CN115611606B - One-time fired TiO 2 Photocatalytic ceramic and preparation method thereof - Google Patents
One-time fired 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 preparation method thereof, and preparation method of one-time sintered TiO 2 The components of the photocatalytic ceramic comprise 30-70% of silicate mineral by mass, 0-30% of titanium pigment or titanium-containing mineral by mass, and 4-18% of nano TiO by mass (calculated on dry basis) of titanium-containing waste residue by mass 2 Sol, the mass fraction of which is 0-30% of natural electric polar minerals. The preparation of the one-time sintered TiO 2 Raw materials of each component of the photocatalytic ceramic are subjected to wet ball milling, dehydration and molding to prepare a green body, and nano TiO is sprayed on the green body 2 Sol containing Ti 4+ One or more of the solution and the suspension of (C) are sintered at 600-700 ℃ and then are heat-preserved for 1-2 hours with high fire to prepare the primary sintered TiO 2 Photocatalytic ceramic. The method only needs one-time firing, has simple process, reduces energy consumption and cost, and reduces carbon emission; at the same time 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.
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 is discovered by Fujishiam et al in 1972 2 TiO since the surface energy of water undergoes continuous oxidation-reduction reaction 2 As a semiconductor photocatalytic material, has been widely studied and used.
In the preparation of photocatalytic materials, the prior art generally uses TiO in the form of particles or sols 2 Preparing a suspension: tiO is mixed with 2 The suspension is made to form a flow cell through annular, straight-through or coaxial quartz tube clamping layers, and the radiation source directly irradiates the flow cell. The reactor has a simple structure, but the catalyst cannot be continuously used, the catalyst is separated and recovered by filtering, centrifuging, flocculating and other methods in the later treatment, the process is complicated, the recovery is not thorough, and the radiation depth is influenced due to the absorption of the solvent and other components of the suspension liquid to light.
In order to improve the catalytic efficiency, more efficient and practical photocatalytic reactors have been developed, and research on immobilization of photocatalysts has been conducted. The catalyst can be fixed on some solid substrates, such as kaolin, diatomite, zeolite, attapulgite, perfluorosulfonic acid film, silica gel, sand, glass beads, honeycomb ceramics, etc., or can be fixed on the inner wall of a container or the outer wall of a light source lamp tube, etc. One of the fixing methods is as follows: the carrier is coated with nano TiO 2 Soaking in titanium-containing solution such as sol, drying, and sintering at 400-600deg.C, repeating the process for 4-5 times (literature honeycomb ceramics loaded with TiO) 2 Degradation methyl orange test study "Liang Huayin, wang Zhumei, luo Minhua, journal of ceramic school", 2011 second, pages 235-238). Not only has complicated process, high energy consumption and large carbon emission, but also can lead the nano TiO which is impregnated initially to be sintered repeatedly 2 The crystal grows up, the specific surface area is reduced, and even the phase change can occur to be changed into rutile type crystal, so that the photocatalysis efficiency is reduced; in addition, tiO 2 The photocatalyst is attached to kaolin, diatomite, zeolite and attapulgite, and is in the form of powder, and when in use, the photocatalyst has the problems of poor strength, difficult recovery and the like.
The method needs to be sintered for multiple times, and has high energy consumption, large carbon emission and poor physical properties and photocatalytic activity of the prepared ceramic material.
Disclosure of Invention
In order to solve the problems, the invention provides a one-time sintered TiO 2 The photocatalytic ceramic and the preparation method thereof only need one-time firing, have simple process, reduce energy consumption and cost, and 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-time sintered TiO 2 Photocatalytic ceramic, the preparation of one-time sintered TiO 2 The components of the photocatalytic ceramic comprise 30-70% of silicate mineral by mass, 0-30% of titanium pigment or titanium-containing mineral by mass, and 4-18% of nano TiO by mass (calculated on dry basis) of titanium-containing waste residue by mass 2 Sol, the mass fraction of which is 0-30% of natural electric polar minerals.
Nanometer TiO 2 The sol has stronger cohesiveness, and particles such as silicate mineral, titanium pigment and the like are coated with nano TiO after being mixed with the silicate mineral, the titanium pigment and the like 2 O-Ti-O three-dimensional network structure formed by sol is surrounded, and nano TiO is adopted between particles 2 The adhesion of the sol is maintained in a whole, and the dried nano TiO 2 The sol can still keep the adhesiveness among particles, even if the nanometer TiO is repeatedly coated, poured and sprayed on the green body 2 Sol containing Ti 4+ One or more of the solutions and suspensions of (a) can also make the green body not loose, 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 ceramic material has certain strength.
