CN115445605A - Application of aluminum-doped lanthanum-manganese perovskite catalyst - Google Patents
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Abstract
The invention provides an application of an aluminum-doped lanthanum manganese perovskite catalyst. The application comprises the following steps: in the presence of ozone, degrading organic pollutants by using the aluminum-doped lanthanum-manganese perovskite catalyst, wherein the molecular formula of the aluminum-doped lanthanum-manganese perovskite catalyst is LaAl 1‑x Mn x O 3 Wherein 0 is<x<1. The molecular formula of the aluminum-doped lanthanum manganese perovskite catalyst is LaAl 1‑x Mn x O 3 Perovskite can be formed by B-site dopingMore surface oxygen vacancies are formed on the surface, and the oxygen vacancies can be used as an electron donor to react with ozone and water molecules to generate active free radicals, so that the degradation of organic pollutants is enhanced; the degradation efficiency of the lanthanum-manganese perovskite catalyst for removing organic pollutants can be effectively improved through B-site doping, the catalyst has a good degradation effect in a wide pH range, and the catalyst can be repeatedly used.
Description
Technical Field
The invention relates to the technical field of chemical industry, in particular to application of an aluminum-doped lanthanum-manganese perovskite catalyst.
Background
With the rapid development of national economy and the acceleration of industrialization process, environmental pollution is increasingly severe, and the development of a green pollution control technology with high efficiency, stability and low cost is urgent. Organic pollutants, such as 2, 4-dichlorophenoxyacetic acid (2, 4-D), are the first industrially selected highly effective organic herbicides in the world and have been one of the major herbicide species in the world due to their low use levels and low cost. Due to the benzene ring structure and the existence of chlorine atoms, the 2,4-D has stronger toxicity and carcinogenicity and is difficult to biodegrade. At present, advanced oxidation technology with outstanding characteristics of strong oxidizing property, high efficiency, environmental protection and the like has gradually become one of the most promising technologies for treating organic pollutants in the aspect of environmental remediation. Ozone is often used as an oxidizing agent to remove organic pollutants in wastewater due to its strong oxidizing property and environmental protection during use. However, ozone is not readily available in water due to its unstable and inefficient decomposition, and in addition, ozone is selective for the degradation of some organic pollutants, making it difficult to achieve efficient removal and mineralization of the pollutants.
The use of the catalyst provides a new idea for ozone oxidation. Among them, the heterogeneous catalyst has the advantages of high ozone utilization rate, good catalyst stability, easy recovery and reutilization, and no secondary pollution. The perovskite is a mineral with abundant sources and low price, and the structural general formula of the perovskite is ABO 3 Wherein A is typically a rare earth cation and B is typically a transition metal cation. In recent years, perovskite materials as heterogeneous catalysts have been developed in the field of research on advanced oxidative degradation of organic pollutants. At present, although the materials have better catalytic effect, the materials are heavily dependent on transition metal ions at the B site, and a large amount of elution of the transition metal ions can cause certain influence on the environment.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The present invention is directed to solving, at least in part, one of the technical problems in the related art. Therefore, the invention aims to provide the application of the aluminum-doped lanthanum-manganese perovskite catalyst, wherein the molecular formula of the aluminum-doped lanthanum-manganese perovskite catalyst is LaAl 1-x Mn x O 3 More surface oxygen vacancies can be formed on the surface of the perovskite by B-site doping, and the oxygen vacancies can be used as electron donors to react with ozone and water molecules to generate active free radicals, so that the degradation of organic pollutants is enhanced; the degradation efficiency of the lanthanum-manganese perovskite catalyst for removing organic pollutants can be effectively improved through B-site doping, the catalyst has a good degradation effect in a wide pH range, and the catalyst can be repeatedly used.
In one aspect of the present invention, the present invention provides an application of an aluminum-doped lanthanum manganese-based perovskite catalyst, which is characterized by comprising: in the presence of ozone, the aluminum-doped lanthanum-manganese perovskite catalyst is utilized to degrade organic pollutants,
the molecular formula of the aluminum-doped lanthanum-manganese perovskite catalyst is LaAl 1-x Mn x O 3 Wherein 0 is<x<1。
Further, the degradation of organic pollutants by using the aluminum-doped lanthanum manganese-based perovskite catalyst comprises the following steps:
placing the aluminum-doped lanthanum-manganese perovskite catalyst in sewage containing organic pollutants;
and introducing ozone into the sewage under the condition of stirring, and filtering 10mL of water sample at intervals to determine the concentration of the organic pollutants.
