CN113171783B - Microporous honeycomb ozone catalyst and preparation method and application thereof - Google Patents

Microporous honeycomb ozone catalyst and preparation method and application thereof Download PDF

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CN113171783B
CN113171783B CN202110428985.8A CN202110428985A CN113171783B CN 113171783 B CN113171783 B CN 113171783B CN 202110428985 A CN202110428985 A CN 202110428985A CN 113171783 B CN113171783 B CN 113171783B
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carbon fiber
catalyst
microporous
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superfine powder
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CN113171783A (en
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刘艳
张源
刘凯
王叶鑫
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Sinochem Environmental Holdings Ltd
Sinochem Environmental Technology Engineering Co Ltd
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Sinochem Environmental Technology Engineering Co Ltd
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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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/20—Carbon compounds
    • B01J27/22—Carbides
    • B01J27/224—Silicon carbide
    • B01J27/228—Silicon carbide with phosphorus, arsenic, antimony or bismuth
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/20—Carbon compounds
    • B01J27/22—Carbides
    • B01J27/224—Silicon carbide
    • B01J35/56—
    • B01J35/618—
    • B01J35/633—
    • B01J35/635—
    • B01J35/638—
    • 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
    • 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
    • C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • 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]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters

Abstract

The invention relates to an ozone catalysis method, in particular to a microporous honeycomb ozone catalyst and a preparation method and application thereof. The modified microporous carbon carrier is roasted in gradient mode, then active ingredients are added and mixed, and the mixture is loaded on the surface of the modified pretreated carbon fiber, so that the specific surface area of the carbon fiber is 1200-1800 m 2 A microporous honeycomb catalyst per gram; wherein the active component accounts for 2-15% of the carrier. Through the gradient roasting pretreatment, the catalyst can realize internal micro-gaps and increase the contact area, and meanwhile, through the interaction between the catalyst carrier and the active component, the catalyst can be applied to wide temperature, can efficiently decompose ozone for a long time to generate free radicals, can reduce the filling amount of the catalyst, further increase the contact specific surface area of catalytic reaction, effectively improve the utilization rate of ozone, avoid energy waste and secondary pollution, and improve the process treatment effect.

Description

Microporous honeycomb ozone catalyst and preparation method and application thereof
Technical Field
The invention relates to an ozone catalysis method, in particular to a microporous honeycomb ozone catalyst and a preparation method and application thereof.
Background
The catalytic ozone technology is an advanced oxidation technology based on ozone, combines the strong oxidizing property of ozone with the adsorption and catalytic properties of a catalyst, and can effectively solve the problem of incomplete degradation of organic matters. The catalytic ozonation is divided into homogeneous catalytic ozonation and heterogeneous catalytic ozonation according to the phase state of the catalyst, and in the homogeneous catalytic ozonation technology, the catalyst is uniformly distributed, high in catalytic activity, clear in action mechanism and easy to study and grasp. However, the disadvantages of the catalyst are also obvious, and the catalyst is mixed and dissolved in water, so that the catalyst is easy to run off, difficult to recover, generates secondary pollution, has higher operation cost and increases the water treatment cost. The heterogeneous catalytic ozonation method utilizes a solid catalyst to accelerate the oxidation reaction of a liquid phase (or a gas phase) under normal pressure, the catalyst exists in a solid state, is easy to separate from water, has less secondary pollution, and simplifies the treatment process, thereby more and more arousing the attention of people. At present, the conventional catalyst has low catalytic efficiency, and the catalyst is easily passivated and the ozone is easily decomposed in a high-salt environment, such as the existence of a large amount of Cl ions, so that the addition amount can only be increased for ensuring the standard discharge, and the operation cost is greatly increased; the existing heterogeneous catalyst mainly takes particles as main materials, the pressure drop of a packed bed layer is large, and bubbles are not uniformly distributed in the flowing process of ozone. In addition, the irregular accumulation of particles easily causes a channeling phenomenon, so that ozone cannot be fully contacted with the catalyst and wastewater, the catalytic efficiency is greatly reduced, and the treatment of wastewater is not facilitated.
