CN112521142A - Photocatalytic ceramic, preparation method thereof and method for degrading organic dye RhB - Google Patents
Photocatalytic ceramic, preparation method thereof and method for degrading organic dye RhB Download PDFInfo
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- CN112521142A CN112521142A CN202011421959.4A CN202011421959A CN112521142A CN 112521142 A CN112521142 A CN 112521142A CN 202011421959 A CN202011421959 A CN 202011421959A CN 112521142 A CN112521142 A CN 112521142A
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- photocatalytic
- photocatalytic ceramic
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- 239000000919 ceramic Substances 0.000 title claims abstract description 117
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 102
- 238000000034 method Methods 0.000 title claims abstract description 27
- 230000000593 degrading effect Effects 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 239000002893 slag Substances 0.000 claims abstract description 41
- 239000010936 titanium Substances 0.000 claims abstract description 41
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 40
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- 238000000605 extraction Methods 0.000 claims abstract description 29
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- 239000000203 mixture Substances 0.000 claims abstract description 9
- 239000002253 acid Substances 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 8
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- 238000000227 grinding Methods 0.000 claims abstract description 7
- 238000003825 pressing Methods 0.000 claims abstract description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 31
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 26
- 239000013078 crystal Substances 0.000 claims description 25
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 17
- NWXHSRDXUJENGJ-UHFFFAOYSA-N calcium;magnesium;dioxido(oxo)silane Chemical compound [Mg+2].[Ca+2].[O-][Si]([O-])=O.[O-][Si]([O-])=O NWXHSRDXUJENGJ-UHFFFAOYSA-N 0.000 claims description 17
- 229910052637 diopside Inorganic materials 0.000 claims description 17
- 229910052661 anorthite Inorganic materials 0.000 claims description 16
- 238000006731 degradation reaction Methods 0.000 claims description 16
- GWWPLLOVYSCJIO-UHFFFAOYSA-N dialuminum;calcium;disilicate Chemical compound [Al+3].[Al+3].[Ca+2].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] GWWPLLOVYSCJIO-UHFFFAOYSA-N 0.000 claims description 16
- 229910052596 spinel Inorganic materials 0.000 claims description 16
- 239000011029 spinel Substances 0.000 claims description 16
- 230000015556 catabolic process Effects 0.000 claims description 15
- 229910052742 iron Inorganic materials 0.000 claims description 15
- 230000007797 corrosion Effects 0.000 claims description 14
- 238000005260 corrosion Methods 0.000 claims description 14
- 239000000395 magnesium oxide Substances 0.000 claims description 13
- 239000011148 porous material Substances 0.000 claims description 10
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- 239000000126 substance Substances 0.000 claims description 7
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- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 239000002994 raw material Substances 0.000 abstract description 7
- 238000005498 polishing Methods 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 2
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- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 22
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
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- 230000007423 decrease Effects 0.000 description 2
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- 239000011941 photocatalyst Substances 0.000 description 2
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- 238000001878 scanning electron micrograph Methods 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- -1 TiO)2 Chemical class 0.000 description 1
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- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 1
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- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 239000002667 nucleating agent Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
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- 229910052905 tridymite Inorganic materials 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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Abstract
The invention provides a photocatalytic ceramic, a preparation method thereof and a method for degrading organic dye RhB. The method for preparing the photocatalytic ceramic by extracting the titanium slag comprises the following steps: grinding the titanium extraction slag to obtain blank powder with the particle size of 200-325 meshes(ii) a Mixing the blank powder with 10-20% of polyvinyl alcohol solution with the concentration of 5-8%: 1kg/L of the mixture is granulated to obtain green body granules with the particle size of 20-40 meshes; the blank granules are processed at 250-380 kgf/cm2Pressing and molding under pressure to obtain a blank; preheating the blank to remove water in the blank, heating the blank to 1150-1200 ℃ at a heating rate of 5-15 ℃/min, preserving the heat for 15-60 min, cooling, and polishing to obtain the photocatalytic ceramic. The beneficial effects of the invention can include: provides a new photocatalytic ceramic and a preparation method thereof, has the advantages of low cost of raw materials, capability of degrading organic dye in an acid environment for a long time and the like.
Description
Technical Field
The invention relates to the field of titanium slag solid waste resource utilization and inorganic nonmetal functional materials, in particular to photocatalytic ceramic, a preparation method thereof and a method for degrading organic dye RhB (rhodamine B).
