CN111468105B - Multi-layer structure catalyst for catalytic oxidation of nbsCOD by ozone and preparation method and application thereof - Google Patents

Multi-layer structure catalyst for catalytic oxidation of nbsCOD by ozone and preparation method and application thereof Download PDF

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CN111468105B
CN111468105B CN202010327914.4A CN202010327914A CN111468105B CN 111468105 B CN111468105 B CN 111468105B CN 202010327914 A CN202010327914 A CN 202010327914A CN 111468105 B CN111468105 B CN 111468105B
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catalyst
granulating
multilayer structure
ozone
particles
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CN111468105A (en
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刘晓静
于豹
石伟
王冠平
孙琦
夏梦
于华芹
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Everbright Water Shenzhen Co ltd
Everbright Water Technology Development Nanjing Co ltd
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Everbright Water Shenzhen Co ltd
Everbright Water Technology Development Nanjing 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/745—Iron
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • 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
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/32—Manganese, technetium or rhenium
    • B01J23/34—Manganese
    • B01J35/396—
    • B01J35/40—
    • B01J35/50—
    • B01J35/615—
    • 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
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/34—Organic compounds containing oxygen
    • C02F2101/345—Phenols
    • 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
    • C02F2101/38—Organic compounds containing nitrogen
    • 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
    • C02F2103/06—Contaminated groundwater or leachate
    • 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 discloses a catalyst with a multilayer structure for catalyzing and oxidizing nbsCOD by ozone, and a preparation method and application thereof, and belongs to the technical field of sewage treatment. Firstly, mixing a catalyst carrier and active raw materials to obtain a mixed material; screening and preprocessing the inner cores, putting the screened and preprocessed inner core hard particles into a granulator, and adding a mixture and a binder at a proper rotating speed for granulating to obtain prefabricated particles; finally, the high-strength multi-layer structure ozone catalyst is obtained through calcination treatment. The catalyst with the multilayer structure for catalytic oxidation of nbsCOD by ozone comprises a core and a shell, has the advantages of high catalytic activity, high strength, low manufacturing cost and the like, and is suitable for sewage treatment.

Description

Multi-layer structure catalyst for catalytic oxidation of nbsCOD by ozone and preparation method and application thereof
Technical Field
The invention belongs to the technical field of sewage treatment, and particularly relates to a catalyst with a multilayer structure for catalytic oxidation of nbsCOD by ozone, and a preparation method and application thereof.
Background
Ozone catalytic oxidation is one of the important processes in advanced oxidation technology, and is to utilize a catalyst to catalyze ozone to generate hydroxyl free radicals (OH) with strong oxidability, so as to degrade soluble refractory organic matters (nbsCOD) in water and achieve the purpose of deeply treating sewage. Organic pollutants in the water body are degraded on the surface of the catalyst through complex processes such as adsorption, reaction, desorption and the like, and meanwhile, the water body also obtains deodorizing, decolorizing and sterilizing effects.
At present, most of ozone catalysts in the market use materials such as alumina, silicon oxide, active carbon and the like as carriers, spherical particles are obtained by utilizing a granulating process, and then metals such as iron, cerium, copper, manganese and the like are loaded, so that the supported catalyst is formed by sintering. For example, application publication number CN104759286a, the invention patent application publication number 2015, 7, 8, discloses a method for preparing an ozone catalyst, comprising mixing amorphous alumina powder, catalyst powder, and pore-forming agent to form a catalytic mixture; placing amorphous alumina into a granulator, spraying an adhesive to form alumina mother balls; then putting the alumina mother balls and the catalytic mixture into a ball forming machine, spraying adhesive to form catalyst forming balls; and drying and roasting the prepared catalyst molded sphere to obtain the ozone catalyst. Because the catalytic mixture is sintered on the outer layer of the alumina mother sphere and the components are similar, the adhesion strength of the catalytic mixture is high, the loss of active components is less, and the effective utilization of the active components is ensured.
In addition, the physicochemical properties of the ozone catalyst determine the catalytic efficiency and rate, directly affecting the effectiveness of the ozone catalytic oxidation process. Alumina or activated carbon is a common carrier for preparing catalysts, can provide larger pore volume and specific surface area, and is favorable for adsorbing pollutants in water body to the surface of the catalyst and the active sites of pore channels to react.
According to the search, the application publication number CN106732509A, the invention patent application with the application publication date of 2017, 5 and 31 discloses a preparation method of a modified alumina carrier, a catalytic ozonation catalyst and application thereof, and the invention carries out primary modifier spray dipping, primary drying and primary roasting on an alumina substrate, and naturally cools to room temperature; spraying and soaking the aluminum oxide base material with the modifier for the second time, drying for the second time, roasting for the second time, and naturally cooling to room temperature; obtaining a modified alumina carrier, and using the modified alumina carrier for preparing a catalytic ozonation catalyst. By modifying the alumina substrate, the pore channel structure and polarity of the carrier are changed, which is favorable for the formation of catalytic active sites and the performance of the catalytic active sites, so that the COD removal rate is greatly improved.
