CN110813315A - Photodegradation catalyst for organic sewage treatment and preparation method thereof - Google Patents
Photodegradation catalyst for organic sewage treatment and preparation method thereof Download PDFInfo
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- CN110813315A CN110813315A CN201911161130.2A CN201911161130A CN110813315A CN 110813315 A CN110813315 A CN 110813315A CN 201911161130 A CN201911161130 A CN 201911161130A CN 110813315 A CN110813315 A CN 110813315A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 48
- 238000001782 photodegradation Methods 0.000 title claims abstract description 44
- 239000010865 sewage Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 191
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 92
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 30
- 239000002131 composite material Substances 0.000 claims abstract description 18
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 18
- 150000002500 ions Chemical class 0.000 claims abstract description 16
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 10
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 10
- 239000000919 ceramic Substances 0.000 claims description 55
- 238000009210 therapy by ultrasound Methods 0.000 claims description 35
- 238000002156 mixing Methods 0.000 claims description 21
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 14
- -1 rare earth metal salt Chemical class 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 229910052691 Erbium Inorganic materials 0.000 claims description 9
- 229910052693 Europium Inorganic materials 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 8
- 229910052772 Samarium Inorganic materials 0.000 claims description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 229910052719 titanium Inorganic materials 0.000 claims description 8
- 239000010936 titanium Substances 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 230000001788 irregular Effects 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- 239000011148 porous material Substances 0.000 claims description 6
- 238000004065 wastewater treatment Methods 0.000 claims 9
- 238000006731 degradation reaction Methods 0.000 abstract description 9
- 230000015556 catabolic process Effects 0.000 abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 2
- 230000001699 photocatalysis Effects 0.000 abstract description 2
- 238000005215 recombination Methods 0.000 abstract description 2
- 230000006798 recombination Effects 0.000 abstract description 2
- 230000002035 prolonged effect Effects 0.000 abstract 1
- 239000002351 wastewater Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000003911 water pollution Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 206010034972 Photosensitivity reaction Diseases 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- 238000012271 agricultural production Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002894 organic compounds Chemical group 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- 231100000378 teratogenic Toxicity 0.000 description 1
- 230000003390 teratogenic effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/894—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
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Abstract
The invention relates to the technical field of degradation catalysts, in particular to a photodegradation catalyst for organic sewage treatment and a preparation method thereof3+And Ag+Wherein the addition amount of the rare earth metal element ions is 0.1-0.5% of the mass of the titanium dioxide, and Fe3+The addition amount of the titanium dioxide is 0.1-0.5 percent of the mass of the titanium dioxide, and the Ag+The addition amount of (A) is 0.1-0.5% of the mass of titanium dioxide; the photodegradation catalyst for treating organic sewage is added with composite metal ions to form a shallow capture trap of a photoproduction electron-hole pair, inhibit the recombination of electrons and holes and improve the existence of the photoproduction electron-hole pairThe product life is prolonged, so that the photocatalytic activity of the titanium dioxide is improved, the titanium dioxide is compounded with the graphene, the dispersity of the titanium dioxide can be improved, the surface photosensitive property of the titanium dioxide is improved, and the photodegradability of the titanium dioxide is promoted.
Description
Technical Field
The invention relates to the technical field of degradation catalysts, in particular to a photodegradation catalyst for organic sewage treatment and a preparation method thereof.
Background
With the rapid development of industrial and agricultural production, the water pollution is more and more serious, more than two thousand organic matters are detected in the water, and the water pollution causes a series of social problems, wherein the number of carcinogenic and teratogenic organic matters is hundreds. At present, the treatment method of organic wastewater comprises the following steps: biological treatment, chemical treatment, adsorption filtration treatment and the like. In recent years, the photosensitive catalytic oxidation method for treating pollutants in water becomes a new technology for sewage treatment.
The light-sensitive catalyst is also called as photodegradant, photosensitizer or photodegradable catalyst, the photodegradant is a high molecular material which is irradiated by sunlight to carry out degradation reaction of free radicals, the photodegradant is added for accelerating the degradation reaction, the long-used photodegradant is an organic compound containing double bonds and transition metals, the degradation principle is that chemical reaction is carried out under the irradiation of the sunlight to generate a free radical compound, and then active hydrogen on a polymer molecular chain is transferred to cause the polymer molecular chain to be broken, thereby realizing the degradation of the polymer. The photocatalytic degradation can effectively remove organic pollutants and avoid secondary pollution to water.
