CN110981199B - Treatment method of waste SCR denitration catalyst, composite opacifier for ceramics, ceramic glaze and ceramic product - Google Patents

Treatment method of waste SCR denitration catalyst, composite opacifier for ceramics, ceramic glaze and ceramic product Download PDF

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CN110981199B
CN110981199B CN201911407962.8A CN201911407962A CN110981199B CN 110981199 B CN110981199 B CN 110981199B CN 201911407962 A CN201911407962 A CN 201911407962A CN 110981199 B CN110981199 B CN 110981199B
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scr denitration
denitration catalyst
waste scr
treating
ceramics
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CN110981199A (en
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敖卫华
丁浩
孙思佳
林昌恒
张啸
林陈鑫
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China University of Geosciences Beijing
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China University of Geosciences Beijing
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
    • C04B41/5022—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with vitreous materials
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
    • C04B41/81—Coating or impregnation
    • C04B41/85—Coating or impregnation with inorganic materials
    • C04B41/86—Glazes; Cold glazes

Abstract

The invention provides a treatment method of a waste SCR denitration catalyst, a composite opacifier for ceramics, a ceramic glaze and a ceramic product, and relates to the technical field of treatment of waste SCR denitration catalysts. Mixing and crushing the pretreated waste SCR denitration catalyst, wollastonite and calcium carbonate with an optional dispersing agent to obtain a composite opacifier for ceramics; the waste SCR denitration catalyst is used as a raw material of the composite opacifier for the ceramic, so that the problem of recycling of the waste SCR denitration catalyst is solved, the utilization value of the waste SCR denitration catalyst is greatly improved, the production cost of the composite opacifier for the ceramic is greatly reduced, and the obtained composite opacifier for the ceramic has good opacifying performance when being used. The invention also provides a composite opacifier for ceramics, which is prepared by adopting the treatment method of the waste SCR denitration catalyst.

Description

Treatment method of waste SCR denitration catalyst, composite opacifier for ceramics, ceramic glaze and ceramic product
Technical Field
The invention relates to the technical field of treatment of waste SCR denitration catalysts, in particular to a treatment method of a waste SCR denitration catalyst, a composite opacifier for ceramics, a ceramic glaze and a ceramic product.
Background
The Selective Catalytic Reduction (SCR) denitration technology is an efficient, reliable and mature flue gas denitration technology and is widely applied to a boiler flue gas denitration system of a coal-fired power plant, wherein an SCR denitration catalyst is a key component of the technology. The SCR denitration catalyst mainly comprises titanium dioxide, vanadium pentoxide, tungsten trioxide or molybdenum trioxide. In the actual operation of the SCR device, the continuous high temperature environment and the large amount of flue gas with alkali metals poisoning the catalyst can cause the active centers on the surface of the catalyst to be reduced, thereby reducing the catalytic effect of the catalyst. A large amount of waste SCR denitration catalysts are eliminated every year. Therefore, the waste SCR denitration catalyst has become a significant solid waste treatment problem which plagues the field. Under the premise that a mature waste SCR denitration catalyst treatment technology is not available at home at present, in order to solve the important environmental problem to be faced, the waste SCR denitration catalyst recovery technology becomes a research hotspot in the field of domestic environmental protection at present.
At present, the utilization of the waste SCR denitration catalyst mainly has two directions, namely, the vanadium element, the tungsten element and the molybdenum element are extracted as research and application directions, and the waste SCR denitration catalyst is reactivated and utilized. The former has the problems of low comprehensive extraction efficiency, low recovery rate and high cost. The waste SCR denitration catalyst is reactivated and reused, but not all the failed SCR denitration catalysts can be recycled in a regeneration mode, and 20-30% of damaged catalysts cannot be reactivated according to incomplete statistics. The activated SCR denitration catalyst has a relatively short catalytic life after activation, which is far inferior to that of a newly prepared SCR denitration catalyst. And generally, the SCR denitration catalyst can be regenerated at most 3 times, and if the spent catalyst cannot recover its activity by regeneration, it needs to be disposed of. Therefore, a large amount of the waste SCR denitration catalyst also faces a problem of landfill. Therefore, how to comprehensively utilize and treat the waste SCR denitration catalyst becomes an urgent problem to be solved.
In view of the above, the present invention is particularly proposed to solve at least one of the above technical problems.
Disclosure of Invention
The first object of the present invention is to provide a method for treating a waste SCR denitration catalyst, which solves the problem of recycling the waste SCR denitration catalyst and greatly improves the use value of the waste SCR denitration catalyst.
The second object of the present invention is to provide a composite opacifier for ceramics.
The third purpose of the invention is to provide a ceramic glaze which comprises the composite opacifier for ceramics.
The fourth purpose of the invention is to provide a ceramic product, which comprises the ceramic glaze.
In order to achieve the purpose, the technical scheme of the invention is as follows:
the invention provides a method for treating a waste SCR denitration catalyst, which comprises the following steps:
mixing the pretreated waste SCR denitration catalyst, wollastonite and calcium carbonate with an optional dispersing agent, and then crushing to obtain a composite opacifier for ceramics;
wherein, TiO in the pretreated waste SCR denitration catalyst2The content of (B) is 88-95 wt%;
the mass ratio of the pretreated waste SCR denitration catalyst, wollastonite and calcium carbonate is (50-80): (10-20): (10-40);
the mass of the dispersing agent accounts for 0-3 per mill of the mass of the pretreated waste SCR denitration catalyst.