Further, the chemical oxygen demand is determined and/or the mineralization efficiency of the organic pollutants is calculated at the same time as the concentration of the organic pollutants is determined.
Further, the mass ratio of the aluminum-doped lanthanum-manganese perovskite catalyst to the volume ratio of the sewage is (0.04 g-0.16 g): 400mL.
Further, the initial pH value of the sewage is 4-9.
Further, the concentration of organic contaminants was determined by high performance liquid chromatography.
Further, the organic contaminants include 2,4-D.
Further, the introduction rate of the ozone is 1-5 mg/min.
Further, the preparation method of the aluminum-doped lanthanum manganese perovskite catalyst comprises the following steps:
dissolving lanthanum nitrate, aluminum nitrate and manganese nitrate in 20mL of water, then adding 6mmol of citric acid until the citric acid is dissolved, evaporating to dryness at 80 ℃ until gel is formed, drying the obtained product at 100 ℃ for 10-24 hours, taking out and grinding to obtain a powdery product;
and calcining the powdery product at 270 ℃ for 2-5 hours, and then calcining at 800 ℃ for 5-10 hours to obtain the aluminum-doped lanthanum manganese perovskite catalyst.
Furthermore, the molar ratio of manganese element to aluminum element in the aluminum-doped lanthanum-manganese perovskite catalyst is 1 (2-9).
Compared with the prior art, the invention can at least obtain the following beneficial effects:
according to the invention, the aluminum element which is rich in natural content, environment-friendly and stable in performance is selected as the B site element of the lanthanum-based perovskite, so that the stability and the reusability of the catalyst are improved, and the pollution to the environment caused by the dissolution of harmful excessive elements is reduced; according to the aluminum-doped lanthanum-manganese perovskite structure, the two atomic radiuses at the B site are close to each other, so that in-situ doping is easy to realize, meanwhile, due to the difference of the atomic radiuses and the valence states, a plurality of oxygen vacancy structures are formed on the surface of the doped perovskite, the decomposition of ozone and the formation of free radicals are facilitated, the degradation efficiency of the catalyst is improved, and the catalyst has a good degradation effect in a wide pH range.
Drawings
FIG. 1 is an XRD pattern of the aluminum doped lanthanum manganese perovskite catalysts of examples 1-3 and the catalysts of comparative examples 1-2;
FIG. 2 (a) is a graph of the degradation effect on 2,4-D for the aluminum-doped lanthanum-manganese-based perovskite catalysts of examples 1-3 and the catalysts of comparative examples 1-2 and no catalyst;
FIG. 2 (b) is the COD removal efficiency of the aluminum-doped lanthanum manganese-based perovskite catalysts of examples 1-3 and the catalysts of comparative examples 1-2 and no catalyst;
FIG. 3 (a) shows the effect of 2,4-D degradation at different catalyst loadings;
FIG. 3 (b) shows the removal efficiency of COD at different catalyst dosages;
a in FIG. 4 is the degradation effect of 2,4-D under different pH conditions;
b in FIG. 4 is the removal efficiency of COD under different pH conditions;
a and B in FIG. 5 are the catalyst LaAl of example 3 0.8 Mn 0.2 O 3 The reuse effect graph of (2).
Detailed Description
The following describes in detail embodiments of the present invention. The following examples are illustrative only and are not to be construed as limiting the invention. The examples do not specify particular techniques or conditions, and are performed according to techniques or conditions described in literature in the art or according to the product specification. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
In one aspect of the present invention, the present invention provides an application of an aluminum-doped lanthanum manganese-based perovskite catalyst, which is characterized by comprising: in the presence of ozone, the aluminum-doped lanthanum-manganese perovskite catalyst is utilized to degrade organic pollutants,
the molecular formula of the aluminum-doped lanthanum-manganese perovskite catalyst is LaAl 1-x Mn x O 3 Wherein 0 is<x<1。
According to the invention, the aluminum element which is rich in natural content, environment-friendly and stable in performance is selected as the B site element of the lanthanum-based perovskite, so that the stability and the reusability of the catalyst are improved, and the pollution to the environment caused by the dissolution of harmful excessive elements is reduced; according to the aluminum-doped lanthanum-manganese perovskite structure, the two atomic radiuses at the B site are close, so that in-situ doping is easy to realize, and meanwhile, due to the difference of the atomic radiuses and valence states, a structure with more oxygen vacancies is formed on the surface of the doped perovskite, so that the decomposition of ozone and the formation of free radicals are facilitated, the degradation efficiency of the catalyst is improved, and the catalyst has a good degradation effect in a wider pH range.