Light can excite electrons in the titanium dioxide semiconductor, the electrons are excited from a valence band to a conduction band to generate photoproduction electrons, corresponding photoproduction holes are generated in the valence band, and the electrons and the holes are respectively diffused to the surface of the semiconductor and react with different reaction objects on the surface. The photogenerated electrons have reducibility and the holes have oxidability, and the two types of photogenerated electrons and holes can be respectively applied to different fields. However, titanium dioxide has a high forbidden band width (3.2 eV), has a low utilization rate for sunlight, can only absorb light energy in an ultraviolet band, and cannot show corresponding catalytic activity under visible light. The utilization rate of the titanium dioxide to sunlight is improved by carrying out surface oxidation and reduction treatment or surface sensitization treatment on the titanium dioxide, but the light energy utilization rate of the modified titanium dioxide reported at present is still to be improved.
Disclosure of Invention
The purpose of the invention is: overcomes the defects in the prior art, and provides the photodegradation catalyst for organic sewage treatment with high light energy utilization rate.
Another object of the invention is: the preparation method of the photodegradation catalyst for organic sewage treatment is simple in process, and the prepared photodegradation catalyst is high in light energy utilization rate and sewage treatment efficiency.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
the photodegradation catalyst for organic sewage treatment comprises a ceramic carrier, wherein the ceramic carrier is loaded with titanium dioxide-composite metal ions-graphene, and the composite metal ions are rare earth metal ions and Fe3+And Ag+Wherein the addition amount of the rare earth metal element ions is 0.1-0.5% of the mass of the titanium dioxide, and Fe3+The addition amount of the titanium dioxide is 0.1-0.5 percent of the mass of the titanium dioxide, and the Ag+The addition amount of (B) is 0.1-0.5% of the mass of titanium dioxide.
Furthermore, the rare earth metal element ions are selected from a mixture of Eu, Er, Sm and Gd.
Furthermore, the molar ratio of Eu, Er, Sm and Gd is 1:1-2:1: 1.
Further, the titanium dioxide is nano flaky titanium dioxide, the thickness of the nano flaky titanium dioxide is 2-18nm, and the side length of the nano flaky titanium dioxide is 10-30 nm.
Further, the titanium dioxide is rutile type titanium dioxide.
Further, the ceramic carrier is irregular, and the bulk density of the ceramic carrier is 360-600kg/m3Volume specific surface area of 120-2/m3。
Furthermore, the diameter of the pore diameter on the ceramic carrier is 0.12-0.24 mm.
A preparation method of a photodegradation catalyst for organic sewage treatment comprises the following steps:
(1) placing the ceramic carrier in an ultrasonic reaction kettle, and carrying out ultrasonic treatment for 2-3 h;
(2) mixing titanium dioxide, rare earth metal salt and Fecl3、AgNO3And (2) mixing with absolute ethyl alcohol to obtain a colloidal solution, mixing the colloidal solution with the ceramic carrier obtained by treatment in the step (1), performing ultrasonic treatment, taking out, drying at the temperature of 120-plus-one (130 ℃) for 3-5h, and finally roasting at the temperature of 380-plus-one (640 ℃) for 3-5h to obtain the photodegradation catalyst.
Further, the ultrasonic treatment temperature in the step (1) is 55-65 ℃.
Further, the ultrasonic treatment temperature in the step (2) is 50-60 ℃, and the ultrasonic treatment time is 1-2 h.
The technical scheme adopted by the invention has the beneficial effects that:
according to the photodegradation catalyst for treating organic sewage, titanium dioxide-composite metal ions-graphene is loaded on a ceramic carrier and used as the photodegradation catalyst, and the composite metal ions are added to form a shallow capture trap of a photoproduction electron hole pair, inhibit the recombination of electrons in the holes and prolong the storage life of the photoproduction electron hole pair, so that the photocatalytic activity of titanium dioxide is improved, and the composite metal ions are compounded with graphene to improve the dispersity of titanium dioxide and increase the surface photosensitivity of the titanium dioxide, so that the photodegradation performance of the titanium dioxide is promoted.
The preparation method of the photodegradation catalyst for organic sewage treatment has the advantages of simple preparation process, low cost and high degradation performance of the prepared photodegradation catalyst.
Detailed Description
The invention will now be further illustrated with reference to specific examples.
