CN112791732A - Ozone catalytic oxidation catalyst and preparation method and application thereof - Google Patents
Ozone catalytic oxidation catalyst and preparation method and application thereof Download PDFInfo
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- CN112791732A CN112791732A CN201911108158.XA CN201911108158A CN112791732A CN 112791732 A CN112791732 A CN 112791732A CN 201911108158 A CN201911108158 A CN 201911108158A CN 112791732 A CN112791732 A CN 112791732A
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- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0207—Pretreatment of the support
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
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- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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- C—CHEMISTRY; METALLURGY
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- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
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- 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
Abstract
The invention relates to the technical field of water treatment, and particularly discloses an ozone catalytic oxidation catalyst, and a preparation method and application thereof. The ozone catalytic oxidation catalyst comprises a carrier, an active component and an auxiliary agent; the carrier is gamma-Al2O3The active component is one or more of Co oxide and Mn, Ce, Cu, Ni and Fe oxide, and the auxiliary agent is Ca oxide. The invention also provides a preparation method of the catalyst.Compared with the traditional catalyst prepared by directly impregnating the active component into the carrier, the catalyst has the advantages of tight combination of the carrier and the active component, difficult loss of the active component, high catalytic activity, stable catalytic performance, long service life and the like. Is suitable for treating high CODcrThe concentration and the organic matter form complex industrial wastewater.
Description
Technical Field
The invention relates to the technical field of water treatment, in particular to an ozone catalytic oxidation catalyst and a preparation method and application thereof.
Background
With the continuous promotion of industrialization, water pollution becomes a major problem for environmental management, and industrial wastewater is a main cause of water pollution, and the discharge of industrial wastewater can cause serious water pollution, damage to surrounding ecological environment and great threat to human health. Therefore, as the discharge standard of industrial wastewater in industrial production is continuously improved, the treatment of industrial wastewater is gradually emphasized.
The industrial wastewater has complex components (containing polycyclic aromatic compounds, benzene series such as halogenated benzene, unsaturated aldehyde ketone, amide, nitrogen-containing heterocyclic series, phenols, organic acids and the like) and variable properties (difficult biochemical degradation and toxicity), so that the industrial wastewater is difficult to treat, and the emission requirement is difficult to meet by a single treatment method at one time. In order to realize advanced treatment of industrial wastewater, advanced oxidation methods have been widely used in industry due to their advantages of wide application range, high oxidation rate, high efficiency, and the like. The advanced oxidation technology mainly comprises an ozone catalytic oxidation technology, a Fenton oxidation technology, an iron-carbon micro-electrolysis oxidation technology and the like. Compared with Fenton and iron-carbon micro-electrolysis, the ozone catalysis technology has the advantages of good stability, no secondary pollution, no need of additional medicament, no sludge generation, renewable and reusable ozone catalyst and the like.
The ozone catalysis technology is characterized in that the catalysis effect of a catalyst is utilized to promote ozone to be rapidly decomposed to generate hydroxyl radicals with strong oxidizing property (the oxidation-reduction potential reaches 2.8eV), the hydroxyl radicals have no selectivity on pollutants, the effect of rapidly and efficiently removing organic matters in water can be realized, and heavy metal and organic matter pollution in heavy metal ion-containing production wastewater such as electroplating, circuit boards, ore dressing, smelting and the like is removed. And the ozone catalytic oxidation technology has low operating cost, is suitable for the reconstruction of the original sewage station, reduces the operating cost and meets the operating requirements of consumption reduction and energy conservation.
However, when the pretreatment is performed on high-concentration, difficult-to-biochemical and toxic organic wastewater (such as wastewater from pharmaceutical industry, petrochemical coking coal chemical industry, leather industry, electrophoretic coating industry, pickling fermentation industry and the like), the conventional catalyst in the ozone catalytic oxidation technology has the problems of low activity, poor stability, short service life and the like.
Therefore, it is desirable to provide a new ozone catalytic oxidation catalyst, a preparation method and an application thereof to solve the above problems.
Disclosure of Invention
In order to solve the problems in the prior art, the invention aims to provide a method which is particularly suitable for the pretreatment and advanced treatment of high-concentration, difficult-to-biochemically-treated and toxic organic wastewater, namely COD (chemical oxygen demand) in the wastewatercrHigh removal efficiency and good stability.
