CN115611606A - One-time sintered TiO 2 Photocatalytic ceramic and preparation method thereof - Google Patents
One-time sintered TiO 2 Photocatalytic ceramic and preparation method thereof Download PDFInfo
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Abstract
The invention provides a one-time sintered TiO 2 Photocatalytic ceramic and method for preparing same, and single-fired TiO 2 The components of the photocatalytic ceramic comprise 30-70% of silicate mineral, 0-30% of titanium dioxide or titanium-containing mineral and titanium-containing waste residue, and 4-18% (calculated on a dry basis) of nano TiO 2 Sol, 0-30% of natural electric polarity mineral. The preparation of the one-shot TiO 2 Preparing a green body by dehydrating and forming raw materials of each component of the photocatalytic ceramic after wet ball milling, and spraying nano TiO on the green body 2 Sol containing Ti 4+ One or more of the solution and the suspension is sintered at 600-700 ℃ and then is subjected to high fire heat preservation for 1-2 hours to prepare TiO sintered at one time 2 Photo catalysisAnd (4) melting the ceramic. The method only needs one-time sintering, has simple process, reduces energy consumption and cost, and also reduces carbon emission; at the same time, the TiO content can be improved 2 The utilization rate of the ceramic material, and the physical property and the photocatalytic activity of the ceramic material are enhanced.
Description
Technical Field
The invention relates to the field of ceramic materials, in particular to a one-time sintered TiO 2 Photocatalytic ceramic and a preparation method thereof.
Background
TiO 2 Is an inorganic compound, and TiO irradiated by ultraviolet light was discovered by Fujishiam et al in 1972 2 TiO from the surface of which a continuous redox reaction of water takes place 2 Has been widely studied and applied as a semiconductor photocatalytic material.
In the preparation of photocatalytic materials, the prior art generally provides for the preparation of granular or sol-like TiO 2 Preparing a suspension: adding TiO into the mixture 2 The prepared suspension liquid forms a flow cell through an annular-ring type, straight-through type or coaxial quartz tube clamping layer, and a radiation light source directly radiates the flow cell. The reactor has a simple structure, but the catalyst cannot be continuously used, the catalyst must be separated and recovered by filtration, centrifugation, flocculation and other methods in the post treatment, the process is complicated, the recovery is not thorough, and the radiation depth is influenced due to the absorption of light by the solvent and other components of the suspension.
In order to improve the catalytic efficiency, a more efficient and practical photocatalytic reactor has been developed, and studies have been made on the immobilization of photocatalysts. The catalyst can be fixed on some solid matrixes, such as kaolin, diatomite, zeolite, attapulgite, perfluorosulfonic acid film, silica gel, sand, glass beads, honeycomb ceramic and the like, and can also be fixed on the inner wall of a container or the outer wall of a light source lamp tube and the like. One of the fixing methods is as follows: the carrier is coated with nano TiO 2 Sol, etc. containingSoaking titanium in solution, drying, and calcining at 400-600 deg.C for 4-5 times (honeycomb ceramic supported TiO described in literature) 2 The research on the methyl orange degradation test "Lianghuayin, wangzhu Mei, luo-Wai," ceramics journal of the second stage 2011, pages 235-238). Not only the process is complicated, the energy consumption is high, and the carbon emission is enlarged, but also the nano TiO which is initially impregnated can be repeatedly sintered 2 The crystal grows up, the specific surface area is reduced, and even the phase change can be generated to be rutile crystal so as to reduce the photocatalysis efficiency; in addition, tiO 2 The photocatalyst is adhered to kaolin, diatomaceous earth, zeolite, and attapulgite, and is in the form of powder, and has problems of poor strength and difficulty in recovery when used.
The method needs to carry out multiple sintering, has high energy consumption and large carbon emission, and the prepared ceramic material has poor physical properties and photocatalytic activity.
Disclosure of Invention
In order to solve the problems, the invention provides TiO calcined at one time 2 The photocatalytic ceramic and the preparation method thereof only need one-time sintering, have simple process, reduce energy consumption and cost, and simultaneously can improve TiO 2 The utilization rate of the ceramic material is enhanced, and the physical property and the photocatalytic activity of the ceramic material are enhanced.
The invention provides a one-step sintered TiO 2 Photocatalytic ceramic, preparation of one-shot TiO 2 The components of the photocatalytic ceramic comprise 30-70% of silicate mineral, 0-30% of titanium dioxide or titanium-containing mineral and titanium-containing waste residue, and 4-18% (calculated on a dry basis) of nano TiO 2 Sol, 0-30% of natural electric polarity mineral.
