CN109876822B - Copper-manganese bimetallic ozone catalyst, preparation method and application thereof - Google Patents
Copper-manganese bimetallic ozone catalyst, preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a copper-manganese bimetallic ozone catalyst, a preparation method and application thereof in tricyclazole wastewater treatment. The catalyst is prepared by taking copper-containing porous silica gel as a carrier, loading a metal manganese oxide, soaking the copper-containing porous silica gel carrier in a manganese acetate solution, then carrying out ultrasonic soaking, and finally calcining at 400-500 ℃ for 550-600 min. The catalyst provided by the invention is applied to catalytic ozone oxidation degradation of tricyclazole, has good catalytic ozone oxidation effect and stable catalytic performance, can be repeatedly used, reduces the using amount of ozone, saves the treatment cost, realizes high-efficiency degradation of tricyclazole, and has a tricyclazole removal rate as high as 96%.
Description
Technical Field
The invention belongs to the technical field of advanced wastewater treatment, and relates to a copper-manganese bimetallic ozone catalyst, a preparation method and application thereof in tricyclazole wastewater treatment.
Technical Field
Tricyclazole (5-methyl-1, 2, 4-triazole- (3,4-b) -benzothiazole, Tricyclazole, TC), an N, S-heterocyclic compound, is mainly used for controlling rice blast caused by rice blast fungus, has toxicity, mutagenicity and carcinogenicity, and can be stably present in soil and water for a long time. It poses a great threat to the ecological environment and human health, since it is difficult to completely biodegrade in the environment. Since the high toxicity and the difficult degradability of tricyclazole, the low treatment cost, and the environmentally friendly biological wastewater treatment Technology are limited, and although the removal efficiency of tricyclazole can be improved by the bio-augmentation process of specific microorganisms, the removal time of tricyclazole of 100mg/L is as long as 102 hours (bioauthentication potential of a new isolated strain sp. njus t37for the treatment of the waste association high yield and recycling tertiary. biological Technology, 2018, No. 264, P98-105), more environmentally friendly Technology is required to treat tricyclazole wastewater.
At present, the treatment method of wastewater containing tricyclazole mainly focuses on an adsorption method and an extraction method, but the used adsorbent and the used extraction agent still need further treatment, and serious secondary pollution to the environment is easily caused. Advanced Oxidation Processes (AOPs) are widely used for treating wastewater containing various toxic and refractory pollutants because of their ability to non-selectively mineralize most organic substances into carbon dioxide, water and inorganic ions due to hydroxyl radicals (& OH) generated during the process, but have a problem of expensive treatment costs. ZHong et al studied TiO2-NTs/SnO2-Sb/PbO2The anode can degrade the tricyclazole electrochemically, and after electrochemical oxidation treatment, the acute toxicity of the tricyclazole can be reduced remarkably. However, the electricity consumption per ton of wastewater is higher than 250 kilowatts, and the economic cost is too high (Electrochemical classification of tricyclic in aqueous solution using Ti/SnO2-Sb/PbO2Journal of Electroanalytical Chemistry, 2013, 705, P68-74).
The catalytic ozonation technology is one of advanced oxidation technologies, and can rapidly oxidize organic matters which are difficult to biodegrade at normal temperature and normal pressure, even organic matters which are difficult to oxidize and degrade by ozone alone, so the catalytic ozonation technology is rapidly developed in recent years. The catalyst is an important factor influencing the catalytic ozonation efficiency, the carrier does not have catalytic activity generally, and a transition metal element is loaded on the carrier and is used as a proper catalyst for catalyzing ozonation, wherein the common transition metal element mainly comprises Fe, Cu, Ni, Al, Mn, Co and the like. Li et Al supported Cu-Mn bimetallic on gamma-Al2O3The catalytic ozonation degradation of acid scarlet shows that the catalytic effect of the copper-manganese bimetallic ozone catalyst is obviously superior to that of a single-metal ozone catalyst, the removal rate of the acid scarlet can reach 99%, and the copper-manganese bimetallic has obvious synergistic effect (Efficiency) in the aspect of catalyzing ozonation and kinetics of catalytic ozonation of Acid Red B over Cu-Mn/γ-Al2O3catalysts.Ozone:Science&Engineering, 2015, stage 37, P287-293). However, most of supported catalysts have the problems of small metal component loading, poor catalytic activity of the catalysts, easy loss of active components and the like, so that the supported catalysts have certain limitations in the aspect of advanced treatment of wastewater.