In order to achieve the purpose of the invention, the technical scheme of the invention is as follows:
an ozone catalytic oxidation catalyst comprises a carrier, an active component and an auxiliary agent; the carrier is gamma-Al2O3The active component is one or more of Co oxide and Mn, Ce, Cu, Ni and Fe oxide, and the auxiliary agent is Ca oxide.
γ-Al2O3The invention has large specific surface area, good stability and high hardness, is suitable for being used as a carrier, but has relatively low activity, so the invention adopts various metal pairs of gamma-Al2O3The modified Mn, Ce, Co, Cu, Ni and Fe have multiple valence states and good redox ability, so the invention uses their oxides (Co, Co)3O4、MnO2、CeO2、NiO、Fe3O4) As the active component of the catalyst. And the present invention has been madeParticularly, the discovery that when the active component comprises Co oxide and the auxiliary agent is Ca oxide (CaO), and one or more of Mn, Ce, Cu, Ni and Fe oxides are matched as the active component, the catalyst can be greatly improved in treating high CODcrThe method has the advantages of ensuring the catalytic activity, reducing the fluctuation of the catalytic efficiency and realizing the high-efficiency and full wastewater treatment effect, along with complex concentration and components, treatment speed and stability in the wastewater difficult to treat, and is particularly suitable for treating the wastewater containing various difficult-to-treat and toxic organic wastes such as polycyclic aromatic hydrocarbon compounds, unsaturated aldehyde ketones, amide compounds, nitrogen-containing heterocyclic compounds, phenolic compounds, organic carboxylic acid compounds, halogenated benzene, other benzene series except the halogenated benzene and the like.
In the invention, the active components are the Co oxide and the oxides of Mn, Ce and Cu, so that the catalytic rate is high and the performance is stable; or the active components are Co oxide and Mn, Ce, Ni and Fe oxide, and the catalyst performance is kept high-efficiency and stable, so that the cost is further reduced.
In the present invention, the mass ratio of the oxide of Co to the oxide of Ca is 1: (1-2).
When the oxide content of Co and the oxide content of Ca in the catalyst of the present invention are in the above-mentioned specific ratio, the activity and stability of the catalyst are ensured.
In the invention, the content of the Co oxide, the content of the Mn oxide, the content of the Ce oxide, the content of the Cu oxide, the content of the Ni oxide and the content of the Fe oxide are respectively 1-5 wt% based on the weight of the carrier; the content of the Ca oxide is 1-4 wt%.
The active component comprises one or more of oxides of Mn, Ce, Cu, Ni and Fe, and when the active component comprises the oxide of Mn, the amount of the oxide is 1-5 wt% of the weight of the carrier; when oxide of Ce is included, it is used in an amount of 1-5 wt% based on the weight of the support; when an oxide of Cu is contained, it is used in an amount of 1 to 5 wt% based on the weight of the support; when an oxide of Ni is contained, it is used in an amount of 1 to 5 wt% based on the weight of the support; when an oxide of Fe is included, it is used in an amount of 1 to 5 wt% based on the weight of the support.
Preferably, in the present invention, the content of the oxide of Co is 1 to 3 wt%; the content of the Ca oxide is 1-3 wt%; the content of Mn oxide is 1-5 wt%; the content of Ce oxide is 1-3 wt%; the content of Cu oxide is 1-3 wt%; the content of Ni oxide is 1-3 wt%; the content of Fe oxide is 1-5 wt%. Thereby being beneficial to further reducing the cost while ensuring the catalytic effect.
As a preferred mode, the catalyst of the present invention comprises, based on the weight of the support: 2 wt% of the oxide of Co, 3 wt% of the oxide of Mn, 2 wt% of the oxide of Ce, 2 wt% of the oxide of Cu, 2 wt% of the oxide of Ca;
or, based on the weight of the carrier, comprises: 1 wt% of the oxide of Co, 3 wt% of the oxide of Mn, 1 wt% of the oxide of Ce, 1 wt% of the oxide of Ni, 3 wt% of the oxide of Fe, 2 wt% of the oxide of Ca. The Co content in the scheme is low, and the catalyst cost is favorably reduced.
It is another object of the present invention to provide a process for preparing the above catalyst.