Patent CN 112264030A discloses an ozone catalytic treatment agent for treating organic matters in wastewater and a preparation method thereof, and the ozone catalytic treatment agent comprises diatomite-based porous filler, transition metal oxide and rare earth oxide loaded in the porous filler; the transition metal oxide is one of titanium oxide and nickel oxide; the rare earth oxide is lanthanum oxide or yttrium oxide. The ozone catalyst can improve the removal rate of COD in the water body, and simultaneously, also discloses a preparation method of the ozone catalytic treating agent. The invention provides a preparation method and application of a mesoporous ZSM-5-based ozone catalyst, and provides a preparation method and application of a patent CN202011110974.7 mesoporous ZSM-5-based ozone catalyst, wherein the preparation method comprises the following steps: a. cleaning ZSM-5 powder with deionized water, and performing suction filtration and drying to obtain powder A; b. placing the powder A into a sodium hydroxide solution, treating for 20-40 min under the water bath condition of 50-80 ℃, and then performing suction filtration, washing and drying to obtain powder B; c. dissolving cobalt salt and cerium salt in deionized water to obtain a mixed solution C; d. and mixing the mixed solution C with the powder B, drying after ultrasonic treatment, then placing in a tubular furnace, and roasting at 500-600 ℃ for 5-8 h in a nitrogen atmosphere to obtain the ozone catalyst. The invention greatly improves the removal rate of the phenol-containing wastewater catalytically degraded by ozone and the utilization rate of ozone. The preparation method is simple, the raw materials are cheap and easy to obtain, and the method has a good industrial application prospect. The invention discloses a preparation method of a supported ozone catalyst, which comprises the following steps of (1) preparing a catalyst carrier: mixing a zirconium oxide solution and an aluminum nitrate solution to obtain a precursor solution, adding a dispersing agent into the precursor solution, uniformly stirring at 50 ℃, adding pretreated ammonia water into the precursor solution, reacting for 20min, aging for 9h, taking out a product, filtering, separating, cleaning, drying and calcining to obtain the catalyst. (2) preparing an ozone catalyst: and (3) soaking the catalyst carrier in a mixed solution of water-soluble manganese salt and water-soluble iron salt, taking out, drying and roasting at high temperature to obtain the ozone catalyst. The sampling catalyst prepared by the invention takes ZrO2-Al2O3 as a carrier, and the carrier has the advantages of small particle size, uniform particle size distribution, large specific surface area and the like, and can improve the contact area of the catalyst and ozone, thereby accelerating the catalytic efficiency.
The investigation of the above patents shows that the technical economy of the catalyst is poor, and the heterogeneous catalyst prepared by taking diatomite and rare metal as carriers to load metal/heavy metal/rare earth oxide has the problems of complex preparation process, high cost and loss of active components in the preparation process.
Disclosure of Invention
The invention aims to provide a microporous honeycomb ozone catalyst and a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the technical scheme that:
a microporous cellular ozone catalyst is prepared through gradient calcining modified microporous carbon carrier, adding active component, mixing, and loading it on the surface of pretreated carbon fibres to obtain the catalyst whose specific surface area is 1200-1800 m 2 A microporous honeycomb catalyst per gram; wherein, the active component accounts for 2-15% of the carrier by mass, and the preferred range is 2% -12%.
The active component is an oxide containing one or more metal elements of manganese, titanium, selenium, nickel, copper and lanthanum; wherein the manganese-containing metal element oxide is manganese sesquioxide; the titanium-containing metal element oxide is titanium dioxide; the selenium-containing metal element oxide is selenium dioxide; the metal element oxide containing nickel is nickel sulfate; the copper-containing metal element oxide is copper sulfate; the lanthanum-containing metal element oxide is lanthanum oxide;
in a further aspect of the present invention,
when the active ingredients are manganese and copper or nickel and copper, the mass ratio is 8-20: 1-6 mixing;
when the active ingredients are manganese, titanium or manganese, selenium or manganese and lanthanum, the mass ratio is 8-20: 0.5 to 1;
when the active ingredients are copper and titanium or copper and selenium or copper and lanthanum, the mass ratio of the active ingredients is 1-6: 0.5 to 1;
manganese or/and nickel: copper: the mass ratio of one or more of titanium, selenium or lanthanum is 8-20: 1 to 6:0.5 to 1, for example, when the active component is manganese, copper, titanium or nickel, copper, selenium or nickel, copper and lanthanum, the mass ratio is 8 to 20:1 to 6:0.5 to 1; that is to say that the first and second electrodes,
the gradient roasting modified microporous carbon carrier is prepared by mixing precursor liquid and silicon carbide, heating to 250-280 ℃, keeping the temperature for 0.3-0.5 h, adding pretreated carbon fiber into the mixture after treatment, heating to 320-380 ℃, introducing nitrogen gas for 1-1.5 h, adding phosphoric acid into the system to ensure that the pH value of the system is 3-5, heating to 500-580 ℃, continuously introducing nitrogen gas for 0.5-1 h, and keeping the heating for later use.
The obtained microporous carbon carrier with gradient roasting modification has internal micropores of 0.4-2.0cm 3 /g。
The pretreated carbon fiber is prepared by roasting carbon fiber at 380-580 deg.C for 60-120min under the protection of nitrogen, soaking in sodium chloride solution for 60min after roasting, taking out, and anodizing the carbon fiber for 20-60min with graphite as cathode.