Background
The preparation of ceramics from industrial waste residues has proven to be one of the important means for effective treatment of waste residues. Because the components of the industrial waste residue are complex, volatile components (such as carbonate, Cl and the like) in the waste residue can escape in the form of gas during the heat treatment process, and heavy metal ions (such as Cr6+、Co3+Etc.) will be lattice solidified, some metal oxides (e.g., TiO)2、Fe2O3Etc.) then act as a nucleating agent to aid in the growth of the crystallite particles in the ceramic. The titanium extraction slag is secondary industrial waste residue obtained after titanium extraction process treatment of titanium-containing blast furnace slag through high-temperature carbonization-low-temperature chlorination, and contains 5-10% of TiO under the influence of the process2And 2-5% Cl. Therefore, the titanium extraction slag is used as the raw material to prepare the ceramic, so that the harm caused by Cl can be reduced, the Ti resource can be fully utilized, and the method can be used as an effective means for treating and utilizing the titanium extraction slag.
At present, the technology for preparing ceramics by industrial waste residues is mature. By adjusting the formula composition and the heat treatment system, the building ceramic with high strength, high density and low water absorption can be prepared. However, the functionality of slag ceramics is less studied. At present, no photocatalytic ceramic prepared from titanium extraction slag exists.
Disclosure of Invention
In view of the deficiencies in the prior art, it is an object of the present invention to address one or more of the problems in the prior art as set forth above. For example, one of the objects of the present invention is to provide a method for preparing photocatalytic ceramics by extracting titanium slag from industrial waste slag, and a photocatalytic ceramic. Another object of the present invention is to provide a method for degrading organic dye RhB by using the photocatalytic ceramic.
In order to achieve the above object, the present invention provides a method for preparing photocatalytic ceramic from titanium slag. The method comprises the following steps: grinding the titanium extraction slag to a predetermined particle size to obtain blank powder; mixing the blank powder with a polyvinyl alcohol solution with the concentration of 5-8% according to the mass-volume ratio of 10-20: 1kg/L of the mixture is granulated to obtain green body granules with the particle size of 20-40 meshes; pressing and molding the green body granules to obtain a green body; preheating the blank to remove water in the blank, heating the blank to 1150-1200 ℃ at a heating rate of 5-15 ℃/min, preserving heat for 15-60 min, and cooling to obtain the photocatalytic ceramic.
In an exemplary embodiment of an aspect of the present invention, the preheating may include heating the green body to 200 to 250 ℃ at a heating rate of 2 to 3 ℃/min.
The invention also provides a photocatalytic ceramic. The photocatalytic ceramic can be prepared by the preparation method, all phase phases in the photocatalytic ceramic are microcrystalline phases, and the photocatalytic ceramic can comprise the following components in a mass ratio of 42-51: 36-39: 9-11: 2-10 of an anorthite phase, an iron-containing diopside phase, a perovskite phase and a magnesia-alumina spinel phase.
In an exemplary embodiment of the photocatalytic ceramic of the present invention, the chemical composition of the photocatalytic ceramic may include 30 to 32% CaO, 29 to 31% SiO by mass2、15～17％Al2O3、9～11％TiO2、7～9％MgO、3～4％Fe2O3。
In one exemplary embodiment of the photocatalytic ceramic of the present invention, the anorthite phase may be short columnar grains, the iron-containing diopside phase may be massive grains, the perovskite phase may be irregular granular grains, and the magnesia alumina spinel phase may be tapered grains.
In an exemplary embodiment of the photocatalytic ceramic of the present invention, the anorthite phase crystal grain diameter may be 1.16 to 2.73 μm, the iron-containing diopside phase crystal grain diameter may be 2.21 to 2.63 μm, the perovskite phase crystal grain diameter may be 0.88 to 1.28 μm, and the magnesia alumina spinel phase crystal grain diameter may be 0.47 to 0.65 μm.
In an exemplary embodiment of the photocatalytic ceramic of the present invention, the photocatalytic ceramic may further include pores, the pores are located in inter-granular voids and exist in an isolated and/or connected state, and the porosity of the photocatalytic ceramic may be 0.5 to 14.5%.
In an exemplary embodiment of the photocatalytic ceramic of the present invention, the photocatalytic ceramic may have a bulk density of 1.9 to 2.85g/cm3The water absorption rate can be 0.24-15%, the bending strength can be 19-45 MPa, and the corrosion rate can be 0.03-2% after 24h of corrosion in an acidic solution with the pH value of 1-3.
