, tap water treatment and sewage treatment and terminal solid products in solid waste treatment such as soil remediation, garbage treatment and the like is a major environmental protection bottleneck faced by human beings at present. Therefore, more optional elements of the catalyst are found, more catalytic elements and formulas thereof are developed, and various elements in an environment-friendly treatment end product are used as much as possible.
Disclosure of Invention
The invention aims to provide a multiphase advanced oxidation catalytic filter material with low impedance and high porosity and application thereof, which aims to solve the problems of high impedance, low catalytic efficiency, high energy consumption and large using amount of the conventional oxidation catalytic filter material, and simultaneously expand a multi-element formula so as to adapt the technology to the application and recycling of sludge and garbage undersize containing various elements and incinerated fly ash.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the components of the catalytic filter material comprise at least two of manganese oxide, iron oxide, silicon dioxide, calcium oxide, titanium dioxide, chromium oxide, copper oxide, zinc oxide, magnesium oxide, aluminum oxide, rubidium oxide, strontium oxide, silver, nickel and phosphorus pentoxide.
Wherein, aiming at different processing materials, working conditions such as different processing procedures, processing environments and the like and standard standards after post-processing, the final formula of the catalytic filter material is prepared by combining trace (for example, 0.01 percent by w/w) to single use (100 percent by w/w) according to the processing materials and the working conditions.
The mixed components are beneficial to improving different convex-concave degrees among components on the surface of the catalytic filter material, forming polymorphic affinity and acid-base environment, particularly forming polymorphic resistance or tolerance to poisoning of certain components with the same functions, and maintaining stable anti-aging catalytic capability under complex use environment.
Preferably, the components of the catalytic filter material comprise a catalyst component and a filter material framework component;
when the catalyst component is calcium peroxide, the framework components of the filter material are chromium oxide, manganese dioxide, ferric oxide, ferroferric oxide, ferric oxide, copper oxide, zinc oxide, rubidium oxide, strontium oxide, aluminum oxide, silver, nickel, silicon dioxide and phosphorus pentoxide.
Preferably, when the catalyst component is manganese dioxide, the framework component of the filter material is silicon dioxide, magnesium oxide, calcium oxide, manganese oxide, phosphorus pentoxide, strontium oxide and aluminum oxide.
Preferably, when the catalyst component is titanium dioxide, the framework components of the filter material are chromium oxide, manganese dioxide, iron oxide, ferroferric oxide, ferric oxide, copper oxide, zinc oxide, rubidium oxide, strontium oxide, aluminum oxide, silver, nickel, silicon dioxide and phosphorus pentoxide.
Preferably, when the catalyst component is silicon dioxide, the framework components of the filter material are titanium dioxide, magnesium oxide, calcium oxide, manganese oxide, phosphorus pentoxide, strontium oxide and aluminum oxide.
Preferably, when the catalyst component is calcium peroxide, the framework components of the filter material comprise the following components in parts by weight: 0.1 part of chromium sesquioxide, 16 parts of manganese dioxide, 16 parts of iron oxide, 2.5 parts of ferroferric oxide, 2.5 parts of iron sesquioxide, 0.1 part of copper oxide, 0.1 part of zinc oxide, 0.1 part of rubidium oxide, 0.1 part of strontium oxide, 2.5 parts of aluminum sesquioxide, 0.1 part of silver, 0.1 part of nickel, 0.1 part of silicon dioxide and 0.1 part of phosphorus pentoxide.
The calcium peroxide is white or light yellow crystalline powder, is insoluble in water, is insoluble in organic solvents such as ethanol, ether and the like, can be dissolved in dilute acid to generate hydrogen peroxide, can be gradually and slowly decomposed in humid air or water to release oxygen for a long time, is a nontoxic and environment-friendly excellent oxygen supply agent with wide application, and can be used for various aspects such as fish culture, crop cultivation, waste gas, sewage sludge treatment, soil treatment and the like. Due to its own consumption, it is used when the working conditions are short-term and replenishable, according to the characteristics of the gases, liquids and solids being treated. Therefore, the migration range and the catalytic reaction active center of the catalytic filter material prepared by taking the calcium peroxide as the catalyst component are stabilized in a pollution-dense area, and a durable contact treatment belt is formed. The average diameter of the individual particles can be set to control the time limit by radical flow rate, drag limitation, filter material composition and support morphology, attrition losses and self-losses. Typically, calcium peroxide particles are incorporated on the surface of the filter media framework in a particle size range of 1-3 mm.