However, when ozone molecules contact the catalyst in the water body, hydroxyl radicals are converted and released in a short time and react with pollutants in a contact way, the process mainly occurs in the outer layer part of the catalyst, namely the shell part of the catalyst is a main reaction area catalyzed by ozone, and the internal reaction is weaker, even the core part hardly participates in the reaction. Therefore, the inner core part of the ozone catalyst has more supporting and strengthening effects and smaller catalytic contribution effect, but the strength of the granular catalyst is limited due to the porous property of the alumina or the activated carbon, so that the theoretical service life of the catalyst is influenced. This results in lower practical utilization of the ozone catalyst and higher production cost, and if performance and price cannot be considered in the popularization process, the application of the technology will be severely limited, and market acceptance cannot be obtained.
Disclosure of Invention
1. Problems to be solved
Aiming at the problem of low strength of the catalyst for catalytic oxidation of nbsCOD by ozone in the prior art, the invention provides a multilayer structure catalyst for catalytic oxidation of nbsCOD by ozone, and a preparation method and application thereof. The method comprises the steps of screening a core material with a proper particle size and preprocessing the core material to obtain a preprocessed core; granulating the mixture of the inner core, the catalyst carrier and the catalyst activity and the binder, and then calcining to firmly combine the inner core and the outer shell to form a whole, thereby obtaining the catalyst finished product particles with high strength, high catalytic activity and controllable cost and a multi-layer structure.
2. Technical proposal
In order to solve the problems, the technical scheme adopted by the invention is as follows:
the invention relates to a preparation method of a catalyst with a multilayer structure for catalytic oxidation of nbsCOD by ozone, which comprises the following steps:
s10, mixing and grinding raw materials
Drying the catalyst carrier and the catalyst active raw materials, mixing and ball milling to obtain a uniformly dispersed mixed material;
s20, screening and preprocessing of kernel materials
Screening out a core material with an average particle size of 1-5mm, and then placing the core material into silica sol or water glass solution for pretreatment to obtain a pretreated core;
s30, preparation of catalyst prefabricated particles with multilayer structure
Putting the inner core obtained in the step S20 into a granulating disc, adding the mixed material and the binder obtained in the step S10, and granulating to obtain the catalyst prefabricated particles with the multilayer structure;
s40, calcining treatment
And (3) calcining the multilayer catalyst prefabricated particles obtained in the step (S30), oxidizing the catalyst active raw material into metal oxide to become active ingredients, and firmly combining the inner core and the outer shell to form a whole to obtain the catalyst finished product particles with the multilayer structure.
Preferably, in step S10, the catalyst carrier is ρ -alumina carrier with specific surface area of more than 200m 2 And/g, particle size of 300 mesh.
Preferably, in the step S10, the rotation speed of the ball milling is 300-600r/min, and the time of the ball milling is 0.5-2h.
Preferably, in the step S10, the active raw material of the catalyst is ferric salt or manganese salt, and the granularity is less than or equal to 300 meshes; wherein the ferric salt is one or more of ferric chloride, ferric nitrate and ferric oxalate, and the manganese salt is one or more of manganese chloride, manganese nitrate and manganese oxalate.
Preferably, in step S20, the core material is one or more of ceramsite, sand or volcanic particles.
More preferably, the ceramsite is crushed stone particles obtained by crushing natural ores, the sand particles are quartz or mineral particles, and the volcanic rock particles are lava powder formed by cooling and crystallizing volcanic sprayed out of the ground surface.
Preferably, in step S20, the mass ratio of the core material to the silica sol or water glass solution is 1:1-1:5.
Preferably, in step S30, granulation is carried out in stages in a granulation disc, and in the first granulation stage, the granulation speed is 10-20r/min; granulating for 30-60min; in the second granulation stage, the granulation rotating speed is 20-35r/min; the granulating time is 10-40min.
Preferably, in step S30, the mass ratio of the core to the mixed material is 1:1-1:3; the mass ratio of the binder to the mixed material is 1:8-1:15.
More preferably, in step S30, the binder is a silica sol solution having a mass fraction of 5% -25%.
Preferably, in step S40, the calcination temperature of the calcination treatment is 400-700 ℃ and the calcination time is 2-6 hours.
The catalyst with the multilayer structure for catalytic oxidation of nbsCOD by ozone is prepared by the preparation method of the catalyst with the multilayer structure for catalytic oxidation of nbsCOD by ozone, wherein the ratio of the shell thickness to the core particle size of the catalyst with the multilayer structure is 1:1-5:1.
More preferably, the finished catalyst particles have a particle size of from 6 to 12mm.
Preferably, the mass of the catalyst active ingredient in the catalyst with the multilayer structure is 2% -10% of the mass of the catalyst carrier.
The application of the catalyst with the multilayer structure for catalyzing and oxidizing the nbsCOD by ozone in sewage treatment.
