CN117443372A - Manganese-oxidized microalgae-carbon-based PMS catalyst and preparation method and application thereof - Google Patents
Manganese-oxidized microalgae-carbon-based PMS catalyst and preparation method and application thereof Download PDFInfo
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- 239000011572 manganese Substances 0.000 claims abstract description 48
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 32
- 238000001354 calcination Methods 0.000 claims abstract description 22
- FFGPTBGBLSHEPO-UHFFFAOYSA-N carbamazepine Chemical compound C1=CC2=CC=CC=C2N(C(=O)N)C2=CC=CC=C21 FFGPTBGBLSHEPO-UHFFFAOYSA-N 0.000 claims abstract description 22
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- OGJPXUAPXNRGGI-UHFFFAOYSA-N norfloxacin Chemical compound C1=C2N(CC)C=C(C(O)=O)C(=O)C2=CC(F)=C1N1CCNCC1 OGJPXUAPXNRGGI-UHFFFAOYSA-N 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
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Abstract
The invention provides a manganese oxide microalgae-carbon-based PMS catalyst, and a preparation method and application thereof. The raw material comprises manganese oxidized microalgae containing Mn 2+ Is a liquid medium of (a); the preparation method comprises the following steps: manganese oxide microalgae in Mn 2+ Culturing in a culture medium with the concentration of 0.1-5mM until manganese oxidation is completed, and performing solid-liquid separation to obtain a mixture of algae and biological manganese oxide; drying the obtained mixture, and grinding into powder of 20+/-10 meshes; calcining the obtained powder, and grinding into a manganese oxide microalgae-carbon-based PMS catalyst with the particle size of 50-150 meshes; the manganese oxide microalgae-carbon-based PMS catalyst is used for degrading carbamazepine. The invention can utilize artificially cultured manganese oxide microalgae or manganese oxide microalgae after sewage treatment, and calcine the manganese oxide microalgae after simple solid-liquid separation and drying, thereby realizing the purpose ofThe natural manganese doped biochar-based PMS catalyst is formed by step-by-step pyrolysis, the preparation process is simple and easy to operate, the waste recycling is realized, and the production cost is reduced.
Description
Technical Field
The invention belongs to the technical field of PMS (peroxymonosulfate) catalysts, and particularly relates to a manganese-oxidized microalgae-carbon-based PMS catalyst, and a preparation method and application thereof.
Background
In recent years, how to effectively degrade and remove the drug pollutants before entering the environment, and prevent the water environment pollution from becoming a research hot spot in various fields. Among the water treatment technologies, the advanced oxidation technology is widely used for removing various refractory organic pollutants due to the advantages of high oxidation capacity, mild reaction conditions, good removal effect, short reaction time and the like. Wherein, the advanced oxidation technology using Peroxomonosulfate (PMS) as oxidant has the remarkable advantages of good water solubility, convenient storage and transportation, strong oxidizing ability, and the like, and is widely studied and applied
PMS itself has limited ability to oxidize organic contaminants and must rely on external substances and energy activation to generate oxidative free radicals to effectively oxidize and degrade the organic contaminants. At present, the PMS activation method mainly uses external energy such as heat, ultrasound or illumination, and uses materials such as transition metal and oxides thereof as catalysts to activate PMS to generate various free radicals. The PMS activated by various catalysts has the characteristics of high activation efficiency, low energy consumption and the like, and is widely researched and applied.
Among the many PMS catalysts, manganese-based materials and carbon-based materials have significant advantages. For example, manganese-based materials have the advantage of being rich in reserves and low in toxicity compared to other transition metal materials. However, the existing chemically prepared manganese-based material has the problems of high synthesis cost, easy aggregation, reduced catalytic effect and secondary pollution caused by metal ion dissolution, so that the application of the manganese-based material is limited. The carbon-based material can effectively solve the problem of secondary pollution caused by metal ion dissolution of the metal catalyst, and has large specific surface area to promote pollutant adsorption and aggregation, so that the degradation effect of PMS activated degradation pollutants is effectively improved. However, the existing carbon-based material is mainly obtained by carrying out various load doping modification on the basis of graphene, graphene oxide and biochar, and has the defects of complex production process, high production cost and difficult large-scale application.