Preferably, when the catalyst component is manganese dioxide, the framework components of the filter material comprise the following components in parts by weight: 0.1 part of silicon dioxide, 16 parts of magnesium oxide, 16 parts of calcium oxide, 5 parts of manganese oxide, 0.1 part of phosphorus pentoxide, 0.1 part of oxygen, 2.5 parts of strontium oxide and 2.5 parts of aluminum oxide.
Manganese dioxide is an amphoteric oxide, has an octahedral structure in its molecules, and is a black powdery solid which is very stable at normal temperature. Manganese dioxide is a strong oxidant in acidic media. The manganese dioxide is used as a catalyst in the process of preparing oxygen by decomposing hydrogen peroxide, but the catalytic action of the manganese dioxide is influenced by the toxicity of the manganese dioxide, so that the manganese dioxide is used as a catalyst component in the application, and a catalytic filter material prepared by adding a filter material framework can catalyze the hydrogen peroxide to generate hydroxyl radicals and effectively reduce the polarization resistance of the catalyst, thereby compensating the poisoning of the manganese dioxide and prolonging the whole catalytic aging. For example, in the advanced oxidative catalysis of manganese dioxide-based degradation of tetracyclines, cl-and NO 3 - Can inhibit the degradation of tetracycline in the system to different degrees, thereby showing manganese dioxide poisoning, and can effectively increase the number of surface hydroxyl free radicals of the catalyst, reduce the polarization resistance of the catalyst, make up the poisoning of manganese dioxide and prolong the overall catalytic aging by mixing the added filter material skeleton.
Preferably, when the catalyst component is titanium dioxide, the framework components of the filter material comprise the following components in parts by weight: 0.1 part of chromium sesquioxide, 16 parts of manganese dioxide, 16 parts of iron oxide, 2.5 parts of ferroferric oxide, 2.5 parts of iron sesquioxide, 0.1 part of copper oxide, 0.1 part of zinc oxide, 0.1 part of rubidium oxide, 0.1 part of strontium oxide, 2.5 parts of aluminum sesquioxide, 0.1 part of silver, 0.1 part of nickel, 0.1 part of silicon dioxide and 0.1 part of phosphorus pentoxide.
Titanium dioxide, abbreviated as titanium oxide, having the chemical formula of TiO 2 The mineral is commonly called titanium dioxide, and is mainly used for photocatalyst catalytic oxidation, radiation-resistant cosmetics and radiation-mediated oxidation reaction. In the catalytic reaction, the catalyst is coated on the surface of the filter material framework, so that the catalytic effect of the advanced oxidation catalytic reaction can be obviously improved.
Preferably, when the catalyst component is silicon dioxide, the framework components of the filter material comprise the following components in parts by weight: 0.1 part of titanium dioxide, 16 parts of magnesium oxide, 16 parts of calcium oxide, 5 parts of manganese oxide, 0.1 part of phosphorus pentoxide, 0.1 part of strontium oxide and 2.5 parts of aluminum oxide.
The invention also provides a preparation method of the catalytic filter material, which comprises the following steps:
s1, dissolving components of a filter material framework by adopting a solvent, and then extruding to prepare the filter material framework; wherein, the shape of the filter material skeleton comprises but is not limited to sphere, ellipse, hollow sphere and/or hollow ellipse;
and S2, coating, spraying or sintering the catalyst on the surface of the filter material framework.
Preferably, in the step S1, the solvent is water, and the volume ratio of water to the catalytic filter material is 5 to 9.
Preferably, the sintering temperature is controlled between 900 and 1200 ℃, and dioxin is easily generated by sintering below 900 ℃; too high a temperature consumes energy.
Preferably, the catalyst is used for coating on the surface of aggregate, the particle size of the catalyst is 5 nm-1 mm, catalyst granules after sintering are screened by a screen with 16 meshes or more, ground by a mill and sieved again to form catalyst powder with different particle sizes, the catalyst powder is coated, sprayed or sintered on the surface of the aggregate, and the thickness of the optimized catalyst layer is 1mm.