Disclosure of Invention
The invention aims to solve the problems of high cost, secondary pollution and the like in the existing treatment technology of wastewater containing tricyclazole and the defects of low catalytic activity and easy loss of active components of the existing ozone catalyst, and provides the application of the copper-manganese bimetallic ozone catalyst in the treatment of the wastewater containing tricyclazole, wherein the catalyst has high degradation efficiency on tricyclazole.
The technical scheme for realizing the purpose of the invention is as follows:
the copper-manganese bimetallic ozone catalyst takes copper-containing porous silica gel as a carrier and loads an active metal element Mn.
The invention also provides a preparation method of the copper-manganese bimetallic ozone catalyst, which comprises the following specific steps:
and soaking the copper-containing porous silica gel in a manganese acetate solution under mechanical stirring, then carrying out ultrasonic soaking, removing supernatant, washing with water, drying, and finally calcining at 400-500 ℃ for 550-600 min to obtain the copper-manganese bimetallic ozone catalyst.
Preferably, the rotating speed of the mechanical stirring is 500-700 r/min, and the dipping time is 30-40 min.
Preferably, the ultrasonic dipping temperature is 28-35 ℃, and the ultrasonic dipping time is 55-65 min.
Preferably, the drying temperature is 50-60 ℃, and the drying time is 90-120 min.
Further, the invention provides an application of the copper-manganese bimetallic ozone catalyst in the treatment of tricyclazole wastewater, which comprises the following specific steps:
adding a copper-manganese bimetallic ozone catalyst into the tricyclazole wastewater, adjusting the initial pH to 6.0-9.0, adding ozone at room temperature, realizing solid-liquid-gas three-phase mixing, and carrying out catalytic reaction; the copper-manganese bimetallic ozone catalyst is a catalyst which takes copper-containing porous silica gel as a carrier and loads an active metal element Mn.
Preferably, the adding amount of the copper-manganese bimetallic ozone catalyst is 7-13 g/L, and the adding amount of ozone is 5-20 mg/L.
Preferably, the initial pH is 7.0.
Preferably, the catalytic reaction time is 50-60 min.
Compared with the prior art, the invention has the following advantages:
(1) the metal-loaded ozone catalyst prepared by the invention has good catalytic ozone oxidation effect, stable catalytic performance and reusability, reduces the usage amount of ozone and saves the treatment cost;
(2) the treatment method for degrading tricyclazole in water by catalytic ozonation realizes high-efficiency degradation of tricyclazole, the removal rate of tricyclazole is up to 96%, the treatment cost is greatly reduced compared with that of electrochemical ozonation degradation of tricyclazole, and secondary pollution is avoided.
Drawings
FIG. 1 is a scanning electron microscope image and an element distribution diagram before and after loading of a Cu-Mn bimetallic ozone catalyst (a. a catalyst carrier before loading; b. a catalyst obtained after loading; c.Cu element distribution; d.Mn element distribution; e.O element distribution; f.Si element distribution).
FIG. 2 is a graph showing the removal of tricyclazole by catalytic ozonation under different conditions in example 1 (a.O)3Adding amount; b. an initial pH value; c. adding amount of catalyst; d. the removal rate of tricyclazole by different systems).
FIG. 3 is a graph showing the stability of the Cu-Mn bimetallic ozone catalyst prepared in example 1.
FIG. 4 is a graph of tricyclazole and TOC removal in a continuous flow system under different conditions as in example 2 (a. HRT; b. catalyst dosage; c.O3The amount of addition).
Detailed Description
The present invention is further described with reference to the following specific examples and accompanying drawings, but should not be construed as limiting the scope of the invention. Any insubstantial modifications or adaptations of the invention from the foregoing disclosure by those skilled in the art are intended to be covered by the present invention.