The preparation of the one-time sintered TiO 2 The components of the photocatalytic ceramic are ball-milled by a wet method, dehydrated and molded to prepare a green body, and nano TiO is sprayed on the green body 2 Sol containing Ti 4+ One or more of the group consisting of a solution and a suspension.
Repeatedly coating, pouring and spraying nano TiO on the green body 2 Sol containing Ti 4+ One or more of the solutions and suspensions of (a) to cause the multilayer TiO to be 2 Attached to the green body to achieve the desired photocatalyst layer thickness on the surface of the green body. And the ceramic green body has more pores than the finished ceramic product, thus being easier for the Ti-containing ceramic green body to contain 4+ The sol, the solution and the suspension are infiltrated and absorbed, and the nano TiO is coated on the surface of the green body 2 The adhesion amount of the catalyst is higher, and the photocatalysis effect is improved.
The one-time fired TiO 2 The sintering temperature of the photocatalytic ceramic is 600-700 ℃, and the high fire heat preservation is carried out for 1-2 hours to prepare the once-sintered TiO 2 Photocatalytic ceramic.
The one-time firing photocatalysis ceramic is fired at low temperature to avoid TiO 2 The crystal is changed from anatase type to rutile type, and the sintering temperature is not higher than 700 ℃ generally, so the one-time sintering TiO provided by the invention 2 The firing temperature of the photocatalytic ceramic is 600-700 ℃, and the high fire is used for heat preservation 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 ferroelectric stone, magnesium tourmaline and lithium tourmaline.
Tourmaline can effectively reduce hole-electron recombination in photocatalysis reaction, and silicate minerals such as bentonite, zeolite, diatomite and the like have high pores and high specific surface area to facilitate nano TiO 2 Sol or Ti-containing 4+ TiO in solution and suspension 2 The titanium dioxide grains grow to coarse grains during sintering to form fine grain or microcrystal structure, so as to obtain optimal photocatalysis effect.
The titaniferous ore comprises one or more of ilmenite, titanomagnetite, primary rutile, perovskite and titanium concentrate, the titaniferous waste residue comprises titaniferous blast furnace slag, and the titanium white powder comprises anatase titanium white powder.
The invention also provides a method for preparing the one-time sintered TiO 2 A method of photocatalytic ceramic, the method of making comprising: silicate mineral with mass fraction of 30-70%, titanium dioxide or titanium-containing ore with mass fraction of 0-30%Titanium-containing waste residue with mass fraction of 4-18% of nano TiO 2 The sol, the mass fraction of which is 0-30%, is taken as a raw material, and the raw material is dehydrated and molded after wet ball milling to prepare a green body, and then the green body is sintered for one time, thus obtaining the one-time sintered TiO 2 Photocatalytic ceramic.
TiO prepared by dry process technology path 2 Photocatalytic ceramic, which is made of nano TiO 2 The O-Ti-O three-dimensional network structure formed by sol is only maintained in the interior of the granulating particles, no O-Ti-O three-dimensional network structure exists between the granulating particles, and during roasting, nano TiO is formed between the granulating particles due to no maintenance of O-Ti-O network 2 The effect of sol on promoting sintering cannot be well exerted, so that TiO prepared by a dry process 2 The photocatalytic ceramic has lower strength. And TiO prepared by adopting wet process 2 Photocatalytic ceramic, tiO 2 The particles of each component in the photocatalytic ceramic are all coated with nano TiO 2 O-Ti-O three-dimensional network structure formed by sol is uniformly coated into a whole, and nano TiO is formed during roasting 2 The sol network structure can keep the state until the later sintering stage, and nano TiO 2 The sol can also play a role of sintering aid, so that the material has high strength and corrosion resistance, and especially the mechanical strength is superior to that of TiO prepared by a dry process 2 Photocatalytic ceramic.
The one-time firing TiO preparation method 2 The method of photocatalytic ceramic further comprises: spraying nano TiO on the green body 2 Sol containing Ti 4+ One or more of the solutions and suspensions of (a) are then calcined.
