CN109772327B - Ozone oxidation catalyst and preparation method thereof - Google Patents
Ozone oxidation catalyst and preparation method thereof Download PDFInfo
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- CN109772327B CN109772327B CN201711128497.5A CN201711128497A CN109772327B CN 109772327 B CN109772327 B CN 109772327B CN 201711128497 A CN201711128497 A CN 201711128497A CN 109772327 B CN109772327 B CN 109772327B
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Abstract
The invention belongs to the technical field of catalysts, and particularly relates to an ozone oxidation catalyst for organic wastewater treatment. The invention aims to provide a supported ozone oxidation catalyst with the advantages of high pollutant removal rate, good catalyst stability, less loss of active components and the like and a preparation method thereof. The ozone oxidation catalyst is prepared by taking alumina as a carrier and adopting a coprecipitation method to prepare Fe2O3、CuO、ZnO、Co2O3Transition metal oxides such as NiO and the like and/or CeO2、La2O3The preparation method of the supported ozone oxidation catalyst with the rare earth metal oxide as an active component comprises five processes of precipitation, peptization, balling, washing and roasting. The ozone oxidation catalyst can be used for carrying out catalytic ozone oxidation treatment on organic wastewater, and has the advantages of high removal efficiency, high ozone utilization rate, good catalyst stability, less loss of active components and the like.
Description
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to an ozone oxidation catalyst for organic wastewater treatment.
Background
Ozone oxidation technology has found wide application in the field of water treatment, such as sterilization of municipal water supply and advanced treatment of industrial wastewater. At present, the technology receives more and more attention in the aspect of organic wastewater treatment, particularly the treatment of organic wastewater difficult to biodegrade. But because of the low oxidation selectivity and ozone utilization rate, the popularization and application of the ozone oxidation technology are severely limited. The catalytic ozonation technology is characterized in that a catalyst is introduced into a traditional single ozone system, the oxidation potential of ozone in the system is improved, the generation of active species-hydroxyl free radicals (OH) with stronger oxidation capacity than ozone molecules is accelerated, and the purpose of quickly removing organic pollutants is achieved. The ozone catalysis technology is considered to have the most application potential in sewage treatment application due to the rapid reaction of oxidizing and degrading organic matters and low treatment cost.
The heterogeneous ozone catalytic oxidation technology overcomes the defects that the catalyst is difficult to recover, the concentration of metal ions in the effluent is high and the like in the homogeneous ozone catalytic process, and becomes a hotspot of the technical research of ozone degradation of organic matters. At present, the heterogeneous ozone oxidation catalyst mainly adopts an impregnation method to load an active component on a carrier, but the active component and the carrier are not firmly combined, the dispersibility is low, the dissolution is easy, and the activity and the stability of the catalyst are seriously limited. Therefore, it is necessary to prepare an ozone oxidation catalyst with high activity, good stability and less loss of active components.
Disclosure of Invention
The invention aims to provide a supported ozone oxidation catalyst which has the advantages of high pollutant removal rate, good catalyst stability, less loss of active components and the like in view of the defects of the prior art.
In order to achieve the aim, the ozone oxidation catalyst is a supported ozone oxidation catalyst which is prepared by taking alumina as a carrier and loading an active component by a coprecipitation method, wherein the active component is Fe2O3、CuO、MnO2、ZnO、Co2O3Transition metal oxides such as NiO and the like and/or CeO2、La2O3And one or more of the rare earth metal oxides.
Preferably, the total loading (in terms of oxide mass fraction) of the active components in the catalyst is 0.1-10%.