The copper-containing porous silica gel adopted in the embodiment of the invention is purchased from Jiangxi Jiujiang Huaxiong chemical industry Co., Ltd, and the pore volume of the carrier is 0.8cm3Per g, specific surface area 478cm2/g。
Example 1
The preparation method of the copper-manganese bimetallic ozone catalyst comprises the following specific steps:
(1) weighing 6.97g of manganese acetate, dissolving in 400mL of deionized water, and fully mixing and stirring to obtain a steeping fluid;
(2) soaking a catalyst carrier in the soaking solution obtained in the step (1) for 30min under mechanical stirring at the rotating speed of 500r/min, and then performing ultrasonic soaking for 60min at the temperature of 30 ℃;
(3) after the impregnation is finished, removing redundant solution, washing for 2-3 times by using deionized water, and then putting into a constant-temperature drying oven at 55 ℃ for drying for 120 min;
(4) after cooling, the mixture is put into a tubular furnace for calcination. After calcination is finished at 450 ℃ for 600min, the temperature of the tubular furnace is reduced to room temperature by adopting a natural cooling mode, and the prepared catalyst is taken out of the tubular furnace.
The prepared catalyst can obtain 3.7 percent of manganese element load capacity through the detection of an inductively coupled plasma optical emission spectrometer, and is a common commercially available carrier gamma-Al2O33 times of the loading amount of the manganese element. FIGS. 1(a-f) are scanning electron micrographs of the prepared catalyst showing SEM images of the catalyst before and after loading. The shapes before and after loading are regular small spherical particles, and no obvious difference exists. The elemental distribution diagrams of fig. 1(c-d) show that on the surface of the carrier, manganese, which is an active metal element supported thereon by a dip-calcination method, and copper, which is a copper metal element mixed in the catalyst carrier itself during the preparation process, are present in the catalyst. As can be seen from fig. 1(d), the Mn element is well distributed on the surface of the support.
In the embodiment, a sequencing batch reactor is adopted, pure oxygen passes through an ozone generator to generate ozone gas, the ozone concentration is detected by a concentration detector connected behind the ozone generator, air begins to enter the reactor after the index of the concentration detector of the ozone generator is stable under the set concentration, an aeration head is arranged at the tail end of an air inlet pipe, and ozone in tail gas is absorbed by a KI solution connected with the tail end. The influence of different ozone adding amounts, catalyst adding amounts, pH values and other operation conditions on the treatment effect is researched, and meanwhile, the efficiency of degrading tricyclazole by different ozone systems is compared. The initial concentration of the solution is 100mg/L, the running time of each group of experiments is 60min, samples are taken at intervals of 5min, the sampling amount is 5mL, and the concentration of the tricyclazole is determined on the water sample obtained each time.
FIG. 2(a-d) shows the removal rate of tricyclazole by Cu-Mn bimetallic catalytic ozonation, from which the optimal reaction conditions of batch experiments are initial pH 7.0, catalyst dosage 13g/L, and ozone dosage 15mg/L, the removal rate of tricyclazole can reach 96 percent after the reaction is carried out for 60min under the optimal reaction condition, by comparing the removal rates of different systems in fig. 2(d), it can be seen that the reaction in the single ozone oxidation degradation tricyclazole system is carried out for 60min, the removal rate of tricyclazole is only 66%, the removal rate of tricyclazole in the single metal catalyst catalytic ozone oxidation degradation tricyclazole system is only 70%, and the addition of a free radical scavenger tert-butyl alcohol (TBA) into the system can show that the copper-manganese bimetallic catalyst has obvious synergistic effect on catalyzing the ozone oxidation process. Fig. 3 shows the stability of the copper-manganese bimetallic ozone catalyst, and after 5 times of repeated experiments on the same catalyst, the removal rate of tricyclazole can be basically maintained above 90%, and the removal rate of TOC can be maintained above 70%.
Example 2
In the embodiment, a simulated fluidized bed reactor is constructed, the method is applied to the treatment process of the wastewater generated by the catalytic oxidation and degradation of tricyclazole by continuous flow ozone, and from the viewpoint of an optimization process, the optimal working condition parameters are determined and applied to engineering practice by observing the removal rate of tricyclazole in the effluent of the system.
The preparation method of the copper-manganese bimetallic ozone catalyst used in this example is the same as that of example 1.