Example 1
The photodegradation catalyst for organic sewage treatment comprises a ceramic carrier, wherein the ceramic carrier is loaded with titanium dioxide-composite metal ions-graphene, and the composite metal ions are rare earth metal ions and Fe3+And Ag+Wherein the addition amount of the rare earth metal element ions is 0.1 percent of the mass of the titanium dioxide, and Fe3+The addition amount of (B) is 0.1% of the mass of titanium dioxide, and Ag+The addition amount of the rare earth metal element is 0.1 percent of the mass of the titanium dioxide, and Eu and Er are selected as rare earth metal element ionsThe Eu, the Er, the Sm and the Gd are mixed according to a molar ratio of 1:1:1:1, the titanium dioxide is nano-flaky titanium dioxide, the thickness of the nano-flaky titanium dioxide is 2nm, the side length of the nano-flaky titanium dioxide is 10nm, the titanium dioxide is rutile type titanium dioxide, the ceramic carrier is an irregular ceramic carrier, and the bulk density of the ceramic carrier is 360 kg/m3Volume specific surface area of 120m2/m3The diameter of the pore diameter on the ceramic carrier is 0.12 mm.
The preparation method of the photodegradation catalyst comprises the following steps:
(1) placing the ceramic carrier into an ultrasonic reaction kettle, and carrying out ultrasonic treatment for 2 hours at the ultrasonic treatment temperature of 55 ℃;
(2) mixing titanium dioxide, rare earth metal salt and Fecl3、AgNO3And (2) mixing with absolute ethyl alcohol to obtain a colloidal solution, mixing the colloidal solution with the ceramic carrier obtained by treatment in the step (1), performing ultrasonic treatment, drying at 120 ℃ for 5 hours, and finally roasting at 380 ℃ for 5 hours to obtain the photodegradation catalyst, wherein the ultrasonic treatment temperature is 50 ℃ and the ultrasonic treatment time is 2 hours.
Example 2
The photodegradation catalyst for organic sewage treatment comprises a ceramic carrier, wherein the ceramic carrier is loaded with titanium dioxide-composite metal ions-graphene, and the composite metal ions are rare earth metal ions and Fe3+And Ag+Wherein the addition amount of the rare earth metal element ions is 0.2 percent of the mass of the titanium dioxide, and Fe3+The addition amount of (B) is 0.2% of the mass of titanium dioxide, and Ag+The addition amount of the titanium dioxide is 0.2 percent of the mass of the titanium dioxide, the rare earth metal element ions are a mixture of Eu, Er, Sm and Gd, the molar ratio of the Eu, the Er, the Sm and the Gd is 1:1, the titanium dioxide is nano-flaky titanium dioxide, the thickness of the nano-flaky titanium dioxide is 4nm, the side length of the nano-flaky titanium dioxide is 12nm, the titanium dioxide is rutile type titanium dioxide, the ceramic carrier is an irregular ceramic carrier, and the bulk density of the ceramic carrier is 380 kg/m3Volume specific surface area of 150m2/m3Ceramic carrierThe diameter of the aperture on the body is 0.15 mm.
The preparation method of the photodegradation catalyst comprises the following steps:
(1) placing the ceramic carrier into an ultrasonic reaction kettle, and carrying out ultrasonic treatment for 2.4 hours at the ultrasonic treatment temperature of 58 ℃;
(2) mixing titanium dioxide, rare earth metal salt and Fecl3、AgNO3And (2) mixing with absolute ethyl alcohol to obtain a colloidal solution, mixing the colloidal solution with the ceramic carrier obtained by treatment in the step (1), performing ultrasonic treatment, drying at 120 ℃ for 3.5h, and finally roasting at 420 ℃ for 3.5h to obtain the photodegradation catalyst, wherein the ultrasonic treatment temperature is 50 ℃ and the ultrasonic treatment time is 1.5 h.
Example 3
The photodegradation catalyst for organic sewage treatment comprises a ceramic carrier, wherein the ceramic carrier is loaded with titanium dioxide-composite metal ions-graphene, and the composite metal ions are rare earth metal ions and Fe3+And Ag+Wherein the addition amount of the rare earth metal element ions is 0.3 percent of the mass of the titanium dioxide, and Fe3+The addition amount of (B) is 0.3% of the mass of titanium dioxide, and Ag+The addition amount of the titanium dioxide is 0.3 percent of the mass of the titanium dioxide, the rare earth metal element ions are a mixture of Eu, Er, Sm and Gd, the molar ratio of the Eu, the Er, the Sm and the Gd is 1:1, the titanium dioxide is nano-flaky titanium dioxide, the thickness of the nano-flaky titanium dioxide is 10nm, the side length of the nano-flaky titanium dioxide is 20nm, the titanium dioxide is rutile type titanium dioxide, the ceramic carrier is an irregular ceramic carrier, and the bulk density of the ceramic carrier is 400 kg/m3Volume specific surface area of 160m2/m3The diameter of the pore diameter on the ceramic carrier is 0.15 mm.