The design idea of the invention is as follows: the general formula of the perovskite structure is ABO 3 Wherein A is typically a rare earth cation and B is typically a transition metal cation. The inventors of the present application have found that perovskite materials can be substituted at both cation sites by other cations without changing the crystal structure. Substitution of the a-site or B-site of the perovskite can create structural defects (anion vacancies or cation vacancies). The formation of the surface structure defect of the material has important influence on the activity of the material in the field of catalysis, and the surface defect can be obtained by doping the A site or the B site of the perovskite so as to improve the reaction activity of the perovskite catalyst. The invention selects aluminum element with abundant and environment-friendly natural content as B-site element of lanthanum-based perovskite, and adopts a small amount of manganese element with better catalytic activity to LaAlO 3 The B site of (a) is partially substituted to improve catalytic ozonation performance.
In some embodiments of the invention, degrading organic contaminants with the aluminum-doped lanthanum manganese-based perovskite catalyst comprises: placing the aluminum-doped lanthanum-manganese perovskite catalyst in 400mL of sewage containing organic pollutants; and introducing ozone into the sewage under the condition of stirring, and filtering 10mL of water sample at intervals to determine the concentration of the organic pollutants. Therefore, the method for removing the organic pollutants is more efficient, economic and environment-friendly.
In some embodiments of the invention, the chemical oxygen demand is measured and/or the mineralization efficiency of the organic pollutants is calculated at the same time as the organic pollutant concentration.
In some embodiments of the invention, the ratio of the mass of the aluminum-doped lanthanum manganese-based perovskite catalyst to the volume of the wastewater is (0.04 g to 0.16 g): 400mL (for example, 0.04g.
In some embodiments of the invention, the initial pH of the wastewater is 4 to 9 (e.g., can be 4, 5, 6, 7, 8, or 9, etc.).
In some embodiments of the invention, the concentration of the organic contaminant is determined using high performance liquid chromatography.
In some embodiments of the invention, the organic contaminant comprises 2,4-D (2, 4-dichlorophenoxyacetic acid).
In some embodiments of the invention, the ozone is introduced at a rate of 1 to 5mg/min.
In some embodiments of the present invention, the step of degrading organic pollutants using the aluminum-doped lanthanum manganese-based perovskite catalyst comprises: under the condition of room temperature, preparing a simulated sewage solution by taking 2,4-D organic pesticide, adding a certain amount of the prepared aluminum-doped lanthanum-manganese perovskite catalyst into the sewage, and introducing ozone. And taking out a part of water sample from the reactor at regular intervals in the reaction process to detect the concentration of the residual pollutants in the solution.
In other embodiments of the present invention, the step of degrading organic pollutants using the aluminum-doped lanthanum manganese-based perovskite catalyst comprises: taking 400mL of simulated sewage containing 2,4-D and a certain amount of catalyst, stirring and introducing ozone, taking 10mL of water sample at intervals, filtering, determining the concentration of 2,4-D by adopting a high performance liquid chromatography, simultaneously determining Chemical Oxygen Demand (COD) and calculating the mineralization efficiency of pollutants.
In some embodiments of the invention, the method for preparing the aluminum-doped lanthanum manganese-based perovskite catalyst comprises: dissolving a certain amount of lanthanum nitrate, aluminum nitrate and manganese nitrate in water, adding a proper amount of citric acid until the lanthanum nitrate, the aluminum nitrate and the manganese nitrate are completely dissolved, curing the mixture into gel at a constant temperature, placing the gel in an oven at the constant temperature for 24 hours to remove water to form dry gel, taking out the dry gel and grinding the dry gel into powder, placing the powder in a tubular furnace, heating and calcining the powder, and naturally cooling the powder to the room temperature to obtain the aluminum-doped lanthanum-manganese perovskite catalyst. Therefore, the aluminum-doped lanthanum-manganese perovskite catalyst is synthesized by a sol-gel method, and the operation is simple and convenient.