Nano TiO 2 2 The sol has strong caking property, and after being mixed with silicate mineral, titanium dioxide and the like, the particles of the silicate mineral, the titanium dioxide and the like are coated with nano TiO 2 The sol is surrounded by an O-Ti-O three-dimensional network structure, and nano TiO is arranged between particles 2 The sol is adhered and integrated, and the dried nano TiO 2 The sol can still keep the adhesiveness among particles even if the green body is repeatedly coated, poured and sprayed with nano TiO 2 Sol gelContaining Ti 4+ The blank is not loosened, deformed or cracked due to one or more of the solution and the suspension; at the same time, nano TiO 2 The high activity of the sol can promote the sintering of the green body, so that the ceramic material has certain strength.
The preparation of the one-shot TiO 2 Preparing a green body by dehydrating and forming components of the photocatalytic ceramic after wet ball milling, and spraying nano TiO on the green body 2 Sol containing Ti 4+ One or more of a solution and a suspension of (a).
Repeatedly coating, pouring and spraying nanometer TiO on the green body 2 Sol containing Ti 4+ Of one or more of solutions and suspensions of (a) in (b), making the multilayer TiO 2 Attached to the green body to achieve the desired photocatalyst layer thickness on the surface of the body. Furthermore, the ceramic green body has more pores than the fired ceramic product, thereby making it easier to contain Ti 4+ The sol, the solution and the suspension are infiltrated and absorbed, so that the nano TiO on the surface layer of the blank body 2 The amount of adhesion is higher, increasing the photocatalytic effect.
The primary sintered TiO 2 The firing temperature of the photocatalytic ceramic is 600-700 ℃, and the primary firing TiO is prepared by keeping the temperature for 1-2 hours with high fire 2 A photocatalytic ceramic.
The one-time sintered photocatalytic ceramic needs to be sintered at low temperature to avoid TiO 2 The crystal is changed from anatase type to rutile type, and the general firing temperature is not higher than 700 ℃, so the TiO once fired provided by the invention 2 The firing temperature of the photocatalytic ceramic is 600-700 ℃, and the high-temperature heat preservation is carried out for 1-2 hours.
The silicate mineral comprises one or more of bentonite, rectorite, kaolin, attapulgite, ball clay, sepiolite, magnesia clay, chlorite, diatomite, zeolite, vermiculite, perlite and pumice.
The natural electric polarity mineral comprises one or more of iron tourmaline, magnesium tourmaline and lithium tourmaline.
Tourmaline can effectively reduce hole-electron recombination in photocatalytic reaction, and silicate mineral such as bentoniteThe high porosity and high specific surface area of the soil, zeolite, diatomite, etc. contribute to the nano TiO 2 Sol or containing Ti 4+ TiO in solution or suspension 2 High dispersion, and can prevent titanium dioxide crystal grain from growing into coarse crystal when the catalyst is fired so as to form fine crystal or microcrystal structure and obtain optimum photocatalysis effect.
The titanium-containing mineral comprises one or more of ilmenite, titanomagnetite, primary rutile, perovskite and titanium concentrate, the titanium-containing waste residue comprises titanium-containing blast furnace slag, and the titanium pigment comprises anatase titanium pigment.
The invention also provides a method for preparing the TiO through one-time sintering 2 A method of preparing a photocatalytic ceramic, the method comprising: silicate mineral with the mass fraction of 30-70%, titanium dioxide or titanium-containing mineral with the mass fraction of 0-30%, titanium-containing waste residue with the mass fraction of 4-18%, and nano TiO 2 Sol, natural electric polarity mineral with the mass fraction of 0-30 percent is used as a raw material, and the TiO is obtained by wet ball milling, dehydration, molding to prepare a green body and then primary sintering 2 A photocatalytic ceramic.
TiO prepared by dry process technical route 2 Photocatalytic ceramic made of nano TiO 2 The O-Ti-O three-dimensional network structure formed by the sol is only maintained in the granulation particles, the O-Ti-O three-dimensional network structure does not exist between the granulation particles, and nano TiO is not present between the granulation particles due to no O-Ti-O network system during roasting 2 The effect of sol promoting sintering cannot be well exerted, so that the TiO prepared by the dry process cannot be well exerted 2 The photocatalytic ceramic has low strength. And the TiO prepared by adopting a wet process 2 Photocatalytic ceramics, tiO 2 All the component particles in the photocatalytic ceramic are coated with nano TiO 2 The sol is formed into an O-Ti-O three-dimensional network structure which is uniformly coated into a whole, and the nano TiO is roasted 2 The sol network structure can keep the state till the later sintering stage, and the nano TiO 2 The sol can also play a role of a sintering aid, so that the material has high strength and corrosion resistance, and particularly the mechanical strength of the material is superior to that of TiO prepared by a dry process 2 A photocatalytic ceramic.
