CN115999547A - Preparation method and application of supported bi-component metal oxide catalytic ozonation catalyst - Google Patents
Preparation method and application of supported bi-component metal oxide catalytic ozonation catalyst Download PDFInfo
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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Abstract
The invention belongs to the technical field of catalyst preparation, and particularly relates to a preparation method and application of a supported bi-component metal oxide catalytic ozonation catalyst. The preparation method of the supported bi-component metal oxide catalytic ozonation catalyst specifically comprises the following steps: activating the catalyst carrier, dipping, drying and calcining to obtain the supported bi-component metal oxide catalytic ozonation catalyst. The invention adopts the supported copper-cobalt bi-component metal oxide catalyst to catalyze the ozone oxidation to cooperatively degrade the antibiotics and the ammonia nitrogen, and under the same condition, the degradation efficiency of the antibiotics is higher than that of the antibiotics which singly use ozone or use unsupported gamma-Al 2 O 3 Ball with ball shapeThe method is obviously accelerated, is also greatly improved compared with the method using a single-component catalyst loaded with manganese or cerium, and can be used for synergistically degrading ammonia nitrogen generated by oxidation of antibiotics and ammonia nitrogen originally existing in wastewater, so that the method has higher selectivity and catalytic activity.
Description
Technical Field
The invention belongs to the technical field of catalyst preparation, and particularly relates to a preparation method and application of a supported bi-component metal oxide catalytic ozonation catalyst.
Background
Due to the imperfect use and management of antibiotics, 30% -90% of antibiotic precursors and metabolites thereof can finally enter the culture wastewater or the surrounding water body along with animal feces and urine. The long-term accumulation of antibiotics in water can lead to the emergence of microbial resistance and resistance genes in water or soil, constituting a potential health risk to the environment and human health. Ammonia nitrogen is also a common pollutant in aquaculture water, and many nitrogen-containing antibiotics also produce ammonia nitrogen during the treatment process. At present, the treatment methods for antibiotics in aquaculture wastewater mainly comprise physical methods such as coagulating sedimentation and activated carbon adsorption, chemical treatment methods such as Fenton oxidation, photocatalytic oxidation, electrochemical oxidation and the like, and biological methods such as aerobic/anaerobic microbial decomposition; ammonia nitrogen is mainly removed by microorganisms. However, the methods have limitations, such as low removal rate of soluble substances and low recycling rate of activated carbon; the traditional Fenton oxidation has high cost, and iron sludge can be generated in the degradation process, so that secondary pollution is caused; the high-salinity environment is unfavorable for the growth of microorganisms, and the phenomenon of microbial poisoning and the like can occur.
Ozone is used as a strong oxidant, most of organic matters in wastewater can be rapidly oxidized and decomposed during reaction, and the wastewater can be automatically decomposed in a short time without secondary pollution, but the application of the ozone in the field of water treatment is limited due to the defects of low solubility in water, low utilization rate, high energy consumption, high cost, incomplete oxidation of the organic matters and the like. The catalytic ozonation technology is based on the characteristic that the catalyst is easy to generate active oxygen species such as hydroxyl free radicals (OH) under the condition of ozone excitation, and the nature is that the catalyst is used for promoting the generation of the active oxygen species, so that the catalyst is free of organic matters which have high selective and rapid oxidative decomposition stability and are difficult to degrade, and the aim of efficiently degrading the organic matters in the wastewater is fulfilled. The core of the catalytic ozonation technology is the preparation of a catalytic ozonation catalyst, generally, alumina, activated carbon and the like are selected as carriers, and metal oxides are loaded on the surfaces of the carriers to prepare the heterogeneous catalytic ozonation catalyst.
Many metal oxides (e.g. MnO 2 、Co 3 O 4 CuO, mgO, etc.) can be used as an ozone oxidation catalyst to accelerate the decomposition of organic pollutants. The bimetallic oxide catalyst can cooperatively exert respective advantages to realize synergistic degradation, such as Mn-Ce, mn-Cu, fe-Co and the like, and can improve the catalytic activity and improve the stability of materials by increasing the density of surface reaction sites, introducing mixed valence transition metals, cooperatively coupling oxidation-reduction of different metals and the like. However, most of the currently combined metal components are used for degrading organic matters alone, and few of the currently combined metal components are used for synergistically degrading the organic matters and ammonia nitrogen. Meanwhile, no related research report on the use of the copper-cobalt composite catalyst for the synergistic degradation of antibiotics and ammonia nitrogen in aquaculture wastewater exists at present.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a preparation method and application of a supported bi-component metal oxide catalytic ozonation catalyst by using gamma-Al 2 O 3 As a carrier, in gamma-Al 2 O 3 The oxides of Cu and Co are loaded simultaneously, so that the efficiency of electron transfer on the surface of the catalyst is improved, ammonia nitrogen is selectively adsorbed and converted, and the catalyst has higher activity of synergistically degrading antibiotics and ammonia nitrogen.