Research shows that manganese oxide is loaded on various carbon-based materials to prepare PMS catalysts to generate synergistic effect, so that the activation effect of PMS is greatly enhanced. For example, the catalyst obtained by loading nano needle-shaped manganese dioxide on graphene oxide can greatly improve the PMS activation effect, and has a very high removal effect on norfloxacin.
In the existing research of preparing the PMS catalyst by loading manganese oxide on a carbon-based material, although the obtained catalyst has the characteristics of good catalytic effect, high recycling efficiency, difficult generation of toxic metal ion dissolution and the like, the synthesis method is mainly carried out by using a chemical synthesis mode, the preparation process is complex, the production cost is high, and the development and the application of the catalyst are definitely limited. Therefore, there is a need to develop a novel PMS catalyst with a simple production process and low cost.
Disclosure of Invention
The invention aims at providing a manganese oxide microalgae-carbon-based PMS catalyst, and a preparation method and application thereof.
The invention adopts the following technical scheme.
A manganese oxide microalgae-carbon-based PMS catalyst comprises manganese oxide microalgae and Mn 2+ Is a liquid medium of (a).
As a preferred scheme, microalgae concentration (dry weight) is 500mg/L, and manganese oxide microalgae mother liquor is inoculated in 2L of manganese-containing solution according to an inoculation proportion of 5% 2+ Is used as a medium for the culture medium. The culture conditions were set as follows: light-to-dark ratio 12h: the culture temperature is 25 ℃ for 12 hours, the illumination intensity is set to 5000Lux, and the aeration rate is 2L/min.
Preferably, the manganese oxidized microalgae is microalgae with the capability of oxidizing low-valence manganese into high-valence manganese, namely, microalgae capable of converting Mn (II) into Mn (III) and Mn (IV) oxides.
The preparation method of the manganese oxide microalgae-carbon-based PMS catalyst comprises the following steps:
step 1, manganese oxidizing microalgae in Mn 2+ Culturing in a culture medium with the concentration of 0.1-5mM until manganese oxidation is completed, and performing solid-liquid separation to obtain a mixture of algae and biological manganese oxide;
step 2, drying the obtained mixture and grinding the mixture into powder of 20+/-10 meshes;
and 3, calcining the obtained powder, and grinding into a manganese oxide microalgae-carbon-based PMS catalyst with the particle size of 50-150 meshes.
Preferably, the calcination process comprises: anaerobic calcination is carried out by the mode of '10 ℃/min to 850 ℃ heat preservation for 3h and cooling to room temperature', and then calcination is carried out in air by the mode of '10 ℃/min to 350 ℃ heat preservation for 3h and cooling to room temperature'.
Preferably, the temperature during the drying in step 2 is controlled to be 60+ -3deg.C.
In the invention, the manganese oxide microalgae-carbon-based PMS catalyst is used for degrading carbamazepine.
As a preferable scheme, when the concentration of carbamazepine is 5mg/L, the dosage of the manganese oxide microalgae-carbon-based PMS catalyst is controlled to be 0.4g/L, PMS, and the concentration is controlled to be 1mmol/L, pH, and is controlled to be 7.
The beneficial effects are that: the invention can utilize artificially cultured manganese oxide microalgae or manganese oxide microalgae after sewage treatment, and calcine the manganese oxide microalgae after simple solid-liquid separation and drying, thereby realizing stepwise pyrolysis to form the natural manganese doped biochar-based PMS catalyst. The scheme has simple preparation flow and easy operation, and the raw materials can be derived from manganese oxide microalgae grown after sewage treatment, so that the waste recycling is realized, and the production cost is reduced.