Further, on the basis of the technical scheme of the invention, the mass ratio of the pretreated waste SCR denitration catalyst, wollastonite and calcium carbonate is (60-78): (12-18): (23-35);
preferably, the dispersant comprises any one or a combination of at least two of sodium polyacrylate, ammonium polymethacrylate or ammonium polyacrylate, preferably sodium polyacrylate.
Further, on the basis of the technical scheme of the invention, the treatment method of the waste SCR denitration catalyst comprises the following steps:
mixing the pretreated waste SCR denitration catalyst, wollastonite, calcium carbonate and a dispersing agent, then grinding by a wet method, and drying to obtain a composite opacifier for ceramics;
the mass of the dispersant accounts for 0-3 per mill but not 0, preferably 1.5-3 per mill of the mass of the pretreated waste SCR denitration catalyst.
Further, on the basis of the technical scheme of the invention, the treatment method of the waste SCR denitration catalyst comprises the following steps:
mixing the pretreated waste SCR denitration catalyst with a dispersing agent, grinding, mixing the ground product, wollastonite and calcium carbonate, then carrying out wet grinding, and drying to obtain a composite opacifier for ceramics;
the mass of the dispersant accounts for 0-3 per mill of the mass of the pretreated waste SCR denitration catalyst but does not comprise 0, and preferably 1.5-3 per mill;
preferably, the D90 particle size of the milled product is less than or equal to 20 μm.
Further, on the basis of the technical scheme of the invention, the method for treating the waste SCR denitration catalyst comprises the following steps:
and mixing the pretreated waste SCR denitration catalyst, wollastonite and calcium carbonate, and then grinding by a dry method to obtain the composite opacifier for ceramics.
Further, on the basis of the technical scheme of the invention, the mesh number of the pretreated waste SCR denitration catalyst is 100-300 meshes;
preferably, the mesh number of the wollastonite is 80 to 200 meshes;
preferably, the mesh size of the calcium carbonate is 100-200 mesh.
Further, on the basis of the technical scheme of the invention, the pretreated waste SCR denitration catalyst is obtained by adopting the following steps:
cleaning the waste SCR denitration catalyst, drying and crushing to obtain a pretreated waste SCR denitration catalyst;
preferably, the cleaning comprises the steps of sootblowing and pickling;
preferably, the soot blowing comprises the step of blowing the surface and pore channels of the waste SCR denitration catalyst by a high-pressure air gun;
preferably, the pickling comprises the step of sequentially placing the waste SCR denitration catalyst in an acid solution and clean water for washing;
preferably, the acid solution includes any one of a sulfuric acid solution, a nitric acid solution, a mixed acid solution of sulfuric acid and nitric acid, an acetic acid solution, or a hydrofluoric acid solution;
preferably, the acid solution is a sulfuric acid solution, and the concentration of the sulfuric acid solution is 5-10%;
preferably, the washing time of the waste SCR denitration catalyst in the acid solution is 0.5-1 h;
preferably, the washing temperature of the waste SCR denitration catalyst in the acid solution is 40-60 ℃;
preferably, the temperature for drying the waste SCR denitration catalyst after being cleaned is 80-105 ℃;
preferably, the time for drying the waste SCR denitration catalyst after being cleaned is 2-4 h;
preferably, the mesh number of the waste SCR denitration catalyst after being crushed to the pretreatment is 100-300 meshes.
The invention also provides a composite opacifier for ceramics, which is prepared by adopting the treatment method of the waste SCR denitration catalyst.
The invention also provides a ceramic glaze which comprises the composite opacifier for ceramics.
The invention also provides a ceramic product comprising the ceramic glaze.
Compared with the prior art, the treatment method of the waste SCR denitration catalyst, the composite opacifier for ceramics and the ceramic glaze provided by the invention have the following technical effects:
(1) the invention provides a treatment method of a waste SCR denitration catalyst, which is characterized in that the pretreated waste SCR denitration catalyst, wollastonite, calcium carbonate and an optional dispersant are mixed and then crushed to obtain a composite opacifier for ceramics; the waste SCR denitration catalyst in the treatment method is used as the raw material of the composite opacifier for the ceramic, so that the problem of recycling the waste SCR denitration catalyst is solved, the utilization value of the waste SCR denitration catalyst is greatly improved, the production cost of the composite opacifier for the ceramic is greatly reduced, and the obtained composite opacifier for the ceramic has good opacifying property when being used.
(2) The invention provides a composite opacifier for ceramics, which is prepared by adopting the treatment method of the waste SCR denitration catalyst. In view of the advantages of the method for treating the waste SCR denitration catalyst, the composite opacifier for ceramics also has the same advantages.
(3) The invention provides a ceramic glaze, which comprises the composite opacifier for ceramics. In view of the advantages of the composite opacifier for ceramics, the ceramic glaze material also has the same advantages. The compound opacifier for ceramics is applied to the firing formation of porcelain glaze, a sphene phase structure can be formed in situ, the generation of rutile phase is greatly inhibited, and the glaze surface is white, bright and attractive.
