CN114853503B - Ceramic product with sulfur doped stable cobalt tungstate based photocatalytic activity and preparation method thereof - Google Patents
Ceramic product with sulfur doped stable cobalt tungstate based photocatalytic activity and preparation method thereof Download PDFInfo
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- CN114853503B CN114853503B CN202210403396.9A CN202210403396A CN114853503B CN 114853503 B CN114853503 B CN 114853503B CN 202210403396 A CN202210403396 A CN 202210403396A CN 114853503 B CN114853503 B CN 114853503B
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- 239000000919 ceramic Substances 0.000 title claims abstract description 116
- OMAWWKIPXLIPDE-UHFFFAOYSA-N (ethyldiselanyl)ethane Chemical compound CC[Se][Se]CC OMAWWKIPXLIPDE-UHFFFAOYSA-N 0.000 title claims abstract description 81
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 32
- 239000011593 sulfur Substances 0.000 title claims abstract description 21
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000013078 crystal Substances 0.000 claims abstract description 58
- 238000010304 firing Methods 0.000 claims abstract description 25
- 238000001354 calcination Methods 0.000 claims abstract description 11
- 239000012298 atmosphere Substances 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims description 48
- 239000000843 powder Substances 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 239000002994 raw material Substances 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 18
- 239000005995 Aluminium silicate Substances 0.000 claims description 17
- 235000012211 aluminium silicate Nutrition 0.000 claims description 17
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 17
- 239000002002 slurry Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 14
- 238000007873 sieving Methods 0.000 claims description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000002270 dispersing agent Substances 0.000 claims description 11
- 239000010453 quartz Substances 0.000 claims description 8
- 229910017119 AlPO Inorganic materials 0.000 claims description 7
- 229910052708 sodium Inorganic materials 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 238000003892 spreading Methods 0.000 claims description 4
- 230000007480 spreading Effects 0.000 claims description 4
- 229910018119 Li 3 PO 4 Inorganic materials 0.000 claims description 3
- 238000010791 quenching Methods 0.000 claims description 3
- 230000000171 quenching effect Effects 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000000047 product Substances 0.000 description 30
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- 238000000227 grinding Methods 0.000 description 21
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 20
- 230000000694 effects Effects 0.000 description 19
- 238000001035 drying Methods 0.000 description 17
- 238000006731 degradation reaction Methods 0.000 description 15
- 230000015556 catabolic process Effects 0.000 description 14
- 230000003197 catalytic effect Effects 0.000 description 13
- 230000006911 nucleation Effects 0.000 description 12
- 238000010899 nucleation Methods 0.000 description 12
- 239000005711 Benzoic acid Substances 0.000 description 11
- 238000000498 ball milling Methods 0.000 description 11
- 238000005245 sintering Methods 0.000 description 11
- 235000010233 benzoic acid Nutrition 0.000 description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- 229920000058 polyacrylate Polymers 0.000 description 9
- 235000012239 silicon dioxide Nutrition 0.000 description 9
- 239000004575 stone Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 239000000292 calcium oxide Substances 0.000 description 7
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 7
- 238000002844 melting Methods 0.000 description 7
- 230000008018 melting Effects 0.000 description 7
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 7
- 238000002425 crystallisation Methods 0.000 description 6
- 230000008025 crystallization Effects 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 5
- 239000011521 glass Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000004615 ingredient Substances 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 244000105624 Arachis hypogaea Species 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 description 2
- MULYSYXKGICWJF-UHFFFAOYSA-L cobalt(2+);oxalate Chemical compound [Co+2].[O-]C(=O)C([O-])=O MULYSYXKGICWJF-UHFFFAOYSA-L 0.000 description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000010433 feldspar Substances 0.000 description 2
- 235000020232 peanut Nutrition 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 235000017060 Arachis glabrata Nutrition 0.000 description 1
- 235000010777 Arachis hypogaea Nutrition 0.000 description 1
- 235000018262 Arachis monticola Nutrition 0.000 description 1
- 235000007516 Chrysanthemum Nutrition 0.000 description 1
- 244000189548 Chrysanthemum x morifolium Species 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- CNLSPQQMAJCIFB-UHFFFAOYSA-N benzoic acid;ethanol Chemical compound CCO.OC(=O)C1=CC=CC=C1 CNLSPQQMAJCIFB-UHFFFAOYSA-N 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 210000003746 feather Anatomy 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/049—Sulfides with chromium, molybdenum, tungsten or polonium with iron group metals or platinum group metals
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- 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
- C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
- C03C8/08—Frit compositions, i.e. in a powdered or comminuted form containing phosphorus
-
- 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
- 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
-
- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Ceramic Engineering (AREA)
- Inorganic Chemistry (AREA)
- Structural Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a sulfur-doped stable cobalt tungstate based photocatalytic activity ceramic product and a preparation method thereof. The preparation method comprises the following steps: applying cobalt tungstate-based ceramic crystal glaze to the surface of a ceramic body; firing the ceramic body after applying the cobalt tungstate based ceramic crystal glaze; calcining the sintered ceramic body and sulfur powder in inert atmosphere to obtain the ceramic product with stable photocatalytic activity of cobalt tungstate base doped with sulfur.