The preparation method of the catalyst comprises the following steps:
(1) carrying out vacuum-pumping pretreatment on the carrier;
(2) preparation of metal salt solution: dissolving cobalt salt, calcium salt and one or more selected from manganese salt, cerium salt, copper salt, nickel salt and iron salt in water;
(3) dipping: impregnating the carrier with the metal salt solution to obtain an impregnating solution;
(4) coprecipitation: and (3) dropwise adding and mixing the impregnation liquid and ammonia water in a parallel flow manner to obtain a precipitation liquid, stirring, and standing to obtain a precipitate.
The method comprises the steps of firstly placing the carrier in a vacuum environment to remove air in a carrier pore channel, then placing the carrier into a metal salt solution for dipping, and finally precipitating metal ions in the carrier pore channel and on the surface of the carrier in a mode of adding the dipping solution and ammonia water in a concurrent flow manner, so that the subsequent catalyst carrier and active components can be tightly and firmly combined, the active components are not easy to lose, and the stability of the catalyst is improved.
In the invention, the carrier vacuumizing pretreatment is specifically as follows: and putting the carrier alumina in a vacuum oven, and vacuumizing for 2-5h to remove air and moisture in the carrier pore channels.
In the invention, the water is deionized water, and the addition amount of the water is preferably enough to ensure that the salt of each metal is completely dissolved.
In the invention, the impregnation in the step (3) is carried out under stirring, and the impregnation time is 1-10h, preferably 3-6h, so as to ensure the contact time of the active components in the solution and the carrier, and ensure the uniform concentration of the active components and the full contact with the carrier.
In the present invention, the concentration of ammonia water is 10%.
In the invention, the specific way of coprecipitation is as follows: and (3) dropwise adding the prepared impregnation liquid and ammonia water into the same beaker in a concurrent flow manner, continuously stirring the precipitation liquid in the process, continuously stirring for 1-5h after dropwise adding is finished, and then standing for 1-12 h.
In the invention, the cobalt salt is a hydrate of cobalt nitrate, the calcium salt is a hydrate of calcium nitrate, the manganese salt is manganese nitrate, the cerium salt is a hydrate of cerium nitrate, the copper salt is a hydrate of copper nitrate, the nickel salt is a hydrate of nickel acetate, and the iron salt is a hydrate of ferric nitrate.
Wherein, the manganese salt can be selected from a manganese nitrate solution with the mass concentration of 50%.
In the step (4) of the invention, the pH value of the precipitation solution is 9-11. The pH value can be controlled by controlling the dropping speed of the two solutions.
The process of the invention also comprises the steps of filtering (preferably suction filtration), drying in a water bath and calcining (optionally with a muffle furnace) the precipitate.
In the invention, the temperature of the water bath drying is 60-100 ℃, and the time is 5-10h, so as to ensure that the water in the catalyst is fully evaporated to dryness.
In the invention, the calcining temperature is 400-600 ℃, the heating rate is 5 ℃/min, and the calcining time is 3-7h, so as to ensure that the catalyst is completely calcined and has a complete structure.
It is still another object of the present invention to provide a use of the above catalyst or method in industrial wastewater treatment.
Preferably, the industrial wastewater comprises polycyclic aromatic hydrocarbon compounds, unsaturated aldehyde ketones, amide compounds, nitrogen-containing heterocyclic compounds, phenolic compounds, organic carboxylic acid compounds, halogenated benzene and other benzene series except the halogenated benzene.
Preferably, the pH value of the industrial wastewater is 6-8, CODcrThe value is 100-350 mg/L.
The industrial wastewater is taken from MBR effluent, and after being treated by the processes of homogenizing adjustment, hydrolytic acidification, AO biochemistry and MBR, COD is obtainedcrThe value is still as high as 100-350mg/L, and the biodegradability is very poor.
Preferably, in the invention, the industrial wastewater is wastewater in the fields of pharmacy, petrifaction, coking coal chemical industry, leather, printing and dyeing, electrophoretic coating, pickling fermentation, paper making and the like.