In a further aspect, the present invention provides a method for degrading an organic dye RhB, wherein the method can degrade an organic dye RhB solution by using the photocatalytic ceramic as described in any one of the above.
In an exemplary embodiment of the further aspect of the present invention, the concentration of the organic dye RhB solution is 10 to 20mg/L, the pH is 1 to 3, and the ratio of the amount of the photocatalytic ceramic to the amount of the organic dye RhB solution is 0.5 to 1: 1g/L, ultraviolet irradiation under the reaction condition, 160-200 min of degradation time, and 35-77% of degradation rate of the photocatalytic ceramic.
Compared with the prior art, the beneficial effects of the invention can include: the titanium extraction slag is utilized to prepare the photocatalytic ceramic, so that a new utilization way is provided for the titanium extraction slag; compared with photocatalytic ceramics prepared by pure chemical reagents, the cost of raw materials is reduced; the catalytic degradation rate of the prepared photocatalytic ceramic on organic dye RhB can reach 77%; the acid corrosion rate of the prepared photocatalytic ceramic in an acidic environment with the pH value of 2 is only 0.03%, and pollutants can be degraded in the acidic environment for a long time.
Drawings
The above and other objects and features of the present invention will become more apparent from the following description taken in conjunction with the accompanying drawings, in which:
FIG. 1 shows an X-ray diffraction pattern of a photocatalytic ceramic made in accordance with an exemplary embodiment of the present invention;
FIG. 2 shows a scanning electron micrograph of the photocatalytic ceramic of FIG. 1;
fig. 3 shows a power spectrum diagram corresponding to A, B, C and the D region in fig. 2.
Detailed Description
Hereinafter, the photocatalytic ceramic of the present invention and the method for preparing the same and the method for degrading the organic dye RhB will be described in detail with reference to the exemplary embodiments and the accompanying drawings.
The titanium extraction slag is secondary industrial waste slag obtained by treating titanium-containing blast furnace slag through a high-temperature carbonization-low-temperature chlorination titanium extraction process. The titanium extraction slag mainly comprises CaO and SiO2、Al2O3And the like, which are consistent with the main components for preparing the ceramic; with a certain amount of TiO2、Fe2O3It can be used as crystal nucleus agent to promote grain growth. Therefore, theoretically, the ceramics prepared by carrying out a series of activation treatments such as mechanical crushing, heat treatment, acid treatment and the like on the titanium-containing blast furnace slag have certain photocatalytic activity, and can be used as a photocatalyst for degrading pollutants. The main principle of the catalytic degradation is that the titanium-containing blast furnace slag generates a crystal phase (such as perovskite, iron-containing diopside and the like) with photoresponse in the interior after being activated, and the crystal phase can be used for degrading organic pollutants or reducing metal ions under certain conditions. In addition, the content of Cl in the titanium extraction slag is 2-5%, and Cl can be effectively removed after the titanium extraction slag is roasted. Research shows that after being roasted at 1100 ℃, the Cl content in the titanium extraction slag is only 0.3 percent.
The invention provides a method for preparing photocatalytic ceramics by using titanium extraction slag.
In a first exemplary embodiment of the present invention, a method for preparing a photocatalytic ceramic from titanium slag may include the steps of:
and grinding the titanium extraction slag to a preset particle size to obtain blank powder. For example, the particle size of the green body powder may be 200 to 325 mesh. Specifically, the titanium extraction slag is dried and dehydrated, and then ground to obtain blank powder with the particle size of 200-325 meshes. The green body powder material can comprise the following components in percentage by massDividing into: 28-33% CaO, 20-25% SiO2、10～14％Al2O3、2～7％MgO、2～10％TiO2、2～4％Fe2O3、2～5％Cl、0.5～1％H2O。
Mixing the blank powder with a polyvinyl alcohol solution with the concentration of 5-8% according to the mass-volume ratio of 10-20: mixing and granulating the mixture at a rate of 1kg/L to obtain blank granules with the particle size of 20-40 meshes. Specifically, 10-20 kg of green body powder is uniformly mixed with 1-2L of 5-8% polyvinyl alcohol solution, then the mixture is granulated and sieved by using 20-mesh and 40-mesh sieves, and particles on the 40-mesh sieves below the 20-mesh sieves are taken as green body particles.