In order to achieve the above object, one of the technical solutions of the present invention is: the preparation method of the supported bi-component metal oxide catalytic ozonation catalyst adopts an impregnation method, and specifically comprises the following steps:
(1) Activating the catalyst carrier: gamma-Al 2 O 3 Washing the pellets, soaking in 0.08-0.12mol/L HCl solution, activating for 10-14h, repeatedly washing to pH 6.8-7.2, and oven drying at 60-100deg.C to obtain activated gamma-Al 2 O 3 Pellets as catalyst carriers;
(2) Dipping and drying: separately preparing Cu (NO) 3 ) 2 · 3 H 2 O and Co (CH) 3 COO) 2 · 4 H 2 O aqueous solution, mixing to obtain impregnating solution, and activating the gamma-Al in the step (1) 2 O 3 Soaking the pellets in the soaking solution, and shaking and vibrating for 1-3 hours at the rotating speed of 130-170 rpm; then filtering and washing with ultrapure water, and then drying at 90-120 ℃ for 1-3h;
(3) Calcining: calcining the product immersed and dried in the step (2) at a high temperature of 300-700 ℃ for 2-6h
Obtaining the supported bi-component metal oxide catalytic ozonation catalyst.
The supported copper cobalt oxide catalytic ozonation catalyst prepared by the invention is light blue pellets.
In a preferred embodiment of the present invention, the Cu (NO) selected in the step (2) 3 ) 2 ·3H 2 O is analytically pure blue crystal, contains 3 crystal water, and the content is not less than 99.0%; selected Co (CH) 3 COO) 2 ·4H 2 O is analytically pure pink crystals, contains 4 crystal water, and has a content of not less than 99.5%.
In a preferred embodiment of the present invention, cu (NO 3 ) 2 ·3H 2 O aqueous solution and Co (CH) 3 COO) 2 ·4H 2 The concentration ratio of the O aqueous solution is 5-0.2:1, co (CH) 3 COO) 2 ·4H 2 The concentration of the O aqueous solution is 0.15-0.5mol/L.
In a preferred embodiment of the present invention, cu and Co in the impregnation liquid in the step (2) and the activated gamma-Al 2 O 3 The mass ratio of the pellets is 0.1-0.4.
γ-Al 2 O 3 The diameter of the small ball is 3-10mm.
In a preferred embodiment of the present invention, the catalyst calcination temperature in the step (3) is 400-600 ℃ and the calcination time is 2-4 hours, so as to obtain the supported bi-component metal oxide catalytic ozonation catalyst.
In a preferred embodiment of the present invention, the calcination temperature in the step (3) is 500 ℃ and the calcination time is 2 hours.
In order to achieve the purpose, the second technical scheme of the invention is a supported bi-component metal oxide catalytic ozonation catalyst.
In order to achieve the purpose, the third technical scheme of the invention is the application of the supported bi-component metal oxide catalytic ozonation catalyst in degrading typical antibiotics and ammonia nitrogen concentration in aquaculture wastewater.
In a preferred embodiment of the invention, the specific method of application comprises adding 80-120mg/L (CuO and Co as effective components) to a water sample containing antibiotics and ammonia nitrogen 2 O 3 The mass concentration is 1.8-2.2 mg/L), the catalytic ozonation is carried out under the conditions that the pH value of the reaction solution is 7.5-8.5 and the ozone addition amount is 15-20mg/L, and the reaction time is 20-40 min.