Preferably, the catalyst and the aggregate are mixed and sintered to form the catalyst filter material, the catalyst is granulated or molded and then sintered in diameter, and the sintering temperature is 900-1200 ℃.
The invention also provides application of the advanced oxidation catalytic filter material, and the catalytic filter material is applied as a catalyst in the waste gas and wastewater treatment or soil remediation process.
In order to recycle solid waste, the formula of the co-catalysis of the elements can be used for recycling solid waste such as sludge, waste undersize products, fly ash after waste incineration and the like containing the elements.
Preferably, the sludge or fly ash components are analyzed (table 3), and the formulation of the above-described co-catalysis of various elements according to the present invention, wherein the catalyst elements already present can be balanced and the missing ones can be supplemented as appropriate. Then, a catalyst material was prepared according to the present invention by using S1 and S2.
TABLE 3 content of several metals in the sludge after sewage treatment
Na 2.1 % w/w dry weight
K 1.2 % w/w dry weight
Ca 8.9 % w/w dry weight
Al 7.3 % w/w dry weight
As 17.6 mg/kg (dry weight)
Cr 96.2 mg/kg (dry weight)
Cu 403.8 mg/kg (dry weight)
Cd 4.2 mg/kg (dry weight)
Pb 76.5 mg/kg (dry weight)
Hg 17.6 mg/kg (dry weight)
Ni 254.7 mg/kg (dry weight)
Fe 3128.9 mg/kg (dry weight)
Zn 1381.4 mg/kg (dry weight)
Mn 36.9 mg/kg (dry weight)
Sr 15.2 mg/kg (dry weight)
Ti 3.3 mg/kg (dry weight)
Preferably, when the solid waste such as sludge or fly ash is tested to contain catalyst components, the sludge of different batches is subjected to primary balancing, then the most effective formula which is closest to one of the catalyst formulas is balanced by adding catalytic elements, and the mixture is granulated and molded and then baked into the catalyst filter material at 900 ℃.
Preferably, the porosity and the amount of released water-soluble ions of the sintered product of the catalyst filter material can be controlled by adding a water-soluble salt containing, for example, naCl, or leaching or eluting with a solvent an excessive amount of a water-soluble salt such as NaCl. Preferably, the leaching or eluting solvent is water.
The invention has the beneficial effects that:
the invention relates to a multiphase high-flux catalytic filter material with low impedance and high porosity, which is prepared by changing the components, shapes and structures of the high-flux catalytic filter material, and provides a using method of the multiphase high-flux catalytic filter material, thereby overcoming the problems of high impedance, low catalytic efficiency, high investment and high energy consumption of the existing high-flux catalytic filter material, simplifying the pollutant treatment process, and realizing low-investment and high-efficiency upgrading and reconstruction of the traditional old treatment process and equipment. Meanwhile, the invention expands the formula of various elements and has more choices so that the technology is suitable for the application and the resource utilization of sludge and garbage undersize containing various elements and incinerated fly ash.
Drawings
FIG. 1 is a partial flow diagram of the use of a catalytic filter of the present invention in an exhaust gas treatment process;
FIG. 2 is a graph comparing the flow resistance of catalytic filter materials of different sizes and morphologies for the catalytic filter made in example 1;
FIG. 3 is a graph showing the results of bacterial colonies obtained after the soil was treated with the advanced oxidation catalyst filter in example 1;
FIG. 4 shows the COD content before and after the petrochemical wastewater treatment in example 2.
Detailed Description
Other advantages and effects of the present invention will become apparent to those skilled in the art from the disclosure herein, wherein the embodiments of the present invention are described in detail with reference to the accompanying drawings and preferred embodiments. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention. It should be understood that the preferred embodiments are illustrative of the invention only and are not limiting upon the scope of the invention.