3. Advantageous effects
Compared with the prior art, the invention has the beneficial effects that:
(1) According to the preparation method of the catalyst with the multilayer structure for catalyzing and oxidizing the nbsCOD by using ozone, natural mineral particles with rough surfaces, high-low concave-convex shapes and pore channels are adopted as the inner core material, and the particle size of the inner core material is screened and pretreated, so that catalyst fine materials can be better adhered to the inner core under the action of a binder and even are embedded into gaps or holes on the concave-convex surfaces of the inner core, high binding force is further formed, the inner layer and the outer layer of the catalyst is reduced, and the strength of the catalyst particles is enhanced;
(2) According to the preparation method of the catalyst with the multilayer structure for catalyzing and oxidizing the nbsCOD by using ozone, natural ceramsite, sand grains or volcanic rock particles are adopted as core materials, the sources of the core materials are wide, the cost is low, the core materials are utilized to replace part of the catalyst raw materials to form the catalyst with the multilayer structure, the raw material cost and the production cost can be effectively reduced, and the comprehensive cost can be reduced by about 30%;
(3) According to the preparation method of the catalyst with the multilayer structure for catalytic oxidation of nbsCOD by ozone, in the granulating process, granulating is carried out in a staged mode, and in the first granulating stage, the granulating rotating speed is controlled to be 10-20r/min; granulating for 30-60min; in the second granulation stage, the granulation rotating speed is controlled to be 20-35r/min; the granulating time is 10-40min, and the mixed material powder can be continuously compacted layer by layer and coated on the inner core in the rolling process of the inner core, so that the gaps among the powder particles are continuously reduced, the granulating problem caused by irregular size of the inner core material is solved, the local non-uniformity of the strength is avoided, and the overall strength of the catalyst particles is further increased;
(4) The multi-layer structure catalyst for catalyzing and oxidizing nbsCOD by ozone disclosed by the invention has the advantages that the ratio of the shell thickness to the core particle size is 1:1-5:1, and the mixed material powder can be firmly attached to the core by controlling the shell thickness to the core particle size within a proper ratio range, so that the catalyst has higher strength;
(5) The catalyst with the multilayer structure for catalytic oxidation of nbsCOD by ozone is used for sewage treatment, has the advantages of high catalytic activity, good treatment effect, low cost and the like, and is beneficial to popularization of the catalytic oxidation technology by ozone in the field of sewage treatment.
Drawings
FIG. 1 is a flow chart of a preparation method of a catalyst with a multilayer structure for catalytic oxidation of nbsCOD by ozone;
FIGS. 2a-c are photographs of core materials selected in the preparation process of the catalyst with a multilayer structure for ozone catalytic oxidation of nbsCOD, FIG. 2a is a volcanic core, FIG. 2b is a ceramsite core, and FIG. 2c is a sand core;
fig. 3 is an external view and a cross-sectional view of the iron-based multi-layer structure ozone catalyst of example 1.
Detailed Description
The invention is further described below in connection with specific embodiments.
As shown in FIG. 1, the preparation method of the catalyst with the multilayer structure for catalyzing and oxidizing nbsCOD by ozone comprises the following specific steps:
s10, mixing and grinding raw materials
Drying the catalyst carrier and the catalyst active raw material at 65-85 ℃ for 5-10h; after drying, mixing the catalyst carrier and the catalyst active raw material, ball milling, wherein the ball milling speed is 300-600r/min, and the ball milling time is 0.5-2h, so as to obtain a uniformly dispersed mixed material;
wherein the catalyst carrier is rho-alumina carrier with specific surface area more than 200m 2 G, particle size of 300 meshes; the active raw material of the catalyst is ferric salt or manganese salt, the granularity is less than or equal to 300 meshes, the ferric salt is one or more of ferric chloride, ferric nitrate and ferric oxalate, and the manganese salt is one or more of manganese chloride, manganese nitrate and manganese oxalate.
The particle size of the catalyst carrier is controlled to be 300 meshes or less, so that the contact with water in the forming process can be further increased, the binding force is improved, the smaller the particle size is, the larger the specific surface area is, the more the attachment points of the supported active components can be provided, and the catalytic performance and strength of the catalyst are improved;
in addition, the particle size of the catalyst active raw material is reduced to below 300 meshes, so that the catalyst active raw material and the rho-alumina carrier can be fully contacted and mixed, more active sites are released, and as the active components and water can not form binding force, only the particle size is small enough to adhere to the surface of the alumina, the alumina can be hydrated into a whole when meeting water, so that the catalyst active raw material is firmly loaded.
S20, screening and preprocessing of kernel materials
One or more of ceramsite, sand grain or volcanic rock particles are selected as the core material, and the core material particles with the average particle size of 1-5mm are screened out through a screen, wherein the surfaces of the particles are in irregular shapes with uneven surfaces, as shown in figures 2 a-c. The ceramsite can be crushed stone particles obtained by crushing natural ores, the sand particles are quartz or mineral particles, and the volcanic rock particles are lava powder formed by cooling and crystallizing after volcanic is sprayed out of the ground surface.
