CN114700086B - Preparation method of alpha-MnS catalyst, alpha-MnS catalyst obtained by preparation method and application of alpha-MnS catalyst - Google Patents
Preparation method of alpha-MnS catalyst, alpha-MnS catalyst obtained by preparation method and application of alpha-MnS catalyst Download PDFInfo
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- CN114700086B CN114700086B CN202210062122.8A CN202210062122A CN114700086B CN 114700086 B CN114700086 B CN 114700086B CN 202210062122 A CN202210062122 A CN 202210062122A CN 114700086 B CN114700086 B CN 114700086B
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
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- 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
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract
The invention relates to a preparation method of an alpha-MnS catalyst, which comprises the following steps: s1, dissolving trimesic acid in a sodium hydroxide solution to obtain a first solution to be treated, dissolving manganese chloride in deionized water to obtain a second solution to be treated, mixing the first solution to be treated and the second solution to be treated, and reacting to obtain a precursor; s2, heating the precursor to 400-500 ℃ in an air atmosphere, calcining, cooling and grinding to obtain manganese-based MOFs; s3, adding manganese-based MOFs and thioacetamide into ethanol, stirring, transferring the solution into an autoclave, heating to 140-160 ℃ and carrying out hydrothermal reaction to obtain the alpha-MnS catalyst. The invention also relates to the alpha-MnS catalyst obtained by the preparation method and application thereof. The alpha-MnS catalyst obtained by the preparation method can catalyze and activate PMS to effectively degrade levofloxacin wastewater in a short time, and has high degradation efficiency.
Description
Technical Field
The invention relates to a wastewater catalyst, in particular to a preparation method of an alpha-MnS catalyst, the alpha-MnS catalyst obtained by the preparation method and application thereof.
Background
Based on peroxomonosulphate (PMS, HSO) 5 - ) Advanced Oxidation Processes (AOPs) are of great interest due to their efficient performance in organic degradation processes. The PMS activation method comprisesTransition metals, ultraviolet, heat, alkalinity, microwaves, and the like. Wherein Fe is 2+ 、Co 2+ 、Mn 2+ 、Ce 3+ 、Cu 2+ The transition metals are widely used for PMS activation due to the characteristics of high efficiency and low energy consumption. However, in view of the unavoidable detrimental environmental impact of heavy metal release in a homogeneous process, the development of transition metal-based heterogeneous PMS-activated catalysts is highly desirable.
In recent years, the high catalytic capacity of transition metal sulfides in the energy storage and supercapacitor fields suggests their potential as efficient catalysts for PMS activation.
Antibiotics are commonly used in the treatment of infectious diseases in humans and animals and as animal growth promoters. However, antibiotics are excreted as parent compounds or metabolites outside the body due to malabsorption or incomplete metabolism in the intestinal tract. Antibiotics are difficult to remove completely during sewage treatment and are thus released continuously into the environment, often detected in aquatic environments. Antibiotics can cause selective stress on water bacteria and induce the formation of drug resistant bacteria, reducing their therapeutic potential against human and animal pathogens. Thus, antibiotic residues in aquatic environments can pose a potential threat to the environment and human health. Levofloxacin is a broad-spectrum antibacterial drug which can treat serious bacterial infection and is widely used for human, animal, agricultural and aquatic breeding, and is inevitably discharged into the environment. In recent years, levofloxacin has been detected in surface water, groundwater, wastewater from sewage treatment plants, and even drinking water in many countries. The presence of levofloxacin in the water body can produce adverse reaction to aquatic organisms, so that the drug resistance of bacteria is enhanced. Unfortunately, conventional wastewater treatment processes are not effective in removing levofloxacin due to its antimicrobial properties.
Disclosure of Invention
In order to solve the problems that levofloxacin is difficult to remove and the like in the prior art, the invention provides a preparation method of an alpha-MnS catalyst, the alpha-MnS catalyst obtained by the preparation method and application of the alpha-MnS catalyst.
The invention provides a preparation method of an alpha-MnS catalyst, which comprises the following steps: s1, dissolving trimesic acid in a sodium hydroxide solution to obtain a first solution to be treated, dissolving manganese chloride in deionized water to obtain a second solution to be treated, mixing the first solution to be treated and the second solution to be treated, and reacting to obtain a precursor; s2, heating the precursor to 400-500 ℃ in an air atmosphere, calcining, cooling and grinding to obtain manganese-based MOFs; s3, adding manganese-based MOFs and thioacetamide into ethanol, stirring, transferring the solution into an autoclave, heating to 140-160 ℃ and carrying out hydrothermal reaction to obtain the alpha-MnS catalyst.