The wastewater contains polycyclic aromatic hydrocarbon compounds, benzene series such as halogenated benzene, unsaturated aldehyde ketone, amide, nitrogen-containing heterocyclic series, phenols, organic acid and other substances, and has complex components and poor biodegradability, so that the conventional catalyst cannot ensure COD (chemical oxygen demand)crThe catalyst of the invention is used for treating complex organic matters with high CODcrCan ensure COD when the wastewater is concentratedcrThe removal efficiency can be ensured, the catalytic stability can be ensured, and the method is suitable for industrial popularization and application.
The invention has the beneficial effects that:
(1) according to the invention, through the matching of the specific active component and the auxiliary agent, the catalytic activity of the catalyst is increased, the effect is fast, the catalytic efficiency is improved, the ozone can be rapidly decomposed to generate hydroxyl radicals, and the utilization rate of the ozone is improved.
(2) The preparation method of the invention can ensure the close and firm combination of the catalyst carrier and the active component, has rich pore channels, strong adsorption performance, difficult loss of the active component, more active sites of the catalyst, stable performance and long service life.
(3) The catalyst of the invention is suitable for advanced treatment of industrial wastewater, in particular to wastewater which is high in concentration, difficult to be biochemically treated and toxic (such as wastewater in pharmacy, petrochemical coking coal chemical industry, leather, electrophoretic coating, pickling fermentation, paper making and the like)) The pretreatment and the advanced treatment can efficiently remove CODcrAmmonia nitrogen, chromaticity and the like, and the biodegradability of the wastewater is improved. Can be transformed on the basis of the original sewage station, reduces the operation cost and meets the operation requirements of consumption reduction and energy conservation.
Drawings
FIG. 1 shows COD values of examples 1 to 3 of the present invention and comparative examples 1 to 5crThe efficiency map is removed.
Detailed Description
Preferred embodiments of the present invention will be described in detail with reference to the following examples. It is to be understood that the following examples are given for illustrative purposes only and are not intended to limit the scope of the present invention. Various modifications and alterations of this invention will become apparent to those skilled in the art without departing from the spirit and scope of this invention.
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified. Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
In the specific embodiment of the invention, the industrial wastewater is taken from a centralized sewage treatment plant in a chemical industrial park, and park enterprises comprise chemical synthetic medicine enterprises, biological medicine enterprises, pesticide enterprises, leather-making enterprises and fine chemical enterprises.
Through ultraviolet, GC-MS and fluorescence spectrum analysis and detection, the wastewater contains polycyclic aromatic hydrocarbon compounds, halogenated benzene, other benzene series, unsaturated aldehyde ketone, amides, nitrogen-containing heterocycles, phenols, organic acids and the like.
COD treated by homogenizing regulation, hydrolytic acidification, AO biochemistry and MBR processcrThe value is 293-295 mg/L; the pH was 6.5.
In the present invention, the Mn, Ce, Co, Cu, Ni, Fe, Mg, Ca are components representing the respective elements in the catalyst, unless otherwise stated.
Example 1
This example prepares a catalyst of the present invention and tests its catalyst activity.
The preparation method comprises the following steps:
mixing gamma-Al2O3Putting the powder in a vacuum oven and vacuumizing for 3 h;
0.741g of a 50% (mass fraction) manganese nitrate solution, 0.435g of Co (NO)3)2·6H2O，0.303g Ce(NO3)2·6H2O，0.365g Cu(NO3)2·3H2O，0.505g Ca(NO3)2·4H2Dissolving O in 30ml of deionized water, and stirring for 2 hours at room temperature;
6g of treated gamma-Al2O3Adding the carrier into a metal salt solution, and stirring for 4 hours;
and (3) dropwise adding the impregnation liquid and ammonia water (with the concentration of 10%) into the same beaker in a concurrent flow manner, continuously stirring the precipitation liquid in the process, and controlling the dropping speed of the two solutions to control the pH value of the precipitation liquid to be 10. After the dropwise addition is finished, stirring is continuously carried out for 3 hours, and then standing is carried out for 8 hours;
filtering the precipitated solution, drying a filter cake in a water bath kettle at the temperature of 80 ℃ for 6h, then calcining in a muffle furnace at the temperature of 500 ℃ for 5h, wherein the heating rate of the muffle furnace is 5 ℃/min, and obtaining the catalyst Mn (3%) -Co (2%) -Ce (2%) -Cu (2%) -Ca (2%)/gamma-Al2O3。
And (3) testing the activity of the catalyst:
CODcr100ml of industrial wastewater with the concentration of 295mg/L (the pH value is 6.5), ozone is continuously added as an oxidant, the gas flow rate is 62ml/min, and O is added3The gas phase concentration was 27mg/L and the catalyst amount was 5 g.