Example 1
A preparation method of a multiphase advanced oxidation catalytic filter material with low impedance and high porosity comprises the following steps;
s1, dissolving a filter material framework by adopting water, and extruding to form the filter material framework, wherein the shape of the filter material framework comprises a solid cylinder with the size of L3cm x 3cm, a hollow cylinder (the external dimension is L3cm x 3cm, the internal diameter is 1 cm), a solid cylinder with the size of L5cm x 5cm and a hollow cylinder (the external dimension is L5cm x 5cm, the internal diameter is 2 cm);
s2, coating adhesives on the filter material frameworks in the S1 in different shapes, and then coating a catalyst, wherein the thickness of the catalyst coating is 0.1cm;
wherein, the catalyst is calcium peroxide, and the filter material skeleton comprises the following components in parts by weight: 0.1 part of chromium sesquioxide, 16 parts of manganese dioxide, 16 parts of iron oxide, 2.5 parts of ferroferric oxide, 2.5 parts of iron sesquioxide, 0.1 part of copper oxide, 0.1 part of zinc oxide, 0.1 part of rubidium oxide, 0.1 part of strontium oxide, 2.5 parts of aluminum sesquioxide, 0.1 part of silver, 0.1 part of nickel, 0.1 part of silicon dioxide and 0.1 part of phosphorus pentoxide.
The advanced oxidation catalyst prepared in example 1 was used for exhaust gas treatment
As shown in figure 1, the waste gas discharged from the dye production plant enters the advanced oxidation reaction system after being dedusted at the front end. The solid cylindrical catalyst filter of L3cm x 3cm, the hollow cylindrical catalyst filter of L3cm x 3cm (outer dimension of L3cm x 3cm, inner diameter of 1 cm), the solid cylindrical catalyst filter of L5cm x 5cm or the hollow cylindrical catalyst filter of L5cm x 5cm (outer dimension of L5cm x 5cm, inner diameter of 2 cm) prepared in example 1 were filled in the catalyst filter reaction tower of the advanced oxidation reaction system, respectively, and the flow rate of the exhaust gas was 100000m 3 H, comparison of different gasesThe hydromechanical properties of catalyst filter materials with different catalyst filter material monomer sizes (3 cm vs 5 cm) and different morphological structures (solid vs hollow) are achieved under the flow velocity (1 m/s vs 0.5 m/s). Wherein the position of the catalyst filter in figure 1 is the position where the catalyst filter was added in example 1. The results are shown in FIG. 2.
From the analysis in fig. 2, it can be seen that the morphological structure of the catalytic filter material has a significant influence on the wind resistance, wherein the wind resistance of the hollow cylinder with the same external dimension is smaller than that of the solid catalytic filter material, and the wind resistance is larger if the external dimension is smaller than that of the solid or hollow cylinder.
The hollow (the external dimension is L5cm phi 5cm, the internal diameter is 2 cm) cylindrical advanced oxidation catalysis filter material prepared in the embodiment 1 is used for treating the aquaculture sewage
The aquaculture sewage enters an anaerobic treatment process section comprising anaerobic treatment, flocculation, biogas slurry collection, intermediate sedimentation, sewage allocation and the like from a pretreatment process section comprising a grating, sewage collection, solid-liquid separation, sewage regulation, flocculation, primary sedimentation and the like, then enters a primary aerobic treatment process section comprising primary anoxic reaction, primary contact oxidation reaction, secondary anoxic reaction, secondary contact oxidation reaction, sedimentation and the like, further enters a secondary aerobic treatment process section comprising advanced oxidation reaction, oxidation transition, tertiary anoxic reaction, tertiary advanced oxidation and sedimentation, and finally enters an advanced treatment system comprising four-stage advanced oxidation, coagulation, sedimentation and five-stage advanced oxidation to be discharged. The sludge is subjected to precipitation collection and concentration for subsequent treatment.
In the advanced oxidation reaction section, adding a raw material which is 1:1 to accelerate the reaction of the advanced oxidation, especially in the fourth and fifth advanced oxidation treatment stages downstream of the process, a counterflow type catalyst packing may be added to homogenize and accelerate the reaction. The water quality comparison before and after the culture sewage treatment is shown in Table 1.
TABLE 1 comparison of Water quality before and after treatment of cultivation Sewage
Figure BDA0003914185860000061
From the analysis in table 1, it can be known that the high-grade oxidation catalytic filter material with a hollow (the external dimension is L5cm x phi 5cm, the internal diameter is 2 cm) cylindrical structure is used for treating the aquaculture sewage, the water quality is obviously improved, and the catalytic filter material can not influence the pH value of the sewage.