The preparation of the one-step sintered TiO 2 The method of photocatalytic ceramics further comprises: spraying nano TiO on the green body 2 Sol containing Ti 4+ And firing the solution or suspension.
The TiO sintered at one time 2 The firing temperature of the photocatalytic ceramic is 600-700 ℃, and the high-temperature heat preservation is carried out for 1-2 hours.
The molding method comprises the following steps: wet plastic forming, foam sponge dipping slurry forming and dry powder rolling slush molding.
Preferably, the wet method plastic forming method includes: drying and dewatering the slurry until the water content is 17-22% and the slurry is in a plastic pug state, and extruding the slurry into one or more of a bar column shape, a hollow ring shape and a flat plate shape by using an extruder.
Preferably, the wet method plastic forming method includes: drying the slurry to dehydrate until the water content is less than 0.5%, adding hydroxypropyl methyl cellulose, mixing and grinding, pouring into a kneading machine, and spraying nano TiO 2 Continuously stirring the sol, adding grease, forming into paste, vacuum pugging, ageing for 72 hours, and performing piston type hydraulic extrusion to form a honeycomb ceramic green body.
Preferably, the foam sponge dipping mud forming mode comprises the following steps: drying the slurry, dehydrating until the water content is less than 1.5%, pulverizing into fine powder, and mixing the fine powder with nano TiO 2 Preparing slurry from sol, aluminum dihydrogen phosphate, silica sol and aluminum sol, and impregnating the slurry with foam sponge to obtain a foam ceramic green body; or concentrating and dehydrating to obtain slurry with water content less than 30%, adding nanometer TiO 2 Preparing slurry from the sol, aluminum dihydrogen phosphate, silica sol and aluminum sol, and then soaking the slurry in foam sponge to prepare a foam ceramic green body.
Preferably, the dry powder rolling forming mode comprises the following steps: drying the slurry, dehydrating until the water content is less than 0.5%, pulverizing into fine powder, and processing the nano TiO by enameling process 2 The sol is sprayed into a balling disk filled with powder to prepare a round particle green compact with the diameter of 0.1-1.0 mm.
Nano TiO 2 The sol forms an O-Ti-O three-dimensional network structure, has stronger cohesiveness, improves the bonding strength and the drying strength of a green body, and thus, the nano TiO-containing nano TiO is sprayed on the surface of the green body 2 Sol or containing Ti 4+ The solution and the suspension can ensure that the green body is not loose, deformed and cracked. Therefore, the invention adds the nano TiO into the blank 2 And (3) sol. Despite the nano TiO 2 The cost of sol is high, but the wall thickness of honeycomb ceramics and foamed ceramics can be made into 0.1mm thickness, the spherical particles can be used for enameling the blank body to 0.1mm size by means of rolling enameling granulation balling process, and TiO on the blank body 2 The layer also needs to have a certain thickness to exert the photocatalytic effect, and TiO 2 The ratio of the surface area to the weight of the photocatalytic ceramic is highest in a honeycomb shape, for example, the geometric specific surface area of 325-mesh honeycomb ceramic is 3000 square meters per meter 3 And the specific weight of the honeycomb ceramics is generally 0.5 to 0.6 ton/m 3 Adding 20% of nano TiO into the blank 2 Sol, only 100-120kg of nano TiO is needed 2 Sol, no need of adding extra cost and simultaneously improving TiO 2 The utilization ratio of (2).
The one-time sintered TiO provided by the invention 2 The photocatalytic ceramic and the preparation method thereof have the following beneficial effects:
1. in the preparation of primary-fired TiO 2 Nano TiO is added into blank components of photocatalytic ceramic 2 The sol can be used to spray green body containing nano TiO by its strong cohesiveness 2 Sol or containing Ti 4+ When the solution and the suspension are used, the blank is ensured not to be loosened, deformed and cracked. At the same time, nano TiO 2 The high activity of the sol can promote the sintering of the green body, so that the material has certain strength.