When the reaction time is 15min, the catalyst can be used for treating COD of waste watercrThe removal rate was 41%, and the removal rate at 30min was 43.35% (see FIG. 1). The catalyst has quick effect and stable catalytic efficiency.
Example 2
This example prepares a catalyst of the present invention and tests its catalyst activity.
The preparation method comprises the following steps:
mixing gamma-Al2O3Putting the powder in a vacuum oven and vacuumizing for 3 h;
0.741g of 50% manganese nitrate solution, 0.218g of Co (NO)3)2·6H2O，0.151g Ce(NO3)2·6H2O，0.2g Ni(CH3COO)2·4H2O，0.909g Fe(NO3)2·9H2O，0.505g Ca(NO3)2·4H2Dissolving O in 30ml of deionized water, and stirring for 2 hours at room temperature;
6g of treated gamma-Al2O3Adding the carrier into a metal salt solution, and stirring for 4 hours;
and (3) dropwise adding the impregnation liquid and ammonia water (with the concentration of 10%) into the same beaker in a concurrent flow manner, continuously stirring the precipitation liquid in the process, and controlling the dropping speed of the two solutions to control the pH value of the precipitation liquid to be 10. After the dropwise addition is finished, stirring is continuously carried out for 3 hours, and then standing is carried out for 8 hours;
filtering the precipitated solution, drying a filter cake in a water bath kettle at the temperature of 80 ℃ for 6h, then calcining in a muffle furnace at the temperature of 500 ℃ for 5h, wherein the heating rate of the muffle furnace is 5 ℃/min, and obtaining the catalyst Mn (3%) -Co (1%) -Ce (1%) -Ni (1%) -Fe (3%) -Ca (2%)/gamma-Al2O3。
And (3) testing the activity of the catalyst:
CODcr294mg/L industrial wastewater 100ml (pH value is 6.5), ozone is used as oxidant to be continuously added, gas flow rate is 62ml/min, O3The gas phase concentration was 27mg/L and the catalyst amount was 5 g.
When the reaction time is 15min, the catalyst can be used for treating COD of waste watercrThe removal rate was 37.2%, and the removal rate reached 41.5% at 30min (see fig. 1). The catalyst has quick effect and stable catalytic efficiency.
Example 3
This example prepares a catalyst of the present invention and tests its catalyst activity.
The specific preparation method is the same as that of example 1, and only differs from the following steps: 0.741g of a 50% (mass fraction) manganese nitrate solution, 0.435g of Co (NO)3)2·6H2O，0.303g Ce(NO3)2·6H2O，0.365g Cu(NO3)2·3H2O，0.253g Ca(NO3)2·4H2O。
Catalyst Mn (3) is obtained％)-Co(2％)-Ce(2％)-Cu(2％)-Ca(1％)/γ-Al2O3。
And (3) testing the activity of the catalyst:
CODcr100ml of industrial wastewater with the concentration of 295mg/L (the pH value is 6.5), ozone is continuously added as an oxidant, the gas flow rate is 62ml/min, and O is added3The gas phase concentration was 27mg/L and the catalyst amount was 5 g.
When the reaction time is 15min, the catalyst can be used for treating COD of waste watercrThe removal rate was 35%, and the removal rate at 30min was 39%. The catalyst has quick effect and stable catalytic efficiency.
Comparative example 1
This comparative example directly used ozone (O)3) The industrial wastewater treatment is carried out without adopting a catalyst.
Get CODcr100ml of industrial wastewater with the concentration of 295mg/L (the pH value is 6.5), ozone is continuously added as an oxidant, the gas flow rate is 62ml/min, and O is added3The gas phase concentration was 27 mg/L.
Sampling and detecting at an interval of 15min within 0-30min of the contact time of the ozone and the industrial wastewater. When the reaction time is 15min, COD iscrThe removal rate was 8.2%, and the removal rate at 30min was 21% (see fig. 1).
