CN116139852A - Tea biochar-loaded manganese oxide composite material and preparation method and application thereof - Google Patents
Tea biochar-loaded manganese oxide composite material and preparation method and application thereof Download PDFInfo
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- CN116139852A CN116139852A CN202211286148.7A CN202211286148A CN116139852A CN 116139852 A CN116139852 A CN 116139852A CN 202211286148 A CN202211286148 A CN 202211286148A CN 116139852 A CN116139852 A CN 116139852A
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- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 title claims abstract description 76
- 239000002131 composite material Substances 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 56
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000002105 nanoparticle Substances 0.000 claims abstract description 31
- 239000000843 powder Substances 0.000 claims abstract description 29
- 239000003054 catalyst Substances 0.000 claims abstract description 24
- 238000001354 calcination Methods 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 241001122767 Theaceae Species 0.000 claims abstract 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 38
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 14
- 239000002957 persistent organic pollutant Substances 0.000 claims description 12
- 239000012286 potassium permanganate Substances 0.000 claims description 10
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 10
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 230000032683 aging Effects 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000012265 solid product Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 3
- 239000012528 membrane Substances 0.000 claims description 2
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- 238000010525 oxidative degradation reaction Methods 0.000 claims description 2
- 239000000725 suspension Substances 0.000 claims description 2
- 238000003828 vacuum filtration Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 5
- 239000002699 waste material Substances 0.000 abstract description 24
- 239000000463 material Substances 0.000 abstract description 16
- 239000011572 manganese Substances 0.000 abstract description 13
- 230000015556 catabolic process Effects 0.000 abstract description 11
- 238000006731 degradation reaction Methods 0.000 abstract description 11
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 abstract description 10
- 230000008569 process Effects 0.000 abstract description 8
- 229910000019 calcium carbonate Inorganic materials 0.000 abstract description 5
- 238000011068 loading method Methods 0.000 abstract description 3
- 239000003513 alkali Substances 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 244000269722 Thea sinensis Species 0.000 description 44
- 235000013616 tea Nutrition 0.000 description 42
- 230000003197 catalytic effect Effects 0.000 description 23
- 230000000052 comparative effect Effects 0.000 description 12
- 238000005516 engineering process Methods 0.000 description 7
- 239000003575 carbonaceous material Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 229910044991 metal oxide Inorganic materials 0.000 description 5
- 150000004706 metal oxides Chemical class 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- 239000002351 wastewater Substances 0.000 description 5
- 230000000593 degrading effect Effects 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 238000006385 ozonation reaction Methods 0.000 description 4
- 150000003216 pyrazines Chemical class 0.000 description 4
- IAEGWXHKWJGQAZ-UHFFFAOYSA-N trimethylpyrazine Chemical compound CC1=CN=C(C)C(C)=N1 IAEGWXHKWJGQAZ-UHFFFAOYSA-N 0.000 description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
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- 235000009569 green tea Nutrition 0.000 description 3
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- 229910052748 manganese Inorganic materials 0.000 description 3
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
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- 230000007547 defect Effects 0.000 description 2
- 235000020188 drinking water Nutrition 0.000 description 2
- 239000003651 drinking water Substances 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 230000009141 biological interaction Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
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- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
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- 235000013305 food Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 239000004570 mortar (masonry) Substances 0.000 description 1
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- 230000007935 neutral effect Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 239000012450 pharmaceutical intermediate Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- -1 pyrazine compound Chemical class 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
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- 230000004083 survival effect Effects 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
-
- C—CHEMISTRY; METALLURGY
- 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
-
- C—CHEMISTRY; METALLURGY
- 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
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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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
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
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- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
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Abstract
The invention discloses a tea biochar-loaded manganese oxide composite material and a preparation method and application thereof. The composite material is obtained by fully mixing manganese dioxide nano particles and tea powder according to the mass ratio of 1 (1) - (7) and calcining. The invention uses the reducing substances contained in the tea to reduce manganese dioxide into MnO and Mn in the process of loading manganese oxide 3 O 4 And Mn of 2 O 3 Thereby improving the composite materialCatalytic performance of the material. The waste tea derived biochar loaded manganese oxide composite material prepared by the invention contains uniformly distributed calcium carbonate nano particles; the calcium carbonate nano particles can be used as alkali active sites, so that the degradation efficiency of ozone on organic matters is improved. In addition, the manganese oxide in the composite material provided by the invention is uniformly dispersed on the waste tea derived biochar, and the manganese oxide is not easy to agglomerate in the ozone catalyzing process, so that the active site of the catalyst is effectively increased, and the degradation efficiency of refractory organic matters is improved.
Description
Technical Field
The invention belongs to the technical field of nano materials and water purification environments, and particularly relates to a tea biochar-loaded manganese oxide composite material, a preparation method and application thereof.
The background technology is as follows:
pyrazine compounds are commonly used as pharmaceutical intermediates, condiments for foods, beverages and perfumes, are widely present in the environment, and cause odor problems in drinking water. At present, only a few methods for biodegradation of pyrazine are recorded, but the problems of long period, harsh microorganism survival conditions, low degradation efficiency and the like exist in biodegradation. It is therefore urgent to find a method for efficiently degrading pyrazines.