Soaking the selected kernel material with clear water for 1-3h in the mass ratio of 3:1-5:1, dripping 1mol/L sodium hydroxide solution with the volume of 20-80ml, oscillating and cleaning to remove powder and greasy dirt on the surface of the kernel material, filtering, and drying to remove water; soaking the dried hard core material in a silica sol or water glass solution with the mass ratio of 10-40% and the silica sol or water glass solution of 1:1-1:5 for 2-6h, filtering and drying after soaking to obtain a pretreated core;
it should be noted that, because natural ceramsite, sand or volcanic rock particles have certain dust and greasy dirt in the process of processing and crushing, impurities on the surface of the material need to be removed firstly, otherwise, the forming is not facilitated; in addition, the surfaces of the materials are rough, have concave-convex shapes and pore channels with high and low, the surfaces of the materials can be soaked into the surfaces and pore channels of the materials by utilizing silica sol or water glass solution to treat the surfaces, so that uniform adhesive films are formed, the outer layer powder of the catalyst is covered on the inner core in the subsequent forming process, and meanwhile, part of the powder can be embedded into gaps or holes on the concave-convex surfaces of the inner core, so that the materials are firmly adhered to form high binding force, the particle forming is facilitated, and the phenomenon of inner and outer layer unshelling after the forming is avoided.
S30, preparation of catalyst prefabricated particles with multilayer structure
Putting the inner core obtained in the step S20 into a granulating disc, adding the mixed material obtained in the step S10 and a binder (for example, a silica sol solution with the mass fraction of 5% -25%) into the granulating disc for granulating, wherein the mass ratio of the inner core to the mixed material is 1:1-1:3; the mass ratio of the binder to the mixed material is 1:8-1:15; wherein, granulating is carried out in stages in a granulating disc, and the granulating rotating speed is 10-20r/min in the first granulating stage; granulating for 30-60min; in the second granulation stage, the granulation rotating speed is 20-35r/min; granulating for 10-40min to obtain multilayer catalyst prefabricated particles;
it should be noted that, because the size of the kernel is irregular, the rotation speed of the granulation disc needs to be adjusted in stages in the process of adhering and forming the powder of the mixed material to carry out granulation, in the first granulation stage, the powder of the mixed material just begins to adhere, the rotation speed is appropriately slow, so that the powder of the mixed material can be gradually and firmly adhered to the kernel, when the powder of the first layer and the powder of the second layer are gradually and firmly adhered, the rotation speed can be appropriately increased to carry out the second granulation stage, thus not only improving the forming speed, but also enabling the powder of the mixed material to be continuously compacted layer by layer and coated on the kernel in the process of rolling the kernel, continuously reducing the gaps among the powder particles, overcoming the uneven adhesion caused by the irregular size of the kernel material, avoiding the uneven local strength, and further increasing the integral strength of the catalyst particles.
S40, calcining treatment
And (3) calcining the multilayer catalyst prefabricated particles obtained in the step (S30), wherein the calcining temperature is 400-700 ℃, the calcining time is 2-6 hours, the catalyst active raw materials are oxidized into metal oxides to become active ingredients in the calcining process, the mass of the catalyst active ingredients is 2-10% of the mass of the catalyst carrier, and the inner core and the outer shell are firmly combined to form a whole, so that the multilayer catalyst finished product particles are obtained.
The catalyst finished product prepared by the preparation method of the catalyst with the multilayer structure for catalyzing and oxidizing nbsCOD by ozone is 6-12mm in particle size, and the ratio of the shell thickness to the core particle size is 1:1-5:1.
Generally, the larger the particle size, the higher the strength of the catalyst particles, the longer the theoretical service life, and the water head resistance in the water body can be reduced when the catalyst is applied, which is beneficial to reducing the energy consumption. The smaller the particle size of the catalyst particles, the catalyst is piled up in the same volume, and the specific surface area of the catalyst with small particle size is higher, which is more beneficial to catalytic reaction. Therefore, the particle size of the catalyst finished product is controlled within the range of 6-12mm, so that the catalytic reaction efficiency is improved, and the energy consumption is reduced during application.
It is further described that the catalyst shell is formed by wrapping powder layer by layer and then calcining to finally integrate with the inner core, if the thickness of the shell is small, the dosage of the catalyst carrier and the active components can be saved, and the preparation cost can be controlled. However, we have found that the strength of the particulate catalyst during the rolling process is increased by virtue of the powder being continuously coated onto the cores layer by layer during the rolling process and being gradually compacted, thereby continuously reducing the gaps between the powder particles. Although the thin shell can be molded, the catalyst is continuously flushed by gas and liquid in water, the thin shell reduces the strength of the catalyst and also influences the service life. In addition, the larger the particle diameter of the core particles as a core supporting material, the more difficult the catalyst powder is to adhere to the core particles, and the more difficult the catalyst powder is to be balled; too small a particle size is detrimental to the strength of the catalyst.
Therefore, the catalyst has high strength and ideal catalytic activity by screening the inner core with proper size and controlling the thickness of the attached catalyst layer outer shell within a proper proportion range.