The preparation method of the photodegradation catalyst comprises the following steps:
(1) placing the ceramic carrier into an ultrasonic reaction kettle, and carrying out ultrasonic treatment for 2.5 hours at the ultrasonic treatment temperature of 60 ℃;
(2) mixing titanium dioxide, rare earth metal salt and Fecl3、AgNO3And (2) mixing with absolute ethyl alcohol to obtain a colloidal solution, mixing the colloidal solution with the ceramic carrier obtained by treatment in the step (1), performing ultrasonic treatment, drying at 125 ℃ for 4h, and finally roasting at 500 ℃ for 4h to obtain the photodegradation catalyst, wherein the ultrasonic treatment temperature is 55 ℃ and the ultrasonic treatment time is 1.5 h.
Example 4
The photodegradation catalyst for organic sewage treatment comprises a ceramic carrier, wherein the ceramic carrier is loaded with titanium dioxide-composite metal ions-graphene, and the composite metal ions are rare earth metal ions and Fe3+And Ag+Wherein the addition amount of the rare earth metal element ions is 0.4 percent of the mass of the titanium dioxide, and Fe3+The addition amount of (B) is 0.4% of the mass of titanium dioxide, and Ag+The addition amount of the titanium dioxide is 0.4 percent of the mass of the titanium dioxide, the rare earth metal element ions are a mixture of Eu, Er, Sm and Gd, the molar ratio of the Eu, the Er, the Sm and the Gd is 1:1, the titanium dioxide is nano-flaky titanium dioxide, the thickness of the nano-flaky titanium dioxide is 12nm, the side length of the nano-flaky titanium dioxide is 24nm, the titanium dioxide is rutile type titanium dioxide, the ceramic carrier is an irregular ceramic carrier, and the bulk density of the ceramic carrier is 500kg/m3Volume specific surface area of 200m2/m3The diameter of the pore diameter on the ceramic carrier is 0.18 mm.
The preparation method of the photodegradation catalyst comprises the following steps:
(1) placing the ceramic carrier into an ultrasonic reaction kettle, and carrying out ultrasonic treatment for 2.5 hours at the ultrasonic treatment temperature of 60 ℃;
(2) mixing titanium dioxide, rare earth metal salt and Fecl3、AgNO3And (2) mixing with absolute ethyl alcohol to obtain a colloidal solution, mixing the colloidal solution with the ceramic carrier obtained by treatment in the step (1), performing ultrasonic treatment, drying at 125 ℃ for 4h, and finally roasting at 600 ℃ for 4.5h to obtain the photodegradation catalyst, wherein the ultrasonic treatment temperature is 55 ℃ and the ultrasonic treatment time is 1.5 h.
Example 5
A for organic sewage treatmentThe photodegradation catalyst comprises a ceramic carrier, wherein the ceramic carrier is loaded with titanium dioxide-composite metal ions-graphene, and the composite metal ions are rare earth metal element ions and Fe3+And Ag+Wherein the addition amount of the rare earth metal element ions is 0.5 percent of the mass of the titanium dioxide, and Fe3+The addition amount of (B) is 0.5% of the mass of titanium dioxide, and Ag+The addition amount of the titanium dioxide is 0.5 percent of the mass of the titanium dioxide, the rare earth metal element ions are a mixture of Eu, Er, Sm and Gd, the molar ratio of the Eu, the Er, the Sm and the Gd is 1:2:1:1, the titanium dioxide is nano-flaky titanium dioxide, the thickness of the nano-flaky titanium dioxide is 18nm, the side length of the nano-flaky titanium dioxide is 30nm, the titanium dioxide is rutile type titanium dioxide, the ceramic carrier is an irregular ceramic carrier, and the bulk density of the ceramic carrier is 600kg/m3Volume specific surface area of 240m2/m3The diameter of the pore diameter on the ceramic carrier is 0.24 mm.
The preparation method of the photodegradation catalyst comprises the following steps:
(1) placing the ceramic carrier into an ultrasonic reaction kettle, and carrying out ultrasonic treatment for 3 hours at the ultrasonic treatment temperature of 65 ℃;
(2) mixing titanium dioxide, rare earth metal salt and Fecl3、AgNO3And (2) mixing with absolute ethyl alcohol to obtain a colloidal solution, mixing the colloidal solution with the ceramic carrier obtained by treatment in the step (1), performing ultrasonic treatment, drying at 130 ℃ for 3h, and finally roasting at 640 ℃ for 3h to obtain the photodegradation catalyst, wherein the ultrasonic treatment temperature is 60 ℃ and the ultrasonic treatment time is 1 h.