(4) The invention provides a ceramic product, which comprises the ceramic glaze. In view of the advantages of the ceramic glaze, the ceramic product has the same advantages.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is an electron microscope image of a composite opacifier for ceramics according to example 1 of the present invention;
FIG. 2 is an electron microscope image of the composite opacifier for ceramics according to example 2 of the present invention;
FIG. 3 is an electron microscope image of the composite opacifier for ceramics according to example 3 of the present invention;
FIG. 4 is an electron micrograph of the composite opacifier for ceramics according to example 4 of the present invention.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, and it should be understood that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
According to a first aspect of the present invention, there is provided a method for treating a waste SCR denitration catalyst, comprising the steps of:
mixing the pretreated waste SCR denitration catalyst, wollastonite and calcium carbonate with an optional dispersing agent, and then crushing to obtain a composite opacifier for ceramics;
wherein, TiO in the pretreated waste SCR denitration catalyst2The content of (B) is 88-95 wt%;
the mass ratio of the pretreated waste SCR denitration catalyst, wollastonite and calcium carbonate is (50-80): (10-20): (20-40);
the mass of the dispersing agent accounts for 0-3 per mill of the mass of the pretreated waste SCR denitration catalyst.
Specifically, the "waste SCR denitration catalyst" in the present invention may refer to a deactivated and renewable SCR denitration catalyst, or may refer to a deactivated and non-renewable SCR denitration catalyst.
Because the SCR denitration catalyst needs to continuously work for years in a high-temperature environment (350-400 ℃) before being abandoned, the surface of the SCR denitration catalyst is molten, and tiny pores and a large surface area can adsorb harmful substances such as coal-fired smoke dust brought by smoke. In the recycling process of the waste SCR denitration catalyst, harmful substances such as coal-fired smoke dust and the like on the surface of the waste SCR denitration catalyst are subjected to pretreatment operations such as cleaning and the like, so that the influence of the coal-fired smoke dust on a final product, namely the composite opacifier for ceramics is reduced. The specific step of the pretreatment is not limited as long as the purpose of cleaning the waste SCR denitration catalyst can be achieved. It should be noted that the pretreatment does not change the actual chemical composition of the spent SCR denitration catalyst.
Because the composite opacifier for ceramics needs to have certain content of TiO2Therefore, the method is used for the TiO in the pretreated waste SCR denitration catalyst2The content of (A) is also correspondingly required. Typical but not limiting TiO in pretreated spent SCR denitration catalyst2Is 88 wt%, 89 wt%, 90 wt%, 91 wt%, 92 wt%, 93 wt%, 94 wt% or 95 wt%.
Except TiO in the pretreated waste SCR denitration catalyst2And may also contain other chemical components such as calcium oxide and the like. The content of other chemical components such as calcium oxide is not limited.
Wollastonite is a kind of chain metasilicate, its appearance is needle-like, its iron content is low, whiteness degree is high, it is non-toxic, chemical corrosion-resistant, heat stability and size stability are good, and it has glass and pearl luster.
The term "optionally dispersing agent" means that the dispersing agent may or may not be added, and may be selected according to the actual situation. For example, when wet milling is employed for pulverization, a dispersant may be added at this time; when dry milling is used for the pulverization, the dispersant may not be added at this time.
Typical but not limiting fractions of the dispersant by mass of the pretreated waste SCR denitration catalyst are 0, 0.5%, 1.0%, 1.2%, 1.4%, 1.5%, 1.6%, 1.8%, 2.0%, 2.2%, 2.4%, 2.5%, 2.6%, 2.8%, or 3.0%.
In the crushing process, a large amount of hydroxyl is easily formed on the surface layer of wollastonite, and the hydroxyl can be mixed with calcium carbonate and TiO in the waste SCR denitration catalyst2Form strong physical adsorption combination effect, thereby forming unique needle winding shape. The composite opacifier for ceramics prepared by the treatment method has unique structural form, and when the composite opacifier is applied to the firing of porcelain glaze, a sphene phase structure can be formed in situ, so that the generation of a rutile phase is greatly inhibited, and the glaze is white, bright and attractive. In addition, the mineral composite opacifier has the advantages of a specific structure, so that the mineral composite opacifier can be uniformly dispersed in glaze slurry, the glazing viscosity is moderate, and the loss of the glaze is reduced.
Typical but not limiting mass ratios of the pretreated waste SCR denitration catalyst, wollastonite, and calcium carbonate are 50:10:40, 60:10:30, 70:10:20, 80:10:20, 50:15:35, 60:15:25, 70:15:20, 80:15:20, 50:20:30, 60:20:20, 70:20:20, or 80:20: 20.
The invention provides a treatment method of a waste SCR denitration catalyst, which is characterized in that the pretreated waste SCR denitration catalyst, wollastonite, calcium carbonate and an optional dispersant are mixed and then crushed to obtain a composite opacifier for ceramics; the waste SCR denitration catalyst is used as the raw material of the composite opacifier for the ceramic, so that the problem of recycling of the waste SCR denitration catalyst is solved, the utilization value of the waste SCR denitration catalyst is greatly improved, and meanwhile, the production cost of the composite opacifier for the ceramic is greatly reduced.