A preparation method of a microporous honeycomb ozone catalyst comprises the steps of roasting a modified microporous carbon carrier in a gradient manner, adding active ingredients, and mixing to enable the active ingredients to be loaded on the surface of modified pretreated carbon fibers, so as to obtain the microporous honeycomb catalyst; wherein the active component accounts for 2-15% of the carrier.
In a further aspect of the present invention,
1) The pretreated carbon fiber is carbon fiber which is roasted for 60-120min at 380-580 ℃ under the protection of nitrogen, is immersed in sodium chloride solution for 60min after being roasted, is taken out and is used as an anode, graphite is used as a cathode, the carbon fiber is anodized for 20-60min, and is cleaned and dried for standby application after being treated;
2) Mixing and heating a precursor solution serving as a microporous carbon carrier modified by gradient roasting with silicon carbide to 250-280 ℃ for 0.3-0.5 hour, adding pretreated carbon fiber into the mixture after treatment, heating the mixture to 320-380 ℃, introducing nitrogen into the mixture for 1-1.5 hours, adding phosphoric acid into the system to adjust the pH of the system to 3-5, heating the mixture to 500-580 ℃, continuously introducing nitrogen into the mixture, and heating the mixture for 0.5-1 hour for later use;
3) Catalyst acquisition: adding the active ingredients when the temperature is reduced to 300-380 ℃ after the modification by the gradient roasting, introducing nitrogen, adding and reducing the water aqua when the temperature of the materials is reduced to 150-200 ℃, continuing for 1-1.5 hours, stopping introducing the nitrogen, pouring the mixture into a mold after uniformly stirring, and quickly reducing the temperature to the normal temperature; and cooling the material in the die and then demoulding to obtain the microporous honeycomb catalyst.
The mass ratio of the precursor liquid to the silicon carbide of the pretreated carbon fiber is 60-80.
The precursor solution is prepared by mixing and grinding aluminum oxide, kaolin and calcium oxide into superfine powder, fully mixing and then adding a mixture of a foaming agent, diethyl ether and n-hexanol;
wherein the mass ratio of the mixture of aluminum oxide, kaolin and calcium oxide to the mixture of foaming agent, diethyl ether and n-hexanol is 10-1; the mass fraction of the aluminum oxide accounts for 75-85% of the total amount of the superfine powder, the mass fraction of the calcium oxide accounts for 2-10% of the total amount of the superfine powder, and the mass fraction of the kaolin accounts for 5-20% of the total amount of the superfine powder; the mass ratio of the foaming agent to the diethyl ether to the n-hexanol is 2:3:5.
the water reducing agent is an anionic surfactant, such as lignosulfonate, naphthalene sulfonate formaldehyde polymer and the like; the foaming agent is azodicarbonamide, azodiisobutyronitrile, diethyl azodicarboxylate, etc.
The catalyst can be processed into a sphere, a rectangular saddle, a Raschig ring, a column and the like according to different moulds, and the size of the appearance dimension can be adjusted according to a grinding tool.
The application of a microporous honeycomb ozone catalyst in treating organic wastewater.
The invention has the advantages that:
the catalyst obtained by the invention has the internal micropore of 0.4-2.0cm by the carrier modified by gradient calcination 3 Adding active ingredients and mixing to load the active ingredients on the surface of the modified pretreated carbon fiber; wherein the active component accounts for 2-15% of the carrier. Through the gradient roasting pretreatment, the catalyst can realize internal micro-gaps and increase the contact area, and meanwhile, through the interaction between the catalyst carrier and the active component, the catalyst can be applied to wide temperature, can efficiently decompose ozone for a long time to generate free radicals, can reduce the filling amount of the catalyst, and effectively improve the wastewater treatment effect. Thereby increasing the contact specific surface area of the catalytic reaction.
1. The catalyst can be processed into a spherical shape, a rectangular saddle shape, a Raschig ring shape, a cylindrical shape and the like, the size of the appearance dimension can be adjusted according to a grinding tool, the device can be customized according to the shape of the device, the filling and the system maintenance and cleaning are convenient, and meanwhile, the designed catalyst layer can effectively reduce the pressure drop and ensure the uniform flow field of the filler layer.
2. The microporous ozone catalyst obtained by the method has the advantages of larger specific surface agent, catalytic activity and directional selectivity, small catalyst bed layer bulk density, reduced catalyst bed layer system pressure drop, and uniform distribution. The catalyst is applied to industrial wastewater treatment, and a better effect is achieved.
Drawings
Fig. 1 is an electron microscope image of the catalyst provided in example 1 of the present invention.
FIG. 2 is an electron micrograph of a catalyst provided in example 2 of the present invention.
FIG. 3 is an electron micrograph of a catalyst provided in example 3 of the present invention.
FIG. 4 is an electron micrograph of a catalyst according to a comparative example of the present invention.