The catalyst with the multilayer structure for catalytic oxidation of nbsCOD by ozone can be applied to sewage treatment. The method comprises the following specific steps:
the catalyst with the multilayer structure for catalytic oxidation of nbsCOD by ozone is added into sewage, the filling rate of the catalyst is 10-50%, ozone is introduced into the sewage through a microporous aeration disc or a jet aerator by utilizing an ozone adding unit, the ozone adding amount is 5-100mg/L, catalytic reaction is carried out in a reaction tank to remove COD, and the reaction time is 10-120min.
Example 1
The preparation method of the catalyst with the multilayer structure for catalyzing and oxidizing nbsCOD by ozone in the embodiment comprises the following specific steps:
s10, mixing and grinding raw materials
Drying the catalyst carrier rho-alumina and the active raw material ferric oxalate, wherein the drying temperature is 65 ℃ and the drying time is 5 hours; after drying, mixing and ball milling rho-alumina and ferric oxalate, wherein the ball milling speed is 300r/min, and the ball milling time is 0.5h, so as to obtain a uniformly dispersed mixed material;
s20, screening and preprocessing of kernel materials
Volcanic rock particles are selected as a hard core material, and particles with an average particle diameter of 2mm are screened out through a screen, wherein the appearance of the particles is in an irregular shape with uneven surface, as shown in figure 2 a. Then, the volcanic rock particles are soaked by clear water, the mass ratio of the clear water to the volcanic rock particles is 3:1, the soaking time is 1h, a sodium hydroxide solution with the volume of 40ml and the concentration of 1mol/L is dripped, the powder and the greasy dirt on the surfaces of the volcanic rock particles are removed by shaking and cleaning, and the water is removed by filtering and drying; soaking the dried volcanic rock particles in a silica sol or water glass solution with the mass ratio of 15% to 1:1.5, soaking for 2 hours, filtering after soaking, and drying to obtain a pretreated inner core;
s30, preparation of catalyst prefabricated particles with multilayer structure
Putting the core hard volcanic rock particles with the particle size of 2mm obtained in the step S20 into a granulating disc, adding the mixed material obtained in the step S10 and a silica sol solution with the mass content of 15% into the granulating disc for granulating, wherein the mass ratio of the volcanic rock particles to the mixed material is 1:1; the mass ratio of the silica sol solution to the mixed material is 1:8; wherein, granulating is carried out in stages in a granulating disc, and the granulating rotating speed is 12r/min in the first granulating stage; granulating for 60min; in the second granulation stage, the granulation rotating speed is 23r/min; granulating for 20min to obtain catalyst prefabricated particles with a multilayer structure;
s40, calcining treatment
And (3) calcining the multilayer catalyst prefabricated particles obtained in the step (S30), wherein the calcining temperature is 550 ℃, the calcining time is 3 hours, the catalyst active raw material ferric oxalate is decomposed into ferric oxide to become active ingredients in the calcining process, the mass of the ferric oxide is 8% of the mass of the catalyst carrier, the mixed components of the inner core volcanic rock, the outer shell aluminum oxide and the ferric oxide are firmly combined to form a whole, and the catalyst finished product particles with the multilayer structure are obtained, and the particle size of the catalyst finished product particles is about 6mm. The appearance and cross-sectional view of the iron-based multilayer catalyst of this example are shown in fig. 3.
Example 2
The basic content of this embodiment is the same as that of embodiment 1, except that: the preparation method of the catalyst with the multilayer structure for catalyzing and oxidizing nbsCOD by ozone in the embodiment comprises the following specific steps:
s10, mixing and grinding raw materials
Drying the catalyst carrier rho-alumina and the active raw material manganese oxalate, wherein the drying temperature is 65 ℃ and the drying time is 6 hours; after drying, carrying out mixed ball milling on rho-alumina and manganese oxalate, wherein the ball milling speed is 400r/min, and the ball milling time is 1h, so as to obtain a uniformly dispersed mixed material;
s20, screening and preprocessing of kernel materials
Volcanic rock particles are selected as a hard core material, and particles with the average particle diameter of 3mm are screened out through a screen, wherein the appearance of the particles is in an irregular shape with uneven surface, as shown in figure 2 a. Soaking volcanic rock particles with clear water for 1.5h in a mass ratio of 3:1, dropwise adding a sodium hydroxide solution with a volume of 30ml and a concentration of 1mol/L, oscillating and cleaning to remove powder and greasy dirt on the surfaces of the volcanic rock particles, filtering, and drying to remove water; soaking the dried volcanic rock particles in a silica sol or water glass solution with the mass ratio of 18% to 1:1.8, soaking for 2.5h, filtering after soaking, and drying to obtain a pretreated inner core;
s30, preparation of catalyst prefabricated particles with multilayer structure
Putting the inner core hard volcanic particles with the particle size of 3mm obtained in the step S20 into a granulating disc, adding the mixed material obtained in the step S10 and the silica sol solution with the mass content of 18% into the granulating disc for granulating, wherein the mass ratio of the volcanic particles to the mixed material is 1:1.4; the mass ratio of the silica sol solution to the mixed material is 1:9; wherein, granulating is carried out in stages in a granulating disc, and the granulating rotating speed is 15r/min in the first granulating stage; granulating for 30min; in the second granulation stage, the granulation rotating speed is 25r/min; granulating for 30min to obtain catalyst prefabricated particles with a multilayer structure;
s40, calcining treatment
And (3) calcining the multilayer catalyst prefabricated particles obtained in the step (S30), wherein the calcining temperature is 500 ℃, the calcining time is 2 hours, the manganese oxalate serving as the active raw material of the catalyst is decomposed into manganese oxide to become an active ingredient, the mass of the manganese oxide is 6% of the mass of the catalyst carrier, the mixed components of the inner core volcanic rock, the outer shell aluminum oxide and the manganese oxide are firmly combined to form a whole, and the catalyst finished product particles with the multilayer structure are obtained, and the particle size of the catalyst finished product particles is about 8mm.