In addition, the treatment method is simple and easy to implement and is suitable for large-scale production.
As an optional embodiment of the present invention, the pretreated waste SCR denitration catalyst is obtained by the following steps:
and cleaning the waste SCR denitration catalyst, drying and crushing to obtain the pretreated waste SCR denitration catalyst.
The method has the advantages that the pre-treated waste SCR denitration catalyst with high cleanliness is obtained by limiting the pre-treatment step of the waste SCR denitration catalyst.
As an alternative embodiment of the invention, the cleaning comprises the steps of sootblowing and pickling.
As an alternative embodiment of the present invention, the soot blowing includes a step of blowing the surface and the pore channels of the waste SCR denitration catalyst with a high-pressure air gun.
The purpose of purging with the high-pressure air gun is to remove dust brought in by flue gas attached to the surface of the waste SCR denitration catalyst.
As an alternative embodiment of the present invention, the pickling includes a step of washing the waste SCR denitration catalyst in an acid solution and clean water in this order.
The waste SCR denitration catalyst is washed by an acid solution, so that quartz, mercury, arsenic, lead and other elements which are easy to migrate in the environment and possibly attached to the surface of the waste SCR denitration catalyst and the coal-fired flue gas can be removed, and organic pollutants generated by the combustion of coal on the surface can be cleaned. After acid washing, water washing is carried out again, and the residual acid solution can be washed away.
As an alternative embodiment of the present invention, the acid solution includes any one of a sulfuric acid solution, a nitric acid solution, a mixed acid solution of sulfuric acid and nitric acid, an acetic acid solution, or a hydrofluoric acid solution.
Preferably, the acid solution is a sulfuric acid solution, and the concentration of the sulfuric acid solution is 5-10%.
Typical but non-limiting concentrations of sulfuric acid solutions are 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, or 10%.
The specific type of the acid solution is limited, so that harmful substances on the surface of the waste SCR denitration catalyst can be removed.
As an optional embodiment of the invention, the washing time of the waste SCR denitration catalyst in the acid solution is 0.5-1 h.
Preferably, the temperature of washing the waste SCR denitration catalyst in the acid solution is 40 to 60 ℃.
Typical but non-limiting washing time of the waste SCR denitration catalyst in the acid solution is 0.5h, 0.6h, 0.7h, 0.8h, 0.9h or 1.0 h; typical, but non-limiting, washing temperatures of the waste SCR denitration catalyst in an acid solution are 40 ℃, 42 ℃, 44 ℃, 45 ℃, 46 ℃, 48 ℃, 50 ℃, 52 ℃, 54 ℃, 55 ℃, 56 ℃, 58 ℃ or 60 ℃.
In an optional embodiment of the present invention, the temperature of the waste SCR denitration catalyst after being washed and then dried is 80 to 105 ℃.
Preferably, the time for drying the waste SCR denitration catalyst after being washed is 2-4 h.
Typical but non-limiting drying times are 2h, 2.5h, 3.0h, 3.5h or 4.0 h; typical but non-limiting drying temperatures are 80 deg.C, 82 deg.C, 85 deg.C, 88 deg.C, 90 deg.C, 92 deg.C, 95 deg.C, 98 deg.C, 100 deg.C, 102 deg.C, 104 deg.C or 105 deg.C.
Through the limitation to drying temperature and drying time for most moisture in abandonment SCR denitration catalyst can be effectively got rid of, makes abandonment SCR denitration catalyst exist in the form of powder.
As an optional embodiment of the invention, the mesh number of the waste SCR denitration catalyst after being crushed to the pretreatment is 100-300 meshes.
The waste SCR denitration catalyst after pretreatment typically, but not by way of limitation, has a mesh size of 100 mesh, 120 mesh, 140 mesh, 150 mesh, 170 mesh, 180 mesh, 200 mesh, 230 mesh, 250 mesh, 270 mesh, 280 mesh, or 300 mesh.
As an optional embodiment of the invention, the mass ratio of the pretreated waste SCR denitration catalyst, wollastonite and calcium carbonate is (60-78): (12-18): (23-35).
Through further limiting the mass ratio of the pretreated waste SCR denitration catalyst, wollastonite and calcium carbonate, the chemical components in the composite opacifier for ceramics are more reasonable in proportion, and the improvement of the overall performance of the composite opacifier for ceramics is facilitated.
As an alternative embodiment of the present invention, the dispersant comprises any one or a combination of at least two of sodium polyacrylate, ammonium polymethacrylate or ammonium polyacrylate, preferably sodium polyacrylate.
By further limiting the types of the dispersing agents, the dispersibility of the waste SCR denitration catalyst, wollastonite and calcium carbonate in a liquid phase medium can be effectively improved.
As an alternative embodiment of the present invention, a method for treating a waste SCR denitration catalyst includes the steps of:
mixing the pretreated waste SCR denitration catalyst, wollastonite, calcium carbonate and a dispersing agent, then grinding by a wet method, and drying to obtain a composite opacifier for ceramics;
the mass of the dispersant accounts for 0-3 per mill but not 0, preferably 1.5-3 per mill of the mass of the pretreated waste SCR denitration catalyst.