And pressing and molding the blank granules to obtain a blank. For example, the press molding pressure may be 250 to 380kgf/cm2. Specifically, uniformly paving the blank granules in a mold at 250-380 kgf/cm2Is pressed and molded under the pressure of the pressure to obtain the photocatalytic ceramic body with the preset shape. For example, the press-formed green body is a rectangular parallelepiped, a cube, or a cylinder.
Preheating the blank to remove water in the blank, heating the blank to 1150-1200 ℃ at a heating rate of 5-15 ℃/min, preserving the heat for 15-60 min, and cooling to obtain the photocatalytic ceramic. Here, the preheating may include heating the green body to 200 to 250 ℃ at a heating rate of 2 to 3 ℃/min. Specifically, the green body is placed into a kiln, and is heated to 200-250 ℃ at a heating rate of 2-3 ℃/min so as to remove water in the green body; and heating to 1150-1200 ℃ sintering temperature at a heating rate of 5-15 ℃/min, preserving heat for 15-60 min after reaching the sintering temperature, and cooling to room temperature after finishing the heat preservation to obtain the photocatalytic ceramic. Here, the photocatalytic ceramic may be polished in order to improve the sensory effect and surface gloss of the photocatalytic ceramic.
In the present exemplary embodiment, pores are also present in the green body. For example, the porosity of the green body is about 16 to 20%. In the sintering process, along with the increase of the sintering temperature, the form of the air holes in the green body is changed from a mutually communicated state to an isolated and communicated concurrent transition state, and then is changed from the isolated and communicated concurrent transition state to an isolated state. Here, at the initial stage of sintering, the pores in the green body are interconnected gaps formed between green body pellets; along with the rise of sintering temperature, in the middle stage of sintering, the rearrangement and aggregation among granules promote the clearance removal, and simultaneously, as the crystal grains grow and grow, the air holes are changed from a mutual communication state to a mutual communication and isolated coexistence transition state; in the latter stage of sintering, the degree of aggregation among the granules is maximized, most of the formed gaps are eliminated, and the pores become isolated due to the sufficient growth of the crystal grains.
The invention also provides a photocatalytic ceramic.
FIG. 1 shows an X-ray diffraction pattern of a photocatalytic ceramic made in accordance with an exemplary embodiment of the present invention; FIG. 2 shows a scanning electron micrograph of the photocatalytic ceramic of FIG. 1; fig. 3 shows a power spectrum diagram corresponding to A, B, C and the D region in fig. 2.
In a second exemplary embodiment of the invention, the photocatalytic ceramic can be prepared by the preparation method of the first exemplary embodiment, wherein all phase phases in the photocatalytic ceramic are microcrystalline phases, and the photocatalytic ceramic can comprise the following components in a mass ratio of 42-51: 36-39: 9-11: 2-10 of an anorthite phase, an iron-containing diopside phase, a perovskite phase and a magnesia-alumina spinel phase. Further, the photocatalytic ceramic can comprise a component with a mass ratio of 42.1-50.6: 36.3-38.9: 9.0-10.8: 2.3-9.4 of an anorthite phase, an iron-containing diopside phase, a perovskite phase and a magnesia-alumina spinel phase. As shown in fig. 1, the photocatalyst ceramic has a main crystal phase of anorthite, a secondary crystal phase of diopside, perovskite and magnesia-alumina spinel, and the mass fractions of the phases are 42.1%, 38.9%, 10.2% and 8.7%, respectively.
In the present exemplary embodiment, as shown in FIG. 3 and Table 1, the chemical composition of the photocatalytic ceramic includes 30-32% CaO, 29-31% SiO by mass2、15～17％Al2O3、9～11％TiO2、7～9％MgO、3～4％Fe2O3。
TABLE 1 percentage of element content corresponding to A, B, C, D region in FIG. 2
In the present exemplary embodiment, the anorthite phase may be short columnar grains, the iron-containing diopside phase may be massive grains, the perovskite phase may be irregular granular grains, and the magnesia alumina spinel phase may be tapered grains. As shown in fig. 2, the grain morphology of the microcrystalline phase in the photocatalytic ceramic may include short columnar grains, irregular granular grains, blocky grains, and pyramidal grains. The energy spectrum test is carried out by selecting grains with different shapes, and the result shows that short columnar grains at the position A are anorthite phases, massive grains at the position C are diopside phases containing iron, irregular granular grains at the position D are perovskite phases, and conical grains at the position B are magnesia-alumina spinel phases. For example, the anorthite phase crystal grain diameter can be 1.16-2.73 μm, the iron-containing diopside phase crystal grain diameter can be 2.21-2.63 μm, the perovskite phase crystal grain diameter can be 0.88-1.28 μm, and the magnesia alumina spinel phase crystal grain diameter can be 0.47-0.65 μm.