Detailed Description
The following examples are presented to further illustrate embodiments of the present invention, and it should be understood that the embodiments described herein are for purposes of illustration and explanation only and are not intended to limit the invention.
Example 1
Preparation of an ozone catalyst:
1) Mixing and grinding the prepared aluminum oxide, kaolin and calcium oxide into superfine powder, fully mixing, adding a foaming agent, diethyl ether and n-hexanol, and further uniformly mixing to obtain a precursor solution; the total amount of the foaming agent, the diethyl ether and the n-hexanol accounts for 10% of the mass of the superfine powder system, wherein the mass fraction of aluminum oxide accounts for 80% of the total amount of the superfine powder, the mass fraction of calcium oxide accounts for 2% of the total amount of the superfine powder, and the mass fraction of kaolin accounts for 18% of the total amount of the superfine powder; the mass ratio of the foaming agent to the diethyl ether to the n-hexanol is 2:3:5; the foaming agent is azodicarbonamide.
2) Adding silicon carbide into the obtained precursor solution, heating to 250 ℃, and keeping the temperature for 0.5 hour;
3) Adding pretreated carbon fiber into the product obtained in the step 2), uniformly mixing, heating to 320 ℃, and introducing nitrogen for 1 hour;
4) Adding phosphoric acid to enable the pH value of the system to be 4, heating to 500 ℃, continuously introducing nitrogen, and heating for 1 hour to obtain the microporous carbon carrier modified by gradient roasting; when the temperature of the carrier is reduced to 300 ℃, adding manganese sesquioxide, copper sulfate and lanthanum sesquioxide, stirring and mixing the materials, introducing nitrogen, pouring the materials into a hopper, quickly cooling by adopting a mold temperature machine, adding and reducing a water aqua when the temperature of the materials is reduced to 200 ℃, continuing for 1 hour, stopping introducing the nitrogen, after stirring uniformly, pouring the materials into a spherical mold with the diameter of 20mm, and quickly cooling to the normal temperature; cooling the material in the mold, demolding to obtain a coarse microporous honeycomb catalyst product, and placing the coarse microporous honeycomb catalyst product into a shaking table to perform vibration blowing to obtain a finished product (see fig. 1 and table 1); wherein, manganese sesquioxide: copper sulfate: the mass ratio of lanthanum sesquioxide is 8:1:0.5, the water reducing agent is lignosulfonate.
The mass ratio of the pretreated carbon fiber to the precursor liquid to the silicon carbide is 75:15:10; the active substance accounts for 10.36 percent of the mass of the microporous carbon carrier modified by the gradient roasting.
The pretreatment carbon fiber is PAN-based carbon fiber, the carbon fiber is immersed in 5% potassium chloride solution for 140min after being subjected to high temperature of 380 ℃ under the protection of nitrogen for 60min, the carbon fiber is used as an anode, graphite is used as a cathode, the voltage is 15 volts, the carbon fiber is anodized for 20min under the condition of 3A current, the surface of the carbon fiber is cleaned by distilled water after treatment, and the carbon fiber is dried for 2h at 105 ℃ in a drying box for later use.
The obtained pretreated carbon fiber is a low-density material with the characteristics of high specific strength, high specific modulus, friction resistance, high temperature resistance, low thermal expansion coefficient and the like, and Carbon Fiber (CF) is used as a reinforcement of a composite material due to excellent mechanical property and has the conductivity of 25s/m.
As can be seen from the scanning of the surface morphology of the catalyst by an electron microscope in fig. 1, the grooves on the surface of the carbon fiber after surface treatment are generally increased, and the interfacial adhesion between CF and resin (EP) is improved after modification; the obtained carrier has internal micropores of 2cm 3 A catalyst having a uniform microporous structure and an active groupThe catalyst is uniformly dispersed on the microporous framework, the active component is uniformly loaded, and the components of the obtained catalyst are shown in Table 1. The nominal value of the specific surface area of the obtained catalyst is 1707m 2 /g。
TABLE 1 Electron microscopy and energy Spectroscopy analysis of the catalysts are given in Table 1
Spectrogram 1
Element(s) Line type Weight percent of Wt％Sigma
C K line system 41.42 0.41
O K line system 25.58 0.25
Al K line system 21.5 0.21
K K line system 0.22 0.2
Manganese (Mn) K line system 8.67 8.67
Cl K line system 0.21 0.21
Copper (Cu) K line system 1.19 1.19
Lanthanum K line system 0.5 1.26
Total amount of 100.00
Example 2
1) Mixing and grinding the prepared aluminum oxide, kaolin and calcium oxide into superfine powder, fully mixing, adding a foaming agent, diethyl ether and n-hexanol, and further uniformly mixing to obtain a precursor solution; the total amount of the foaming agent, the diethyl ether and the n-hexanol accounts for 11% of the mass of the superfine powder system, wherein the mass fraction of aluminum oxide accounts for 80% of the total amount of the superfine powder, the mass fraction of calcium oxide accounts for 3% of the total amount of the superfine powder, and the mass fraction of kaolin accounts for 17% of the total amount of the superfine powder; the mass ratio of the foaming agent to the diethyl ether to the n-hexanol is as follows: 2:3:5; the foaming agent is diethyl azodicarboxylate.