In the invention, biological manganese oxide generated by manganese oxidation microalgae is naturally and uniformly distributed on the surface of the microalgae biochar, and the porous structure of the microalgae biochar can play a role in fixing and dispersing the biological manganese oxide, prevent the aggregation of the manganese oxide and reduce the catalytic effect, and simultaneously reduce the reduction of the activity of the catalyst generated by manganese element loss and the secondary pollution generated by ion dissolution. In the process of catalyzing PMS to degrade organic pollutants by the catalyst, the microalgae biochar can generate a synergistic effect with the biological manganese oxide, so that the catalytic efficiency of PMS and the degradation effect of the organic pollutants are greatly enhanced, and particularly the microalgae biochar can provide more effective adsorption and reaction active sites to promote PMS activation to generate free radicals, and the organic pollutants are adsorbed and concentrated into gaps for oxidative degradation. In addition, the biological manganese oxide is naturally loaded on the microalgae biochar, so that the density of the biological manganese oxide is increased, and the catalyst is recovered and recycled.
According to the invention, the natural manganese doped biochar-based PMS catalyst is prepared simply and conveniently by using the manganese oxidized microalgae and the in-situ generated biological manganese oxide thereof through a two-step calcination method, no chemical reagent is needed to be added in the preparation process, and the resource utilization problem of the microalgae after sewage treatment and the low-cost acquisition problem of the PMS catalyst are synchronously realized. The invention uses manganese oxidized microalgae and the in-situ generated biological manganese oxide as raw materials, and obtains the natural manganese doped biochar-based catalyst through a simple anaerobic high-temperature cracking process. The catalyst production raw material can be derived from manganese oxide microalgae after sewage treatment, the raw material is easy to obtain, the microalgae after sewage treatment can be recycled, no toxic and harmful raw material or auxiliary material is used in the production process, the process is simple and convenient, and the production cost is low. Meanwhile, the prepared PMS catalyst has good PMS catalytic effect and good repeated use stability, and is expected to be widely applied to catalytic oxidation of refractory organic matters, in particular refractory organic medicines.
The manganese oxide microalgae-carbon-based PMS catalyst can efficiently degrade carbamazepine which is an organic drug pollutant difficult to degrade in water, the degradation efficiency of the catalyst to 5mg/L carbamazepine can reach 100% within 10min, and the degradation efficiency to carbamazepine can still reach more than 95% after 5 times of circulation through simple precipitation recovery.
Drawings
FIG. 1 is a powder of the mixture of microalgae and biological manganese oxide in example 1;
FIG. 2 is a schematic diagram of a microalgae manganese oxide-carbon-based PMS catalyst prepared in example 1;
FIG. 3 is a graph showing the surface morphology of the microalgae manganese oxide-carbon-based PMS catalyst prepared in example 1;
FIG. 4 is a graph showing the effect of different concentrations of the microalgae manganese oxide-carbon-based PMS catalyst in example 1 on catalyzing PMS to reduce Jie Kama Xiping;
FIG. 5 is a graph showing the degradation efficiency of carbamazepine according to the number of cycles in example 1.
Detailed Description
The following description of the embodiments of the present invention will be made more apparent and fully hereinafter with reference to the accompanying drawings, in which some, but not all embodiments of the invention are shown. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
A preparation method of a manganese oxide microalgae-carbon-based PMS catalyst comprises the following steps:
step 1, microalgae manganese oxide (with an inoculum size of 5%) is added in Mn 2+ Culturing with 3mM culture medium (2L) until manganese oxidation is completed, and performing solid-liquid separation to obtain a mixture of algae and biological manganese oxide (shown in figure 1); wherein the solid-liquid separation is specifically carried out by utilizing a centrifugal separation mode, the rotating speed is 4000rpm, and the time is 10min; the manganese oxidation is judged to be completed according to the condition that Mn2+ contained in the culture medium is lower than 0.1mM;
step 2, drying the obtained mixture at 60+/-3 ℃ and grinding the mixture into powder of 20+/-10 meshes;
step 3, calcining the obtained powder, and grinding into a manganese oxide microalgae-carbon-based PMS catalyst with the particle size of 50-150 meshes (shown in figure 2);
wherein the calcination process comprises the following steps: anaerobic calcination is carried out by the method of '10 ℃/min-850 ℃ heat preservation for 3 h-cooling to room temperature of 25 ℃, and then calcination is carried out in air by the method of' 10 ℃/min-350 ℃ heat preservation for 3 h-cooling to room temperature of 25 ℃.