Description
Technical Field
The invention belongs to the field of ceramic glaze, and particularly relates to a sulfur-doped ceramic product with stable cobalt tungstate-based photocatalytic activity and a preparation method thereof.
Background
The crystal glaze is an artistic ceramic glaze with good decorative effect, and is characterized by that on the glaze surface the crystal flowers with various shapes are distributed, and these crystal flowers are not manually drawn or stuck on in advance, and under the saturated state the nucleation substances in the glaze melt can be used, and can be quickly cooled or properly heat-insulated, so that the glaze surface style is natural and beautiful, and is very popular with consumers. The crystal glaze can be classified into chrysanthemum shape, radial shape, strip shape, water flower shape, star shape, pine needle shape, spiral shape, flash star shape, granular shape, feather shape and the like according to crystal form; the high-temperature crystal glaze with the firing temperature of about 1300 ℃ and the low-temperature crystal glaze with the firing temperature of 710-900 ℃ are classified according to the firing temperature.
Disclosure of Invention
The technical aim of the invention is to provide a ceramic product with stable photocatalytic activity of cobalt tungstate base doped with sulfur and a preparation method thereof. The ceramic product with the sulfur doped stable cobalt tungstate based photocatalytic activity has an excellent photocatalytic effect, can catalyze and degrade organic matters such as toluene, benzoic acid and the like, and the glaze formed after firing is blue. If cobalt tungstate is replaced by cobalt oxide, the same catalytic degradation effect cannot be achieved.
In a first aspect, the invention provides a method for preparing a sulfur-doped stable cobalt tungstate-based photocatalytic activity ceramic product. The preparation method comprises the following steps:
applying cobalt tungstate-based ceramic crystal glaze to the surface of a ceramic body; the cobalt tungstate-based ceramic crystal glaze comprises the following raw materials in parts by weight: 70-90% of powder A, 8-10% of cobalt tungstate and 8-10% of kaolin in percentage by mass; the powder A comprises the following raw materials: in mass percent, siO 2 15～25％、AlPO 4 16～22％、CoC 2 O 4 6 to 10 percent, 15 to 20 percent of quartz and Li 3 PO 4 14～18％、Na 3 PO 4 8～13％、K 3 PO 4 7～9％、CaO 5～8％；
Firing the ceramic body after applying the cobalt tungstate based ceramic crystal glaze;
calcining the sintered ceramic body and sulfur powder in inert atmosphere to obtain the ceramic product with stable photocatalytic activity of cobalt tungstate base doped with sulfur.
The traditional glaze composition composed of oxides such as silicon oxide, aluminum oxide, calcium oxide, sodium oxide and the like is difficult to fully expose crystalline components on the surface of the glaze layer, and active ingredients of the glaze are difficult to show good photocatalytic activity. The primer component of the phosphate system has a different melt liquid viscosity and metal ion diffusion rate at high temperature compared to the glaze composition of the oxide system,under such conditions, the orientation growth rate and normal distribution of the crystalline glaze component within the overall crystalline glaze layer will exhibit significant variation. Specifically, under a phosphate-based under-glaze system, the oriented growth of the cobalt tungstate-based crystalline glaze can be preferentially distributed on the surface of the glaze layer, and one-dimensional orientation is formed, so that conditions for full exposure and growth of a high-activity crystalline glaze system can be provided. The silicon dioxide is introduced into the cobalt tungstate base crystal glaze taking the phosphate as a main system, so that the melting temperature can be increased, the melting temperature range can be widened, the fluidity of the glaze can be reduced, the thermal expansion coefficient can be reduced, and the hardness of the glaze surface can be increased; and CoC 2 O 4 The effect of the (cobalt oxalate) is to promote the nucleation of cobalt tungstate in the high-temperature liquid environment of the glaze and improve the crystallization rate, so that cobalt tungstate crystals which grow in a remarkable orientation are obtained. If the use of cobalt oxalate is omitted from the cobalt tungstate-based crystalline glaze, the nucleation rate and the crystallization growth rate of the cobalt tungstate crystalline glaze are severely limited, and obvious crystal flower effects are difficult to obtain even under the same sintering conditions. In addition, the sintered ceramic body and sulfur powder are calcined in inert atmosphere, so that sulfur element can be embedded into the surface of glass phase of the glaze in the form of solid solution, and the surface cation migration can be stabilized by sulfur doping in repeated catalytic circulation, so that the structural activity is maintained, and the degradation efficiency is further improved.