Preferably, the concentration of trimesic acid in the first solution to be treated is 0.25-0.30mol/L, and the concentration of manganese chloride in the second solution to be treated is 0.10-0.15mol/L.
Preferably, the concentration of the sodium hydroxide solution in the first solution to be treated is 0.5-1.5M. In a preferred embodiment, the concentration of sodium hydroxide solution in the first solution to be treated is 1M.
Preferably, the manganese chloride in the step S1 is MnCl 2 ·4H 2 O。
Preferably, the mixing in the step S1 is to add the first liquid to be treated into the second liquid to be treated dropwise.
Preferably, the volume ratio of the first to-be-treated liquid to the second to-be-treated liquid in the step S1 is 1:3.5.
Preferably, the step S1 includes: 1.47-1.7g of trimesic acid is dissolved in 26-30ml of 1M sodium hydroxide solution to obtain a first solution to be treated, and 2.26-2.6g of MnCl is added 2 ·4H 2 O is dissolved in 91-105mL of deionized water to obtain a second solution to be treated, the first solution to be treated is dropwise added into the second solution to be treated, magnetic stirring is carried out for 24 hours at room temperature, and the precursor is prepared by centrifugation, washing and vacuum drying.
Preferably, the calcination temperature is 420-470 ℃. In a preferred embodiment, the calcination temperature is 450 ℃. Practice has shown that temperatures too high, for example 650 ℃, are certainly not feasible.
Preferably, the calcination time is 120-150min.
Preferably, the mass ratio of manganese-based MOFs to thioacetamide is 1:2.5-3.5. It should be appreciated that the amount of thioacetamide, if too small, will not react completely with the manganese-based MOFs.
Preferably, the autoclave is a polytetrafluoroethylene-lined stainless steel autoclave.
Preferably, the step S3 includes: manganese-based MOFs were added to ethanol with stirring, thioacetamide was added with continued stirring, and the solution was transferred to an autoclave.
Preferably, the hydrothermal reaction temperature is 145-155 ℃. In a preferred embodiment, the hydrothermal reaction temperature is 150 ℃. Practice has shown that temperatures too high, for example 180 ℃, are certainly not feasible.
Preferably, the hydrothermal reaction time is 8-12 hours.
Preferably, the step S3 includes: adding 1.5g of manganese-based MOFs into 45mL of ethanol, magnetically stirring for 15-20min, adding 3.75-4.5g of thioacetamide, continuously stirring for 15-20min, transferring the solution into a polytetrafluoroethylene lining stainless steel autoclave, carrying out hydrothermal reaction for 10h at 150 ℃, centrifuging, washing and vacuum drying after the reaction is finished, and obtaining the manganese-based MOFs-derived alpha-MnS catalyst.
The invention also provides an alpha-MnS catalyst obtained by the preparation method.
Preferably, the α -MnS catalyst has a uniform polyhedral structure.
The invention also provides an application of the alpha-MnS catalyst in activating PMS to degrade levofloxacin.
Preferably, the alpha-MnS catalyst is used for degrading levofloxacin in wastewater. Specifically, the alpha-MnS catalyst is mixed with the waste water containing the levofloxacin, and PMS is added for reaction.
Preferably, the concentration of alpha-MnS catalyst is between 0.01g/L and 0.07g/L and the concentration of PMS is between 0.05mM and 0.25mM. In a preferred embodiment, the concentration ratio of levofloxacin, alpha-MnS catalyst to PMS is 1 mg/L0.04 g/L0.15 mM.
Preferably, the degradation time is between 10 and 120 min. More preferably, the degradation time is between 30 and 60 minutes. In a preferred embodiment, the degradation time is 45 minutes.
Preferably, the α -MnS catalyst is reusable.
The preparation method of the alpha-MnS catalyst has the advantages of simple integral process, low calcining temperature and hydrothermal reaction temperature and low cost. The alpha-MnS catalyst obtained by the preparation method can catalyze and activate PMS to effectively degrade levofloxacin wastewater in a short time, and has high degradation efficiency. In addition, the alpha-MnS catalyst obtained by the preparation method provided by the invention has high reusability, and has higher catalytic activity after multiple catalytic activation PMS experiments.