In some embodiments of the present invention, the preparation method of the aluminum-doped lanthanum manganese-based perovskite catalyst comprises: dissolving lanthanum nitrate, aluminum nitrate and manganese nitrate in 20mL of water, then adding 6mmol of citric acid until the citric acid is dissolved, evaporating to dryness at 80 ℃ until gel is formed, drying the obtained product at 100 ℃ for 10-24 hours, taking out and grinding to obtain a powdery product; and calcining the powdery product at 270 ℃ for 2-5 hours, and then calcining at 800 ℃ for 5-10 hours to obtain the aluminum-doped lanthanum-manganese perovskite catalyst. Therefore, the preparation method for preparing the aluminum-doped lanthanum manganese perovskite catalyst by adopting the citric acid complexation method is simple, easy to operate and suitable for industrial production.
In some embodiments of the present invention, the molar ratio of the manganese element to the aluminum element in the aluminum-doped lanthanum-manganese-based perovskite catalyst is 1 (2 to 9) (for example, 1. It should be noted that the contents of manganese element and aluminum element in the aluminum-doped lanthanum manganese perovskite catalyst are measured by an ICPMS (atomic emission spectroscopy mass spectrometry) method, and the value X and the ratio of the two are calculated according to the measured contents.
The lanthanum-manganese perovskite is doped by aluminum element to synthesize LaAl with different manganese-aluminum ratios 1-x Mn x O 3 The perovskite catalyst realizes the improvement of the catalytic ozonization performance of the catalyst. Specific experiments show that the aluminum-doped lanthanum manganese perovskite catalyst can efficiently degrade common herbicide 2,4-D in water under the condition of ozone, and the removal rate of 2,4-D in 60min can reach 98%, wherein the removal rate of COD is up to 65%. Confirming that LaAl is present 1-x Mn x O 3 The perovskite has better ozonization capacity and mineralization capacity and can be used as an efficient ozone catalyst for the treatment of purified water.
For better understanding of the present invention, the following examples are given for further illustration of the present invention, but the present invention is not limited to the following examples.
Examples
Example 1
The preparation method of the aluminum-doped lanthanum-manganese perovskite catalyst comprises the following steps:
adding 3mmol of La (NO) 3 ) 3 ·6H 2 O，2.8mmol Al(NO 3 ) 3 ·9H 2 O，0.35mmol Mn(NO 3 ) 3 ·4H 2 Dissolving O in 30mL of water (ethanol: water = 3), adding 6mmol of citric acid until the mixture is dissolved, evaporating to dryness at 80 ℃ until the mixture is gelled, then drying at 100 ℃ for 24 hours, taking out the dried sample, grinding the dried sample into powder by using a mortar, finally putting the powder sample into a nitrogen-protected tubular furnace, calcining at 270 ℃ for 2h, and calcining at 800 ℃ for 5h to obtain the aluminum-doped lanthanum-manganese perovskite catalyst marked as LaAl 0.9 Mn 0.1 O 3 。
Example 2
The preparation method of the aluminum-doped lanthanum manganese perovskite catalyst comprises the following steps:
adding 3mmol of La (NO) 3 ) 3 ·6H 2 O，2.8mmol Al(NO 3 ) 3 ·9H 2 O，1.0mmol Mn(NO 3 ) 3 ·4H 2 Dissolving O in 30mL of water (ethanol: water = 3), adding 6mmol of citric acid until the citric acid is dissolved, evaporating to dryness at 80 ℃ until gel is formed, then drying at 100 ℃ for 10 hours, taking out the dried sample, grinding the sample into powder by using a mortar, finally putting the powder sample into a nitrogen-protected tubular furnace, calcining at 270 ℃ for 5hours, calcining at 800 ℃ for 10 hours to obtain the aluminum-doped lanthanum-manganese perovskite catalyst marked as LaAl 0.7 Mn 0.3 O 3 。
Example 3
The preparation method of the aluminum-doped lanthanum-manganese perovskite catalyst comprises the following steps:
adding 3mmol of La (NO) 3 ) 3 ·6H 2 O，2.8mmol Al(NO 3 ) 3 ·9H 2 O，0.7mmol Mn(NO 3 ) 3 ·4H 2 Dissolving O in 30mL of water (ethanol: water = 3), adding 6mmol of citric acid until dissolving, evaporating to dryness at 80 ℃ until gel is formed, then drying for 15h at 100 ℃, taking out the dried sample, grinding the sample into powder by using a mortar, finally putting the powder sample into a nitrogen-protected tubular furnace, calcining for 5h at 270 ℃, calcining for 10h at 800 ℃ to obtain the aluminum-doped lanthanum manganese perovskite catalyst, and marking as LaAl 0.8 Mn 0.2 O 3 。