The heterogeneous catalytic ozonation technology is a convenient and effective advanced oxidation technology, and utilizes a catalyst to catalyze ozone to generate a large amount of active oxygen species such as hydroxyl free radicals, so that organic pollutants in water bodies are not selectively degraded, and the heterogeneous catalytic ozonation technology is widely applied to drinking water and wastewater treatment.
The metal oxide is widely used as a catalyst in a heterogeneous catalytic ozonation technology, but the metal oxide generally has the defects of large metal consumption, easy agglomeration in water, large leaching amount, secondary pollution and the like. In recent years, metal-free carbon-based materials have been widely used as catalysts and catalytic support materials for heterogeneous catalytic ozonation technologies because of their abundant functional groups and defective structures on their surfaces. However, the independent carbon-based material has the defects of unstable part of active groups, easy consumption, better biological interaction of the carbon-based material, easy inactivation caused by being covered by biological films or natural organic matters, and the like. In recent years, there have been a great deal of studies reporting that composite materials of metal oxides and carbon-based materials can not only exert the advantages of metal oxides and carbon-based materials, but also improve the avoidance of the problems of metal oxides and carbon-based materials. However, most of the composite materials reported at present are complicated in preparation procedures and are not economical enough. Therefore, it is necessary to find a catalyst which is simple in preparation method, low in cost and has good catalytic activity for efficiently degrading pyrazine compounds by ozone.
Disclosure of Invention
The invention aims to provide a preparation method of a waste tea derived biochar loaded manganese oxide composite material (Mn-nWT, n represents the mass ratio of manganese dioxide nano particles to tea powder) and application of the composite material in efficiently catalyzing ozone to degrade organic pollutants, wherein the preparation method has the advantages of simple process, low cost, no toxicity and no harm, and manganese oxide is uniformly dispersed on the waste tea derived biochar; meanwhile, the obtained composite material contains uniformly distributed calcium carbonate nano particles. The composite material can be applied to efficiently catalyzing ozone to degrade organic pollutants in tap water or town sewage.
In a first aspect, the invention provides a tea biochar-supported manganese oxide composite material, which is obtained by fully mixing manganese dioxide nano particles with tea powder in a mass ratio of 1 (1-7) and calcining.
Preferably, the mass ratio of the manganese dioxide nano-particles to the tea powder is 1:5.
Preferably, the calcination temperature of the manganese dioxide nano-particles and tea powder after mixing is 400-500 ℃.
In a second aspect, the invention provides a preparation method of a tea biochar-supported manganese oxide composite material, which comprises the following steps:
and step one, drying the tea leaves and grinding to obtain tea powder.
And step two, mixing manganese dioxide nano particles and tea powder according to a mass ratio of 1:5, adding deionized water, uniformly mixing under an ultrasonic condition, and drying.
And thirdly, grinding the solid product obtained in the second step, and calcining to obtain the tea biochar-loaded manganese oxide composite material.
Preferably, the tea leaves in the first step are waste Longjing green tea leaves.
Preferably, the tea leaves in step one are brewed and washed several times before grinding. The brewing is specifically to brew tea leaves by using deionized water at 80 ℃, and the dosage of the deionized water is 50 times of the mass of the tea leaves; the drying conditions were oven dried overnight at 60 ℃ in a vacuum oven and sieved with a 70 mesh screen.
Preferably, the preparation process of the manganese dioxide nanoparticle in the second step is as follows:
a. respectively dissolving sodium thiosulfate and potassium permanganate in deionized water, heating the obtained solutions in an ultrasonic cleaning bath at 60 ℃, dripping the sodium thiosulfate solution into the potassium permanganate solution magnetically stirred in a water bath at 60 ℃ until dripping is complete, and aging in the water bath at 60 ℃ for 2 hours.
b. And taking out the suspension after the water bath aging, naturally cooling to room temperature, and carrying out solid-liquid separation in a centrifugal or filtering mode.
c. And (3) drying the separated solid components, and then sending the solid components into a tube furnace for calcination.
Preferably, in the step a, the concentration of the sodium thiosulfate solution and the potassium permanganate solution is 0.376mol/L and 0.2mol/L respectively; the volume ratio of the sodium thiosulfate solution to the potassium permanganate solution is 1:5.
Preferably, in step b, the centrifugation conditions are 10000 revolutions per minute, 3 minutes, and the washing is performed a plurality of times; the conditions for filtration and separation were vacuum filtration using a 0.45 μm-sized filter membrane, and water washing was performed multiple times.
Preferably, in the step c, the drying conditions are as follows: drying in an oven at 110℃for 12h. The conditions for calcination are: adding the mixture into a tube furnace under the protection of high-purity nitrogen, heating to 400 ℃ per minute at 5 ℃, calcining for 4 hours, and naturally cooling.
Preferably, in the second step, the drying is performed in a water bath at 80 ℃ or in an oven at 80 ℃.