The invention also aims to provide a preparation method of the ozone oxidation catalyst, which comprises five processes of coprecipitation, peptization, balling, washing and roasting, and comprises the following specific steps:
first-step coprecipitation: firstly, preparing a mixed aqueous solution with the total concentration of 0.1-2.5 mol/L by using aluminum salt and soluble salt corresponding to an active component oxide according to a metering ratio; subsequently, the concentration (as NH) is adjusted with stirring3In terms of mass fraction) of 2.0 to 12.5wt.% of ammonia water solution is added into the mixed aqueous solution to form coprecipitation, the pH of the solution at the end of the dropwise addition is 7 to 11, the filtration is carried out, and pure water is used for washing to obtain gel;
and a second step of peptization: grinding the gel obtained in the first step, and stirring the ground gel according to certain HNO3Gradually adding 0.5-5 mol/L nitric acid solution for peptizing until stable and uniform sol is formed according to the mol ratio of Al;
thirdly, balling: dropwise adding the sol obtained in the second step into an oil ammonia column with kerosene as the upper layer and ammonia water solution as the lower layer to form gel spheres;
and a fourth step of washing: washing the gel balls obtained in the third step with pure water for 3-5 times until the pH value of the washing liquid is 7-8 to obtain catalyst precursor gel balls;
and fifthly, roasting: and (3) drying the catalyst precursor gel spheres obtained in the fourth step in a 120 ℃ drying oven for 2h, then heating to a roasting temperature in a muffle furnace at a heating rate of 1-10 ℃/min, and roasting at a constant temperature for 2-8h to finally obtain the ozone oxidation catalyst.
Preferably, the HNO in the second step3The molar ratio of Al to Al is 0.025-0.25.
Preferably, the ammonia water concentration (as NH) in the oil ammonia column in the third step3In mass fraction) of 2.0 to 18.0 wt.%.
Preferably, the roasting temperature in the fifth step is 350-950 ℃.
The ozone oxidation catalyst provided by the invention has the advantages of high pollutant removal rate, good catalyst stability, less loss of active components and the like, and has a wide application prospect in the field of catalytic ozone oxidation treatment of organic wastewater.
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples.
Example 1:
preparing 1L solution from 1mol of aluminum nitrate and 5mmol of ferric nitrate, adding 8.0wt.% of ammonia water solution while stirring to form a precipitate, finally adjusting the pH value of the solution to 8.5, filtering, and washing for 3 times to obtain a filter cake; grinding the filter cake, adding 50mL of 1mol/L nitric acid solution for peptization (HNO) under stirring3Al ═ 0.05), a sol was obtained; and (3) dropwise adding the sol into an oil ammonia column for forming, wherein the concentration of the lower-layer ammonia water is 8.0wt.%, aging in the column for 60min, taking out a gel ball, washing for 3 times, drying in a 120 ℃ oven for 2h, placing in a muffle furnace, heating to 550 ℃ at the speed of 5 ℃/min, and keeping the temperature for 4h to finally obtain the ozone oxidation catalyst with a single active component, which is marked as OCC-1-FeAl.
Example 2:
preparing 1L solution from 1mol of aluminum nitrate and 10mmol of manganese nitrate, adding 8.0wt.% of ammonia water solution while stirring to form a precipitate, finally adjusting the pH value of the solution to 8.5, filtering, and washing for 3 times to obtain a filter cake; grinding the filter cake, adding 50mL of 1mol/L nitric acid solution for peptization (HNO) under stirring3Al ═ 0.05), a sol was obtained; and (3) dropwise adding the sol into an oil ammonia column for forming, wherein the concentration of the lower-layer ammonia water is 10.0 wt.%, aging in the column for 60min, taking out a gel ball, washing for 4 times, drying in a 120 ℃ oven for 2h, placing in a muffle furnace, heating to 550 ℃ at the speed of 5 ℃/min, and keeping the temperature for 4h to finally obtain the ozone oxidation catalyst with a single active component, which is marked as OCC-2-MnAl.
Example 3:
preparing 1L solution from 1mol of aluminum chloride and 5mmol of cerium nitrate, adding 8.0wt.% ammonia water solution while stirring to form a precipitate, finally adjusting the pH value of the solution to 8.0, filtering, and washing for 3 times to obtain a filter cake; grinding the filter cake, adding 50mL of 1mol/L nitric acid solution for peptization (HNO) under stirring3Al ═ 0.05), a sol was obtained; dripping the sol into oil ammonia column drop by drop for molding, aging the lower layer ammonia water at concentration of 10.0 wt.% in the column for 60min, taking out gel ball, washing for 4 times, and oven drying at 120 deg.CBaking for 2h, then placing in a muffle furnace, heating to 450 ℃ at the speed of 5 ℃/min, and keeping the temperature for 4h to finally obtain the ozone oxidation catalyst with single active component, which is marked as OCC-3-CeAl.