The one-time sintered TiO 2 The firing temperature of the photocatalytic ceramic is 600-700 ℃, and the high fire is used for heat preservation for 1-2 hours.
The molding mode comprises the following steps: wet method plastic forming, foam sponge dipping slurry forming and dry powder rolling slush molding.
Preferably, the wet plastic forming method comprises the following steps: drying and dehydrating 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 strip column shape, a hollow ring shape and a flat plate shape by an extruder.
Preferably, the wet plastic forming method comprises the following steps: drying and dehydrating the slurry until the water content is less than 0.5%, adding hydroxypropyl methylcellulose, mixing, grinding, pouring into a kneader, and spraying nano TiO 2 The sol is stirred continuously, grease is added into the sol to form paste, then the paste is subjected to vacuum pugging, and after the paste is aged for 72 hours, the paste is extruded and formed into a honeycomb ceramic green body by piston type hydraulic extrusion.
Preferably, the foam sponge impregnating mud forming mode comprises the following steps: drying and dehydrating the slurry until the water content is less than 1.5%, pulverizing into fine powder, and mixing the powder with nano TiO 2 Preparing slurry from sol, aluminum dihydrogen phosphate, silica sol and aluminum sol, and soaking the slurry in foam sponge to obtain foamed ceramic green body; or concentrating and dehydrating to obtain slurry with water content less than 30%, adding nano TiO 2 Preparing slurry from sol, aluminum dihydrogen phosphate, silica sol and aluminum sol, and soaking the slurry in foam sponge to prepare the foamed ceramic green body.
Preferably, the dry powder rolling forming mode comprises the following steps: drying and dehydrating the slurry until the water content is less than 0.5%, pulverizing into fine powder, and granulating to obtain nano TiO 2 Spraying the sol into a ball forming tray filled with powder to prepare round particle green bodies with the diameter of 0.1-1.0 mm.
Nanometer TiO 2 The sol forms an O-Ti-O three-dimensional network framework, has stronger cohesiveness, improves the bonding strength and the drying strength of the green body, and thus, the surface of the green body is sprayed with the nano TiO 2 Sol or Ti-containing 4+ The solution and the suspension can ensure that the green body is not loose, deformed and cracked. Therefore, the invention adds nano TiO into the blank 2 And (3) sol. Although nano TiO 2 The sol has high price, but the wall thickness of the honeycomb ceramics and the foamed ceramics can be 0.1mm thick, spherical particles can also be used for enamelling the green body to 0.1mm through a rolling enamel-grain balling process, and TiO on the green body 2 The layer also needs 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 the highest in honeycomb form, for example, the geometric specific surface area of a 325 mesh honeycomb ceramic is 3000 square meters/m 3 While the specific weight of the honeycomb ceramics is generally 0.5-0.6 ton/m 3 Adding 20% of nano TiO (titanium dioxide) into the blank 2 Sol, also only 100-120kg of nano TiO is needed 2 The sol does not need to increase extra cost, and simultaneously improves the TiO 2 Is used for the utilization of the system.
The invention provides one-time burned TiO 2 The photocatalytic ceramic and the preparation method thereof have the beneficial effects that:
1. preparation of one-time fired TiO 2 Adding nano TiO into blank components of photocatalytic ceramic 2 Sol, which can make green body spray-coat with nano TiO by utilizing its strong cohesiveness 2 Sol or Ti-containing 4+ When in solution or suspension, the green body is ensured not to be loose, 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-step sintering 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-time firing TiO prepared by adopting wet process 2 Photocatalytic ceramic, tiO 2 The particles of each component in the photocatalytic ceramic are all coated with nano TiO 2 O-Ti-O three-dimensional network structure formed by sol is uniformly coated into a whole, and nano TiO is formed in the later period of sintering 2 Can also play a role of sintering auxiliary agent, so that the material has high strength and corrosion resistance.
4. Spraying nano TiO on the surface of the green body 2 Sol or Ti-containing 4+ Solutions, suspensions, multi-layered TiO 2 Attached to the green body to achieve the desired thickness of the photocatalytic layer on the surface of the green body. And the ceramic green body has more pores than the finished ceramic product, so that titanium sol and Ti-containing ceramic green body are easier to let 4+ Is infiltrated into and adsorbed by the solution and suspension liquid of the green body surface layer nano TiO 2 The adhesion amount of the catalyst is higher, and the photocatalytic performance is further enhanced.