In the exemplary embodiment, the photocatalytic ceramic may further include pores, the pores are located in gaps between grains, and exist in an isolated and/or connected state, the porosity of the photocatalytic ceramic is 0.5 to 14.5%, and the porosity gradually decreases as the firing temperature increases. Specifically, the pores in the photocatalytic ceramic are isolated and/or connected and are polygonal ring-shaped and/or short and narrow slit-shaped. As the porosity decreases, the catalytic performance of the photocatalytic ceramic increases. The porosity is reduced, so that the electron transmission path is shortened, the electron transmission efficiency is increased, and the catalytic performance is improved.
In the exemplary embodiment, the volume density of the photocatalytic ceramic can be 1.9-2.85 g/cm by performing physical and chemical performance tests on the photocatalytic ceramic3The water absorption rate can be 0.24-15%, the bending strength can be 19-45 MPa, and the corrosion rate can be 0.03-2% after 24h of corrosion in an acidic solution with the pH value of 1-3. Further, the volume density of the photocatalytic ceramic can be 1.98-2.61 g/cm3The water absorption rate can be 0.45-12.5%, and the bending strength can be 22.23-40.53 MPaThe corrosion rate can be 0.03-1.3% after 24h of corrosion in an acid solution with the pH value of 1-3.
The invention also provides a method for degrading the organic dye RhB.
In a third exemplary embodiment of the present invention, the method of degrading the organic dye RhB may degrade the organic dye RhB solution using the photocatalytic ceramic described in the first or second exemplary embodiment. Of course, the present invention is not limited thereto, and other organic dyes having the same or similar properties may be used, for example, organic dyes such as methylene blue, methyl orange, and the like.
In the exemplary embodiment, the concentration of the organic dye RhB solution may be 10 to 20mg/L, the pH is 1 to 3, and the ratio of the amount of the photocatalytic ceramic to the organic dye RhB solution is 0.5 to 1: 1g/L, ultraviolet irradiation under the reaction condition, 160-200 min of degradation time, and 35-77% of degradation rate of the photocatalytic ceramic. Specifically, the photocatalytic ceramic and an organic dye RhB with the concentration of 10-20 mg/L, pH of 1-3 are mixed according to the mass-volume ratio of 0.5-1: carrying out catalytic degradation reaction in a reactor at a speed of 1g/L, continuously stirring at a speed of 1800-2000 r/min, and carrying out catalytic degradation for 160-200 min under continuous irradiation of ultraviolet light. Here, in order to ensure sufficient contact of the photocatalytic ceramic with the RhB solution, the photocatalytic ceramic sheet was fixed to the bottom of the reactor.
The above-described exemplary embodiments of the present invention are further illustrated and described below with reference to specific examples.
Example 1
Drying and dehydrating the titanium extraction slag, and then grinding the titanium extraction slag into 325 meshes to obtain blank powder; adding a polyvinyl alcohol solution with the concentration of 5% into the blank powder, and controlling the mass-volume ratio of the polyvinyl alcohol solution to the blank powder to be 15: 1kg/L, mixing the powder and the solution for granulation, and taking granules which are obtained by sieving with a sieve of 20 meshes and sieving with a sieve of 40 meshes as blank granules; uniformly laying the blank granules in a mould at 380kgf/cm2Pressing and molding under the pressure of the pressure to obtain a photocatalytic ceramic blank; putting the blank body into a kiln, and heating to 250 ℃ at the heating rate of 2 ℃/min; heating to 1150 deg.C at a rate of 5 deg.C/min, sintering, maintaining at the sintering temperature for 60min, cooling to room temperature, and polishing to obtain photocatalytic ceramicAnd (4) porcelain.