The advanced oxidation catalyst material of hollow cylindrical structure (L5 cm. Phi. 5cm, inner diameter of 2 cm) prepared in this example 1 was used for treating harmful microorganisms in soil. The method specifically comprises the following steps: mixing soil and H 2 O 2 Mixing with high-grade oxidation catalyst filter material, stirring, mixing for 30min, draining off residual liquid, inoculating the treated soil on LB and PDA culture medium, culturing in dark at 28 deg.C for 48h, and observing sterilization result every day. The results are shown in FIG. 3.
In fig. 3, the abscissa represents the addition ratio of the advanced oxidation catalyst filter to the soil. From the analysis in FIG. 3, it can be seen that the number of colonies in the soil is inversely proportional to the amount of the advanced oxidation catalyst. And the advanced oxidation catalysis filter material is proved to be capable of killing different bacterial colonies, which provides reliable reference for the difference treatment of different soil flora.
The hollow (L5 cm. Phi. 5cm, inner diameter 2 cm) cylindrical advanced oxidation catalyst material prepared in this example 1 was used to disinfect the stem segments of roses. Specifically, the method comprises the following steps of; cutting Chinese rose into stem segments of about 5cm, washing with sterile water, shaking in 75% (v/v) alcohol for 30 s, and washing with sterile water for 3 times. The advanced oxidation catalyst filter material prepared in the embodiment 1 is cut and fully mixed with plant roots, stems and leaves, hydrogen peroxide is added, and H is added 2 O 2 Mixing with the advanced oxidation catalyst filter material at a ratio of 0-100%, stirring, mixing for 15min, culturing in MS culture medium at 25 deg.C in dark for 0-120h, and observing and recording colony generation result every day. The results are shown in Table 2.
TABLE 2 number of colonies of Chinese rose stems after in vitro explant culture of plants at different concentrations of catalytic filter
Figure BDA0003914185860000071
As can be seen from the analysis in Table 2, the combination of the advanced oxidation catalyst filter and H 2 O 2 The addition ratio of (1): 4, the number of colonies after culturing was 0, and the oxidative sterilization effect was relatively best.
Example 2
A preparation method of a multiphase advanced oxidation catalytic filter material with low impedance and high porosity comprises the following steps;
s1, dissolving components of a filter material framework by adopting water, and extruding the components into the filter material framework, wherein the shape of the filter material framework is a solid cylinder with the shape of L3cm x phi 3 cm;
s2, coating an adhesive on the solid cylindrical filter material framework in the S1, and then coating a catalyst, wherein the thickness of the catalyst coating is 0.1cm;
wherein the catalyst component is SiO 2 The components of the filter material framework comprise 0.1 part of TiO by weight 2 16 parts of MgO, 16 parts of CaO, 5 parts of MnO and 0.1 part of P 2 O 5 0.1 part of SrO, 2.5 parts of Al 2 O 3 。
The advanced oxidation catalyst prepared in example 2 was used for advanced treatment of petrochemical wastewater. Specifically, the advanced oxidation catalyst material is mixed with petrochemical wastewater in different addition ratios, and the mixture reacts for 1 hour at 25 ℃ under the condition of no radiation, so that the reaction result of COD reduction is obtained, as shown in figure 4.
In fig. 4, 20% indicates that the ratio of the higher oxidation catalyst material added to the petrochemical wastewater is 20%, and 50% indicates that the ratio of the higher oxidation catalyst material added to the petrochemical wastewater is 50%. From the analysis in fig. 4, it can be seen that the higher the addition ratio of the advanced oxidation catalyst filter material, the better the treatment effect on the petrochemical wastewater.
The above embodiments are merely preferred embodiments for fully illustrating the present invention, and the scope of the present invention is not limited thereto. The equivalent substitution or change made by the technical personnel in the technical field on the basis of the invention is all within the protection scope of the invention.

Claims (10)

1. The heterogeneous advanced oxidation catalytic filter material with low impedance and high porosity is characterized in that the catalytic filter material comprises at least two of oxides of manganese, iron, silicon dioxide, calcium, titanium dioxide, chromium oxide, copper oxide, zinc oxide, magnesium oxide, aluminum oxide, rubidium oxide, strontium oxide, silver, nickel and phosphorus pentoxide.