2) Adding silicon carbide into the obtained precursor solution, heating to 260 ℃, and keeping the temperature for 0.5 hour;
3) Adding pretreated carbon fiber into the product obtained in the step 2), uniformly mixing, heating to 350 ℃, and introducing nitrogen for 1 hour;
4) Adding phosphoric acid to ensure that the PH of the system is 4, heating to 550 ℃, continuously introducing nitrogen, and heating for 0.5 hour to obtain the microporous carbon carrier modified by gradient roasting; when the temperature of the carrier is reduced to 300 ℃, adding manganese sesquioxide and copper sulfate to stir the mixed material, introducing nitrogen, pouring the material into a hopper, adopting a mold temperature machine to carry out rapid cooling, adding and reducing a water agent when the temperature of the material is reduced to 200 ℃, continuing for 1 hour, then stopping introducing the nitrogen, after uniformly stirring, pouring the material into a spherical mold with the diameter of 20mm, and rapidly cooling to normal temperature; cooling the material in the mold, demolding to obtain a coarse microporous honeycomb catalyst product, and placing the coarse microporous honeycomb catalyst product on a shaking table to perform vibration blowing to obtain a finished product (see fig. 2 and table 2); wherein, manganese sesquioxide: the mass ratio of the copper sulfate is 10:1, the water reducing agent is lignosulfonate.
The mass ratio of the pretreated carbon fiber to the precursor liquid to the silicon carbide is 72:16:12; the active substance accounts for 3.86 percent of the mass of the microporous carbon carrier modified by the gradient roasting.
The pretreatment carbon fiber is PAN-based carbon fiber, the carbon fiber is immersed in 5% sodium chloride solution for 120min after being subjected to high temperature of 380 ℃ under the protection of nitrogen for 60min, the carbon fiber is used as an anode, graphite is used as a cathode, the voltage is 15 volts, the carbon fiber is anodized for 20min under the condition of 3A current, the surface of the carbon fiber is cleaned by distilled water after treatment, and the carbon fiber is dried for 2h at 105 ℃ in a drying box for later use.
The conductivity of the pretreated carbon fiber obtained above was 23s/m.
As can be seen from the scanning of the surface morphology of the catalyst by an electron microscope in fig. 2, the grooves on the surface of the carbon fiber after surface treatment are generally increased, and the interfacial adhesion property between CF and resin (EP) is improved after modification. The obtained carrier had 1.1cm of internal microporosity 3 The catalyst has a uniform microporous structure, the active components are uniformly dispersed on the microporous framework, the active components are uniformly loaded, and the components of the obtained catalyst are shown in a table 2. The nominal value of the specific surface area of the obtained catalyst is 1500m 2 /g。
TABLE 2
Spectrogram 2
Element(s) Line type Weight percent of Wt％Sigma Atomic percent
O K line system 31.50 31 51.81
Al K line system 29.42 29 31.41
Ca K line system 4.19 4 2.09
C K line system 31.05 31 13.36
Manganese oxide K line system 2.92 2 1.04
Cu L-shaped wire system 0.94 0.94 0.29
Total amount of 100.00 100.00
Example 3
1) Mixing and grinding the prepared aluminum oxide, kaolin and calcium oxide into superfine powder, fully mixing, adding a foaming agent, diethyl ether and n-hexanol, and further uniformly mixing to obtain a precursor solution; the total amount of the foaming agent, the diethyl ether and the n-hexanol accounts for 8% of the mass of the superfine powder system, wherein the mass fraction of aluminum oxide accounts for 75% of the total amount of the superfine powder, the mass fraction of calcium oxide accounts for 8% of the total amount of the superfine powder, and the mass fraction of kaolin accounts for 17% of the total amount of the superfine powder; the mass ratio of the foaming agent to the diethyl ether to the n-hexanol is as follows: 2:3:5; the foaming agent is azodiisobutyronitrile.