Comparative example 2
This comparative example a commercially available commercial ozone catalyst purchased was ground to a powder for use in catalyzing the reaction. CODcr100ml of industrial wastewater with the concentration of 295mg/L (the pH value is 6.5), ozone is continuously added as an oxidant, the gas flow rate is 62ml/min, and O is added3The gas phase concentration was 27mg/L and the catalyst amount was 5 g.
When the reaction time is 15min, the catalyst can be used for treating COD of waste watercrThe removal rate was 12%, and the removal rate at 30min was 25% (see FIG. 1). The efficiency of the ozone is almost the same as that of the pure ozone in the comparative example 1, and the ozone has no obvious effect on the wastewater with complex components.
Comparative example 3
This comparative example prepared a catalyst and tested its catalyst activity.
The preparation method comprises the following steps:
mixing gamma-Al2O3Placing the powder in a vacuum oven for vacuumizing3h；
0.741g of a 50% manganese nitrate solution, 0.435g of Co (NO)3)2·6H2O，0.303g Ce(NO3)2·6H2O，0.365g Cu(NO3)2·3H2O，0.764g Mg(NO3)2·6H2Dissolving O in 30ml of deionized water, and stirring for 2 hours at room temperature;
6g of treated gamma-Al2O3Adding the carrier into a metal salt solution, stirring and dipping for 4 hours;
and (3) dropwise adding the impregnation liquid and ammonia water (with the concentration of 10%) into the same beaker in a concurrent flow manner, continuously stirring the precipitation liquid in the process, and controlling the dropping speed of the two solutions to control the pH value of the precipitation liquid to be 10. After the dropwise addition is finished, stirring is continuously carried out for 3 hours, and then standing is carried out for 8 hours;
filtering the precipitated solution, drying a filter cake in a water bath kettle at the temperature of 80 ℃ for 6h, calcining the filter cake in a muffle furnace at the temperature of 500 ℃ for 5h, wherein the heating rate of the muffle furnace is 5 ℃/min, and obtaining the catalyst Mn (3%) -Co (2%) -Ce (2%) -Cu (2%) -Mg (2%)/gamma-Al2O3。
And (3) testing the activity of the catalyst:
CODcr100ml of industrial wastewater with the concentration of 295mg/L (the pH value is 6.5), ozone is continuously added as an oxidant, the gas flow rate is 62ml/min, and O is added3The gas phase concentration was 27mg/L and the catalyst amount was 5 g.
When the reaction time is 15min, the catalyst can be used for treating COD of waste watercrThe removal rate is 29.2%, and the removal rate at 30min is 27.46% (see figure 1), so that the catalytic efficiency is low, and the catalyst stability is poor.
Comparative example 4
This comparative example prepared a catalyst and tested its catalyst activity.
The preparation method comprises the following steps:
mixing gamma-Al2O3Putting the powder in a vacuum oven and vacuumizing for 3 h; 0.988g of 50% manganese nitrate solution, 0.151g of Ce (NO)3)2·6H2O，0.2g Ni(CH3COO)2·4H2O，0.909g Fe(NO3)2·9H2O，0.505g Ca(NO3)2·4H2Dissolving O in 30ml of deionized water, and stirring for 2 hours at room temperature;
6g of treated gamma-Al2O3Adding the carrier into a metal salt solution, and stirring for 4 hours;
and (3) dropwise adding the impregnation liquid and ammonia water (with the concentration of 10%) into the same beaker in a concurrent flow manner, continuously stirring the precipitation liquid in the process, and controlling the dropping speed of the two solutions to control the pH value of the precipitation liquid to be 10. After the dropwise addition is finished, stirring is continuously carried out for 3 hours, and then standing is carried out for 8 hours;
filtering the precipitated solution, drying a filter cake in a water bath kettle at the temperature of 80 ℃ for 6h, then calcining in a muffle furnace at the temperature of 500 ℃ for 5h, wherein the heating rate of the muffle furnace is 5 ℃/min, and obtaining the catalyst Mn (4%) -Ce (1%) -Ni (1%) -Fe (3%) -Ca (2%)/gamma-Al2O3。
And (3) testing the activity of the catalyst:
CODcr100ml of industrial wastewater with the concentration of 295mg/L (the pH value is 6.5), ozone is continuously added as an oxidant, the gas flow rate is 62ml/min, and O is added3The gas phase concentration was 27mg/L and the catalyst amount was 5 g.