2. The low impedance, high porosity, heterogeneous advanced oxidation catalyst material of claim 1, wherein the components of the catalyst material comprise catalyst components and filter material framework components;
when the catalyst component is calcium peroxide, the framework components of the filter material are chromium oxide, manganese dioxide, iron oxide, ferroferric oxide, iron trioxide, copper oxide, zinc oxide, rubidium oxide, strontium oxide, aluminum oxide, silver, nickel, silicon dioxide and phosphorus pentoxide.
3. The low impedance, high porosity heterogeneous advanced oxidation catalyst media of claim 2 wherein, when the catalyst component is manganese dioxide, the media framework components are silica, magnesia, calcia, manganese oxide, phosphorus pentoxide, strontium oxide and alumina.
4. The low impedance, high porosity heterogeneous advanced oxidation catalyst filter of claim 2 wherein, when the catalyst component is titanium dioxide, the filter framework components are chromium oxide, manganese dioxide, iron oxide, triiron tetroxide, iron sesquioxide, copper oxide, zinc oxide, rubidium oxide, strontium oxide, aluminum oxide, silver, nickel, silica and phosphorus pentoxide.
5. The low impedance, high porosity heterogeneous advanced oxidation catalyst media of claim 2 wherein, when the catalyst component is silica, the media framework components are titania, magnesia, calcia, manganese oxide, phosphorus pentoxide, strontium oxide, and alumina.
6. The multiphase advanced oxidation catalyst filter material with low impedance and high porosity of claim 2, wherein when the catalyst component is calcium peroxide, the filter material skeleton comprises the following components in parts by weight: 0.1 part of chromium sesquioxide, 16 parts of manganese dioxide, 16 parts of iron oxide, 2.5 parts of ferroferric oxide, 2.5 parts of iron sesquioxide, 0.1 part of copper oxide, 0.1 part of zinc oxide, 0.1 part of rubidium oxide, 0.1 part of strontium oxide, 2.5 parts of aluminum sesquioxide, 0.1 part of silver, 0.1 part of nickel, 0.1 part of silicon dioxide and 0.1 part of phosphorus pentoxide.
7. The heterogeneous advanced oxidation catalyst media of low impedance and high porosity as claimed in claim 3 wherein, when the catalyst component is manganese dioxide, the media framework components, in parts by weight, are: 0.1 parts of silicon dioxide, 16 parts of magnesium oxide, 16 parts of calcium oxide, 5 parts of manganese oxide, 0.1 part of phosphorus pentoxide, 0.1 part of oxygen, 2.5 parts of strontium oxide and 2.5 parts of aluminum oxide.
8. The heterogeneous advanced oxidation catalyst of claim 4, wherein when the catalyst component is titanium dioxide, the filter media comprises the following components in parts by weight: 0.1 part of chromium sesquioxide, 16 parts of manganese dioxide, 16 parts of iron oxide, 2.5 parts of ferroferric oxide, 2.5 parts of iron sesquioxide, 0.1 part of copper oxide, 0.1 part of zinc oxide, 0.1 part of rubidium oxide, 0.1 part of strontium oxide, 2.5 parts of aluminum sesquioxide, 0.1 part of silver, 0.1 part of nickel, 0.1 part of silicon dioxide and 0.1 part of phosphorus pentoxide.
9. The filter material of claim 5, wherein when the catalyst component is silica, the filter material comprises the following components in parts by weight: 0.1 part of titanium dioxide, 16 parts of magnesium oxide, 16 parts of calcium oxide, 5 parts of manganese oxide, 0.1 part of phosphorus pentoxide, 0.1 part of strontium oxide and 2.5 parts of aluminum oxide.
10. Use of an advanced oxidation catalyst material as claimed in any one of claims 1 to 9, wherein the advanced oxidation catalyst material is used as a catalyst in exhaust gas, wastewater treatment or soil remediation processes.
CN202211334303.8A 2022-10-28 2022-10-28 Multiphase advanced oxidation catalytic filter material with low impedance and high porosity and application thereof Pending CN115555008A (en)

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