CuO can provide oxygen vacancies as electron-rich active sites, and electrons generated when the valence states of Cu (ii)/Cu (i) are transferred to each other contribute to the decomposition of ozone adsorbed on the catalyst surface into various active oxygen species. Co (Co) 3 O 4 Is a catalyst with good catalytic performance, and can be prepared by Co 2+ And Co 3+ Electron transfer to obtain stronger O 3 Adsorption capacity, and further promotes the progress of catalytic ozonation reaction; and Co is 3 O 4 For the conversion of ammonia nitrogen to N 2 Has higher selectivity. When in gamma-Al 2 O 3 When the oxides of the Cu and Co are loaded simultaneously, not only can the electron transfer efficiency of the surface of the catalyst be improved, but also the selective adsorption conversion ammonia nitrogen of the catalyst can be improved, and the synergistic effect ensures that the copper-cobalt composite catalyst has higher activity of selectively catalyzing and degrading antibiotics and ammonia nitrogen.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention adopts the copper-cobalt-loaded bi-component metal oxide catalyst to catalyze the ozone oxidation to cooperatively degrade the antibiotics and the ammonia nitrogen, and under the same condition, the degradation efficiency of the antibiotics and the ammonia nitrogen is higher than that of the antibiotics and the ammonia nitrogen which are singly used or usedUnsupported gamma-Al 2 O 3 The pellets are obviously accelerated, and are also greatly improved compared with the single-component catalyst with manganese or cerium loading, and have higher catalytic activity.
2. The catalyst prepared by the invention adopts gamma-Al produced industrially 2 O 3 The pellets are used as carriers, the raw materials are wide, the preparation process is simple and safe, the preparation cost is low, and the method is suitable for large-scale industrial production.
3. The catalyst prepared by the invention has better mechanical strength and stability, can be reused, and can still keep better catalytic effect after being used for multiple times.
Drawings
FIG. 1 is a graph showing the differences in the degradation effects of ozonation alone and catalytic ozonation;
FIG. 2 is a graph showing the difference in degradation effect of catalysts prepared with different Cu/Co molar concentrations of the impregnation solutions in example 2;
FIG. 3 is a graph showing the difference in degradation effect of catalysts prepared at different calcination temperatures in example 3;
FIG. 4 is a graph showing the difference in degradation effect of catalysts prepared at different calcination times in example 4;
FIG. 5 is gamma-Al 2 O 3 Blank carrier and Cu-Co/gamma-Al 2 O 3 XRD patterns of the catalyst;
FIG. 6 is a Cu-Co/gamma-Al 2 O 3 XPS broad spectrum of catalyst.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in more detail with reference to the accompanying drawings and specific embodiments, but the scope of the present invention is not limited to these embodiments.
The preparation method of the supported bi-component metal oxide catalytic ozonation catalyst specifically comprises the following steps:
(1) Activating the catalyst carrier: gamma-Al 2 O 3 Washing the pellets, soaking in 0.08-0.12mol/L HCl solution, activating for 10-14h, washing to pH 6.8-7.2, and oven drying at 60-100deg.C to obtain activated gamma-Al 2 O 3 Pellets as catalyst carriers;
(2) Dipping and drying: separately preparing Cu (NO) 3 ) 2 · 3 H 2 O and Co (CH) 3 COO) 2 · 4 H 2 O aqueous solution, mixing to obtain impregnating solution, and activating the gamma-Al in the step (1) 2 O 3 Soaking the pellets in the soaking solution, and shaking and vibrating for 1-3 hours at the rotating speed of 130-170 rpm; then filtering and washing, and then drying at 90-120 ℃ for 1-3 hours;
(3) Calcining: and (3) calcining the dipped and dried product in the step (2) at a high temperature of 300-700 ℃ for 2-6 hours to obtain the supported bi-component metal oxide catalytic ozonation catalyst.
The Cu (NO) selected in the step (2) 3 ) 2 ·3H 2 O is analytically pure blue crystal, the content is not less than 99.0%, and Co (CH) 3 COO) 2 ·4H 2 O is analytically pure pink crystals, the content is not less than 99.5%.
Cu (NO) in the step (2) 3 ) 2 ·3H 2 O aqueous solution and Co (CH) 3 COO) 2 ·4H 2 The concentration ratio of the O aqueous solution is 5-0.2:1, co (CH) 3 COO) 2 ·4H 2 The concentration of the O aqueous solution is 0.15-0.5mol/L.
The calcining temperature in the step (3) is 400-600 ℃, and the calcining time is 2-4h.
The calcination temperature in the step (3) is 500 ℃, and the calcination time is 2 hours.
A supported bi-component metal oxide catalytic ozonation catalyst.
The application of a supported bi-component metal oxide catalytic ozonation catalyst in degrading typical antibiotics and ammonia nitrogen concentrations in aquaculture wastewater.
The specific method of the application comprises the steps of adding 80-120mg/L (the effective components CuO and Co) into a water sample containing antibiotics and ammonia nitrogen 2 O 3 1.8-2.2 mg/L) supported bi-component metal oxide catalytic ozonation catalyst, wherein the pH value of the reaction solution is 7.5-8.5 and the ozone adding amount is 15-Catalytic oxidation is carried out under the condition of 20mg/L, and the reaction time is 20-40 min.