Example 3
The basic content of this embodiment is the same as that of embodiment 1, except that: the preparation method of the catalyst with the multilayer structure for catalyzing and oxidizing nbsCOD by ozone in the embodiment comprises the following specific steps:
s10, mixing and grinding raw materials
Drying the catalyst carrier rho-alumina and the active raw material ferric oxide, wherein the drying temperature is 70 ℃ and the drying time is 6 hours; after drying, mixing and ball milling rho-alumina and ferric oxalate, wherein the ball milling speed is 450r/min, and the ball milling time is 1.5h, so as to obtain a uniformly dispersed mixed material;
s20, screening and preprocessing of kernel materials
Volcanic rock particles are selected as a hard core material, and particles with the average particle diameter of 4mm are screened out through a screen, wherein the appearance of the particles is in an irregular shape with uneven surface, as shown in figure 2 a. Soaking volcanic rock particles with clear water for 1.5h at a mass ratio of 3.5:1, dropwise adding a sodium hydroxide solution with a volume of 20ml and a concentration of 1mol/L, oscillating and cleaning to remove powder and greasy dirt on the surfaces of the volcanic rock particles, filtering, and drying to remove water; soaking the dried volcanic rock particles in a silica sol or water glass solution with the mass ratio of 20% to the silica sol or water glass solution of 1:2 for 3 hours, filtering after soaking, and drying to obtain a pretreated inner core;
s30, preparation of catalyst prefabricated particles with multilayer structure
Putting the core hard ceramsite with the particle size of 4mm obtained in the step S20 into a granulating disc, adding the mixed material obtained in the step S10 and a silica sol solution with the mass content of 20% for granulating, wherein the mass ratio of the volcanic rock particles to the mixed material is 1:1.8; the mass ratio of the silica sol solution to the mixed material is 1:10; wherein, granulating is carried out in stages in a granulating disc, and the granulating rotating speed is 10r/min in the first granulating stage; granulating for 45min; in the second granulation stage, the granulation rotating speed is 20r/min; granulating for 35min to obtain catalyst prefabricated particles with a multilayer structure;
s40, calcining treatment
And (3) calcining the multilayer catalyst prefabricated particles obtained in the step (S30), wherein the calcining temperature is 450 ℃, the calcining time is 4 hours, the catalyst active ingredient is ferric oxide, the mass of the ferric oxide is 4% of the mass of the catalyst carrier in the calcining process, the mixed components of the inner core volcanic rock, the outer shell alumina and the ferric oxide are firmly combined to form a whole, and the catalyst finished product particles with the multilayer structure are obtained, and the particle size of the catalyst finished product particles is about 9mm.
Example 4
The basic content of this embodiment is the same as that of embodiment 1, except that: the preparation method of the catalyst with the multilayer structure for catalyzing and oxidizing nbsCOD by ozone in the embodiment comprises the following specific steps:
s10, mixing and grinding raw materials
Drying the catalyst carrier rho-alumina and the active raw material manganese oxide, wherein the drying temperature is 70 ℃ and the drying time is 6 hours; after drying, carrying out mixed ball milling on rho-alumina and manganese oxide, wherein the ball milling speed is 550r/min, and the ball milling time is 2h, so as to obtain a uniformly dispersed mixed material;
s20, screening and preprocessing of kernel materials
And selecting volcanic rock particles as a hard core material, and screening out particles with the average particle diameter of 2mm through a screen, wherein the appearance of the particles is in an irregular shape with uneven surface. Then, the volcanic rock particles are soaked by clear water, the mass ratio of the clear water to the volcanic rock particles is 3:1, the soaking time is 3 hours, 25ml of sodium hydroxide solution with the concentration of 1mol/L is dripped, the powder and the greasy dirt on the surfaces of the volcanic rock particles are removed by shaking and cleaning, and the water is removed by filtering and drying; soaking the dried hard volcanic rock particles in a silica sol or water glass solution with the mass ratio of 15% to the silica sol or water glass solution of 1:2 for 3.5 hours, filtering after soaking, and drying to obtain a pretreated inner core;
s30, preparation of catalyst prefabricated particles with multilayer structure
Putting the core hard sand grains with the particle size of 2mm obtained in the step S20 into a granulating disc, adding the mixed material obtained in the step S10 and a silica sol solution with the mass content of 25% into the granulating disc for granulating, wherein the mass ratio of the volcanic rock particles to the mixed material is 1:2; the mass ratio of the silica sol solution to the mixed material is 1:12; wherein, granulating is carried out in stages in a granulating disc, and the granulating rotating speed is 16r/min in the first granulating stage; granulating for 35min; in the second granulation stage, the granulation rotating speed is 30r/min; granulating for 20min to obtain catalyst prefabricated particles with a multilayer structure;
s40, calcining treatment
And (3) calcining the multilayer catalyst prefabricated particles obtained in the step (S30), wherein the calcining temperature is 500 ℃, the calcining time is 2 hours, the catalyst active ingredient is manganese oxide, the mass of the manganese oxide is 4% of the mass of the catalyst carrier in the calcining process, the mixed components of the inner core volcanic rock, the outer shell aluminum oxide and the manganese oxide are firmly combined to form a whole, and the catalyst finished product particles with the multilayer structure are obtained, and the particle size of the catalyst finished product particles is about 7mm.