This example uses a simulated fluidized bed continuous flow reaction. The fluidized bed is initially filled with catalyst particles with a certain mass, and a liquid phase enters the reactor through a water inlet at the upper end under the action of a peristaltic pump; the pure oxygen generates ozone gas through an ozone generator, the concentration of the ozone can be adjusted and changed through a concentration adjusting knob, the concentration of the ozone is detected by a concentration detector connected behind the ozone generator, and after the index of the concentration detector of the ozone generator is stable under the set concentration, the pure oxygen penetrates through a gas distribution plate (a porous titanium foam plate) through a gas inlet at the lower end of the reactor to enter the reactor; the sampling port is designed at the lower end of the reactor. The gas phase and the liquid phase enter the reaction zone from opposite directions to contact with the catalyst, the catalyst particles are in a flowing state in the reactor under the stirring of the ozone gas, and the gas phase, the liquid phase and the solid phase are fully connected in the reactor to trigger catalytic ozone oxidation degradation reaction. The top end of the reactor is provided with a tail gas discharge port, and ozone in the tail gas is absorbed by the KI solution connected with the tail end.
The concentration of the intake tricyclazole is 100mg/L, each group of experiments continuously run for 6h, the sampling amount of a water outlet is 5mL, and the concentration of the tricyclazole is measured on the obtained water sample. The influence of the running conditions such as Hydraulic Retention Time (HRT), ozone adding amount, catalyst adding amount and the like on the treatment effect of the tricyclazole is observed. Fig. 4(a-c) shows the removal of tricyclazole from effluent of the continuous flow system in this example, it can be seen that the optimal working condition of the continuous flow system is initial pH 7.0, catalyst dosage is 16g/L, ozone dosage is 20mg/L, and hydraulic retention time is 2.5h, under the optimal working condition, the removal rate of tricyclazole from effluent can be substantially maintained at about 93.09%, and the removal rate of TOC can reach 77.31% after the system is stabilized.
The copper-manganese bimetallic ozone catalyst is prepared by an isometric impregnation method, and the preparation method is easy to operate and environment-friendly. The catalyst is used for catalyzing the treatment of oxidizing and degrading the tricyclazole by ozone, fully embodies the high catalytic activity and excellent stability of the catalyst, and has obvious effect on degrading the tricyclazole in the wastewater.
Claims (6)
1. The application of the copper-manganese bimetallic ozone catalyst in the treatment of tricyclazole wastewater is characterized by comprising the following specific steps:
adding a copper-manganese bimetallic ozone catalyst into tricyclazole wastewater, adjusting the initial pH to 6.0-9.0, adding ozone at room temperature to realize solid-liquid-gas three-phase mixing, and carrying out catalytic reaction, wherein the adding amount of the copper-manganese bimetallic ozone catalyst is 7-13 g/L, and the adding amount of the ozone is 5-20 mg/L; the copper-manganese bimetallic ozone catalyst is a catalyst which takes copper-containing porous silica gel as a carrier and loads an active metal element Mn, and is prepared by the following steps: and soaking the copper-containing porous silica gel in a manganese acetate solution under mechanical stirring, then carrying out ultrasonic soaking, removing supernatant, washing with water, drying, and finally calcining at 400-500 ℃ for 550-600 min to obtain the copper-manganese bimetallic ozone catalyst.
2. The use according to claim 1, wherein the rotation speed of the mechanical stirring is 500 to 700r/min, and the dipping time is 30 to 40 min.
3. The application of claim 1, wherein the ultrasonic dipping temperature is 28-35 ℃ and the ultrasonic dipping time is 55-65 min.
4. The use according to claim 1, wherein the drying temperature is 50-60 ℃ and the drying time is 90-120 min.
5. Use according to claim 1, wherein the initial pH is 7.0.
6. The use of claim 1, wherein the catalytic reaction time is 50-60 min.
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| CN110152639B (en) * | 2019-06-19 | 2022-11-04 | 渤海大学 | Preparation method of modified alumina carrier, preparation method and application of supported bimetallic oxide catalyst |
| CN111977776B (en) * | 2020-08-28 | 2023-01-24 | 吉林大学 | Catalytic ozonation-based pretreatment method for acidic wastewater containing difficultly-degradable water-soluble polymers |
| CN112354543A (en) * | 2020-11-13 | 2021-02-12 | 浙江工业大学 | Adsorption-catalysis ozonization catalyst and preparation method and application thereof |
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