The manganese oxide microalgae-carbon-based PMS catalyst obtained in the embodiment is subjected to electron microscopy scanning detection, and the result is shown in fig. 3, and the surface topography chart shows that the manganese oxide is uniformly loaded on the surface and in the gaps of the algae-based biomass charcoal.
Example 2
A preparation method of a manganese oxide microalgae-carbon-based PMS catalyst comprises the following steps:
step 1, microalgae manganese oxide (with an inoculum size of 5%) is added in Mn 2+ Culturing 1mM culture medium (2L) until manganese oxidation is completed, and performing solid-liquid separation to obtain a mixture of algae and biological manganese oxide (shown in figure 1);
step 2, drying the obtained mixture at 60+/-3 ℃ and grinding the mixture into powder of 20+/-10 meshes;
step 3, calcining the obtained powder, and grinding into a manganese oxide microalgae-carbon-based PMS catalyst with the particle size of 50-150 meshes (shown in figure 2);
wherein the calcination process comprises the following steps: anaerobic calcination is carried out by the method of '10 ℃/min to 850 ℃ heat preservation for 3.2 h-cooling to room temperature of 25 ℃, and then calcination is carried out in air by the method of' 10 ℃/min to 350 ℃ heat preservation for 3 h-cooling to room temperature of 25 ℃.
Example 3
A preparation method of a manganese oxide microalgae-carbon-based PMS catalyst comprises the following steps:
step 1, microalgae manganese oxide (inoculation amount 5%) is added in Mn 2+ Culturing in 5mM culture medium (2L) until manganese oxidation is completed, and performing solid-liquid separation to obtain a mixture of algae and biological manganese oxide (shown in figure 1);
step 2, drying the obtained mixture at 60+/-3 ℃ and grinding the mixture into powder of 20+/-10 meshes;
step 3, calcining the obtained powder, and grinding into a manganese oxide microalgae-carbon-based PMS catalyst with the particle size of 50-150 meshes (shown in figure 2);
wherein the calcination process comprises the following steps: anaerobic calcination is carried out by the method of '10 ℃/min-850 ℃ heat preservation for 3 h-cooling to room temperature of 25 ℃, and then calcination is carried out in air by the method of' 10 ℃/min-350 ℃ heat preservation for 3 h-cooling to room temperature of 25 ℃.
Example 4
The microalgae-carbon-based PMS catalyst used in example 1 was used for degrading carbamazepine, specifically, when the concentration of carbamazepine was controlled to 5mg/L, the amount of the microalgae-carbon-based PMS catalyst was controlled to 0.4g/L, PMS and the concentration was controlled to 1mmol/L, pH to 7. The results show that carbamazepine can be completely degraded within 10min, and the results are shown in fig. 4 and 5. When the dosages of the manganese oxide microalgae-carbon-based PMS catalyst are respectively controlled to be 0.3g/L, 0.2g/L and 0.1g/L, the effect of degrading carbamazepine is shown in figure 4, wherein when the dosages of the manganese oxide microalgae-carbon-based PMS catalyst are respectively controlled to be 0.3g/L and 0.2g/L, the carbamazepine can still be completely degraded within 10 min.