Preferably, the powder A is in the form of a frit; preferably, the preparation process of the frit comprises the following steps: uniformly mixing the raw materials according to the powder material A, sieving the mixture, preserving heat for 30 to 60 minutes at a first temperature, preserving heat for 5 to 25 minutes at a second temperature, preserving heat for 10 to 20 minutes at a third temperature, quenching and crushing to obtain a frit; wherein the first temperature is 500-700 ℃, the second temperature is 600-800 ℃, and the third temperature is 1000-1100 ℃; more preferably, the second temperature is 50 to 200 ℃ higher than the first temperature.
Preferably, the cobalt tungstate based ceramic crystal glaze generates acicular cobalt tungstate crystals in a high-temperature sintering environment.
Preferably, the cobalt tungstate crystal has a one-dimensional orientation growth characteristic.
Preferably, the highest sintering temperature is 1100-1300 ℃, and the sintering period is 110-170 minutes.
Preferably, the inert atmosphere for calcination is argon.
Preferably, the calcination temperature is 400-800 ℃ and the calcination time is 30-90 minutes.
Preferably, the cobalt tungstate-based ceramic crystal glaze is applied to the surface of the ceramic body in the form of glaze slurry; the glaze slurry comprises a dispersing agent and water besides the cobalt tungstate-based ceramic crystal glaze; preferably, the water accounts for 40-60% of the mass of the glaze slip, and the dispersant accounts for 0.1-0.5% of the mass of the glaze slip.
Preferably, the glaze slip forms a crystalline glaze layer of 0.05-0.3 mm on the surface of the ceramic body.
In a second aspect, the invention provides a sulfur-doped stabilized cobalt tungstate-based photocatalytic active ceramic product obtained by any one of the preparation methods described above.
Drawings
FIG. 1 is a graph of the photocatalytic degradation of toluene for examples 1-3 and comparative example 1;
FIG. 2 is a graph showing the photocatalytic degradation of benzoic acid for examples 1-3 and comparative example 1.
Detailed Description
The invention is further illustrated by the following embodiments, which are to be understood as merely illustrative of the invention and not limiting thereof. Unless otherwise specified, each percentage refers to a mass percent.
The following illustrates the preparation method of the sulfur-doped stable cobalt tungstate-based photocatalytic activity ceramic product.
And applying the cobalt tungstate-based ceramic crystal glaze to the surface of the ceramic body. The composition and specification of the ceramic body are not particularly limited, and a construction ceramic body commonly used in the art may be employed.
The cobalt tungstate based ceramic crystal glaze comprises: the powder material A accounts for 70 to 90 percent, the cobalt tungstate accounts for 8 to 10 percent and the kaolin accounts for 8 to 10 percent by mass. The prior art mentions that cobalt oxide is used as pigment and minerals such as feldspar, clay and the like are used for forming crystalline glaze, but the nucleation speed of crystalline glaze crystal nucleus obtained by the method is low, direct nucleation growth is difficult to realize in a short time, the heat preservation time under the high temperature condition needs to be more than 4-8 hours, and the total sintering period is more than 15 hours. The crystal pattern of the cobalt acid-based ceramic crystal glaze is easy to control, the heat preservation time at high temperature (generally 1100-1300 ℃) is only 5-20 minutes, the firing period is 110-170 minutes, and the energy consumption is greatly saved.
Powder A is the main component of the crystalline glaze base glaze. The powder A comprises the following raw materials: in mass percent, siO 2 15～25％、AlPO 4 16～22％、CoC 2 O 4 6 to 10 percent, 15 to 20 percent of quartz and Li 3 PO 4 14～18％、Na 3 PO 4 8～13％、K 3 PO 4 7-9% and 5-8% of CaO. Powder A provides a liquid environment for active cobalt tungstate crystal nucleation growth in a high-temperature environment, so that the active cobalt tungstate crystal nucleation growth can grow at a faster rate. If the composition of the powder A exceeds the above range, the crystal flowers of the crystalline glaze are not easy to nucleate and grow, the size of the crystal flowers is reduced, the decorative effect is poor, and the catalytic degradation effect is obviously limited. If the powder A is replaced by the traditional feldspar and clay, the cobalt tungstate grains in the crystallized glaze are undersized and even can not grow, and the orientation growth structure is difficult to obtain.
The mass percentage of the powder material A in the crystalline glaze is 70-90%. If the mass percentage of the powder material A in the crystalline glaze is lower than 70%, the crystalline component cannot effectively migrate and grow in a high-temperature melting state, crystallization nucleation is difficult, the crystal nucleus size is uneven, and the decorative effect of the crystalline glaze is poor. If the mass percentage of the powder material A in the crystalline glaze is higher than 90%, the generated crystal flowers are easy to dissolve, the quantity of the crystal flowers is small, and the decorative effect is poor.
Preferably, the powder a is in the form of a frit. Although the powder A is prepared into raw materials to promote crystallization, the crystal peanut length of the crystallized glaze is difficult to control, the repeatability is extremely poor, the crystal flower size is limited, and the catalytic effect is limited. In the preparation process of the frit, the raw materials are heated first to enable the primer to be vitrified in advance, so that the powder A in the form of the frit has better mixing uniformity than the raw materials, and the size and the components of crystal flowers generated by nucleation are more uniform.