Drawings
FIG. 1 is an X-ray diffraction pattern of an alpha-MnS catalyst according to example 1 of the present invention;
FIG. 2 is an SEM image of an alpha-MnS catalyst of example 1 according to the present invention;
FIG. 3 is a graph of efficiency of alpha-MnS catalyst activated PMS degradation of Levofloxacin (LEVO) according to example 1 of the present invention;
fig. 4 is a graph of efficiency of activating PMS to degrade LEVO as a function of cycle number for the α -MnS catalyst of example 1 according to the present invention.
Detailed Description
Preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings.
Example 1
1.47g of trimesic acid was dissolved in 26ml of 1M sodium hydroxide solution to give a first solution to be treated, and 2.26g of MnCl was added 2 ·4H 2 O is dissolved in 91mL of deionized water to obtain a second solution to be treated, the first solution to be treated is dropwise added into the second solution to be treated, and the solution is magnetically stirred for 24 hours at room temperature, and then the precursor is prepared through centrifugation, washing and vacuum drying.
And heating the precursor to 450 ℃ in an air atmosphere, preserving heat and calcining for 120min, cooling and grinding to obtain Mn-MOFs-450.
Adding 1.5-gMn-MOFs-450 into 45mL of ethanol, magnetically stirring for 15min, adding 4.5g of thioacetamide, continuously stirring for 15min, transferring the solution into a polytetrafluoroethylene lining stainless steel autoclave, and heating at 150 ℃ for reaction for 8h; after the reaction is completed, the alpha-MnS derived from the manganese-based MOFs is obtained through centrifugation, washing and vacuum drying, the X-ray diffraction diagram of the alpha-MnS is shown in figure 1, and the SEM diagram of the alpha-MnS catalyst is shown in figure 2, so that the alpha-MnS catalyst produced by the embodiment has a uniform polyhedral structure and can be used as a good catalyst for activating PMS.
Example 2
1.7g of trimesic acid was dissolved in 30ml of 1M sodium hydroxide solution to give a first solution to be treated, and 2.6g of MnCl was added 2 ·4H 2 O is dissolved in 105mL of deionized water to obtain a second solution to be treated, the first solution to be treated is dropwise added into the second solution to be treated, and the solution is magnetically stirred for 24 hours at room temperature, and then the precursor is prepared through centrifugation, washing and vacuum drying.
And heating the precursor to 450 ℃ in an air atmosphere, preserving heat and calcining for 120min, cooling and grinding to obtain Mn-MOFs-450.
Adding 1.5-gMn-MOFs-450 into 45mL of ethanol, magnetically stirring for 15min, adding 3.75g of thioacetamide, continuously stirring for 15min, transferring the solution into a polytetrafluoroethylene lining stainless steel autoclave, and heating at 150 ℃ for reaction for 8h; and after the reaction is finished, centrifuging, washing and vacuum drying to obtain the manganese-based MOFs-derived alpha-MnS.
Example 3
1.47g of trimesic acid was dissolved in 26ml of 1M sodium hydroxide solution to give a first solution to be treated, and 2.26g of MnCl was added 2 ·4H 2 O is dissolved in 91mL of deionized water to obtain a second to-be-treated liquid, the first to-be-treated liquid is dropwise added into the second to-be-treated liquid, magnetic stirring is carried out for 24 hours at room temperature, and the precursor is prepared by centrifugation, washing and vacuum drying.
And heating the precursor to 450 ℃ in an air atmosphere, preserving heat and calcining for 150min, cooling and grinding to obtain Mn-MOFs-450.
Adding 1.5-gMn-MOFs-450 into 45mL of ethanol, magnetically stirring for 15min, adding 4.5g of thioacetamide, continuously stirring for 15min, transferring the solution into a polytetrafluoroethylene lining stainless steel autoclave, and heating at 150 ℃ for reaction for 8h; and after the reaction is finished, centrifuging, washing and vacuum drying to obtain the manganese-based MOFs-derived alpha-MnS.
Example 4
1.47g of trimesic acid was dissolved in 26ml of 1M sodium hydroxide solution to give a first solution to be treated, and 2.26g of MnCl was added 2 ·4H 2 O is dissolved in 91mL of deionized water to obtain a second to-be-treated liquid, the first to-be-treated liquid is dropwise added into the second to-be-treated liquid, magnetic stirring is carried out for 24 hours at room temperature, and the precursor is prepared by centrifugation, washing and vacuum drying.
And heating the precursor to 450 ℃ in an air atmosphere, preserving heat and calcining for 120min, cooling and grinding to obtain Mn-MOFs-450.