Example 1
A Cu-Co bi-component supported catalyst is prepared by the following method:
50g of gamma-Al with a diameter of 5mm are taken 2 O 3 Washing the pellets with ultrapure water to obtain sufficient washing, soaking in 0.1mol/L HCl solution for activation for 12h, repeatedly washing with ultrapure water to pH=7.0, and oven drying at 80deg.C in a forced air drying oven to obtain activated gamma-Al 2 O 3 Pellets as catalyst carriers;
cu (NO) was prepared at a molar concentration of 0.1mol/L 3 ) 2 *3H 2 O aqueous solution and Co (CH) 3 COO) 2 *4H 2 Mixing 250ml of O aqueous solution to obtain soaking solution, slowly adding the above activated gamma-Al 2 O 3 The pellets are fully shaken on a shaking table to shake for 2 hours, and then the gamma-Al is taken out 2 O 3 The pellets are dried for 2 hours in a blast drying oven at 105 ℃, are put in a muffle furnace for calcination at 500 ℃ for 2 hours, and the Cu-Co bi-component supported catalyst Cu-Co/gamma-Al is prepared 2 O 3 。
250ml of Cu (NO) at 0.1mol/L was taken separately 3 ) 2 *3H 2 O aqueous solution and 0.1mol/L Co (CH) 3 COO) 2 *4H 2 O is an impregnating solution, and then the Cu single-component supported catalyst Cu/gamma-Al is prepared by adopting the preparation method of the Cu-Co double-component supported catalyst 2 O 3 And Co single-component supported catalyst Co/gamma-Al 2 O 3 。
The performance of the catalyst was evaluated by catalytic ozone degradation experiments: 100mL of solution containing three antibiotics (ciprofloxacin, tetracycline and sulfamethoxazole respectively) and ammonia nitrogen is taken as simulated wastewater, the initial concentration of the three antibiotics is 100umol/L, the initial concentration of the ammonia nitrogen is 2mg/L, and NaOH is added dropwise to control the initial pH of the simulated wastewater to be about 8.0. The catalytic ozone degradation experiment is carried out in an organic glass reactor, the volume of the reactor is 0.5L, ozone is provided by an oxygen source ozone generator, the ozone enters the reactor from the top of the reactor through an aeration head and is mixed with wastewater, the reaction temperature is 25 ℃, and the adding amount of the catalyst is 10g; after 60min of reaction, quench with 1ml of 80g/L sodium thiosulfate solution was used to terminate the reaction, and then the catalytic ozonation reaction was examined for degradation of the three antibiotics and ammonia nitrogen.
The experimental results are shown in figure 1 comparing the differences between ozone alone and catalytic ozone while degrading antibiotics and ammonia nitrogen. It can be seen that the degradation rate of the single ozonization for three specific antibiotics and ammonia nitrogen is only 20% -40%, and the degradation rate of the single ozonization for three specific antibiotics and ammonia nitrogen is only 20% -40% of that of Cu/gamma-Al 2 O 3 The degradation rate of the single-component supported catalyst to three specific antibiotics is close to or reaches 50%, the degradation rate to ammonia nitrogen is close to 70%, and Co/gamma-Al is as high as that of the single-component supported catalyst 2 O 3 The degradation rate of the single-component supported catalyst to three specific antibiotics reaches or exceeds 50 percent, and the degradation rate to ammonia nitrogen is 65 percent, particularly the Cu-Co/gamma-Al is outstanding 2 O 3 The degradation rate of the supported bi-component metal oxide catalyst for three specific antibiotics can reach more than 95 percent, and the degradation rate for ammonia nitrogen is 75.7 percent.
Example 2
The preparation method of the Cu-Co bi-component supported catalyst is the same as that of example 1, and the difference from example 1 is that: the molar concentration ratio of Cu/Co in the impregnating solution is 5:1, 2:1, 1:1, 1:2 and 1:5 respectively. Wherein Co (CH) 3 COO) 2 *4H 2 The concentration of the O aqueous solution is 0.1mol/L, cu (NO) 3 ) 2 *3H 2 The concentrations of the O solutions were 0.02, 0.05, 0.1, 0.2 and 0.5mol/L, respectively.
The steps of the catalytic ozone degradation experiment are the same as those of example 1, the experimental results are shown in fig. 2, and as the molar concentration ratio of Cu and Co in the impregnating solution is gradually reduced, the degradation rates of antibiotics and ammonia nitrogen are firstly increased and then decreased, and the maximum value appears when the molar concentration ratio of the antibiotics and the ammonia nitrogen is 1:1.