The photodegradation catalysts in examples 1-5 were used for industrial wastewater degradation, the wastewater COD was 1300mg/L, the catalyst dosage was 0.5g, the wastewater volume was 500ml, the COD digestion activity test was performed in a fixed bed reactor phi 50x1000mm, the reaction time was 3h, the reaction conditions were 30 ℃ to 50 ℃ at normal pressure, a 20W UV emission lamp and a visible light lamp were used for simultaneous irradiation, and the wastewater COD degradation rate was as high as 98.3%.
In light of the foregoing description of the preferred embodiment of the present invention, many modifications and variations will be apparent to those skilled in the art without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims.
Claims (10)
1. A photodegradation catalyst for organic sewage treatment is characterized in that: the photodegradation catalyst comprises a ceramic carrier, wherein the ceramic carrier is loaded with titanium dioxide-composite metal ions-graphene, and the composite metal ions are rare earth metal element ions and Fe3+And Ag+Wherein the addition amount of the rare earth metal element ions is 0.1-0.5% of the mass of the titanium dioxide, and Fe3+The addition amount of the titanium dioxide is 0.1-0.5 percent of the mass of the titanium dioxide, and the Ag+The addition amount of (B) is 0.1-0.5% of the mass of titanium dioxide.
2. The photodegradation catalyst for organic wastewater treatment according to claim 1, wherein: the rare earth metal element ions are selected from a mixture of Eu, Er, Sm and Gd.
3. The photodegradation catalyst for organic wastewater treatment according to claim 2, wherein: the molar ratio of Eu, Er, Sm and Gd is 1:1-2:1: 1.
4. The photodegradation catalyst for organic wastewater treatment according to claim 1, wherein: the titanium dioxide is nano flaky titanium dioxide, the thickness of the nano flaky titanium dioxide is 2-18nm, and the side length of the nano flaky titanium dioxide is 10-30 nm.
5. The photodegradation catalyst for organic wastewater treatment according to claim 1, wherein: the titanium dioxide is rutile titanium dioxide.
6. The photodegradation catalyst for organic wastewater treatment according to claim 1, wherein: the ceramic carrier is irregular, and the bulk density of the ceramic carrier is 360-600kg/m3Volume specific surface area of 120-2/m3。
7. The photodegradation catalyst for organic wastewater treatment according to claim 1, wherein: the diameter of the pore diameter on the ceramic carrier is 0.12-0.24 mm.
8. The method for preparing a photodegradation catalyst for organic wastewater treatment according to any one of claims 1 to 7, wherein the method comprises the following steps: the preparation method comprises the following steps:
(1) placing the ceramic carrier in an ultrasonic reaction kettle, and carrying out ultrasonic treatment for 2-3 h;
(2) mixing titanium dioxide, rare earth metal salt and Fecl3、AgNO3And (2) mixing with absolute ethyl alcohol to obtain a colloidal solution, mixing the colloidal solution with the ceramic carrier obtained by treatment in the step (1), performing ultrasonic treatment, taking out, drying at the temperature of 120-plus-one (130 ℃) for 3-5h, and finally roasting at the temperature of 380-plus-one (640 ℃) for 3-5h to obtain the photodegradation catalyst.
9. The method for preparing a photodegradation catalyst for organic wastewater treatment according to claim 8, wherein the method comprises the following steps: the ultrasonic treatment temperature in the step (1) is 55-65 ℃.
10. The method for preparing a photodegradation catalyst for organic wastewater treatment according to claim 8, wherein the method comprises the following steps: the ultrasonic treatment temperature in the step (2) is 50-60 ℃, and the ultrasonic treatment time is 1-2 h.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111841569A (en) * | 2020-07-22 | 2020-10-30 | 江苏万贤环境工程有限公司 | Nickel net loaded graphene-TiO2Preparation method of composite nano material |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1724146A (en) * | 2005-07-13 | 2006-01-25 | 北京化工大学 | Preparation for load type nano composite photocatalyst for catalyzing oxidizing degrading organism under sun lighting |
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| WO2022016601A1 (en) * | 2020-07-22 | 2022-01-27 | 江苏万贤环境工程有限公司 | Preparation method for graphene-tio 2 composite nanomaterial loaded with nickel mesh |
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