2) Adding silicon carbide into the obtained precursor solution, heating to 280 ℃, and keeping the temperature for 0.5 hour;
3) Adding pretreated carbon fiber into the product obtained in the step 2), uniformly mixing, heating to 380 ℃, and introducing nitrogen for 1 hour;
4) Adding phosphoric acid to adjust the pH of the system to 5, heating to 580 ℃, continuously introducing nitrogen, and heating for 1 hour to obtain the gradient roasting modified microporous carbon carrier; when the temperature of the carrier is reduced to 300 ℃, adding copper sulfate and lanthanum sesquioxide to stir and mix the materials, introducing nitrogen, pouring the materials into a hopper, adopting a mold temperature machine to quickly reduce the temperature, adding and reducing a water agent when the temperature of the materials is reduced to 200 ℃, continuing for 1 hour, then stopping introducing the nitrogen, after uniformly stirring, pouring the materials into a spherical mold with the diameter of 20mm, and quickly reducing the temperature to normal temperature; cooling the material in the mold, demolding to obtain a coarse microporous honeycomb catalyst product, and placing the coarse microporous honeycomb catalyst product on a shaking table to perform vibration blowing to obtain a finished product (see fig. 2 and table 2); wherein the mass ratio of copper sulfate to lanthanum oxide is 8:1, the water reducing agent is a naphthalene sulfonate formaldehyde polymer.
The mass ratio of the pretreated carbon fiber to the precursor liquid to the silicon carbide is 70:18:12; the active substance accounts for 2.46 percent of the mass of the microporous carbon carrier modified by the gradient roasting.
The pretreatment carbon fiber is PAN-based carbon fiber, the carbon fiber is immersed in 5% sodium chloride solution for 150min after being subjected to high temperature of 380 ℃ under the protection of nitrogen for 60min, the carbon fiber is used as an anode, graphite is used as a cathode, the voltage is 15 volts, the carbon fiber is anodized for 20min under the condition of 3A current, the surface of the carbon fiber is cleaned by distilled water after treatment, and the carbon fiber is dried for 2h at 105 ℃ in a drying box for later use.
The conductivity of the pretreated carbon fiber obtained above was 21s/m.
As can be seen from the scanning of the surface morphology of the catalyst by an electron microscope in fig. 3, the grooves on the surface of the carbon fiber after surface treatment are generally increased, and the interfacial adhesion property between CF and resin (EP) is improved after modification. The obtained carrier had an internal micro-pore of 0.8m 3 The catalyst has a uniform microporous structure, the active components are uniformly dispersed on the microporous framework, the active components are uniformly loaded, and the components of the obtained catalyst are shown in Table 3. The nominal value of the specific surface area of the obtained catalyst is 1307m 2 /g。
TABLE 3
Element(s) Line type Weight percent of Wt％Sigma
O K line system 13.5 13
Al K line system 24.25 10
Calcium carbonate K line system 8.74 8
Lanthanum (La) K line system 0.3 4
C K line system 51.05 31
Copper (Cu) K line system 2.16 0.14
Total amount of 100
Comparative example 1
1) Mixing and grinding the prepared aluminum oxide, kaolin and calcium oxide into superfine powder, fully mixing, adding a foaming agent, diethyl ether and n-hexanol, further uniformly mixing to obtain mixed slurry, and filtering; the total amount of the foaming agent, the diethyl ether and the n-hexanol accounts for 10% of the mass of the superfine micro powder system, and the superfine micro powder system comprises, by weight, 80% of aluminum oxide, 2% of calcium oxide and 18% of kaolin; the mass ratio of the foaming agent to the diethyl ether to the n-hexanol is as follows: 2:3:5, the foaming agent is diethyl azodicarboxylate.
2) Filtering the mixed slurry, adding silicon carbide into the filtrate, mixing the treated superfine high-strength carbon fiber and active ingredients, adjusting the pH to 5 by using phosphoric acid, stirring and uniformly mixing at normal temperature, roasting at 500 ℃ in a muffle furnace for 1h, introducing nitrogen after roasting, pouring the material into a hopper, quickly cooling by using a mold temperature machine, adding and reducing a water aqua when the temperature of the material is reduced to 150 ℃, continuing for 1h, stopping introducing the nitrogen, uniformly stirring, pouring the material into a spherical mold with the diameter of 20mm, and quickly cooling to normal temperature; cooling the materials in the mold, demolding to obtain a crude catalyst, placing the crude catalyst on a shaking table for vibration blowing to obtain a finished product, wherein the specific surface area of the obtained catalyst is 800m 2 (see FIG. 4).
The dosage ratio of the treated superfine high-strength carbon fiber, the precursor solution and the silicon carbide is 70:15:15; wherein the active ingredients are copper sulfate and lanthanum oxide according to the mass ratio of 6:1, the active component accounts for 5.5 percent of the mass of the carrier.
Application example
The embodiment 1, the embodiment 2, the embodiment 3 and the comparative embodiment 1 are used for treating biochemical treatment effluent of a certain chemical industry park in Gansu by a catalytic ozone oxidation technology, and specifically comprise the following steps:
continuously pumping the wastewater into an ozone oxidation tower, wherein the oxidation tower is filled with a certain amount of catalyst, the catalyst filling accounts for one twentieth of the volume of the total oxidation tower, the catalyst is filled in a bulk mode, the ozone adding amount is 10 g/ton of water, the reaction time is 30min, and the treatment effect is as follows:
Figure BDA0003030695550000081
since ozone oxidation requires a surface contact reaction, the smaller the contact surface area, the less the active component is loaded, and the poorer the catalytic effect. In conclusion, the catalyst in the embodiment of the invention has a regular honeycomb structure, and the surface of the comparative example is smooth and is obviously smaller than the specific surface area of the embodiment, so that the catalytic activity in the ozone oxidation process is far lower than that of the embodiment.