5. TiO prepared by the existing precipitation method and gel sol method 2 The invention adopts mixing, which has the disadvantages of high cost, multiple procedures, powder appearance, difficult recovery and reuse after use, etcThe method has low cost and simple process, and can be used for preparing products with high rigidity and high specific surface area in various complex shapes.
6. Preparation of primary burned TiO by silicate mineral, tourmaline and other raw materials 2 The photocatalytic ceramic has wide raw material sources and low cost.
Drawings
FIG. 1 is a graph showing the degradation of methylene blue by examples 1, 2 and 3 and comparative example T.
FIG. 2 is a graph showing the degradation of methyl orange by examples 1, 2 and 3 and comparative example T.
FIG. 3 is a graph showing the degradation of methyl orange by the solutions of examples 1, 2 and 3 and comparative example T with 60mg/L sodium persulfate.
FIG. 4 is an X-ray diffraction pattern of the samples prepared in examples 1, 2, 3 and comparative example T.
Fig. 5 is SEM electron micrographs of samples prepared in examples 1, 2, 3 and comparative example T.
Detailed Description
The invention is further described below with reference to the drawings and specific examples. Those of ordinary skill in the art will be able to implement the invention based on these descriptions. In addition, the embodiments of the present invention referred to in the following description are typically only some, but not all, embodiments of the present invention. Therefore, all other embodiments, which can be made by one of ordinary skill in the art without undue burden, are intended to be within the scope of the present invention, based on the embodiments of the present invention.
Example 1: weighing 30kg 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 percent 2 30kg of sol and 0.2kg of ammonium polyacrylate, adding water, performing wet ball milling for 4 hours, discharging slurry, drying and dehydrating to obtain paste, coarse-grinding the paste into paste segments by a pugging machine, aging for 72 hours, putting the paste into a vacuum pugging machine to extrude into thin strips with the diameter of 4mm, drying, cutting into strips with the length of 3-4mm, naturally drying in the shade for 48 hours, drying, putting into a rotary kiln for roasting, and heating at 600 DEG CAnd (5) after heat preservation for 1.5 hours, cooling and discharging from the kiln.
Example 2: weighing 15kg of anatase type 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 percent 2 30kg of sol and 0.2kg of ammonium polyacrylate, adding water, performing wet ball milling for 4 hours, discharging slurry, drying and dehydrating to obtain paste, coarse-grinding the paste into paste segments by a pugging machine, ageing for 72 hours, putting the paste into a vacuum pugging machine to extrude into thin strips with the diameter of 4mm, drying, cutting into strips with the length of 3-4mm, naturally drying in the shade for 48 hours, drying in a drying room, baking in a rotary kiln, preserving heat for 1.5 hours at 600 ℃, cooling, and discharging from the kiln.
Example 3: weighing 30kg of anatase type titanium dioxide with fineness of 325 meshes, 70kg of calcium bentonite with fineness of 250 meshes and nano TiO with solid content of 20 percent 2 30kg of sol and 0.2kg of ammonium polyacrylate, adding water, performing wet ball milling for 4 hours, discharging slurry, drying and dehydrating to obtain paste, coarse-grinding the paste into paste segments by a pugging machine, ageing for 72 hours, putting the paste into a vacuum pugging machine to extrude into thin strips with the diameter of 4mm, drying, cutting into strips with the length of 3-4mm, naturally drying in the shade for 48 hours, drying, baking in a rotary kiln, preserving heat for 1.5 hours at 600 ℃, cooling, and discharging from the kiln.
Comparative example T: weighing 20kg of tourmaline powder with 325 meshes, 10kg of anatase type titanium dioxide, 70kg of calcium bentonite with 250 meshes, 10kg of an external fluxing agent and 0.2kg of ammonium polyacrylate, adding water, performing wet ball milling for 4 hours, discharging slurry, drying and dehydrating to obtain paste, coarse-grinding the paste into paste segments by a pugging machine, ageing for 72 hours, putting the paste into a vacuum pugging machine, extruding into thin strips with the diameter of 4mm, drying, cutting into strips with the length of 3-4mm, naturally drying in shade for 48 hours, putting into a drying room, baking in a rotary kiln, performing high-fire heat preservation at 600 ℃ for 1.5 hours, cooling, and discharging from the kiln.