As an alternative embodiment of the present invention, a method for treating a waste SCR denitration catalyst includes the steps of:
mixing the pretreated waste SCR denitration catalyst with a dispersing agent, grinding, mixing the ground product with wollastonite and calcium carbonate, then carrying out wet grinding, and drying to obtain a composite opacifier for ceramics;
the mass of the dispersant accounts for 0-3 per mill of the mass of the pretreated waste SCR denitration catalyst but does not comprise 0, and preferably 1.5-3 per mill;
preferably, the D90 particle size of the milled product is less than or equal to 20 μm.
D90 particle size less than or equal to 20 μm means that the volume content of particles less than or equal to 20 μm in the milled product is 90% of the total particles.
The raw materials are mixed in sequence and the adopted crushing mode in the treatment method are limited, so that the materials have good dispersibility in the liquid-phase grinding medium.
As an optional embodiment of the present invention, a method for treating a waste SCR denitration catalyst includes the steps of:
and mixing the pretreated waste SCR denitration catalyst, wollastonite and calcium carbonate, and then grinding by a dry method to obtain the composite opacifier for ceramics.
The crushing process can also adopt dry grinding, and different from the wet grinding, the drying step is not needed after the dry grinding, and the composite opacifier for ceramics can be directly obtained.
As an optional embodiment of the invention, the mesh number of the pretreated waste SCR denitration catalyst is 100-300 meshes. The waste SCR denitration catalyst after pretreatment typically, but not by way of limitation, has a mesh size of 100 mesh, 120 mesh, 140 mesh, 150 mesh, 170 mesh, 180 mesh, 200 mesh, 230 mesh, 250 mesh, 270 mesh, 280 mesh, or 300 mesh.
As an alternative embodiment of the invention, the mesh size of the wollastonite is 80 to 200 mesh, with typical, but not limiting, mesh sizes of the wollastonite being 80 mesh, 100 mesh, 120 mesh, 140 mesh, 150 mesh, 170 mesh, 180 mesh or 200 mesh.
As an alternative embodiment of the invention, the mesh size of the calcium carbonate is 100-200 meshes. Typical, but non-limiting, mesh sizes of the calcium carbonate are 100 mesh, 120 mesh, 140 mesh, 150 mesh, 170 mesh, 180 mesh, or 200 mesh.
The particle sizes of the raw materials are more reasonable by limiting the mesh number of the pretreated waste SCR denitration catalyst, wollastonite and calcium carbonate.
According to the second aspect of the invention, the invention also provides a composite opacifier for ceramics, which is prepared by adopting the treatment method of the waste SCR denitration catalyst.
In view of the advantages of the method for treating the waste SCR denitration catalyst, the composite opacifier for ceramics also has the same advantages. Meanwhile, the waste SCR denitration catalyst, wollastonite, calcium carbonate and other raw materials can form strong physical adsorption binding action, so that the composite opacifier for ceramics with a unique needle-shaped winding form is formed.
According to a third aspect of the invention, a ceramic glaze is also provided, which comprises the composite opacifier for ceramics.
In view of the advantages of the composite opacifier for ceramics, the ceramic glaze material also has the same advantages. The compound opacifier for ceramics is applied to the firing formation of porcelain glaze, a sphene phase structure can be formed in situ, the generation of rutile phase is greatly inhibited, and the glaze surface is white, bright and attractive.
According to a fourth aspect of the present invention, there is also provided a ceramic article comprising the ceramic glaze described above.
In view of the advantages of the ceramic glaze, the ceramic product has the same advantages.
The present invention will be further described with reference to specific examples and comparative examples.
Example 1
The embodiment provides a method for treating a waste SCR denitration catalyst, which comprises the following steps:
(a) blowing the surface and pore channels of the waste SCR denitration catalyst by a high-pressure air gun to perform soot blowing treatment;
then, using a 5% dilute sulfuric acid solution to perform immersion washing on the waste SCR denitration catalyst for 1.0h at the temperature of 40 ℃, and then cleaning with clear water;
finally, the treated waste SCR denitration catalyst is put into a blast type drying oven to be dried, the drying temperature is 80 ℃, and the drying time is 4 hours;
putting the dried waste SCR denitration catalyst into crushing equipment, and crushing to obtain a pretreated waste SCR denitration catalyst with the average particle size of 100 meshes;
TiO in pretreated waste SCR denitration catalyst2The content of (B) is 88 wt%;
(b) mixing the pretreated waste SCR denitration catalyst with a dispersant sodium polyacrylate, grinding by using a stripping machine, wherein the D90 particle size of the ground product is less than or equal to 20 mu m, then mixing the ground product with wollastonite of 200 meshes and calcium carbonate of 200 meshes, and grinding in a water medium by using a horizontal grinding machine for 1h to obtain grinding slurry; wherein the mass of the sodium polyacrylate is 1.5 per mill of the mass of the waste SCR denitration catalyst, and the mass ratio of the pretreated waste SCR denitration catalyst, wollastonite and calcium carbonate is 50:10: 40;
and drying the ground mixture by adopting a flash evaporation dryer to obtain the composite opacifier for the ceramic.