The direct use of powder A in the form of a raw material does not allow crystallization and catalytic effects to be achieved simultaneously with excellent results. The reason is that the frit powder is more uniformly mixed than the raw material, and the distribution of nucleation generated crystal flowers is also more uniform. Meanwhile, the frit powder can also reduce the sintering temperature and expand the sintering range. The melting temperature of the frit is higher, so that various raw materials are fully reacted and melted at high temperature and are converted into glass-shaped substances, and the glass-shaped substances are remelted during the sintering, so that the melting point of the glaze is reduced, the melting range of the glaze is enlarged, and convenience is brought to production control. Moreover, the frit powder improves the glaze quality and reduces the shrinkage of the glaze compared with the raw material. When the frit is manufactured, substances which can be decomposed in the raw materials and certain volatile matters are discharged in advance, and the processes are avoided during glaze firing, so that pinhole defects are reduced. Meanwhile, the glaze after being melted has little loss in firing, hardly contracts, can be better adapted to a green body, and reduces the defects of glaze rolling, glaze shrinkage and the like. Therefore, the cobalt tungstate-based crystalline glaze obtained by the invention has uniform color, improves the coloring efficiency, increases the stability and suspension property of the glaze and the adhesion with a blank body, and reduces bubbles. Although the raw material can realize crystallization and has a certain catalytic effect, the crystal nucleus growth of the obtained crystal glaze is difficult to control, the repeatability is extremely poor, the size of crystal flowers is limited, and the catalytic effect is obviously limited.
Weighing the raw materials according to the raw material composition of the powder A, mixing, grinding and sieving to obtain a mixture. The mixing means may be dry blending. The mesh number of the sieving is 30-100 meshes. Placing the mixture into a crucible, placing the crucible into an electric furnace, preserving heat at a first temperature for 30-60 minutes, preserving heat at a second temperature for 5-25 minutes, preserving heat at a third temperature for 10-20 minutes, taking out, pouring into water, and quenching to obtain a frit; wherein the first temperature is 500-700 ℃, the second temperature is 600-800 ℃, and the third temperature is 1000-1100 ℃; preferably, the second temperature is 50-200 ℃ higher than the first temperature. And taking out the frit from water, drying, putting the frit into a ball milling tank, and taking the diameter particle size of the ball stone to be 5-20 mm and rotating at 100-400 rpm. And (3) controlling materials: grinding balls with the mass ratio of 1:2-1:4, grinding for 1-4 hours, sieving with a 100-300 mesh sieve, and drying for later use. The powder A is prepared into the frit with fine particle size, so that the components of the powder A are fully and uniformly distributed at high temperature. The thinning degree is favorable for the uniformity degree of the growth of the peanuts.
Cobalt tungstate is used as an active material in the crystalline glaze to play a role in photocatalysis. The content of cobalt tungstate is too much or too little, and the photocatalytic effect is obviously weakened. The content of cobalt tungstate is low, crystal flowers are low, photocatalytic degradation components are reduced, and the catalytic effect is weakened; the cobalt tungstate with a large content is more in nucleation crystal flower, but the cobalt tungstate is overlapped with each other during nucleation, so that uneven distribution is caused, and the decoration effect and the photocatalysis effect are also affected.
Cobalt tungstate cannot be designed in the composition of powder A, because the addition of cobalt tungstate to powder A can lead the cobalt tungstate to nucleate and grow in advance in the frit preparation process, so that the crystal glaze cannot grow an oriented crystal structure during high-temperature sintering.
The kaolin contains Al 2 O 3 ·2SiO 2 ·2H 2 O. The kaolin can raise the melting temperature of the glaze at high temperature and improve suspension property so that the glaze is not easy to settle. If the content of kaolin is too small, the dispersion uniformity and stability of the glaze cannot be effectively ensured; if the kaolin content is too large, the active ingredients of the glaze are easily wrapped by the kaolin and cannot be exposed, so that the catalytic degradation performance of the crystalline glaze is limited.
The preparation method of the cobalt tungstate based ceramic crystal glaze comprises the following steps: powder A, cobalt tungstate and kaolin are uniformly mixed and ground in a ball milling tank. In the ball milling process, controlling materials: the mass ratio of the grinding balls is 1:1, grinding for 4-10 hours, sieving with a 300-mesh sieve, and drying for later use.
And (3) firing the ceramic body after the cobalt tungstate-based ceramic crystal glaze is applied. The kiln is oxidized by a roller kiln and is preferably quick-fired. The highest sintering temperature is 1100-1300 ℃, and the sintering period is 110-170 minutes. The holding time for the highest firing temperature may be 5 to 20 minutes.