Example 4:
preparing 1L solution from 1mol of aluminum sulfate, 2.5mmol of zinc chloride and 3.5mmol of ketone nitrate, adding 5.0 wt.% of ammonia water solution while stirring to form a precipitate, finally adjusting the pH value of the solution to 9.0, filtering, and washing for 3 times to obtain a filter cake; the filter cake is ground and peptized by adding 50mL of 1.5mol/L nitric acid solution with stirring (HNO)3Al ═ 0.075), a sol was obtained; and (3) dropwise adding the sol into an oil ammonia column for forming, wherein the concentration of the lower-layer ammonia water is 12.5wt.%, aging in the column for 60min, taking out a gel ball, washing for 5 times, drying in a 120 ℃ oven for 2h, placing in a muffle furnace, heating to 700 ℃ at the speed of 2.5 ℃/min, keeping the temperature for 4h, and finally obtaining the ozone oxidation catalyst with double active components, which is marked as OCC-4-CuZnAl.
Example 5:
preparing 1L solution from 1mol of aluminum sulfate, 2.5mmol of cobalt chloride and 2.0mmol of cerium nitrate, adding 12.5wt.% of ammonia water solution while stirring to form a precipitate, finally adjusting the pH value of the solution to 9.5, filtering, and washing for 3 times to obtain a filter cake; grinding the filter cake, adding 30mL of 2mol/L nitric acid solution under stirring for peptizing (HNO3/Al is 0.06) to obtain sol; and (3) dropwise adding the sol into an oil ammonia column for forming, wherein the concentration of the lower-layer ammonia water is 12.5wt.%, aging in the column for 60min, taking out a gel ball, washing for 5 times, drying in a 120 ℃ oven for 2h, placing in a muffle furnace, heating to 600 ℃ at the speed of 3 ℃/min, keeping the temperature for 4h, and finally obtaining the ozone oxidation catalyst with double active components, which is marked as OCC-5-CoCeAl.
Example 6:
preparing 1L solution from 1mol of aluminum sulfate, 5mmol of ferric nitrate, 1.5mmol of copper nitrate and 2.5mmol of nickel nitrate, adding 8.0wt.% of ammonia water solution while stirring to form a precipitate, finally adjusting the pH value of the solution to 10.0, filtering, and washing for 3 times to obtain a filter cake; the filter cake is ground and peptized by adding 50mL of 1.5mol/L nitric acid solution with stirring (HNO)3Al ═ 0.075), a sol was obtained; dropping the sol into oil ammonia column drop by drop to form lower layer ammoniaThe water concentration is 8.0wt.%, the gel spheres are taken out after the gel spheres are aged in the column for 60min, the gel spheres are washed for 3 times, the gel spheres are dried in a 120 ℃ oven for 2h, then the gel spheres are placed in a muffle furnace, the temperature is raised to 500 ℃ at the speed of 5 ℃/min, the temperature is kept constant for 4h, and finally the ozone oxidation catalyst with three active components is obtained and is marked as OCC-6-FeCuNiAl.
Example 7:
the catalytic ozonation performance of the ozonation catalyst in the invention is further explained by taking a m-cresol solution as model organic wastewater and carrying out ozonation catalytic oxidation treatment.
In four identical 500mL glass reactors, 200mL of 100ppm m-cresol solution with the pH of the initial solution being 6-7 was charged, one of the solutions was used as a blank test without adding a catalyst, and the other three were used as a blank test with 1.0g of commercial alumina and commercial Fe2O3/Al2O3The ozone oxidation catalyst and the ozone oxidation catalyst (OCC-1-FeAl) prepared in the embodiment 1 of the invention (namely the adding concentration is 5.0g/L) are continuously introduced with 160mL/min of ozone with the concentration of 50ppm, samples are taken after 30min of reaction, and the total concentration of TOC of water and the total concentration of metal ions dissolved out of active components are analyzed. Under the same test conditions, the ozone oxidation catalyst obtained in the embodiment 2-6 of the invention is used for treating m-cresol organic wastewater.
The catalytic effects of different ozone oxidation catalysts are compared in table 1.
TABLE 1 comparison of catalytic Effect of different ozone oxidation catalysts
As can be seen from Table 1, under the same experimental conditions, the performance of the ozone oxidation catalyst prepared in the invention is far better than that of commercial alumina and commercial Fe2O3/Al2O3The ozone oxidation catalyst of the present invention is explainedThe chemical performance is excellent.