2. The low-temperature one-time firing is adopted, multiple times of sintering are not needed, the energy consumption is reduced, the energy is saved, and the carbon emission is reduced.
3. One-shot TiO prepared by wet process 2 Photocatalytic ceramics, tiO 2 The component particles in the photocatalytic ceramic are all coated with nano TiO 2 The sol is formed into an O-Ti-O three-dimensional network structure which is uniformly coated into a whole, and the nano-scale coating is carried out at the later stage of sinteringTiO 2 And the material can also play a role of a sintering aid, so that the material has high strength and corrosion resistance.
4. Spraying nano TiO on the surface of the blank 2 Sol or containing Ti 4+ Solutions, suspensions, making multilayer TiO 2 Attached to the green body to achieve the desired thickness of the photocatalytic layer on the surface of the body. Furthermore, the ceramic green body has more pores than the fired ceramic finished product, thereby being easier to lead the titanium sol and the Ti-containing ceramic 4+ The solution and the suspension are infiltrated and adsorbed, so that the nano TiO on the surface layer of the blank body 2 The amount of adhesion is higher, further enhancing the photocatalytic performance.
5. TiO prepared by existing precipitation method and gel sol method 2 The present invention adopts a mixing method process, and has the defects of low cost, simple process and capability of making various products with complex shapes, high rigidity and high specific surface area.
6. Preparing primary-fired TiO by adopting silicate minerals, tourmaline and other raw materials 2 The photocatalytic ceramic has wide raw material source and low cost.
Drawings
FIG. 1 is a graph comparing the degradation of methylene blue in examples 1, 2, 3 and comparative example T.
FIG. 2 is a graph comparing the degradation of methyl orange in examples 1, 2, 3 and comparative example T.
FIG. 3 is a graph showing the degradation of methyl orange in the presence of 60mg/L sodium persulfate added to the solution of examples 1, 2, and 3, and comparative example T.
FIG. 4 is an X-ray diffraction pattern of the samples prepared in examples 1, 2, 3 and comparative example T.
FIG. 5 is an SEM micrograph of samples prepared in examples 1, 2, 3 and comparative example T.
Detailed Description
The invention is further described with reference to the drawings and the detailed description. Those skilled in the art will be able to implement the invention based on these teachings. Moreover, the embodiments of the present invention described in the following description are generally only some embodiments of the present invention, and not all embodiments. Therefore, all other embodiments obtained by a person of ordinary skill in the art based on the embodiments of the present invention without making creative efforts shall fall within the protection scope of the present invention.
Example 1: weighing 30kg of 325 mesh tourmaline powder, 70kg of 250 mesh calcium bentonite and 20% solid nano TiO 2 30kg of sol and 0.2kg of ammonium polyacrylate are added with water and then ball-milled for 4 hours by a wet method, the slurry is discharged, dried and dehydrated to form mud paste, the mud paste is roughly milled into mud segments by a pug mill and is aged for 72 hours, then the mud is put into a vacuum pug mill and is extruded into thin strips with the diameter of 4mm, the thin strips are cut into strip columns with the length of 3-4mm after being dried, naturally dried in the shade for 48 hours, dried, put into a rotary kiln for roasting, and cooled and taken out of the kiln after being insulated for 1.5 hours by high fire at the temperature of 600 ℃.
Example 2: weighing 15kg of anatase titanium dioxide with fineness of 325 meshes, 15kg of tourmaline powder with fineness of 325 meshes, 70kg of calcium bentonite with fineness of 250 meshes and nano TiO with solid content of 20% 2 30kg of sol and 0.2kg of ammonium polyacrylate are added with water and ball-milled for 4 hours by a wet method, then the slurry is discharged, dried and dehydrated to form mud paste, the mud paste is coarsely refined into mud sections by a mud mill and is aged for 72 hours, then the mud is put into a vacuum mud mill and is extruded into thin strips with the diameter of 4mm, the thin strips are cut into strip columns with the length of 3-4mm after being dried, the strips are naturally dried in the shade for 48 hours, then the strips are put into a drying room for drying, are put into a rotary kiln for roasting, and are cooled and taken out of the kiln after being heated by high fire at the temperature of 600 ℃ for 1.5 hours.