The cobalt tungstate-based ceramic crystal glaze can be applied to the surface of the ceramic body in the form of glaze slurry. The glaze slip comprises water and a dispersing agent besides the glaze composition. The mass percentage of water in the glaze slip is 40-60%, and the mass percentage of the dispersing agent is 0.1-0.5%. Such dispersants include, but are not limited to, ammonium polyacrylate salts and the like. The components in the glaze slip are uniformly dispersed by stirring. The glaze slip forms a crystalline glaze layer with the thickness of 0.05-0.3 mm on the surface of the ceramic body. At this time, the ceramic body may be dried prior to firing. For example at 50 to 100 ℃.
Calcining the sintered ceramic body and sulfur powder in inert atmosphere to obtain the ceramic product with stable photocatalytic activity of cobalt tungstate base doped with sulfur. The sulfur powder can be spread on the surface of the ceramic body after firing. Every 100cm 2 0.5-2.0 g sulfur powder can be used on the surface of the ceramic body. As an example, the temperature may be maintained at 400-800 ℃ for 30-90 min under an argon atmosphere, so that the doping of sulfur element may be controlled. The ceramic body surface after the cobalt tungstate-based ceramic crystal glaze is applied can not be paved with sulfur powder and then sintered, because the crystal growth in the glaze layer and the formation of a glass phase structure can be influenced, and the doping effect of sulfur element on the glass phase surface is lost. The introduction of sulfur powder into the composition of the cobalt tungstate-based ceramic crystal glaze can not play an expected doping effect, and can also have adverse effects on the crystal growth in the glaze layer and the formation of a glass phase structure.
The ceramic product with the sulfur doped stable cobalt tungstate based photocatalytic activity has excellent decomposition performance on organic matters such as toluene and benzoic acid after 8 hours of catalytic degradation under the illumination condition, the degradation rate of the toluene and the benzoic acid can reach more than 90%, the ceramic product has obvious promotion effect on household environment purification, and has important significance on improving the environment quality and improving the living standard of people.
Moreover, the ceramic product with the sulfur doped stable cobalt tungstate based photocatalytic activity also has excellent surface decoration effect. The glaze is blue, attractive in color, strong in covering capacity, flat and smooth, free of pinholes and the like.
The present invention will be further illustrated by the following examples. It is also to be understood that the following examples are given by way of illustration only and are not to be construed as limiting the scope of the invention, since numerous insubstantial modifications and adaptations of the invention will be made by those skilled in the art in light of the foregoing disclosureAll falling within the scope of the invention. The specific process parameters and the like described below are also merely examples of suitable ranges, i.e., one skilled in the art can make a suitable selection from the description herein and are not intended to be limited to the specific values described below. The quartz in the embodiment adopts analytically pure quartz sand, and the granularity is mainly 25-50 meshes; siO in the examples 2 Analytically pure silica flour was used.
Example 1
The preparation method of the sulfur doped stable cobalt tungstate based photocatalytic activity ceramic product comprises the following steps:
1) And (3) preparing a material A. The ingredients are prepared according to the following mass and chemical composition proportions: siO (SiO) 2 18％、AlPO 4 16％、CoC 2 O 4 10%, quartz 15%, li 3 PO 4 14％、Na 3 PO 4 10％、K 3 PO 4 9% of CaO and 8%. The raw materials are dry-mixed and ground, sieved by a 100-mesh sieve to obtain a mixture, filled into a crucible, placed into an electric furnace, kept at 700 ℃ for 60 minutes, kept at 800 ℃ for 10 minutes, kept at 1100 ℃ for 20 minutes, taken out, poured into water and quenched to obtain the frit. Taking out the frit from water, drying, putting into a ball milling tank, taking 1/3 of ball stones with the particle sizes of 5mm, 15mm and 20mm according to the mass ratio, rotating at 300 r/min, and controlling the materials: grinding balls with the mass ratio of 1:4, grinding for 4 hours, sieving with a 300-mesh sieve, and drying for later use, and marking as material A.
2) And (3) preparing a material B. The material A, the cobalt tungstate and the kaolin are mixed according to the mass ratio: cobalt tungstate: kaolin = 80%:10%: mixing 10% of materials, uniformly mixing, putting the materials in a ball milling tank, taking 1/3 of ball stones with the particle sizes of 5mm, 15mm and 20mm according to the mass ratio, rotating at 300 r/min, and controlling the materials: grinding balls with the mass ratio of 1:4, grinding for 10 hours, and sieving with a 300-mesh sieve, and marking as material B.
3) And (3) adding water into the material B, stirring and uniformly mixing to prepare a glaze slurry, and simultaneously adding ammonium polyacrylate as a dispersing agent, wherein the mass percentage of water in the glaze slurry is 60%, and the mass percentage of the ammonium polyacrylate is 0.5%.