The main crystal phase of the ceramic product is anorthite phase, the auxiliary crystal phase is iron-containing diopside phase, perovskite phase and magnesia alumina spinel phase, and the mass fractions of the phases are respectively 50.6%, 36.3%, 10.8% and 2.3%. The ceramic product is subjected to physical and chemical property tests, and the bulk density of the product is 1.94g/cm3The water absorption was 14.5%, the bending strength was 19.23MPa, the porosity was 14.38%, and the corrosion rate in an acidic solution at pH 3 for 24 hours was 1.3%. The ceramic product is subjected to a photocatalytic performance test, under ultraviolet light, the pH value of the solution is 3, the degradation time is 180min, and the degradation rate of the photocatalytic ceramic to 20mg/L RhB is 35%.
Example 2
Drying and dehydrating the titanium extraction slag, and then grinding the titanium extraction slag into 325 meshes to obtain blank powder; adding a polyvinyl alcohol solution with the concentration of 5% into the blank powder, and controlling the mass-volume ratio of the polyvinyl alcohol solution to the blank powder to be 10: 1kg/L, mixing the powder and the solution for granulation, and taking granules which are obtained by sieving with a sieve of 20 meshes and sieving with a sieve of 40 meshes as blank granules; uniformly laying the green body granules in a mould at 345kgf/cm2Pressing and molding under the pressure of the pressure to obtain a photocatalytic ceramic blank; putting the green body into a kiln, and heating to 250 ℃ at the heating rate of 2 ℃/min to remove the water in the green body; heating to 1180 ℃ at the heating rate of 7 ℃/min, sintering, preserving heat at the sintering temperature for 60min, cooling to room temperature after heat preservation, and polishing to obtain the series of photocatalytic ceramics.
As shown in fig. 1, the ceramic product has a main crystal phase of anorthite, a secondary crystal phase of diopside, perovskite and magnesia alumina spinel, and the mass fractions of the phases are 42.1%, 38.9%, 10.2% and 8.7%, respectively. As shown in fig. 2, the grain morphology of the microcrystalline phase in the ceramic product includes short columnar, irregular granular, blocky and conical, and the energy spectrum test result shows that the short columnar grains at a position a are anorthite, the blocky grains at a position C are diopside containing iron, the irregular granular grains at a position D are perovskite, and the conical grains at a position B are magnesia-alumina spinel.
The physical and chemical performance of the ceramic product is tested, and the bulk density of the product is 2.81g/cm3Water absorption of 0.53% and bending strength of 44.53MPa, porosity 1.5%, corrosion rate 0.03% in 24h acid solution at pH 2. The ceramic product is subjected to a photocatalytic performance test, under ultraviolet light, the pH value of the solution is 2, the degradation time is 180min, and the degradation rate of 20mg/L RhB by the photocatalytic ceramic is 77%.
Example 3
Drying and dehydrating the titanium extraction slag, and then grinding the titanium extraction slag into 200 meshes to obtain blank powder; adding a polyvinyl alcohol solution with the concentration of 8% into the blank powder, mixing the powder and the solution for granulation, and controlling the mass-volume ratio of the powder to the solution to be 20: 1kg/L, and controlling the mass-volume ratio of the two to be 10: 1 kg/L; uniformly laying the green body granules in a mould at 250kgf/cm2Pressing and molding under the pressure of the pressure to obtain a photocatalytic ceramic blank; putting the blank body into a kiln, and heating to 200 ℃ at the heating rate of 3 ℃/min; heating to 1200 ℃ at the heating rate of 15 ℃/min for sintering, preserving the heat for 15min at the sintering temperature, cooling to room temperature after the heat preservation is finished, and polishing to obtain the series of photocatalytic ceramics.
The main crystal phase of the ceramic product is anorthite phase, the auxiliary crystal phase is iron-containing diopside phase, perovskite phase and magnesia alumina spinel phase, and the mass fractions of the phases are respectively 44.5%, 37.1%, 9.0% and 9.4%. The ceramic product is subjected to physical and chemical property tests, and the bulk density of the product is 2.32g/cm3The water absorption was 0.24%, the flexural strength was 40.83MPa, the porosity was 0.57%, and the corrosion rate in an acidic solution at pH 1 for 24 hours was 0.8%. The ceramic product is subjected to a photocatalytic performance test, under ultraviolet light, the pH value of the solution is 1, the degradation time is 180min, and the degradation rate of the photocatalytic ceramic to 20mg/L RhB is 62%.