Example 3: 30kg of anatase titanium dioxide with fineness of 325 meshes, 70kg of calcium bentonite with fineness of 250 meshes and 20 percent of nano TiO 2 30kg of sol and 0.2kg of ammonium polyacrylate are added with water and then ball-milled for 4 hours by a wet method, the slurry is discharged, dried and dehydrated to form mud paste, the mud paste is roughly milled into mud segments by a pug mill and is aged for 72 hours, then the mud is put into a vacuum pug mill and is extruded into thin strips with the diameter of 4mm, the thin strips are cut into strip columns with the length of 3-4mm after being dried, naturally dried in the shade for 48 hours, dried, put into a rotary kiln for roasting, and cooled and taken out of the kiln after being insulated for 1.5 hours by high fire at the temperature of 600 ℃.
Comparative example T: weighing 20kg of tourmaline powder with the fineness of 325 meshes, 10kg of anatase titanium dioxide, 70kg of calcium bentonite with the fineness of 250 meshes, 10kg of external fluxing agent and 0.2kg of ammonium polyacrylate, adding water, carrying out wet ball milling for 4 hours, discharging slurry, drying and dehydrating to obtain mud paste, roughly milling the mud paste into mud sections by using a mud mill, ageing for 72 hours, putting the mud materials into a vacuum mud extruder to obtain thin strips with the diameter of 4mm, cutting the strips into strip columns with the length of 3-4mm after drying, naturally drying in the shade for 48 hours, putting the strips into a drying room, baking the strips in a rotary kiln, keeping the temperature at 600 ℃ for 1.5 hours, cooling and taking the strips out of the kiln.
The prepared product is subjected to performance detection and characterization by adopting a BELSORP-max-Bayer specific surface area tester, an XRD-6100-Shimadzu X-ray diffractometer, a Jiemio 1920 spectrophotometer, an SNM-3000SM scanning electron microscope and an FT-700A catalyst particle pressure resistance tester.
Photocatalytic experiments and performance tests: methylene blue MB with the concentration of 20mg/L and methyl orange MO solution with the concentration of 20mg/L are respectively prepared, 18mL of catalyst and 80mL of simulated waste liquid are added into each quartz glass culture dish, the quartz glass culture dishes are placed on a reaction device, and an ultraviolet lamp is started. The reaction was carried out from the start to 60min, once every 10min, and every 20min during 60-120min, and the samples were filtered and then measured for absorbance at the maximum peak wavelength (664 nm for MB and 465nm for OB) using a spectrophotometer for each time period. According to the Lambert beer law, the absorbances of MB and OB solutions and the concentration of the solutions are in a linear relation, so that the attenuation condition of the absorbance of the solutions is used as a reference mark for the MB and OB photocatalytic degradation capacity. FIG. 1 shows the result of the degradation of methylene blue, FIG. 2 shows the result of the degradation of methyl orange, and FIG. 3 shows the result of the degradation of methyl orange in the presence of sodium persulfate. The detection of the X-ray diffractometer shows that the TiO in all the samples 2 All anatase type crystal phases, the tourmaline crystal phase is kept complete, and the bentonite decomposes into a quartz crystal phase after being calcined, which shows that the calcination at the low temperature of 600 ℃ is beneficial to forming the required crystal phase; in example 3, it is also found for the first time that the calcium bentonite can be mixed with nano TiO 2 The sol can form CaTiO when being heated at 600 DEG C 3 The crystal also has photocatalytic abilityFig. 4). The scanning electron microscope results are shown in figure 5. The TiO of examples 1, 2, 3, as measured by the Scherrer formula 2 Have a particle size of 35.8, 35.0 and 42.8nm, respectively.
TABLE 1 compression Strength comparison of comparative example T with example 1
| Comparative example T | Example 1 | |
| Radial compressive strength N/cm | 42.2 | 54.7 |
| Catalyst diameter mm | 3.8 | 3.7 |
TABLE 2 comparison of surface Properties of examples 1-3 with comparative example T
| Comparative example T | Example 1 | Example 2 | Example 3 | |
| Specific surface area m 2 /g | 24.219 | 31.126 | 37.333 | 30.981 |
| Total pore volume cm 3 /g | 0.0491 | 0.1087 | 0.1303 | 0.1285 |
| Average pore diameter nm | 8.10 | 13.963 | 18.049 | 16.586 |
Example 4: weighing 70kg of attapulgite clay, 24kg of 325-mesh anatase titanium dioxide powder and 30kg of nano TiO with the solid content of 20% 2 Putting the sol into a ball mill, adding water, wet-milling for 8 hours, and discharging slurry. The slurry dehydration mode has two types: one is drying to water content of 22-25% to obtain pasty plastic, and the other is drying to water content of 1-2% to obtain block. Extruding the paste blank into a strip column shape with the diameter of 4mm by using a piston type extruder after the paste blank is aged, and cutting the blank into a column shape with the length of 4mm after drying; crushing and granulating the block material with the water content of 1-2% to 20 meshes, and pressing the powder material into a column shape with the diameter of 4mm and the height of 5mm by using a hydraulic press. The two materials are both put into the same kiln to be calcined at 600 ℃ and are kept warm for 1.5 hours by high fire.