4) Glazing the prepared glaze slurry on the surface of ceramic, controlling the glazing thickness to be 0.3mm, drying at 100 ℃, firing by roller kiln oxidizing flame, preserving heat at 500 ℃ for 25 minutes at low temperature, heating to 1200 ℃ for 20 minutes, and controlling the firing period to be 165 minutes.
5) Spreading sulfur powder on the surface of the sintered ceramic body per 100cm 2 And (3) calcining 0.5g of sulfur powder on the surface of the ceramic body at 400 ℃ for 90 minutes in an inert atmosphere to obtain the ceramic product with the sulfur doped stable cobalt tungstate based photocatalytic activity.
Example 2
The preparation method of the sulfur doped stable cobalt tungstate based photocatalytic activity ceramic product comprises the following steps:
1) And (3) preparing a material A. The ingredients are prepared according to the following mass and chemical composition proportions: siO (SiO) 2 18％、AlPO 4 16％、CoC 2 O 4 10%, quartz 15%, li 3 PO 4 14％、Na 3 PO 4 10％、K 3 PO 4 9% of CaO and 8%. The raw materials are dry-mixed and ground, sieved by a 100-mesh sieve to obtain a mixture, filled into a crucible, placed into an electric furnace, kept at 700 ℃ for 60 minutes, kept at 800 ℃ for 10 minutes, kept at 1100 ℃ for 20 minutes, taken out, poured into water and quenched to obtain the frit. Taking out the frit from water, drying, putting into a ball milling tank, taking 1/3 of ball stones with the particle sizes of 5mm, 15mm and 20mm according to the mass ratio, rotating at 300 r/min, and controlling the materials: grinding balls with the mass ratio of 1:4, grinding for 4 hours, sieving with a 300-mesh sieve, and drying for later use, and marking as material A.
2) And (3) preparing a material B. The material A, the cobalt tungstate and the kaolin are mixed according to the mass ratio: cobalt tungstate: kaolin = 80%:10%: mixing 10% of materials, uniformly mixing, putting the materials in a ball milling tank, taking 1/3 of ball stones with the particle sizes of 5mm, 15mm and 20mm according to the mass ratio, rotating at 300 r/min, and controlling the materials: grinding balls with the mass ratio of 1:4, grinding for 10 hours, and sieving with a 300-mesh sieve, and marking as material B.
3) And (3) adding water into the material B, stirring and uniformly mixing to prepare a glaze slurry, and simultaneously adding ammonium polyacrylate as a dispersing agent, wherein the mass percentage of water in the glaze slurry is 60%, and the mass percentage of the ammonium polyacrylate is 0.5%.
4) Glazing the prepared glaze slurry on the surface of ceramic, controlling the glazing thickness to be 0.3mm, drying at 100 ℃, firing by roller kiln oxidizing flame, preserving heat at 500 ℃ for 25 minutes at low temperature, heating to 1200 ℃ for 20 minutes, and controlling the firing period to be 165 minutes.
5) Spreading sulfur powder on the surface of the sintered ceramic body per 100cm 2 The ceramic body surface of the ceramic body is calcined at 600 ℃ for 60 minutes in an inert atmosphere by using 1.5g of sulfur powder, so as to obtain the ceramic product with the sulfur doped stable cobalt tungstate based photocatalytic activity.
Example 3
The preparation method of the sulfur doped stable cobalt tungstate based photocatalytic activity ceramic product comprises the following steps:
1) And (3) preparing a material A. The ingredients are prepared according to the following mass and chemical composition proportions: siO (SiO) 2 18％、AlPO 4 16％、CoC 2 O 4 10%, quartz 15%, li 3 PO 4 14％、Na 3 PO 4 10％、K 3 PO 4 9% of CaO and 8%. The raw materials are dry-mixed and ground, sieved by a 100-mesh sieve to obtain a mixture, filled into a crucible, placed into an electric furnace, kept at 700 ℃ for 60 minutes, kept at 800 ℃ for 10 minutes, kept at 1100 ℃ for 20 minutes, taken out, poured into water and quenched to obtain the frit. Taking out the frit from water, drying, putting into a ball milling tank, taking 1/3 of ball stones with the particle sizes of 5mm, 15mm and 20mm according to the mass ratio, rotating at 300 r/min, and controlling the materials: grinding balls with the mass ratio of 1:4, grinding for 4 hours, sieving with a 300-mesh sieve, and drying for later use, and marking as material A.
2) And (3) preparing a material B. The material A, the cobalt tungstate and the kaolin are mixed according to the mass ratio: cobalt tungstate: kaolin = 80%:10%: mixing 10% of materials, uniformly mixing, putting the materials in a ball milling tank, taking 1/3 of ball stones with the particle sizes of 5mm, 15mm and 20mm according to the mass ratio, rotating at 300 r/min, and controlling the materials: grinding balls with the mass ratio of 1:4, grinding for 10 hours, and sieving with a 300-mesh sieve, and marking as material B.