Comparative example 1
The basic content of this comparative example is the same as that of example 1, except that: the preparation method of the catalyst for catalyzing and oxidizing nbsCOD by ozone in the comparative example comprises the following specific steps:
s10, mixing and grinding raw materials
Drying the catalyst carrier rho-alumina and the active raw material ferric oxalate, wherein the drying temperature is 65 ℃ and the drying time is 8 hours; after drying, mixing and ball milling rho-alumina and ferric oxalate, wherein the ball milling speed is 300r/min, and the ball milling time is 0.5h, so as to obtain a uniformly dispersed mixed material;
s20, preparation of catalyst prefabricated particles
Starting a granulator, adding the mixed material obtained in the step S10 and 15% of silica sol solution for granulation, wherein the mass ratio of the silica sol solution to the mixed material is 1:15; wherein, granulating is carried out in stages in a granulating disc, and the granulating rotating speed is 20r/min in the first granulating stage; granulating for 50min; in the second granulation stage, the granulation rotating speed is 35r/min; granulating for 40min to obtain catalyst prefabricated particles;
s30, calcining treatment
And (3) calcining the catalyst prefabricated particles obtained in the step (S30), wherein the calcining temperature is 550 ℃, the calcining time is 3h, the catalyst active raw material ferric oxalate is decomposed into ferric oxide to become active ingredients in the calcining process, the mass of the ferric oxide is 8% of the mass of the catalyst carrier, and the iron-based catalyst finished product particles with a single structure are obtained, and the particle size of the catalyst finished product particles is about 6mm.
Comparative example 2
The basic content of this comparative example is the same as that of example 1, except that: the preparation method of the catalyst with the multilayer structure for catalyzing and oxidizing nbsCOD by ozone in the comparative example comprises the following specific steps:
s10, mixing and grinding raw materials
Drying the catalyst carrier rho-alumina and the active raw material manganese oxide, wherein the drying temperature is 70 ℃ and the drying time is 9 hours; after drying, carrying out mixed ball milling on rho-alumina and manganese oxide, wherein the ball milling speed is 300r/min, and the ball milling time is 0.5h, so as to obtain a uniformly dispersed mixed material;
s20, preparation of catalyst prefabricated particles with multilayer structure
Placing 2 mm-diameter core hard sand grains (without screening and pretreatment) in a granulating disc as shown in fig. 2c, and adding the mixed material obtained in the step S10 and a silica sol solution with 15% mass content for granulating, wherein the mass ratio of the sand grains to the mixed material is 1:1.2; the mass ratio of the silica sol solution to the mixed material is 1:12; wherein the granulation is carried out in stages in a granulation disc, and the granulation rotating speed is 14r/min in the first granulation stage; granulating for 60min; in the second granulation stage, the granulation rotating speed is 23r/min; granulating for 30min to obtain catalyst prefabricated particles with a multilayer structure;
s30, calcining treatment
And (3) calcining the multilayer catalyst prefabricated particles obtained in the step (S30), wherein the calcining temperature is 550 ℃, the calcining time is 3 hours, the catalyst active ingredient is manganese oxide, the mass of the manganese oxide is 8% of the mass of the catalyst carrier in the calcining process, the mixed components of the inner core sand grains, the outer shell aluminum oxide and the manganese oxide are firmly combined to form a whole, and the multilayer catalyst finished product particles are obtained, and the particle size of the catalyst finished product particles is about 6mm.
The ozone catalyst prepared by the preparation method of the catalyst for catalyzing and oxidizing nbsCOD by ozone in examples 1-4 and comparative examples 1-2 is used for sewage treatment, and comprises the following specific steps:
adding the catalysts prepared in examples 1-4 and comparative examples 1-2 into sewage, and introducing ozone into the sewage, wherein the concentration of ozone is 20mg/L, the gas flow is 0.5L/min, the catalyst filling amount is 2L, the test water amount is about 5L, and the total test volume is about 6L; and (3) carrying out catalytic reaction in the reaction tank, taking effluent from the reaction tank to measure COD removal rate in the catalytic reaction for 60min, and taking an experimental group without catalyst as a blank control group in the experimental process, wherein all detection results are shown in table 1. The method for measuring the COD adopts a rapid closed catalytic digestion method (potassium dichromate titration), and the method for calculating the removal rate of the COD comprises the following steps:
COD removal (%) = (COD inlet water-COD outlet water)/COD inlet water x 100%.