Claims (4)

1. A microporous honeycomb ozone catalyst, characterized in that:
the specific preparation method of the microporous honeycomb ozone catalyst comprises the following steps:
1) Mixing and grinding aluminum oxide, kaolin and calcium oxide into superfine powder, fully mixing, adding a foaming agent, diethyl ether and n-hexanol, and further uniformly mixing to obtain a precursor solution; the total amount of the foaming agent, the diethyl ether and the n-hexanol accounts for 10% of the mass of the superfine powder system, wherein the mass fraction of aluminum oxide accounts for 80% of the total amount of the superfine powder, the mass fraction of calcium oxide accounts for 2% of the total amount of the superfine powder, and the mass fraction of kaolin accounts for 18% of the total amount of the superfine powder; the mass ratio of the foaming agent to the diethyl ether to the n-hexanol is 2:3:5; the foaming agent is azodicarbonamide;
2) Adding silicon carbide into the obtained precursor solution, heating to 250 ℃, and keeping the temperature for 0.5 hour;
3) Adding the pretreated carbon fibers into the product obtained in the step 2), uniformly mixing, heating to 320 ℃, and introducing nitrogen for 1 hour;
4) Adding phosphoric acid to enable the pH value of the system to be 4, heating to 500 ℃, continuously introducing nitrogen, and heating for 1 hour to obtain the gradient roasting modified microporous carbon carrier; when the temperature of the carrier is reduced to 300 ℃, adding manganese sesquioxide, copper sulfate and lanthanum sesquioxide, stirring and mixing the materials, introducing nitrogen, pouring the materials into a hopper, quickly cooling by adopting a mold temperature machine, adding and reducing a water aqua when the temperature of the materials is reduced to 200 ℃, keeping for 1 hour, stopping introducing the nitrogen, after uniformly stirring, pouring the materials into a spherical mold with the diameter of 20mm, and quickly cooling to normal temperature; cooling the material in the mold, demolding to obtain a microporous honeycomb catalyst crude product, and placing the microporous honeycomb catalyst crude product into a shaking table to perform vibration blowing to obtain a finished product; wherein, manganese sesquioxide: copper sulfate: the mass ratio of lanthanum sesquioxide is 8:1:0.5, the water reducing agent is lignosulfonate;
the mass ratio of the pretreated carbon fibers to the precursor liquid to the silicon carbide is 75:15:10; the active substance accounts for 10.36 percent of the mass of the microporous carbon carrier modified by the gradient roasting;
the method comprises the following steps of taking PAN-based carbon fiber as the pretreated carbon fiber, immersing the carbon fiber into 5% potassium chloride solution for 140min after the carbon fiber is subjected to high temperature of 380 ℃ under the protection of nitrogen for 60min, anodizing the carbon fiber for 20min under the conditions of taking the carbon fiber as an anode and graphite as a cathode, using voltage of 15 volts and current of 3A, cleaning the surface of the carbon fiber by using distilled water after the carbon fiber is treated, and drying the carbon fiber for 2h at 105 ℃ in a drying box.