Comparative example 1
The preparation method of the catalyst comprises the following steps:
adding 3mmol of La (NO) 3 ) 3 ·6H 2 O，2.8mmol Al(NO 3 ) 3 ·9H 2 Dissolving O in 30mL of water (ethanol: water = 3), adding 6mmol of citric acid to dissolve, evaporating to dryness at 80 ℃ to obtain gel, drying at 100 ℃ for 24h, taking out the dried sample, grinding into powder by using a mortar, putting the powder sample into a nitrogen-protected tubular furnace, calcining at 270 ℃ for 2h, calcining at 800 ℃ for 5h to obtain a catalyst, and marking as LaAlO 3 。
Comparative example 2
The preparation method of the catalyst comprises the following steps:
adding 3mmol of La (NO) 3 ) 3 ·6H 2 O，2mmol Mn(NO 3 ) 3 ·4H 2 Dissolving O in 30mL of water (ethanol: water = 3), adding 6mmol of citric acid to dissolve, evaporating to dryness at 80 ℃ to obtain gel, drying at 100 ℃ for 24h, taking out the dried sample, grinding the sample into powder by using a mortar, putting the powder sample into a nitrogen-protected tubular furnace, calcining at 270 ℃ for 2h, calcining at 800 ℃ for 5h to obtain a catalyst, and marking the catalyst as LaMnO 3 。
Comparative example 3
The preparation method of the catalyst comprises the following steps:
adding 3mmol of La (NO) 3 ) 3 ·6H 2 O，2.8mmol Al(NO 3 ) 3 ·9H 2 Dissolving 0.7mmol of ferric nitrate in 30mL of water (ethanol: water = 3), adding 6mmol of citric acid until the ferric nitrate is dissolved, evaporating to dryness at 80 ℃ until the ferric nitrate is gelled, drying at 100 ℃ for 24h, taking out the dried sample, grinding the dried sample into powder by using a mortar, putting the powder sample into a nitrogen-protected tubular furnace, calcining at 270 ℃ for 2h, and calcining at 800 ℃ for 5h to obtain a catalyst, wherein the label is LaAl 0.8 Fe 0.2 O 3 。
Comparative example 4
Adding 3mmol of La (NO) 3 ) 3 ·6H 2 Dissolving 2.8mmol of ferric nitrate and 0.7mmol of manganese nitrate in 30mL of water (ethanol: water = 3), adding 6mmol of citric acid to dissolve, evaporating to dryness at 80 ℃ to obtain gel, drying at 100 ℃ for 24h, taking out the dried sample, grinding into powder by using a mortar, putting the powder sample into a nitrogen-protected tubular furnace, calcining at 270 ℃ for 2h, calcining at 800 ℃ for 5h to obtain a catalyst, and marking as LaFe 0.8 Mn 0.2 O 3 。
The X-ray diffraction (XRD) patterns of the aluminum-doped lanthanum manganese-based perovskite catalysts of examples 1-3 and the catalysts of comparative examples 1-2 are shown in fig. 1, and it can be seen from fig. 1 that the XRD patterns of the B-site doped perovskites do not change, indicating that the lattice structures of the catalysts of examples 1-3 remain unchanged, probably due to the close radii of the two B atoms.
Catalyst Performance testing
Test example 1
Catalytic ozonation was carried out at room temperature under normal pressure using a 1L high boron glass reactor. Ozone is generated by a laboratory ozone generator (3S-A5, china Tonglin technology) by taking air as raw material gas, 400mL of simulated polluted water (20 mg/L of 2,4-D in the polluted water) and a certain amount of catalyst (the catalyst is selected from the aluminum-doped lanthanum manganese perovskite catalysts of examples 1-3 and the catalysts of comparative examples 1-2) are added into a reactor in the reaction process, the initial pH of the solution is controlled to be 7, the volume ratio of the catalyst dosage (0.16 g of the catalyst dosage) to the polluted water is 0.16g/400mL, the solution is continuously stirred and continuously filled with ozone, and the ozone filling speed is 5mg/min. 10mL of water sample was removed from the reactor every 10 minutes and the catalyst was removed by filtration through a 0.22 μm microporous membrane. Wherein, 20. Mu.L of the filtrate was injected into high performance liquid chromatography (HPLC, ultimate 3000) to detect the concentration of residual 2,4-D in the solution; another portion of the filtrate was taken to measure the Chemical Oxygen Demand (COD) of the solution to calculate the mineralization efficiency.