In summary, the advantages of the photocatalytic ceramic, the preparation method thereof and the method for degrading the organic dye RhB of the present invention include:
(1) the invention prepares the photocatalytic ceramic by taking the titanium extraction slag as a raw material, and provides a new utilization approach for the titanium extraction slag;
(2) compared with photocatalytic ceramics prepared by pure chemical reagents, the photocatalytic ceramics prepared by the method has extremely low cost of raw materials;
(3) according to the invention, titanium extraction slag is used as a raw material to prepare photocatalytic ceramics, and through an acid corrosion test, the corrosion rate of the prepared ceramics in an acid environment with the pH value of 1-3 is only 0.03-2.0%, which indicates that the prepared ceramics can degrade pollutants for a long time in the acid environment;
(4) according to the invention, titanium extraction slag is used as a raw material to prepare photocatalytic ceramic, and the photocatalytic degradation rate of the photocatalytic ceramic to organic dye RhB with the pH value of 1-3 and the concentration of 10-20 mg/L can reach 35-77% under ultraviolet light through a photocatalytic performance test.
Although the present invention has been described above in connection with exemplary embodiments, it will be apparent to those skilled in the art that various modifications and changes may be made to the exemplary embodiments of the present invention without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
1. A method for preparing photocatalytic ceramics by extracting titanium slag is characterized by comprising the following steps:
grinding the titanium extraction slag to a predetermined particle size to obtain blank powder;
mixing the blank powder with a polyvinyl alcohol solution with the concentration of 5-8% according to the mass-volume ratio of 10-20: 1kg/L of the mixture is granulated to obtain green body granules with the particle size of 20-40 meshes;
pressing and molding the green body granules to obtain a green body;
preheating the blank to remove water in the blank, heating the blank to 1150-1200 ℃ at a heating rate of 5-15 ℃/min, preserving heat for 15-60 min, and cooling to obtain the photocatalytic ceramic.
2. The method for preparing photocatalytic ceramics by extracting titanium slag according to claim 1, wherein the preheating comprises heating the blank to 200-250 ℃ at a heating rate of 2-3 ℃/min.
3. The photocatalytic ceramic is characterized in that all phase phases in the photocatalytic ceramic are microcrystalline phases and comprise, by mass, 42-51: 36-39: 9-11: 2-10 of an anorthite phase, an iron-containing diopside phase, a perovskite phase and a magnesia-alumina spinel phase.
4. The photocatalytic ceramic of claim 3, wherein the chemical composition of the photocatalytic ceramic comprises 30-32% CaO, 29-31% SiO by mass2、15～17％Al2O3、9～11％TiO2、7～9％MgO、3～4％Fe2O3。
5. The photocatalytic ceramic of claim 3, wherein the anorthite phase is short columnar grains, the iron-containing diopside phase is massive grains, the perovskite phase is irregular granular grains, and the magnesia alumina spinel phase is pyramidal grains.
6. The photocatalytic ceramic of claim 3, wherein the anorthite phase crystal grain diameter is 1.16 to 2.73 μm, the iron-containing diopside phase crystal grain diameter is 2.21 to 2.63 μm, the perovskite phase crystal grain diameter is 0.88 to 1.28 μm, and the magnesia alumina spinel phase crystal grain diameter is 0.47 to 0.65 μm.
7. The photocatalytic ceramic of claim 3, further comprising pores, wherein the pores are located in inter-granular voids and exist in an isolated and/or connected form, and the porosity of the photocatalytic ceramic is 0.5 to 14.5%.
8. The photocatalytic ceramic of claim 3, wherein the volume density of the photocatalytic ceramic is 1.9 to 2.85g/cm3The water absorption rate is 0.24-15%, the bending strength is 19-45 MPa, and the corrosion rate is 0.03-2% after 24h of corrosion in an acid solution with the pH value of 1-3.
9. A method for degrading an organic dye RhB, which is characterized in that a photocatalytic ceramic as described in any one of claims 3 to 8 is used for degrading an organic dye RhB solution.
10. The method for degrading the organic dye RhB as claimed in claim 9, wherein the concentration of the organic dye RhB solution is 10-20 mg/L, the pH is 1-3, and the ratio of the usage amount of the photocatalytic ceramic to the usage amount of the organic dye RhB solution is 0.5-1: 1g/L, ultraviolet irradiation under the reaction condition, 160-200 min of degradation time, and 35-77% of degradation rate of the photocatalytic ceramic.
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