The prepared product adopts a BELSORP-max-Bayer specific surface area tester, an XRD-6100-Shimadzu X-ray diffractometer, a Jiedao 1920 spectrophotometer, an SNM-3000SM scanning electron microscope and an FT-700A catalyst particle compression resistance tester to detect and characterize the performance.
Photocatalytic experiments and performance testing: respectively preparing methylene blue MB with the concentration of 20mg/L and methyl orange MO with the concentration of 20mg/L, adding 18mL of catalyst and 80mL of simulated waste liquid into each quartz glass culture dish, loading the mixture into a reaction device, and starting an ultraviolet lamp. During the period from the beginning to 60min, samples are taken every 10min, during the period from 60 to 120min, samples are taken every 20min, and the absorbance of the maximum peak wavelength (MB is 664nm and OB is 465 nm) of the samples in each time period is tested by a spectrophotometer after the samples are filtered. According to the lambert beer law, the absorbance of MB and OB solution and the solution concentration are in a linear relation, so that the attenuation condition of the absorbance of the solution is used as a reference mark of the photocatalytic degradation capacity of MB and OB. Fig. 1 shows the results of degradation of methylene blue, fig. 2 shows the results of degradation of methyl orange, and fig. 3 shows the results of degradation of methyl orange with sodium persulfate added. X-ray diffractometer detection showed that the TiO in all samples 2 All are anatase type crystal phases, the tourmaline crystal phases remain intact, and quartz crystal phases are decomposed after bentonite is calcined, which shows that calcination at a low temperature of 600 ℃ is favorable for forming the required crystal phases; it was also found for the first time in example 3 that calcium bentonite can be combined with nano TiO 2 The sol can form CaTiO when heated at 600 DEG C 3 The crystals also have photocatalytic capabilities (fig. 4). The scanning electron microscope result is shown in figure 5. TiO of examples 1, 2, 3, calculated by Scherrer's formula 2 The particle sizes of (2) were 35.8, 35.0 and 42.8nm, respectively.
Table 1 shows the compressive strength of comparative example T versus example 1
| Comparative example T | Example 1 | |
| Radial compressive strength N/cm | 42.2 | 54.7 |
| Diameter of catalyst mm | 3.8 | 3.7 |
Table 2 comparison of the surface properties of examples 1-3 and 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 anatase type titanium dioxide with fineness of 325 meshes, and 30kg of nano TiO with solid content of 20 percent 2 The sol is put into a ball mill, and after being added with water for wet grinding for 8 hours, the slurry is discharged. There are two types of slurry dewatering: one is dried to 22-25% of moisture to form a paste with plasticity, and the other is dried to 1-2% of moisture to form a block. After the paste blank is aged, extruding the paste blank into a bar shape with the diameter of 4mm by a piston type extruder, and cutting the paste blank into a bar shape with the length of 4mm after drying; the block materials with the water content of 1-2% are crushed and granulated to 20 meshes, and the powder materials are pressed into columns with the diameter of 4mm and the height of 5mm by a hydraulic press. Both materials were placed in the same kiln and calcined at 600 c and incubated for 1.5 hours with high fire.
Radial line pressure intensity is tested by adopting FT-700A catalyst particle compression tester, and TiO (titanium dioxide) prepared by plastic forming process 2 The compressive strength of the photocatalytic ceramic is 56.8N/cm, and TiO prepared by dry hydroforming 2 The compressive strength of the photocatalytic ceramic is 49.9N/cm. TiO prepared by dry process technology path 2 Photocatalytic ceramic, which is made of nano TiO 2 The O-Ti-O three-dimensional network structure formed by sol is only maintained in the interior of the granulating particles, no O-Ti-O three-dimensional network structure exists between the granulating particles, and during roasting, no O-Ti-O network is maintained between the granulating particles, so that the nano TiO is prepared 2 The effect of sol on promoting sintering cannot be well exerted, so that TiO prepared by a dry process 2 The photocatalytic ceramic has lower strength. And TiO prepared by adopting wet process 2 Photocatalytic ceramic, tiO 2 The particles of each component in the photocatalytic ceramic are all coated with nano TiO 2 O-Ti-O three-dimensional network structure formed by sol is uniformly coated into a whole, and nano TiO is formed during roasting 2 The sol network structure can keep the state until the later sintering stage, and nano TiO 2 The sol can also play a role of sintering aid, so that the material has very high strength and corrosion resistance, especially mechanical strength superior to TiO prepared by a dry process 2 Photocatalytic ceramic.