When the reaction time is 15min, the catalyst can be used for treating COD of waste watercrThe removal rate was 27.5%, and the removal rate at 30min was 41% (see fig. 1). The initial catalytic efficiency was low (COD at 15min, compared to the cobalt containing scheme of example 2)crThe removal rate is low by about 10 percent), which is not beneficial to the rapid treatment of the wastewater.
Comparative example 5
This comparative example prepared a catalyst and tested its catalyst activity.
The preparation method comprises the following steps:
mixing gamma-Al2O3Putting the powder in a vacuum oven and vacuumizing for 3 h;
0.741g of a 50% manganese nitrate solution, 0.151g of Ce (NO)3)2·6H2O，0.1g Ni(CH3COO)2·4H2O，1.364g Fe(NO3)2·9H2O，0.505g Ca(NO3)2·4H2Dissolving O in 30ml of deionized water, and stirring for 2 hours at room temperature;
6g of treated gamma-Al2O3Adding the carrier into a metal salt solution, and stirring for 4 hours;
and (3) dropwise adding the impregnation liquid and ammonia water (with the concentration of 10%) into the same beaker in a concurrent flow manner, continuously stirring the precipitation liquid in the process, and controlling the dropping speed of the two solutions to control the pH value of the precipitation liquid to be 10. After the dropwise addition is finished, stirring is continuously carried out for 3 hours, and then standing is carried out for 8 hours;
filtering the precipitated solution, drying a filter cake in a water bath kettle at the temperature of 80 ℃ for 6h, and then calcining in a muffle furnace at the temperature of 500 ℃ for 5h, wherein the heating rate of the muffle furnace is 5 ℃/min, so that the catalyst Mn (3%) -Ce (1%) -Ni (0.5%) -Fe (4.5%) -Ca (2%)/gamma-Al is obtained2O3。
And (3) testing the activity of the catalyst:
CODcr294mg/L industrial wastewater 100ml (pH value is 6.5), ozone is used as oxidant to be continuously added, gas flow rate is 62ml/min, O3The gas phase concentration was 27mg/L and the catalyst amount was 5 g.
When the reaction time is 15min, the catalyst can be used for treating COD of waste watercrThe removal rate was 15.2%, and the removal rate at 30min was 38.7% (see fig. 1). The initial catalytic efficiency was low (COD at 15min, compared to the cobalt containing scheme of example 2)crThe removal rate is 22 percent lower), which is not beneficial to the rapid treatment of the wastewater.
Examples of the experiments
The catalysts of example 2 and comparative examples 4-5 were used repeatedly to test the stability of the catalysts. The test results are shown in tables 1-3.
Table 1 catalyst reuse efficiency of example 2
Table 2 efficiency of reuse of comparative example 4 catalyst
Table 3 efficiency of reuse of the catalyst of comparative example 5
As can be seen from tables 1 to 3, the catalyst of example 2 exhibited 34% to 40% catalytic efficiency in 5 tests at 15 minutes of reaction, and 39% to 44% catalytic efficiency in 5 tests at 30 minutes of reaction, with high efficiency and stability.
When the reaction time is 15 minutes, the catalytic efficiency of the catalyst of the comparative example 4 tested 5 times is 27% -37%, and when the reaction time is 30 minutes, the catalytic efficiency is 33% -41%, the efficiency is low, the fluctuation is large, and the catalytic activity of the catalyst is gradually reduced along with the increase of the use times of the catalyst.
When the reaction time is 15 minutes, the catalytic efficiency of the catalyst of the comparative example 5 tested 5 times is 15% -40%, and when the reaction time is 30 minutes, the catalytic efficiency is 20% -44%, the efficiency is low, the fluctuation is large, the stability is poor, and the catalytic activity of the catalyst is gradually reduced along with the increase of the using times of the catalyst.
Although the invention has been described in detail hereinabove with respect to a general description and specific embodiments thereof, it will be apparent to those skilled in the art that modifications or improvements may be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (10)
1. An ozone catalytic oxidation catalyst is characterized by comprising a carrier, an active component and an auxiliary agent; the carrier is gamma-Al2O3The active components are Co oxide and oxygen selected from Mn, Ce, Cu, Ni and FeOne or more of the compounds, wherein the auxiliary agent is Ca oxide.