2. A microporous honeycomb ozone catalyst, characterized in that:
the specific preparation method of the microporous honeycomb ozone catalyst comprises the following steps:
1) Mixing and grinding aluminum oxide, kaolin and calcium oxide into superfine powder, fully mixing, adding a foaming agent, diethyl ether and n-hexanol, and further uniformly mixing to obtain a precursor solution; the total amount of the foaming agent, the diethyl ether and the n-hexanol accounts for 11% of the mass of the superfine powder system, wherein the mass fraction of aluminum oxide accounts for 80% of the total amount of the superfine powder, the mass fraction of calcium oxide accounts for 3% of the total amount of the superfine powder, and the mass fraction of kaolin accounts for 17% of the total amount of the superfine powder; the mass ratio of the foaming agent to the diethyl ether to the n-hexanol is 2:3:5; the foaming agent is azodicarbonic acid diethyl ester;
2) Adding silicon carbide into the obtained precursor solution, heating to 260 ℃, and keeping the temperature for 0.5 hour;
3) Adding the pretreated carbon fibers into the product obtained in the step 2), uniformly mixing, heating to 350 ℃, and introducing nitrogen for 1 hour;
4) Adding phosphoric acid to enable the pH value of the system to be 4, heating to 550 ℃, continuously introducing nitrogen, and heating for 0.5 hour to obtain the gradient roasting modified microporous carbon carrier; when the temperature of the carrier is reduced to 300 ℃, adding manganese sesquioxide and copper sulfate, stirring the mixed material, introducing nitrogen, pouring the material into a hopper, rapidly cooling by adopting a mold temperature machine, adding and reducing a water aqua when the temperature of the material is reduced to 200 ℃, continuing for 1 hour, stopping introducing the nitrogen, after uniformly stirring, pouring the material into a spherical mold with the diameter of 20mm, and rapidly cooling to normal temperature; cooling the material in the mold, demolding to obtain a microporous honeycomb catalyst crude product, and placing the microporous honeycomb catalyst crude product into a shaking table to perform vibration blowing to obtain a finished product; wherein, manganese sesquioxide: the mass ratio of the copper sulfate is 10:1, the water reducing agent is lignosulfonate;
the mass ratio of the pretreated carbon fibers to the precursor liquid to the silicon carbide is 72:16:12; the active substance accounts for 3.86 percent of the mass of the microporous carbon carrier modified by the gradient roasting;
the method comprises the following steps of taking the pretreated carbon fibers as PAN-based carbon fibers, immersing the carbon fibers in a 5% sodium chloride solution for 120min after the carbon fibers are subjected to high temperature of 380 ℃ under the protection of nitrogen for 60min, anodizing the carbon fibers for 20min under the conditions that the carbon fibers are taken as an anode and graphite is taken as a cathode, the voltage is 15 volts and the current is 3A, cleaning the surfaces of the carbon fibers by using distilled water after the carbon fibers are treated, and drying the carbon fibers for 2h at 105 ℃ in a drying box.
3. A microporous honeycomb ozone catalyst, characterized in that:
the specific preparation method of the microporous honeycomb ozone catalyst comprises the following steps:
1) Mixing and grinding aluminum oxide, kaolin and calcium oxide into superfine powder, fully mixing, adding a foaming agent, diethyl ether and n-hexanol, and further uniformly mixing to obtain a precursor solution; the total amount of the foaming agent, the diethyl ether and the n-hexanol accounts for 8% of the mass of the superfine powder system, wherein the mass fraction of aluminum oxide accounts for 75% of the total amount of the superfine powder, the mass fraction of calcium oxide accounts for 8% of the total amount of the superfine powder, and the mass fraction of kaolin accounts for 17% of the total amount of the superfine powder; the mass ratio of the foaming agent to the diethyl ether to the n-hexanol is 2:3:5; the foaming agent is azodiisobutyronitrile;
2) Adding silicon carbide into the obtained precursor solution, heating to 280 ℃, and keeping the temperature for 0.5 hour;
3) Adding the pretreated carbon fibers into the product obtained in the step 2), uniformly mixing, heating to 380 ℃, and introducing nitrogen for 1 hour;
4) Adding phosphoric acid to enable the pH value of the system to be 5, heating to 580 ℃, continuously introducing nitrogen, and heating for 1 hour to obtain the gradient roasting modified microporous carbon carrier; when the temperature of the carrier is reduced to 300 ℃, adding copper sulfate and lanthanum oxide, stirring and mixing the materials, introducing nitrogen, pouring the materials into a hopper, quickly cooling by adopting a mold temperature machine, adding and reducing a water aqua when the temperature of the materials is reduced to 200 ℃, continuing for 1 hour, stopping introducing the nitrogen, uniformly stirring, pouring the materials into a spherical mold with the diameter of 20mm, and quickly cooling to the normal temperature; cooling the material in the mold, demolding to obtain a microporous honeycomb catalyst crude product, and placing the microporous honeycomb catalyst crude product into a shaking table to perform vibration blowing to obtain a finished product; wherein the mass ratio of copper sulfate to lanthanum oxide is 8:1, the water reducing agent is naphthalene sulfonate formaldehyde polymer;
the mass ratio of the pretreated carbon fibers to the precursor liquid to the silicon carbide is 70:18:12; the active substance accounts for 2.46 percent of the mass of the microporous carbon carrier modified by the gradient roasting;
the method comprises the following steps of taking PAN-based carbon fiber as the pretreated carbon fiber, immersing the carbon fiber into a 5% sodium chloride solution for 150min after the carbon fiber is subjected to high temperature of 380 ℃ under the protection of nitrogen, anodizing the carbon fiber for 20min under the conditions that the carbon fiber is taken as an anode and graphite is taken as a cathode, the voltage is 15 volts and the current is 3A, cleaning the surface of the carbon fiber by using distilled water after the carbon fiber is treated, and drying the carbon fiber for 2h at 105 ℃ in a drying box.
4. Use of the microporous honeycomb ozone catalyst of any one of claims 1-3, wherein: the application of the catalyst in treating organic wastewater.
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