Example 2
This example provides a method for treating a waste SCR denitration catalyst, which is the same as example 1 except for step (b) and the remaining steps and process parameters.
In step (b) of this example, the pretreated waste SCR denitration catalyst was mixed with dispersant sodium polyacrylate, 200 mesh wollastonite, and 200 mesh calcium carbonate, and ground in an aqueous medium with a horizontal grinder for 1 hour to obtain a ground slurry; wherein the mass of the sodium polyacrylate is 1.5 per mill of the mass of the waste SCR denitration catalyst, and the mass ratio of the pretreated waste SCR denitration catalyst, wollastonite and calcium carbonate is 50:10: 40;
and drying the ground mixture by adopting a flash evaporation dryer to obtain the composite opacifier for the ceramic.
Example 3
This example provides a method for treating a waste SCR denitration catalyst, which is the same as example 1 except for step (b) and the remaining steps and process parameters.
In step (b) of this example, the pretreated waste SCR denitration catalyst, 200 mesh wollastonite, and 200 mesh calcium carbonate were mixed at a mass ratio of 50:10:40, and dry-ground with a ball mill for 1 hour to obtain a composite opacifier for ceramics.
Example 4
This example provides a method for treating a waste SCR denitration catalyst, which comprises the same steps and process parameters as in example 1, except that the mass ratio of wollastonite to calcium carbonate of the pretreated waste SCR denitration catalyst in step (b) is replaced with 50:20: 30.
Example 5
This example provides a method for treating a waste SCR denitration catalyst, which comprises the same steps and process parameters as in example 1, except that the mass ratio of wollastonite to calcium carbonate of the pretreated waste SCR denitration catalyst in step (b) is replaced by 70:10: 20.
Example 6
This example provides a method for treating a waste SCR denitration catalyst, which comprises the same steps and process parameters as in example 1, except that the mass ratio of wollastonite to calcium carbonate in the step (b) is 60:15:25 instead of the pretreated waste SCR denitration catalyst.
Example 7
This example provides a method for treating a waste SCR denitration catalyst, except that TiO, which is a waste SCR denitration catalyst pretreated in the step (a), is used2Except for the substitution of 95wt%, the remaining steps and process parameters were the same as in example 1.
Example 8
This example provides a method for treating a waste SCR denitration catalyst, which includes the same steps and process parameters as in example 1, except that the mass of sodium polyacrylate in step (b) is changed from 1.5% to 3.0% of the mass of the waste SCR denitration catalyst.
Example 9
The embodiment provides a method for treating a waste SCR denitration catalyst, which comprises the following steps:
(a) blowing the surface and pore channels of the waste SCR denitration catalyst by a high-pressure air gun to perform soot blowing treatment;
then, using 10% dilute sulfuric acid solution to perform immersion washing on the waste SCR denitration catalyst for 0.5h at the temperature of 60 ℃, and then cleaning with clear water;
finally, the treated waste SCR denitration catalyst is put into a blast type drying oven to be dried, wherein the drying temperature is 100 ℃, and the drying time is 2 hours;
putting the dried waste SCR denitration catalyst into crushing equipment, and crushing to obtain a pretreated waste SCR denitration catalyst with the average particle size of 300 meshes;
TiO in pretreated waste SCR denitration catalyst2The content of (B) is 80 wt%;
(b) mixing the pretreated waste SCR denitration catalyst with a dispersant sodium polyacrylate, grinding by using a stripping machine, mixing the ground product with wollastonite of 100 meshes and calcium carbonate of 200 meshes, and grinding in a horizontal grinding machine for 2 hours in an aqueous medium to obtain grinding slurry, wherein the D90 particle size of the ground product is less than or equal to 20 microns; wherein the mass of the sodium polyacrylate is 1.5 per mill of the mass of the waste SCR denitration catalyst, and the mass ratio of the pretreated waste SCR denitration catalyst, wollastonite and calcium carbonate is 65:12: 23;
and drying the ground mixture by adopting a flash evaporation dryer to obtain the composite opacifier for the ceramic.
Example 10
The embodiment provides a method for treating a waste SCR denitration catalyst, which comprises the following steps:
(a) blowing the surface and pore channels of the waste SCR denitration catalyst by a high-pressure air gun to perform soot blowing treatment;
then, using 10% acetic acid solution to perform immersion washing on the waste SCR denitration catalyst for 0.8h at the temperature of 50 ℃, and then cleaning with clear water;
finally, the treated waste SCR denitration catalyst is put into a blast type drying oven to be dried, wherein the drying temperature is 90 ℃, and the drying time is 1 h;
putting the dried waste SCR denitration catalyst into crushing equipment, and crushing to obtain a pretreated waste SCR denitration catalyst with the average particle size of 300 meshes;
TiO in pretreated waste SCR denitration catalyst2Is 75 wt%;
(b) mixing the pretreated waste SCR denitration catalyst with a dispersant sodium polyacrylate, grinding by using a stripping machine, wherein the D90 particle size of the ground product is less than or equal to 20 mu m, then mixing the ground product with wollastonite of 100 meshes and calcium carbonate of 200 meshes, and grinding in a horizontal grinding machine in an aqueous medium for 0.5h to obtain grinding slurry; wherein the mass of the ammonium polymethacrylate is 2 per mill of the mass of the waste SCR denitration catalyst, and the mass ratio of the pretreated waste SCR denitration catalyst, wollastonite and calcium carbonate is 80:10: 40;
and drying the ground mixture by adopting a flash evaporation dryer to obtain the composite opacifier for the ceramic.