Adding 1.5-gMn-MOFs-450 into 45mL of ethanol, magnetically stirring for 15min, adding 3.75g of thioacetamide, continuously stirring for 15min, transferring the solution into a polytetrafluoroethylene lining stainless steel autoclave, and heating at 150 ℃ for reaction for 8h; and after the reaction is finished, centrifuging, washing and vacuum drying to obtain the manganese-based MOFs-derived alpha-MnS.
Example 5
1.47g of trimesic acid was dissolved in 26ml of 1M sodium hydroxide solution to give a first solution to be treated, and 2.26g of MnCl was added 2 ·4H 2 O is dissolved in 91mL of deionized water to obtain a second to-be-treated liquid, the first to-be-treated liquid is dropwise added into the second to-be-treated liquid, magnetic stirring is carried out for 24 hours at room temperature, and the precursor is prepared by centrifugation, washing and vacuum drying.
And heating the precursor to 450 ℃ in an air atmosphere, preserving heat and calcining for 120min, cooling and grinding to obtain Mn-MOFs-450.
Adding 1.5-gMn-MOFs-450 into 45mL of ethanol, magnetically stirring for 20min, adding 4.5g of thioacetamide, continuously stirring for 20min, transferring the solution into a polytetrafluoroethylene lining stainless steel autoclave, and heating at 150 ℃ for reaction for 10h; and after the reaction is finished, centrifuging, washing and vacuum drying to obtain the manganese-based MOFs-derived alpha-MnS.
Application example 1
First, 1mg/L of Levofloxacin (LEVO) solution was added to a 150mL Erlenmeyer flask, then 0.04g/L of the Mn-based MOFs-derived alpha-MnS material prepared in Experimental example 1 was added as a catalyst, and then 0.15mM PMS was introduced under magnetic stirring at 400rpm to start the reaction. It should be understood that the alpha-MnS catalyst and solution order may be altered, but PMS must be added last. The removal rate of levofloxacin is shown in fig. 3, and the effect of alpha-MnS alone on LEVO is not adsorbed, and the effect of PMS alone on LEVO removal in 45min is very limited (about 12%), but in the alpha-MnS/PMS system, LEVO is completely removed in 45min.
Application example 2
To examine reusability of manganese-based MOFs-derived α -MnS, the catalyst after the phase-synchronous reaction of Experimental example 1 was separated by filtration, washed with water and ethanol, and dried in vacuo at 60℃to conduct a second and third reuse experiment in sequence. The results of the three-time reusability experiment are shown in fig. 4, and the efficiency of removing LEVO by activating PMS by the alpha-MnS catalyst is still kept at 96.3% after the three-time cycle experiment, which shows that the catalyst has good reusability.
The foregoing description is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention, and various modifications can be made to the above-described embodiment of the present invention. All simple, equivalent changes and modifications made in accordance with the claims and the specification of this application fall within the scope of the patent claims. The present invention is not described in detail in the conventional art.
Claims (8)
1. An application of an alpha-MnS catalyst in activating PMS to degrade levofloxacin, wherein the PMS is peroxymonosulfate, and the preparation method of the alpha-MnS catalyst comprises the following steps:
s1, dissolving trimesic acid in a sodium hydroxide solution to obtain a first solution to be treated, dissolving manganese chloride in deionized water to obtain a second solution to be treated, mixing the first solution to be treated and the second solution to be treated, and reacting to obtain a precursor;
s2, heating the precursor to 400-500 ℃ in an air atmosphere, calcining, cooling and grinding to obtain manganese-based MOFs;
s3, adding manganese-based MOFs and thioacetamide into ethanol, stirring, transferring the solution into an autoclave, heating to 140-160 ℃ and carrying out hydrothermal reaction to obtain the alpha-MnS catalyst.
2. The use according to claim 1, wherein the concentration of trimesic acid in the first solution to be treated is 0.25-0.30mol/L and the concentration of manganese chloride in the second solution to be treated is 0.10-0.15mol/L.
3. The use according to claim 1, wherein the mixing in step S1 is a drop wise addition of a first liquid to be treated to a second liquid to be treated.
4. The use according to claim 1, wherein the calcination temperature is 420-470 ℃.
5. The use according to claim 1, characterized in that the mass ratio of manganese-based MOFs to thioacetamide is 1:2.5-3.5.
6. Use according to claim 1, characterized in that the hydrothermal reaction temperature is 145-155 ℃.
7. Use according to claim 1, characterized in that the concentration of α -MnS catalyst is between 0.01g/L and 0.07g/L and the concentration of PMS is between 0.05mM and 0.25mM.
8. Use according to claim 1, characterized in that the degradation time is comprised between 10 and 120 min.
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