Using FT-700A catalystTiO prepared by particle compression-resistant tester for testing radial linear compression strength and plastic molding process 2 The compressive strength of the photocatalytic ceramic is 56.8N/cm, and the TiO prepared by dry method hydraulic forming 2 The compressive strength of the photocatalytic ceramic is 49.9N/cm. TiO prepared by dry process technical route 2 Photocatalytic ceramic made of nano TiO 2 The O-Ti-O three-dimensional network structure formed by the sol is only maintained in the granulation particles, the O-Ti-O three-dimensional network structure does not exist between the granulation particles, and the nano TiO is not in a maintenance system of the O-Ti-O network between the granulation particles during roasting 2 The effect of promoting sintering by sol can not be well exerted, so the TiO prepared by the dry process can not be well exerted 2 The photocatalytic ceramic has low strength. And the TiO prepared by adopting a wet process 2 Photocatalytic ceramics, tiO 2 The component particles in the photocatalytic ceramic are all coated with nano TiO 2 The sol-formed O-Ti-O three-dimensional network structure is uniformly coated into a whole, and the nano TiO is roasted 2 The sol network structure can keep the state until the later sintering stage, and the nano TiO is 2 The sol can also play a role of a sintering aid, so that the material has high strength and corrosion resistance, and particularly the mechanical strength of the material is superior to that of TiO prepared by a dry process 2 A photocatalytic ceramic.
Example 5: weighing the ball clay 40kg after acid washing, diatomite powder 20kg, tourmaline 14kg, ilmenite 20kg and nano TiO with solid content of 20% 2 10kg of sol and 0.2kg of ammonium polyacrylate, adding water, carrying out wet ball milling for 8 hours, discharging slurry, drying, dehydrating, preparing into fine powder of 200 meshes by using a pulverizer, fully mixing with hydroxypropyl methyl cellulose, pouring into a kneader, and adding 20-25kg of nano TiO with 20% of solid content while stirring 2 Dissolving in sol, adding oil, making into paste, coarse refining with a pug mill, aging for 72 hr, refining into mud column with a vacuum pug mill, extruding with a piston hydraulic extruder to obtain honeycomb-shaped blank, microwave shaping, far infrared drying, and cutting into blank with height of 15-20 mm. The honeycomb body is too high, the illumination effect is not good, the catalytic efficiency is influenced, and the nano TiO is not easily sprayed into the too high green body 2 Sol forms a surface layer to enhance the photocatalytic effect; the honeycomb is too short and the cutting effort is large, resulting in low production efficiency. Spraying silica sol water solution with solid content of 2-4% to wet the green body, and spraying nano TiO 2 Sol or containing Ti 4+ Drying in shade for 24 hr, baking again, calcining in netted kiln at 610 deg.C for 1 hr to obtain honeycombed TiO 2 A photocatalytic ceramic.
Neutral or weak acid silica sol solution with solid content of 2-4% is used for spraying or dipping green wettable blank to prevent nano TiO from being attached subsequently 2 When coating with sol, solution, etc., the blank is porous and very dry, so the blank adsorbs titaniferous slurry too fast to make TiO 2 The coating is easy to crack on the surface of the blank. In addition, neutral or weakly acidic silica sol solution with solid content of 2-4% and nanometer TiO attached subsequently 2 Sol, solution, etc., which are mutually permeable, siO in silica sol 2 Can enter TiO 2 In the system, nanometer TiO is prevented 2 Agglomeration of particles, prevention of crystal growth, and SiO 2 To TiO 2 2 Has modification effect, can increase the temperature of anatase to rutile crystal, and can increase TiO 2 The surface acidity improves the adsorption capacity to organic pollutants, and is beneficial to improving the photocatalytic efficiency.