Example 3
The preparation method of the Cu-Co bi-component supported catalyst is the same as that of example 1, and the difference from example 1 is that: the calcination temperature was 300 ℃, 400 ℃, 500 ℃, 600 ℃, 700 ℃, respectively.
The procedure for the catalytic ozone degradation experiment was the same as in example 1. The experimental results are shown in fig. 3, and it can be seen from fig. 3 that when the calcination temperature is 500 ℃, the catalytic ozone degradation of three specific antibiotics (ciprofloxacin, tetracycline and sulfamethoxazole respectively) achieves the best effect, and the degradation rates are 92.5%, 94.7% and 90.3% respectively.
Example 4
The preparation method of the Cu-Co bi-component supported catalyst is the same as that of example 1, and the difference from example 1 is that: the calcination time was 2h, 3h, 4h, 5h, 6h, respectively.
The procedure for the catalytic ozone degradation experiment was the same as in example 1. As shown in fig. 4, it can be seen from fig. 4 that the degradation rates for three specific antibiotics decreased slightly and then increased with increasing calcination time, and that the best results were obtained with calcination time of 2 hours, with degradation rates of 83.1%, 93.0% and 85.5%, respectively. At this time, the degradation rate of ammonia nitrogen reaches 70.3%.
The above embodiments are merely preferred embodiments of the present invention to illustrate the principles and the effects of the present invention, and are not intended to limit the invention. It should be noted that modifications to the above-described embodiments may be made by one skilled in the art without departing from the spirit and scope of the invention, and such modifications should also be considered as being within the scope of the invention.
Claims (10)
1. The preparation method of the supported bi-component metal oxide catalytic ozonation catalyst is characterized by comprising the following steps of:
(1) Activating the catalyst carrier: gamma-Al 2 O 3 Washing the pellets, soaking in HCl solution for activation for 10-14h, repeatedly washing to pH 6.8-7.2, and oven drying at 60-100deg.C to obtain activated gamma-Al 2 O 3 Pellets as catalyst carriers;
(2) Dipping and drying: separately preparing Cu (NO) 3 ) 2 · 3 H 2 O and Co (CH) 3 COO) 2 · 4 H 2 O aqueous solution, mixing to obtain impregnating solution, and activating the gamma-Al in the step (1) 2 O 3 Ball dippingSoaking in the soaking solution, and shaking for 1-3 hr at 130-170 rpm; then filtering and washing with ultrapure water, and then drying at 90-120 ℃ for 1-3h;
(3) Calcining: and (3) calcining the dipped and dried product in the step (2) at a high temperature of 300-700 ℃ for 2-6 hours to obtain the supported bi-component metal oxide catalytic ozonation catalyst.
2. The process according to claim 1, wherein the concentration of the HCl solution in step (1) is 0.08-0.12mol/L.
3. The method according to claim 1, wherein Cu (NO 3 ) 2 ·3H 2 O is analytically pure blue crystal, the content is not less than 99.0%, and Co (CH) 3 COO) 2 ·4H 2 O is analytically pure pink crystals, the content is not less than 99.5%.
4. The method according to claim 1, wherein Cu (NO 3 ) 2 ·3H 2 O aqueous solution and Co (CH) 3 COO) 2 ·4H 2 The concentration ratio of the O aqueous solution is 5-0.2:1, co (CH) 3 COO) 2 ·4H 2 The concentration of the O aqueous solution is 0.15-0.5mol/L.
5. The process according to claim 1, wherein Cu and Co in the impregnation liquid in the step (2) are mixed with the activated gamma-Al 2 O 3 The mass ratio of the pellets is 0.1-0.4.
6. The method according to claim 1, wherein the calcination temperature in the step (3) is 400 to 600 ℃ and the calcination time is 2 to 4 hours.
7. The method according to claim 1, wherein the calcination temperature in the step (3) is 500℃and the calcination time is 2 hours.
8. A supported two-component metal oxide catalyzed ozone oxidation catalyst made by the method of any one of claims 1-7.
9. Use of the supported bi-component metal oxide catalyzed ozonation catalyst of claim 8 to degrade typical antibiotic and ammonia nitrogen concentrations in aquaculture wastewater.
10. The use according to claim 9, comprising adding 80-120mg/L of the supported bi-component metal oxide catalytic ozonation catalyst to a water sample containing antibiotics and ammonia nitrogen, and performing catalytic oxidation under the conditions that the pH of the reaction solution is 7.5-8.5 and the ozone addition amount is 15-20mg/L, wherein the reaction time is 20-40 min.
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