Example 8:
200mL of m-cresol solutions with initial concentrations of 50ppm, 150ppm and 200ppm are respectively filled into three identical 500mL glass reactors, the pH value of the initial solution is 6-7, 1.0g of the ozone oxidation catalyst (OCC-6-FeCuNiAl) prepared in the embodiment 6 of the invention is added (namely the adding concentration is 5.0g/L), then 160mL/min of ozone with the concentration of 50ppm is continuously introduced, a sample is taken after the reaction is carried out for 30min, and the TOC of water is analyzed.
The catalytic effect of the different initial concentrations of m-cresol solution is compared in Table 2.
TABLE 2 comparison of catalytic Effect of different initial concentrations of m-cresol solution
As can be seen from Table 2, the ozone oxidation catalyst prepared by the invention has good treatment effect on m-cresol organic wastewater with different concentrations, which indicates that the ozone oxidation catalyst has good application value.
Claims (5)
1. A method for preparing an ozone oxidation catalyst is characterized by comprising the following steps: the catalyst is a supported ozone oxidation catalyst prepared by taking alumina as a carrier and loading an active component by a coprecipitation method, wherein the active component is Fe2O3、CuO、MnO2、ZnO、Co2O3NiO transition metal oxide or CeO2、La2O3One or more of rare earth metal oxides;
the method comprises five processes of coprecipitation, peptization, balling, washing and roasting, and comprises the following specific steps:
first-step coprecipitation: firstly, preparing a mixed aqueous solution with the total concentration of 0.1-2.5 mol/L by using aluminum salt and soluble salt corresponding to an active component oxide according to a metering ratio; subsequently, under stirring, with NH3Adding 2.0-12.5 wt.% ammonia water solution into the mixed aqueous solution to form coprecipitation, adjusting the pH of the solution to 7-11 at the end of the dripping, filtering,washing with pure water to obtain gel;
and a second step of peptization: grinding the gel obtained in the first step, and stirring the ground gel according to certain HNO3Gradually adding 0.5-5 mol/L nitric acid solution for peptizing until stable and uniform sol is formed according to the mol ratio of Al;
thirdly, balling: dropwise adding the sol obtained in the second step into an oil ammonia column with kerosene as the upper layer and ammonia water solution as the lower layer to form gel spheres;
and a fourth step of washing: washing the gel balls obtained in the third step with pure water for 3-5 times until the pH value of the washing liquid is 7-8 to obtain catalyst precursor gel balls;
and fifthly, roasting: and (3) drying the catalyst precursor gel spheres obtained in the fourth step in a 120 ℃ drying oven for 2h, then heating to a roasting temperature in a muffle furnace at a heating rate of 1-10 ℃/min, and roasting at a constant temperature for 2-8h to finally obtain the ozone oxidation catalyst.
2. The production method according to claim 1, characterized in that: the total loading amount of the active components is 0.1-10% by mass of the oxide.
3. The method of claim 1, wherein: HNO described in the second step3The molar ratio of Al to Al is 0.025-0.25.
4. The method of claim 1, wherein: by NH3The ammonia water concentration in the oil ammonia column in the third step is 2.0-18.0 wt.%.
5. The method of claim 1, wherein: and the roasting temperature in the fifth step is 350-950 ℃.
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| CN110339837A (en) * | 2019-07-22 | 2019-10-18 | 格丰科技材料有限公司 | A kind of efficient water ozone catalyst and its preparation method and application |
| CN110975862A (en) * | 2019-11-22 | 2020-04-10 | 南京中衡元环保科技有限公司 | High-efficiency catalyst for ozone reactor and preparation method thereof |
| CN112264030B (en) * | 2020-11-21 | 2022-06-21 | 江西挺进环保科技股份有限公司 | Ozone catalytic treating agent for treating organic matters in wastewater and preparation method thereof |
| CN114210338B (en) * | 2021-12-20 | 2023-11-10 | 河北科技大学 | Perovskite-like catalyst for catalyzing ozone oxidation and preparation method and application thereof |
| CN115445625B (en) * | 2022-09-22 | 2023-12-29 | 山东默同生态有限公司 | Magnetic nano iron-lanthanum-cobalt oxide synthesized by ultrasonic assistance and synthesis method and application thereof |
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| CN105688927A (en) * | 2014-11-27 | 2016-06-22 | 中国海洋石油总公司 | Ozone catalytic oxidation catalyst and application thereof |
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