Example 5: weighing 40kg of ball clay subjected to acid washing, 20kg of diatomite powder, 14kg of tourmaline, 20kg of ilmenite and nano TiO with 20% of solid content 2 10kg of sol and 0.2kg of ammonium polyacrylate, adding water, performing wet ball milling for 8 hours, discharging slurry, drying, dehydrating, preparing into 200-mesh fine powder by using a pulverizer, fully mixing with hydroxypropyl methylcellulose, pouring into a kneader, stirring, and adding 20-25kg of nano TiO with 20% of solid content 2 Adding grease into the sol to prepare paste, coarse-refining the paste by a pugging machine, aging the paste for 72 hours, refining the paste by a vacuum pugging machine to prepare a mud column, extruding a honeycomb-shaped green body by a piston type hydraulic extruder, shaping the honeycomb-shaped green body by microwaves, drying the honeycomb-shaped green body by far infrared rays, and cutting the honeycomb-shaped green body into green bodies with the height of about 15-20 mm. The honeycomb body has too high height, poor illumination effect, influence on the catalytic efficiency, and too high green body is not easy to spray nano TiO 2 Sol forming surface layer to strengthen photocatalysis effect; the honeycomb body is too short, and the cutting workload is large, so that the production efficiency is low. Spraying silica sol water solution with solid content of 2-4% to wet the green body, and spraying nano TiO 2 Sol or contain Ti 4+ Drying in the shade for 24 hours, then drying again, roasting the dried blank in a mesh belt kiln, and preserving heat for 1 hour at 610 ℃ with high fire to obtain honeycomb-shaped TiO 2 Photocatalytic ceramic.
Spraying or impregnating green wettable bodies with neutral or weakly acidic silica sol solutions having solids contents of 2-4% to prevent subsequent attachment of nano TiO 2 When the sol, the solution and other coatings are coated, the green body is porous and very dry, so that the green body is too fast to adsorb the titanium-containing slurry, and the TiO is caused 2 The coating is easy to crack on the surface of the blank body. In addition, solids contentNeutral or weakly acidic silica sol solution with a content of 2-4% and subsequently attached nano-TiO-containing material 2 Coatings such as sol and solution which can be mutually penetrated, siO in silica sol 2 Can enter TiO 2 In the system, prevent nano TiO 2 Agglomeration of particles, prevention of crystal growth, and SiO 2 For TiO 2 Has modification effect, can increase the temperature of converting anatase into rutile type crystal, and can also increase TiO 2 The surface acidity improves the adsorption capacity to organic pollutants and is beneficial to improving the photocatalysis efficiency.
Example 6: weighing 34.5kg of anatase titanium dioxide with fineness of 325 meshes, 15kg of tourmaline powder with fineness of 325 meshes, 5kg of calcium bentonite with fineness of 250 meshes, and 10kg of nano TiO with concentration of 20 percent 2 Sol and 0.25kg of ammonium polyacrylate, adding water, performing wet ball milling for 4 hours, discharging slurry, and drying to prepare 56.5kg of 200-mesh powder; 70kg of 25% concentration nano TiO is weighed 2 Adding sol into a stirrer, adding 0.25kg of carboxymethyl cellulose, stirring thoroughly, gradually adding 26kg of zeolite powder to make zeolite powder and nano TiO 2 Mixing the sol fully, adding 56.5kg of the powder obtained by drying and crushing into a stirrer gradually, adding 0.25kg of ammonium polyacrylate solution and 1kg of aluminum dihydrogen phosphate solution with the concentration of 50% simultaneously, uniformly mixing to obtain slurry with proper consistency, immersing the slurry into polyurethane foam sponge, repeatedly immersing the slurry, extruding the slurry until the slurry hanging is completed, and drying in the shade, drying, selecting and then sintering in a kiln. The firing schedule is as follows: raising the temperature to 250 ℃ at the room temperature, wherein the temperature raising speed is 1 ℃/min; when the temperature in the kiln reaches 250 ℃, the temperature is increased to 450 ℃ at the speed of 0.5 ℃/min, finally the temperature is increased to 600 ℃ from 450 ℃ at the speed of 1 ℃/min, the heat is preserved for 90 minutes after the temperature reaches 600 ℃, and the foam-shaped TiO is obtained after cooling and discharging from the kiln 2 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% of solid content 2 15kg of sol and 0.2kg of ammonium polyacrylate are put into a ball mill, the slurry is discharged after being wet-ground for 8 hours by adding water, the slurry is spray-dried to prepare granules, the granules are poured into a rolling forming machine, and the solid content is sprayed into the granules with 2 percent0% nano TiO 2 The sol is slush-granulated into small balls with the diameter of 0.2-0.4mm, the small balls are dried in the shade for 24 hours until the water content is less than 1 percent, then the small balls are put into a rotary kiln to be roasted at 630 ℃, and the small balls are preserved for 60 minutes with high fire, thus obtaining the microbead-shaped TiO 2 Photocatalytic ceramic.