3) And (3) adding water into the material B, stirring and uniformly mixing to prepare a glaze slurry, and simultaneously adding ammonium polyacrylate as a dispersing agent, wherein the mass percentage of water in the glaze slurry is 60%, and the mass percentage of the ammonium polyacrylate is 0.5%.
4) Glazing the prepared glaze slurry on the surface of ceramic, controlling the glazing thickness to be 0.3mm, drying at 100 ℃, firing by roller kiln oxidizing flame, preserving heat at 500 ℃ for 25 minutes at low temperature, heating to 1200 ℃ for 20 minutes, and controlling the firing period to be 165 minutes.
5) Spreading sulfur powder on the surface of the sintered ceramic body per 100cm 2 2.0g of sulfur powder is used on the surface of the ceramic body, and the ceramic body is calcined at 800 ℃ for 30 minutes in an inert atmosphere, so that the ceramic product with the sulfur doped stable cobalt tungstate based photocatalytic activity is obtained.
Comparative example 1
Preparing a ceramic product:
1) And (3) preparing a material A. The ingredients are prepared according to the following mass and chemical composition proportions: siO (SiO) 2 18％、AlPO 4 16％、CoC 2 O 4 10%, quartz 15%, li 3 PO 4 14％、Na 3 PO 4 10％、K 3 PO 4 9% of CaO and 8%. The raw materials are dry-mixed and ground, sieved by a 100-mesh sieve to obtain a mixture, filled into a crucible, placed into an electric furnace, kept at 700 ℃ for 60 minutes, kept at 800 ℃ for 10 minutes, kept at 1100 ℃ for 20 minutes, taken out, poured into water and quenched to obtain the frit. Taking out the frit from water, drying, putting into a ball milling tank, taking 1/3 of ball stones with the particle sizes of 5mm, 15mm and 20mm according to the mass ratio, rotating at 300 r/min, and controlling the materials: grinding balls with the mass ratio of 1:4, grinding for 4 hours, sieving with a 300-mesh sieve, and drying for later use, and marking as material A.
2) And (3) preparing a material B. The material A, the cobalt tungstate and the kaolin are mixed according to the mass ratio: cobalt tungstate: kaolin = 80%:10%: mixing 10% of materials, uniformly mixing, putting the materials in a ball milling tank, taking 1/3 of ball stones with the particle sizes of 5mm, 15mm and 20mm according to the mass ratio, rotating at 300 r/min, and controlling the materials: grinding balls with the mass ratio of 1:4, grinding for 10 hours, and sieving with a 300-mesh sieve, and marking as material B.
3) And (3) adding water into the material B, stirring and uniformly mixing to prepare a glaze slurry, and simultaneously adding ammonium polyacrylate as a dispersing agent, wherein the mass percentage of water in the glaze slurry is 60%, and the mass percentage of the ammonium polyacrylate is 0.5%.
4) Glazing the prepared glaze slurry on the surface of ceramic, controlling the glazing thickness to be 0.3mm, drying at 100 ℃, firing by roller kiln oxidizing flame, preserving heat at 500 ℃ for 25 minutes at low temperature, heating to 1200 ℃ for 20 minutes, and controlling the firing period to be 165 minutes to obtain the ceramic product.
XRD analysis of the glaze layer of the ceramic product of example 1 revealed that the crystalline glaze formed on the surface of the ceramic tile exhibited three strongest diffraction peaks, known as CoWO, in comparison with the PDF card 4 。
Cleaning and drying the surface of a ceramic product, uniformly coating a certain amount of benzoic acid ethanol solution on the surface of the ceramic product with the length of 6cm multiplied by the width of 1cm, and drying at a low temperature to constant weight; the uv lamp was then fixed over the ceramic product and kept degraded for 4 hours, a 1-time degradation process. And taking out the used ceramic product after the degradation is completed for 1 time, and uniformly coating a certain amount of ethanol solution of benzoic acid on the surface of the ceramic product again to continue the degradation. Repeating the above process until the corresponding degradation times are completed. Degradation efficiency of benzoic acid = amount of change in weight of benzoic acid solution/initial amount of weight of benzoic acid solution. The test conditions were: irradiation intensity 3.0mW/cm 2 The dominant wavelength is 253.7nm, the temperature fluctuation is +/-0.1 ℃, and the humidity fluctuation is +/-1%. When the degradation product is toluene, the benzoic acid is correspondingly replaced by toluene.
The ceramic products containing the crystalline glaze prepared in comparative example 1, example 2 and example 3 were subjected to photocatalytic tests. The photocatalytic performance of the samples was tested using a BL-GHX-V type photocatalyst (Bilang biosciences Co., ltd.).
FIG. 1 is a graph of every 100cm 2 0g sulfur powder (comparative example 1) per 100cm was used for the ceramic bulk surface of (C) 2 0.5g sulfur powder (example 1) per 100cm was used for the ceramic bulk surface of (C) 2 1.5g sulfur powder (example 2) per 100cm was used for the ceramic bulk surface of (C) 2 Performance profile of photocatalytic degradation of toluene using 2.0g sulfur powder (example 3) on the ceramic body surface.