2. The catalyst of claim 1, wherein the active components are the oxide of Co and the oxide of Mn, Ce, Cu, or the active components are the oxide of Co and the oxide of Mn, Ce, Ni, Fe.
3. The catalyst according to claim 1 or 2, wherein the mass ratio of the oxide of Co to the oxide of Ca is 1: (1-2).
4. The catalyst according to claim 3, wherein the content of the oxide of Co, the oxide of Mn, Ce, Cu, Ni, Fe is 1-5 wt% respectively based on the weight of the carrier; the content of the Ca oxide is 1-4 wt%.
5. The catalyst of claim 4, wherein the oxide of Co is present in an amount of 1 to 3 wt%; the content of the Ca oxide is 1-3 wt%; the content of Mn oxide is 1-5 wt%; the content of Ce oxide is 1-3 wt%; the content of Cu oxide is 1-3 wt%; the content of Ni oxide is 1-3 wt%; the content of Fe oxide is 1-5 wt%.
6. The catalyst according to claim 5, comprising, based on the weight of the support: 2 wt% of the oxide of Co, 3 wt% of the oxide of Mn, 2 wt% of the oxide of Ce, 2 wt% of the oxide of Cu, 2 wt% of the oxide of Ca;
or, based on the weight of the carrier, comprises: 1 wt% of the oxide of Co, 3 wt% of the oxide of Mn, 1 wt% of the oxide of Ce, 1 wt% of the oxide of Ni, 3 wt% of the oxide of Fe, 2 wt% of the oxide of Ca.
7. A process for preparing the catalyst of any one of claims 1 to 6, comprising the steps of:
(1) carrying out vacuum-pumping pretreatment on the carrier;
(2) preparation of metal salt solution: dissolving cobalt salt, calcium salt and one or more selected from manganese salt, cerium salt, copper salt, nickel salt and iron salt in water;
(3) dipping: impregnating the carrier with the metal salt solution to obtain an impregnating solution;
(4) coprecipitation: and (3) dropwise adding and mixing the impregnation liquid and ammonia water in a parallel flow manner to obtain a precipitation liquid, stirring, and standing to obtain a precipitate.
8. The method according to claim 7, wherein the cobalt salt is a hydrate of cobalt nitrate, the calcium salt is a hydrate of calcium nitrate, the manganese salt is manganese nitrate, the cerium salt is a hydrate of cerium nitrate, the copper salt is a hydrate of copper nitrate, the nickel salt is a hydrate of nickel acetate, and the iron salt is a hydrate of iron nitrate;
and/or the pH value of the precipitation solution is 9-11.
9. The method according to claim 7 or 8, further comprising the steps of filtering, drying in a water bath, and calcining the precipitate; the temperature of the water bath drying is 60-100 ℃, and the time is 5-10 h;
and/or the calcining temperature is 400-600 ℃, the heating rate is 5 ℃/min, and the calcining time is 3-7 h.
10. Use of a catalyst according to any one of claims 1 to 6 or a method according to any one of claims 7 to 9 in industrial wastewater treatment;
preferably, the industrial wastewater comprises polycyclic aromatic hydrocarbon compounds, unsaturated aldehyde ketones, amide compounds, nitrogen-containing heterocyclic compounds, phenolic compounds, organic carboxylic acid compounds, halogenated benzene and other benzene series except the halogenated benzene;
and/or the pH value of the industrial wastewater is 6-8, and the COD iscrThe value is 100-350 mg/L.
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| CN114289022A (en) * | 2021-12-14 | 2022-04-08 | 煤炭科学技术研究院有限公司 | Ozone catalytic oxidation catalyst and preparation method and application thereof |
| CN114289029A (en) * | 2021-12-14 | 2022-04-08 | 煤炭科学技术研究院有限公司 | Ozone catalytic oxidation composite catalyst and preparation method and application thereof |
| CN114308044A (en) * | 2021-12-14 | 2022-04-12 | 煤炭科学技术研究院有限公司 | Composite carrier catalyst and preparation method and application thereof |
| CN114308045A (en) * | 2021-12-14 | 2022-04-12 | 煤炭科学技术研究院有限公司 | Composite catalyst for coking wastewater treatment and preparation method thereof |
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