Example 6: weighing 34.5kg anatase titanium dioxide powder with fineness of 325 meshes, 15kg ferroelectric powder with fineness of 325 meshes, 5kg calcium bentonite with fineness of 250 meshes and 10kg nano TiO with concentration of 20% 2 Adding water into sol and 0.25kg of ammonium polyacrylate, performing wet ball milling for 4 hours, discharging slurry, and drying to prepare 56.5kg of 200-mesh powder; weighing 70kg of 25 percent nano TiO 2 Adding sol into a stirrer, adding 0.25kg of carboxymethyl cellulose, stirring, gradually adding 26kg of zeolite powder to make the zeolite powder and the nano TiO 2 Mixing the sol sufficiently, adding 56.5kg of the powder prepared by drying and crushing into a stirrer gradually, adding 0.25kg of ammonium polyacrylate solution and 1kg of 50% aluminum dihydrogen phosphate solution simultaneously, mixing uniformly to obtain slurry with proper consistency, and then soakingAdding polyurethane foam sponge, repeatedly soaking the slurry and extruding the slurry until slurry hanging is finished, and putting the slurry into a kiln for firing after drying in the shade, drying and selecting. The firing system is as follows: raising the temperature to 250 ℃ at the temperature raising speed of 1 ℃/min; when the temperature in the kiln reaches 250 ℃, heating to 450 ℃ at the speed of 0.5 ℃/min, finally heating to 600 ℃ from 450 ℃ at the speed of 1 ℃/min, keeping the temperature for 90 min after the temperature reaches 600 ℃, cooling and discharging to obtain the foam TiO 2 A photocatalytic ceramic.
Example 7: weighing 37kg of titanium-containing blast furnace slag, 40kg of attapulgite clay, 20kg of expanded perlite powder and nano TiO with 20 percent of solid content 2 Adding 15kg of sol and 0.2kg of ammonium polyacrylate into a ball mill, adding water, wet-milling for 8 hours, discharging slurry, spray-drying the slurry to prepare granules, pouring the granules into a rolling forming machine, and spraying nano TiO with 20 percent of solid content 2 The sol is turned into small balls with the diameter of 0.2-0.4mm, dried in the shade for 24 hours and dried until the water content is less than 1 percent, then the small balls enter a rotary kiln to be roasted at the temperature of 630 ℃, and the temperature is preserved for 60 minutes by high fire to obtain micro-bead TiO 2 A photocatalytic ceramic.
Example 8: weighing anatase type titanium dioxide 15kg, tourmaline 15kg, attapulgite clay 56kg, vermiculite powder 14kg, and nano TiO with solid content of 20% 2 Adding 25kg of sol and 0.2kg of ammonium polyacrylate into a ball mill, adding water, wet-milling for 8 hours, discharging slurry, thermally drying the slurry until the water content is 19-21% to obtain plastic pug, putting the pug into a pug mill, carrying out rough milling, and ageing for 72 hours; putting the aged pug into a vacuum pug mill, extruding into a plate shape, continuously rolling into a sheet shape with the thickness of 6-8mm by using a double-roller mill, and cutting into a square or a rectangle; conveying the sheet-shaped mud blank into a hot air drier through a conveyer belt, blowing the upper part of the flat plate blank to one surface of the flat plate blank by adopting hot air at 50-65 ℃, and drying the single surface to ensure that the nano TiO is 2 The sol is relatively much concentrated toward the upper surface of the thin plate (i.e., the surface through which hot air is blown) to make the upper surface nano-TiO 2 Drying the green body until the water content is less than 2%, drying in the shade for 24 hr, and spraying nanometer TiO 2 Sol process: the green body is used firstSpraying silica sol with solid content of 2-4% once, and then using nano TiO with solid content of 5-10% 2 Spraying sol for 2 times, drying in shade for 48 hr, oven drying until water content is less than 1%, calcining in roller kiln at 600 deg.C, maintaining at high temperature for 2 hr, taking out, and polishing four edges of the final product plate to obtain flat TiO 2 A photocatalytic ceramic.
Example 9: weighing 8kg of sepiolite, 23kg of perlite, 13kg of attapulgite, 16kg of tourmaline, 30kg of titanium-containing blast furnace slag and nano TiO with 20 percent of solid content 2 50kg of sol, 0.25% of dispersant and water are added, the sol and the water are put into a ball mill together to be mixed and finely ground for 6 to 7 hours, then slurry is led into a concentration tank to be heated to evaporate water, when the slurry is concentrated to 28 to 30% of water, the slurry is discharged into a stirring pool, 5kg of neutral silica sol with 20% of solid content is added, the mixture is mixed and stirred for 20 to 30 minutes, and then the mixture is immersed into polyurethane foam sponge, dried and fired. The sintering temperature is 620 ℃, the high fire is kept for 60 minutes, and the foam TiO is obtained 2 A photocatalytic ceramic.