FIG. 2 is every 100cm 2 0g sulfur powder (comparative example 1) per 100cm was used for the ceramic bulk surface of (C) 2 0.5g sulfur powder was used on the ceramic bulk surface (example 1)) Every 100cm 2 1.5g sulfur powder (example 2) per 100cm was used for the ceramic bulk surface of (C) 2 Performance profile of photocatalytic degradation of benzoic acid using 2.0g sulfur powder (example 3) on the ceramic body surface.
It can be seen that the degradation efficiency of p-toluene after photocatalytic degradation under the same catalytic conditions for 60 times was arranged in the following order: every 100cm 2 0g of sulfur powder was used for the ceramic body surface (comparative example 1)<Every 100cm 2 0.5g sulfur powder was used for the ceramic body surface (example 1)<Every 100cm 2 2.0g sulfur powder was used for the ceramic body surface (example 3)<Every 100cm 2 1.5g sulfur powder (example 2) was used on the ceramic body surface. Similarly, the degradation efficiency of p-benzoic acid after 60 times of photocatalytic degradation was arranged in the following order: every 100cm 2 0g of sulfur powder was used for the ceramic body surface (comparative example 1)<Every 100cm 2 0.5g sulfur powder was used for the ceramic body surface (example 1)<Every 100cm 2 2.0g sulfur powder was used for the ceramic body surface (example 3)<Every 100cm 2 1.5g sulfur powder (example 2) was used on the ceramic body surface. This demonstrates that the sulfur doped stabilized cobalt tungstate based photocatalytic activity ceramic product has a higher stability of catalytic degradation activity than the undoped cobalt tungstate based photocatalytic ceramic product, which is beneficial to maintaining the durability of catalytic degradation activity of the ceramic product.
Claims (9)
1. A method for preparing a sulfur-doped stable cobalt tungstate-based photocatalytic activity ceramic product, which is characterized by comprising the following steps:
applying cobalt tungstate-based ceramic crystal glaze to the surface of a ceramic body; the cobalt tungstate-based ceramic crystal glaze comprises the following raw materials in parts by weight: 70-90% of powder A, 8-10% of cobalt tungstate and 8-10% of kaolin in percentage by mass; the powder A comprises the following raw materials: in mass percent, siO 2 15～25%、AlPO 4 16～22%、CoC 2 O 4 6 to 10 percent, 15 to 20 percent of quartz and Li 3 PO 4 14～18%、Na 3 PO 4 8～13%、K 3 PO 4 7～9%、CaO 5～8%；
Firing the ceramic body after applying the cobalt tungstate based ceramic crystal glaze;
spreading sulfur powder on the surface of the sintered ceramic body and calcining the ceramic body in an inert atmosphere to obtain the ceramic product with the sulfur doped stable cobalt tungstate based photocatalytic activity;
the dosage of sulfur powder is per 100cm 2 Tiling 0.5-2.0 g on the surface of the ceramic body;
the calcination temperature is 400-800 ℃ and the calcination time is 30-90 minutes.
2. The method of claim 1, wherein powder a is in the form of a frit; the preparation process of the frit comprises the following steps: uniformly mixing the raw materials according to the powder material A, sieving the mixture, preserving heat for 30 to 60 minutes at a first temperature, preserving heat for 5 to 25 minutes at a second temperature, preserving heat for 10 to 20 minutes at a third temperature, quenching and crushing to obtain a frit; wherein the first temperature is 500-700 ℃, the second temperature is 600-800 ℃, and the third temperature is 1000-1100 ℃; the second temperature is 50-200 ℃ higher than the first temperature.
3. The method according to claim 1, wherein the cobalt tungstate-based ceramic crystal glaze forms acicular cobalt tungstate crystals in a high-temperature firing environment.
4. A method of preparation according to claim 3 wherein the cobalt tungstate crystal is characterized by one-dimensional epitaxial growth.
5. The method according to claim 1, wherein the maximum firing temperature is 1100 to 1300 ℃ and the firing period is 110 to 170 minutes.
6. The method of claim 1, wherein the inert atmosphere for calcination is argon.
7. The method according to claim 1, wherein the cobalt tungstate-based ceramic crystal glaze is applied to the surface of the ceramic body in the form of glaze slip; the glaze slurry comprises a dispersing agent and water besides the cobalt tungstate-based ceramic crystal glaze; the water accounts for 40 to 60 percent of the mass of the glaze slip, and the dispersant accounts for 0.1 to 0.5 percent of the mass of the glaze slip.
8. The method according to claim 7, wherein the glaze slip forms a crystalline glaze layer of 0.05 to 0.3mm on the surface of the ceramic body.
9. The sulfur-doped stable cobalt tungstate-based photocatalytic ceramic product obtained by the preparation method according to claim 1.
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