Example 8: weighing 15kg of anatase titanium dioxide, 15kg of tourmaline, 56kg of attapulgite clay, 14kg of vermiculite powder and nano TiO with 20% of solid content 2 25kg of sol and 0.2kg of ammonium polyacrylate are put into a ball mill, the slurry is discharged after the ball mill is wet-milled for 8 hours, the slurry is thermally dried until the moisture is 19-21%, and the slurry is put into a pugging machine for coarse refining and aging for 72 hours; putting the stale pug into a vacuum pug mill to be extruded into a plate shape, continuously rolling into a thin plate shape with the thickness of 6-8mm by using a double rolling mill, and cutting into square or rectangle; conveying the thin plate-shaped mud blank into a hot air dryer through a conveying belt, blowing hot air at 50-65 ℃ to one surface of the flat plate blank at the upper part of the flat plate blank, and drying one surface to obtain nano TiO (titanium dioxide) 2 The sol is relatively more enriched toward the upper surface of the sheet (i.e., the surface through which the hot air is blown) so that the upper surface is nano-sized TiO 2 Drying the green body until the water content is less than 2% when the sol is more than the lower surface, discharging the green body from the dryer, drying in the shade for 24 hours, and spraying nano TiO 2 Sol step: spraying the green body with silica sol with solid content of 2-4% once, and then nano TiO with solid content of 5-10% 2 Spraying the sol for 2 times, drying in the shade for 48 hours, drying until the water content is less than 1%, calcining in a roller kiln at 600 ℃, preserving heat for 2 hours with high fire, discharging from the kiln, and polishing four edges of a finished plate to obtain the platy TiO 2 Photocatalytic ceramic.
Example 9: weighing sepiolite 8kg, perlite 23kg, attapulgite 13kg, tourmaline 16kg, titanium-containing blast furnace slag 30kg and nano TiO with solid content of 20% 2 Adding 50kg of sol, 0.25% of dispersing agent and water into a ball mill, mixing and grinding for 6-7 hours, then introducing the slurry into a concentration tank, heating to evaporate water, discharging the slurry into a stirring tank when the slurry is concentrated to 28-30% of water, adding 5kg of neutral silica sol with 20% of solid content,mixing and stirring for 20-30 minutes, immersing into polyurethane foam sponge, drying and sintering. The firing temperature is 620 ℃, and the high fire is kept for 60 minutes to obtain foam TiO 2 Photocatalytic ceramic.
Claims (3)
1. Preparation of one-time sintered TiO 2 A method of photocatalytic ceramic, the method comprising: silicate mineral with mass fraction of 30-70%, titanium dioxide or titanium-containing mineral with mass fraction of 0-30%, titanium-containing waste residue with mass fraction of 4-18% of nano TiO based on dry basis 2 The sol, the mass fraction of which is 0-30%, is used as raw material, the raw material is dehydrated and molded after wet ball milling to prepare green bricks, the firing temperature is 600-700 ℃, and the high fire is kept for 1-2 hours to obtain the one-time fired TiO 2 Photocatalytic ceramic.
2. A method for preparing one-time burned TiO according to claim 1 2 A method for preparing photocatalytic ceramic is characterized by comprising the following steps of 2 The method of photocatalytic ceramic further comprises: spraying nano TiO on the green body 2 Sol containing Ti 4+ One or more of the solutions and suspensions of (a) are then calcined.
3. A method for preparing one-time burned TiO according to claim 1 2 The method for photocatalytic ceramic is characterized in that the forming mode comprises the following steps: wet method 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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