The experimental examples respectively study the degradation effects of the aluminum-doped lanthanum manganese perovskite catalysts of examples 1-3 and the catalysts of comparative examples 1-2 on 2,4-D under the condition of no catalyst, the results are shown in FIG. 2, it can be known from the figure that different catalysts all show similar catalytic degradation effects on 2,4-D, the removal rates all exceed 90%, and in addition, the COD results in the comparative solutions show that different catalysts have different mineralization efficiencies on organic pollutants, laAl 0.8 Mn 0.2 O 3 The removal efficiency is highest and can reach 65%. The removal rate of COD in the solution using the catalysts of examples 1-3 is obviously increased, which shows that the catalytic degradation performance of the perovskite doped with the B site on organic matters is obviously improved.
Test example 2
Catalytic ozonation was carried out at room temperature under normal pressure using a 1L high boron glass reactor. Ozone was generated by a laboratory ozone generator (3S-A5, china Tonglin technology) using air as the feed gas, and during the reaction, 400mL of simulated contaminated water (containing 20mg/L of 2,4-D in the contaminated water) and a certain amount (0.04, 0.08, 0.16g, respectively) of the catalyst LaAl of example 3 were added to the reactor 0.8 Mn 0.2 O 3 The initial pH of the solution was controlled at 7, during which time the solution was stirred continuously and ozone was continuously introduced at a rate of 3 mg/min. 10mL of water sample was removed from the reactor every 10 minutes and the catalyst was removed by filtration through a 0.22 μm microporous membrane. Wherein, 20. Mu.L of the filtrate was injected into high performance liquid chromatography (HPLC, ultimate 3000) to detect the concentration of residual 2,4-D in the solution; another portion of the filtrate was taken to determine the Chemical Oxygen Demand (COD) of the solution to calculate the mineralization efficiency.
This test example discusses the respective amounts of the catalysts used (the catalyst used was LaAl catalyst of example 3) 0.8 Mn 0.2 O 3 ) The catalytic degradation efficiency under the conditions is shown in fig. 3, and the results are shown in fig. 3, and it can be known that the dosage of the catalyst has a great influence on the removal rate of the pollutant COD in the solution. Under the condition that the volume of the polluted water is 400mL, when the dosage of the catalyst is 0.1 g, the removal efficiency of COD in the solution is lower by only 37%, and when the dosage of the catalyst is 0.2 g, the removal rate of COD reaches the maximum. Meanwhile, in this test example, the removal rate of COD in the solution by the lanthanum-aluminum-iron catalyst and the lanthanum-iron-manganese catalyst prepared in example 3 and comparative examples 3 and 4 under the same conditions is compared, and the results are shown in table 1: the results show that the catalyst LaAl invented by the patent 0.8 Mn 0.2 O 3 The catalytic removal efficiency of COD in the wastewater is much higher than that of the catalyst in the comparative example.
TABLE 1
| Name of catalyst | COD removal Rate (%) |
| LaAl 0.8 Mn 0.2 O 3 | 65 |
| LaFe 0.8 Mn 0.2 O 3 | 60 |
| LaAl 0.8 Fe 0.2 O 3 | 55 |
Test example 3
Catalytic ozonation was carried out at room temperature under normal pressure using a 1L high boron glass reactor. Ozone was generated from a laboratory ozone generator (3S-A5, china Tonglin technology) using air as the feed gas, and during the reaction 400mL of simulated contaminated water (containing 20mg/L of 2,4-D in the contaminated water) and a defined amount of the catalyst LaAl of example 3 were added to the reactor 0.8 Mn 0.2 O 3 The initial pH of the solution is controlled to be 4, 7 and 9 respectively, the volume ratio of the catalyst dosage (the catalyst dosage is 0.16 g) to the polluted water is 0.16g/400mL, the solution is continuously stirred and the ozone is continuously introduced, and the ozone introduction speed is 1 mg/min. 10mL of water sample was removed from the reactor every ten minutes and the catalyst was removed by filtration through a 0.22 μm microporous membrane. Wherein 20. Mu.L of the filtrate was injected into high performance liquid chromatography (HPLC, ultimate 3000) to detect the concentration of residual 2,4-D in the solution; another portion of the filtrate was taken to determine the Chemical Oxygen Demand (COD) of the solution to calculate the mineralization efficiency.