Example 5
The waste liquid in example 4 was subjected to centrifugal separation (4000 rpm,10 min) to recover the manganese oxide microalgae-carbon-based PMS catalyst, and carbamazepine was degraded again according to the parameters in example 4, and the result showed that 99.2% of carbamazepine could be degraded within 10min, and the result is shown in FIG. 5.
Example 6
The waste liquid in example 5 was subjected to centrifugal separation (4000 rpm,10 min) to recover the manganese oxide microalgae-carbon-based PMS catalyst, and carbamazepine was degraded again according to the parameters in example 4, and the result showed that 98.7% of carbamazepine could be degraded within 10min, and the result is shown in FIG. 5.
Example 7
The waste liquid in example 6 was subjected to centrifugal separation (4000 rpm,10 min) to recover the manganese oxide microalgae-carbon-based PMS catalyst, and carbamazepine was degraded again according to the parameters in example 4, and the result showed that 97.5% of carbamazepine could be degraded within 10min, and the result is shown in FIG. 5.
Example 8
The waste liquid in example 7 was subjected to centrifugal separation (4000 rpm,10 min) to recover the manganese oxide microalgae-carbon-based PMS catalyst, and carbamazepine was degraded again according to the parameters in example 4, and the result showed that 96.8% of carbamazepine could be degraded within 10min, and the result is shown in FIG. 5.
Claims (8)
1. A manganese oxide microalgae-carbon-based PMS catalyst is characterized in that: the raw material comprises manganese oxidized microalgae containing Mn 2+ Is a liquid medium of (a).
2. The microalgae-carbon-based PMS catalyst for manganese oxidation according to claim 1, wherein: the manganese oxide microalgae adopts manganese oxide microalgae mother liquor with dry weight of 500mg/L, and contains Mn 2+ The amount of the liquid medium used was 2L.
3. The microalgae-carbon-based PMS catalyst for manganese oxidation according to claim 1, wherein: the manganese oxidized microalgae is microalgae with the capability of oxidizing low-valence manganese into high-valence manganese, namely, the microalgae can convert Mn (II) into Mn (III) and Mn (IV) oxides.
4. The method for preparing a microalgae-carbon-based PMS catalyst for manganese oxidation according to claim 1, 2 or 3, wherein the method comprises the steps of:
step 1, manganese oxidizing microalgae in Mn 2+ Culturing in a culture medium with the concentration of 0.1-5mM until manganese oxidation is completed, and performing solid-liquid separation to obtain a mixture of algae and biological manganese oxide;
step 2, drying the obtained mixture and grinding the mixture into powder of 20+/-10 meshes;
and 3, calcining the obtained powder, and grinding into a manganese oxide microalgae-carbon-based PMS catalyst with the particle size of 50-150 meshes.
5. The method according to claim 4, wherein the calcination step comprises: anaerobic calcination is carried out by the mode of '10 ℃/min to 850 ℃ heat preservation for 3h and cooling to room temperature', and then calcination is carried out in air by the mode of '10 ℃/min to 350 ℃ heat preservation for 3h and cooling to room temperature'.
6. The method of manufacturing according to claim 5, wherein: the temperature during the drying in step 2 was controlled to 60.+ -. 3 ℃.
7. The use of the microalgae manganese oxidation-carbon-based PMS catalyst according to claim 1, claim 2 or claim 3, wherein: the manganese oxide microalgae-carbon-based PMS catalyst is used for degrading carbamazepine.
8. The use of the microalgae-carbon-based PMS catalyst for manganese oxidation according to claim 7, wherein: when the concentration of carbamazepine is 5mg/L, the dosage of the manganese oxide microalgae-carbon-based PMS catalyst is controlled to be 0.4g/L, PMS, and the concentration is controlled to be 1mmol/L, pH, and the dosage is controlled to be 7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN202311432349.8A CN117443372A (en) | 2023-10-31 | 2023-10-31 | Manganese-oxidized microalgae-carbon-based PMS catalyst and preparation method and application thereof |
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