Comparative example 1
The comparative example provides a method for treating a waste SCR denitration catalyst, and the steps and process parameters are the same as those in example 1 except that wollastonite is not added in the step (b), the mass ratio of the pretreated waste SCR denitration catalyst to calcium carbonate is 50: 50.
Comparative example 2
The comparative example provides a method for treating a waste SCR denitration catalyst, and the steps and process parameters are the same as those in example 1 except that calcium carbonate is not added in the step (b), the mass ratio of the pretreated waste SCR denitration catalyst to wollastonite is 50: 50.
Comparative example 3
The comparative example provides a method for treating a waste SCR denitration catalyst, which comprises the same steps and process parameters as in example 1, except that the mass ratio of the pretreated waste SCR denitration catalyst, wollastonite and calcium carbonate in the step (b) is replaced by 45:5: 50.
Comparative example 4
The comparative example provides a method for treating a waste SCR denitration catalyst, which comprises the same steps and process parameters as in example 1, except that the mass ratio of the pretreated waste SCR denitration catalyst, wollastonite and calcium carbonate in the step (b) is replaced by 45:15: 40.
Comparative example 5
This comparative example provides a method for treating a waste SCR denitration catalyst, which is the same as example 1 except that a dispersant, sodium polyacrylate, is not added in step (b), and the remaining steps and process parameters are the same as those in example 1.
Comparative example 6
This comparative example provides a method for treating a waste SCR denitration catalyst, except that the step (a) is not performed, and the waste SCR denitration catalyst without pretreatment is directly used in the step (b), and the remaining steps and process parameters are the same as those of example 1.
Comparative example 7
The comparative example provides a composite opacifier for ceramics, which comprises the following raw materials in percentage by mass:
TiO250 percent, wollastonite 10 percent and calcium carbonate 40 percent.
In order to illustrate the technical effects of the above examples and comparative examples, the following experimental examples were specifically set.
Experimental example 1
The performance of the ceramic sample sheets added with the composite opacifier for ceramics provided in each example and comparative example is tested, and the addition amount of the composite opacifier for ceramics in the glaze slurry for the ceramic sample sheets is 10 wt%. The chroma of the ceramic sample is expressed by Lab value, and the Lab value detection method is according to QB/T1503 domestic ceramic whiteness determination method; the gloss of the ceramic sample is measured by adopting the light reflection rate, the detection equipment of the light reflection rate is TC/JFB-I, and the specific result is shown in Table 1.
TABLE 1
Experimental groups whiteness-L value a value b value Reflectance (%)
Example 1 90.6 0.9 3.0 91.3
Example 2 86.5 0.8 3.0 90.0
Example 3 86.3 0.9 3.2 90.3
Example 4 89.5 0.8 3.3 90.1
Example 5 88.9 1.2 3.5 88.6
Example 6 90.7 1.0 2.9 92.0
Example 7 89.5 0.8 3.4 90.1
Example 8 91.0 0.9 3.7 89.3
Example 9 90.6 0.9 3.0 91.0
Example 10 92.6 0.7 3.8 89.1
Comparative example 1 89.1 0.8 4.3 86.5
Comparative example 2 87.1 0.9 4.4 88.6
Comparative example 3 85.6 0.8 4.3 87.5
Comparative example 4 88.1 1.2 4.1 88.6
Comparative example 5 90.5 0.9 4.9 82.3
Comparative example 6 81.6 1.0 5.1 83.4
Comparative example 7 65.9 2.5 9.9 48.3
As can be seen from the data in Table 1, the chroma and gloss of the ceramic samples using the composite opacifier for ceramics provided in the examples of the present invention are generally better than those of the ceramic samples using the composite opacifier for ceramics provided in the comparative examples.
Meanwhile, taking the composite opacifier for ceramics provided in examples 1 to 4 as an example, the morphology of the composite opacifier for ceramics is detected, which is specifically shown in fig. 1, 2, 3 and 4. As can be seen from fig. 1 to 4, the acicular wollastonite crystals are densely enriched with a large number of titanium dioxide crystals and calcium carbonate mineral particles at the periphery, and the structure is favorable for the formation of the sphene structure in the high-temperature process of enamel production.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.

Claims (27)

1. A treatment method of a waste SCR denitration catalyst is characterized by comprising the following steps:
mixing the pretreated waste SCR denitration catalyst, wollastonite and calcium carbonate with an optional dispersing agent, and then crushing to obtain a composite opacifier for ceramics;
wherein, TiO in the pretreated waste SCR denitration catalyst2The content of (B) is 88-95 wt%;
the mass ratio of the pretreated waste SCR denitration catalyst, wollastonite and calcium carbonate is (50-80): (10-20): (10-40);
the mass of the dispersing agent accounts for 0-3 per mill of the mass of the pretreated waste SCR denitration catalyst.