This test example discusses the catalytic degradation efficiency under different initial pH conditions of wastewater (the catalyst used was LaAl catalyst from example 3) 0.8 Mn 0.2 O 3 ) As a result, as shown in fig. 4, it is understood from fig. 4 that the pH condition of the solution has a large influence on the removal rate of the contaminants. When the solution is in alkaline condition (pH value)9), the removal efficiency of COD in the solution is lower to be only 41%, and when the solution is acidic or neutral, the removal rate of COD exceeds 60%, which indicates that the catalyst can be used under the neutral condition.
Test example 4
Using the catalyst LaAl of example 3 was repeated 3 times by the same method as in Experimental example 1 0.8 Mn 0.2 O 3 The results of catalytic degradation of 2,4-D in the wastewater are shown in FIG. 5, and it can be seen from FIG. 5 that the catalyst LaAl 0.8 Mn 0.2 O 3 After 3 times of cyclic utilization, the degradation rate of the catalyst to 2,4-D and the removal rate of COD in the solution are basically kept unchanged, and the catalyst can be recycled for many times.
The above is not relevant and is applicable to the prior art.
In the description of the specification, reference to the description of "one embodiment," "some embodiments," "an example," "a specific example," or "some examples" or the like means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
While certain specific embodiments of the present invention have been described in detail by way of illustration, it will be understood by those skilled in the art that the foregoing is illustrative only and is not limiting of the scope of the invention, as various modifications or additions may be made to the specific embodiments described and substituted in a similar manner by those skilled in the art without departing from the scope of the invention as defined in the appending claims. It should be understood by those skilled in the art that any modifications, equivalents, improvements and the like made to the above embodiments in accordance with the technical spirit of the present invention are included in the scope of the present invention.
Claims (10)
1. The application of the aluminum-doped lanthanum-manganese perovskite catalyst is characterized by comprising the following steps: in the presence of ozone, the aluminum-doped lanthanum-manganese perovskite catalyst is utilized to degrade organic pollutants,
the molecular formula of the aluminum-doped lanthanum-manganese perovskite catalyst is LaAl 1-x Mn x O 3 Wherein 0 is<x<1。
2. The use according to claim 1, wherein degrading organic contaminants with the aluminum-doped lanthanum manganese-based perovskite catalyst comprises:
placing the aluminum-doped lanthanum-manganese perovskite catalyst in sewage containing organic pollutants;
and introducing ozone into the sewage under the condition of stirring, and filtering 10mL of water sample at intervals to determine the concentration of the organic pollutants.
3. Use according to claim 2, wherein the chemical oxygen demand is determined and/or the mineralization efficiency of the organic pollutants is calculated simultaneously with the determination of the concentration of the organic pollutants.
4. The use according to claim 2 or 3, wherein the mass to volume ratio of the aluminium-doped lanthanum manganese-based perovskite catalyst to the effluent is (0.04 g to 0.16 g): 400mL.
5. Use according to claim 2 or 3, wherein the initial pH of the effluent is from 4 to 9.
6. Use according to claim 2 or 3, wherein the concentration of organic contaminants is determined by high performance liquid chromatography.
7. Use according to claim 2 or 3, wherein the organic contaminants comprise 2,4-D.
8. Use according to claim 2 or 3, wherein the ozone is introduced at a rate of 1 to 5mg/min.
9. The use according to claim 1, wherein the preparation method of the aluminum-doped lanthanum manganese-based perovskite catalyst comprises:
dissolving lanthanum nitrate, aluminum nitrate and manganese nitrate in 20mL of water, then adding 6mmol of citric acid until the citric acid is dissolved, evaporating to dryness at 80 ℃ until gel is formed, drying the obtained product at 100 ℃ for 10-24 hours, taking out the product and grinding to obtain a powdery product;
and calcining the powdery product at 270 ℃ for 2-5 hours, and then calcining at 800 ℃ for 5-10 hours to obtain the aluminum-doped lanthanum-manganese perovskite catalyst.
10. The use according to claim 9, wherein the molar ratio of manganese element to aluminum element in the aluminum-doped lanthanum-manganese perovskite catalyst is 1 (2-9).
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