Claims (10)
1. One-time sintered TiO 2 Photocatalytic ceramic, characterized in that the preparation of single-fired TiO is carried out 2 The components of the photocatalytic ceramic comprise 30-70% of silicate mineral, 0-30% of titanium dioxide or titanium-containing mineral and titanium-containing waste residue, and 4-18% (calculated on dry basis) of nano TiO 2 Sol, 0-30% of natural electrically-conductive mineral by mass.
2. A single-fired TiO according to claim 1 2 Photocatalytic ceramic, characterized in that the preparation of single-fired TiO 2 After raw materials of each component of the photocatalytic ceramic are subjected to wet ball milling, dehydrated and formed to prepare a green body, nano TiO is sprayed on the green body 2 Sol of Ti 4+ One or more of a solution and a suspension of (a).
3. A single-fired TiO according to claim 1 or 2 2 The photocatalytic ceramic is characterized in thatThe primary sintered TiO 2 The firing temperature of the photocatalytic ceramic is 600-700 ℃, and the primary firing TiO is prepared by keeping the temperature for 1-2 hours with high fire 2 A photocatalytic ceramic.
4. The single-fired TiO of claim 1 2 The photocatalytic ceramic is characterized in that the silicate mineral comprises one or more of bentonite, rectorite, kaolin, attapulgite, ball clay, sepiolite, magnesia clay, chlorite, diatomite, zeolite, vermiculite, perlite and pumice.
5. The single-fired TiO of claim 1 2 The photocatalytic ceramic is characterized in that the natural electric polarity mineral comprises one or more of iron tourmaline, magnesium tourmaline and lithium tourmaline.
6. A single-fired TiO according to claim 1 2 The photocatalytic ceramic is characterized in that the titanium-containing mineral comprises one or more of ilmenite, titanomagnetite, primary rutile, perovskite and titanium concentrate, the titanium-containing waste residue comprises titanium-containing blast furnace slag, and the titanium pigment comprises anatase type titanium pigment.
7. Preparation of one-time sintered TiO 2 A method of preparing a photocatalytic ceramic, the method comprising: 30-70% of silicate mineral, 0-30% of titanium dioxide or titanium-containing mineral and titanium-containing waste residue, and 4-18% (calculated on dry basis) of nano TiO 2 Sol, 0-30% of natural electric polarity mineral in mass percentage is used as raw material, and the TiO sintered at one time is obtained by wet ball milling, dehydration, molding to prepare green compact and then sintering at one time 2 A photocatalytic ceramic.
8. A method of preparing single-fired TiO according to claim 7 2 The method for preparing the photocatalytic ceramic is characterized in thatTiO 2 The method of photocatalytic ceramics further comprises: spraying nano TiO on the green body 2 Sol of Ti 4+ And firing the solution or suspension.
9. A method of preparing single-fired TiO according to claim 7 or 8 2 The method for photocatalysis of ceramics is characterized in that the TiO which is sintered once is used 2 The firing temperature of the photocatalytic ceramic is 600-700 ℃, and the high-temperature heat preservation is carried out for 1-2 hours.
10. A method of preparing single-fired TiO according to claim 7 2 The method for preparing the photocatalytic ceramic is characterized in that the forming mode comprises the following steps: wet plastic forming, foam sponge dipping slurry forming and dry powder rolling slush molding.
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| CN102285816A (en) * | 2011-06-16 | 2011-12-21 | 曹南萍 | Tourmaline integral honeycomb ceramic and preparation method thereof |
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| CN113797948A (en) * | 2021-08-31 | 2021-12-17 | 江西环宇工陶技术研究有限公司 | Catalyst carrier prepared by taking natural clay mineral as raw material and preparation method thereof |
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| US4113660A (en) * | 1975-12-23 | 1978-09-12 | Sakai Chemical Industry Co., Ltd. | Production of shaped catalysts or carriers comprising titanium oxides |
| CN101138715A (en) * | 2007-09-21 | 2008-03-12 | 浙江大学 | TiO2 column-supporting alta-mud adsorption-photocatalysis integrated process for preparation of catalysts |
| CN101485978A (en) * | 2008-12-25 | 2009-07-22 | 西华大学 | Method for preparing supported nano TiO2 composite photocatalysis material by microwave |
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