2. The method for treating the waste SCR denitration catalyst according to claim 1, wherein the mass ratio of the pretreated waste SCR denitration catalyst, wollastonite and calcium carbonate is (60-78): (12-18): (23-35).
3. The method of treating a spent SCR denitration catalyst according to claim 2, wherein the dispersant comprises any one of sodium polyacrylate, ammonium polymethacrylate, or ammonium polyacrylate, or a combination of at least two thereof.
4. The method of treating a spent SCR denitration catalyst according to claim 3, wherein the dispersant comprises sodium polyacrylate.
5. The method of treating a spent SCR denitration catalyst according to claim 2, comprising the steps of:
mixing the pretreated waste SCR denitration catalyst, wollastonite, calcium carbonate and a dispersing agent, then grinding by a wet method, and drying to obtain a composite opacifier for ceramics;
the mass of the dispersant accounts for 0-3 per mill of the mass of the pretreated waste SCR denitration catalyst, but does not contain 0.
6. The method for treating the waste SCR denitration catalyst according to claim 5, wherein the mass of the dispersant is 1.5 to 3 per mill of the mass of the pretreated waste SCR denitration catalyst.
7. The method of treating a spent SCR denitration catalyst according to claim 2, comprising the steps of:
mixing the pretreated waste SCR denitration catalyst with a dispersing agent, grinding, mixing the ground product, wollastonite and calcium carbonate, then carrying out wet grinding, and drying to obtain a composite opacifier for ceramics;
the mass of the dispersant accounts for 0-3 per mill of the mass of the pretreated waste SCR denitration catalyst, but does not contain 0.
8. The method for treating the waste SCR denitration catalyst according to claim 7, wherein the mass of the dispersant is 1.5 to 3 per mill of the mass of the pretreated waste SCR denitration catalyst.
9. The method of treating a waste SCR denitration catalyst according to claim 7, wherein a D90 particle size of a ground product obtained by mixing a pretreated waste SCR denitration catalyst with a dispersant and grinding the mixture is 20 μm or less.
10. The method of treating a spent SCR denitration catalyst according to claim 1, comprising the steps of:
and mixing the pretreated waste SCR denitration catalyst, wollastonite and calcium carbonate, and then grinding by a dry method to obtain the composite opacifier for ceramics.
11. The method as claimed in any one of claims 1 to 10, wherein the mesh size of the pretreated waste SCR denitration catalyst is 100-300 mesh.
12. The method of claim 11, wherein the wollastonite has a mesh size of 80 to 200 meshes.
13. The method as claimed in claim 11, wherein the mesh size of the calcium carbonate is 100-200 meshes.
14. The method of treating a waste SCR denitration catalyst according to any one of claims 1 to 10, wherein the pretreated waste SCR denitration catalyst is obtained by the steps of:
and cleaning the waste SCR denitration catalyst, drying and crushing to obtain the pretreated waste SCR denitration catalyst.
15. The method of treating a spent SCR denitration catalyst according to claim 14, wherein the washing includes the steps of sootblowing and rinsing.
16. The method of treating the waste SCR denitration catalyst of claim 15, wherein the soot blowing includes a step of blowing surfaces and pores of the waste SCR denitration catalyst with a high pressure air gun.
17. The method of treating a spent SCR denitration catalyst according to claim 15, wherein the pickling includes a step of washing the spent SCR denitration catalyst by sequentially placing the catalyst in an acid solution and clean water.
18. The method of treating a spent SCR denitration catalyst according to claim 17, wherein the acid solution includes any one of a sulfuric acid solution, a nitric acid solution, a mixed acid solution of sulfuric acid and nitric acid, an acetic acid solution, or a hydrofluoric acid solution.
19. The method of treating a spent SCR denitration catalyst according to claim 18, wherein the acid solution is a sulfuric acid solution, and the concentration of the sulfuric acid solution is 5 to 10%.
20. The method of treating a spent SCR denitration catalyst according to claim 17, wherein the washing time of the spent SCR denitration catalyst in the acid solution is 0.5 to 1 hour.
21. The method of treating a spent SCR denitration catalyst according to claim 17, wherein the temperature at which the spent SCR denitration catalyst is washed in the acid solution is 40 to 60 ℃.
22. The method of treating a waste SCR denitration catalyst according to claim 14, wherein a temperature at which the waste SCR denitration catalyst is dried after being washed is 80 to 105 ℃.
23. The method of treating a waste SCR denitration catalyst according to claim 14, wherein the time for drying the waste SCR denitration catalyst after cleaning is 2 to 4 hours.
24. The method as claimed in claim 14, wherein the mesh size of the waste SCR denitration catalyst after the pre-treatment is 100-300 mesh.
25. A composite opacifier for ceramics, characterized in that it is prepared by the method of treating the waste SCR denitration catalyst according to any one of claims 1 to 24.
26. A ceramic glaze comprising the composite opacifier for ceramics according to claim 25.
27. A ceramic article comprising the ceramic glaze of claim 26.
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