And the sewage adopted in the experimental process is sewage secondary sedimentation tank effluent added with aniline and phenol targets and landfill leachate biochemical effluent.
Table 1 experimental data for ozone catalysis of the catalyst
Figure BDA0002463878810000111
As can be seen from table 1, the removal rate of nbs cod was increased to a different extent after the ozone catalytic oxidation reaction of the multi-layered catalyst based on the core hard material according to the present invention was carried out, compared with the blank group without the catalyst, and the catalytic effect of the catalyst in the reaction was remarkable.
Meanwhile, the catalysts of examples 1 to 4 and comparative examples 1 to 2 were characterized, and the obtained data of strength, porosity, water absorption and the like are shown in Table 2.
Table 2 characterization data for catalysts
Figure BDA0002463878810000112
Figure BDA0002463878810000121
As is clear from table 2, although the catalyst of comparative example 1, to which the hard core was not added, had higher porosity and water absorption properties, but had lower strength, the strength of the catalyst particles of the multilayer structure to which the hard core was added was significantly improved, but the strength of the multilayer catalyst of comparative example 2, which was prepared from the core material without pretreatment, was severely reduced due to insufficient binding force, which easily caused a peeling phenomenon.
In conclusion, the multi-layer structure catalyst prepared by the preparation method provided by the invention has the advantages of high catalytic activity, high strength, low manufacturing cost and the like, and is suitable for sewage treatment, and the catalyst has higher strength while keeping higher catalytic effect, solves the problem of low strength of the catalyst for catalytic oxidation of nbsCOD by ozone in the prior art.

Claims (6)

1. The preparation method of the catalyst with the multilayer structure for catalyzing and oxidizing nbsCOD by ozone comprises the following steps:
s10, mixing and grinding raw materials
Drying the catalyst carrier and the catalyst active raw materials, mixing and ball milling to obtain a uniformly dispersed mixed material;
s20, screening and preprocessing of kernel materials
Screening out a core material with an average particle size of 1-5mm, wherein the core material is one or more of ceramsite, sand grains or volcanic rock particles; then soaking the core material in 10-40% of silica sol or water glass solution for pretreatment, wherein the mass ratio of the core material to the silica sol or water glass solution is 1:1-1:5, the soaking time is 2-6h, and filtering and drying are carried out after soaking to obtain a pretreated core;
s30, preparation of catalyst prefabricated particles with multilayer structure
Putting the inner core obtained in the step S20 into a granulating disc, adding the mixed material and the binder obtained in the step S10, and granulating, wherein the mass ratio of the inner core to the mixed material is 1:1-1:3; the mass ratio of the binder to the mixed material is 1:8-1:15, and the catalyst prefabricated particles with the multilayer structure are obtained;
wherein, granulating is carried out in stages in a granulating disc, and the granulating rotating speed is 10-20r/min in the first granulating stage; granulating for 30-60min; in the second granulation stage, the granulation rotating speed is 20-35r/min; granulating for 10-40min;
s40, calcining treatment
And (3) calcining the multilayer catalyst prefabricated particles obtained in the step (S30), oxidizing the catalyst active raw material into metal oxide to become active ingredients, and firmly combining the inner core and the outer shell to form a whole to obtain the catalyst finished product particles with the multilayer structure.
2. The method for preparing the catalyst with the multilayer structure for catalytic oxidation of nbsCOD by ozone according to claim 1, which is characterized in that: in the step S10, the active raw material of the catalyst is ferric salt or manganese salt, and the granularity is less than or equal to 300 meshes; wherein the ferric salt is one or more of ferric chloride, ferric nitrate and ferric oxalate, and the manganese salt is one or more of manganese chloride, manganese nitrate and manganese oxalate.
3. The method for preparing the catalyst with the multilayer structure for catalytic oxidation of nbsCOD by ozone according to claim 1, which is characterized in that: in the step S40, the calcination temperature of the calcination treatment is 400-700 ℃ and the calcination time is 2-6h.
4. A catalyst with a multilayer structure for catalytic oxidation of nbs cod by ozone, which is prepared by the preparation method of the catalyst with a multilayer structure for catalytic oxidation of nbs cod by ozone according to any one of claims 1 to 3, wherein the ratio between the shell thickness and the core particle size of the catalyst with a multilayer structure is 1:1 to 5:1.
5. The catalyst of claim 4, wherein the mass of the catalyst active component in the catalyst is 2% -10% of the mass of the catalyst carrier.
6. The use of a catalyst of a multilayer structure for the catalytic oxidation of nbsCOD by ozone in accordance with claim 4 in the treatment of sewage.
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