Preferably, in the second step, the dosage of deionized water is 10 times of the total mass of the manganese dioxide nano particles and the tea powder.
Preferably, in the third step, the conditions for calcination are: and (3) adding the solid product obtained in the step (II) into a tube furnace, heating to 450 ℃ per minute at 3 ℃ under the protection of high-purity argon, calcining for 3 hours, and naturally cooling.
In a third aspect, the invention provides an application of a tea biochar-supported manganese oxide composite material as a catalyst in oxidative degradation of organic pollutants by ozone.
Preferably, the organic contaminant to be treated is a pyrazine compound.
Compared with the prior art, the invention has the following advantages:
1. in the invention, manganese dioxide is reduced into MnO and Mn in the process of loading manganese oxide by utilizing reducing substances contained in tea 3 O 4 Manganese of low valence (Mn) 2+ ，Mn 3+ ) The ability of Mn atoms to transfer electrons to ozone is enhanced, and the catalytic performance of the obtained composite material is further improved.
2. The invention utilizes the characteristic that tea contains abundant calcium, so that the prepared waste tea derived biochar loaded manganese oxide composite material contains uniformly distributed calcium carbonate nano particles; the calcium carbonate nano particles can be used as alkali active sites, so that the catalytic ozone is improved, and the degradation efficiency of organic matters is improved.
3. Manganese oxide in the waste tea derived biochar supported manganese oxide composite material (Mn-nWT) prepared by the invention is uniformly dispersed on the waste tea derived biochar, and the manganese oxide is not easy to agglomerate in the process of catalyzing ozone, so that the active site of the catalyst is effectively increased, and the degradation efficiency of refractory organic matters is improved.
4. The manganese oxide and the biochar in the waste tea derived biochar loaded manganese oxide composite material (Mn-nWT) are tightly combined and mutually promote the catalysis of ozone to degrade organic pollutants; the biochar can accelerate electron transfer and transmission, so that the valence state of manganese can be smoothly converted between +2, +3 and +4 valence states, and the biochar has a more stable structure under the load of manganese oxide.
5. The waste tea biochar loaded manganese oxide composite material (Mn-nWT) prepared by the invention has stable property in an oxidation system and good repeatability effect.
Description of the drawings:
FIG. 1 is a High Resolution Transmission Electron Microscope (HRTEM) image of the Mn-5WT composite material prepared in example 1 of the present invention;
FIG. 2 is a graph showing the comparison of the performance of the composite materials prepared in examples 1-4 and comparative example 1 in the ozone-catalyzed degradation of pyrazine compounds 2,3, 5-trimethylpyrazine (TrMP).
FIG. 3 is a graph showing the comparison of the concentration of ozone at the outlet of the ozone-catalyzed degradation TrMP for the composite materials prepared in examples 1-4 and comparative example 1 of the present invention.
FIG. 4 is a graph showing the cyclic repeated degradation efficiency of ozone-catalyzed degradation of TrMP of the Mn-5WT composite material prepared in example 1 of the present invention.
FIG. 5 is a graph showing the X-ray diffraction (XRD) contrast of the Mn-5WT composite material prepared in example 1 of the present invention before and after the reaction of catalyzing the ozone degradation TrMP process.
The specific embodiment is as follows:
the present invention will be further described with reference to the accompanying drawings and specific examples, which should not be construed as limiting the invention. Simple modifications and substitutions of the methods, steps or conditions of the present invention without departing from the spirit and nature of the invention are within the scope of the invention and, unless otherwise indicated, the technical means used in the examples are conventional means well known to those skilled in the art. Materials, reagents and the like used in the examples described below are commercially available unless otherwise specified.
Example 1
A preparation method of Mn-5WT composite catalytic material comprises the following steps:
(1) 9.332g of anhydrous sodium thiosulfate is dissolved in 100mL of deionized water, 15.803g of potassium permanganate is dissolved in 500mL of deionized water, the solution is placed in an ultrasonic cleaning bath (working power: 40kHz, 200W) and kept at a constant temperature of 60 ℃ for a period of time, then the potassium permanganate solution is transferred into a 60 ℃ magnetic stirring water bath kettle, stirring is continuously carried out at a rotating speed of 120 revolutions per minute until the sodium thiosulfate solution is completely added dropwise, stirring is stopped, and the solution is aged for 2 hours in the 60 ℃ water bath. After the reaction is finished, solid-liquid separation is carried out by a centrifugal separation method (centrifugal separation condition: 10000r/min,3 min), after the solid component is washed for a plurality of times to reach neutral pH value, the solid component is sent into a drying box, the temperature is 110 ℃, the drying is carried out for 12h, the dried solid is sent into a tube furnace, the temperature is increased to 400 ℃ under the protection of high-purity nitrogen gas by a temperature increasing program of 5 ℃/min, and the temperature is naturally reduced to room temperature after calcination is carried out for 4h, so as to obtain the manganese dioxide nano particles.
(2) 10g of waste Longjing green tea leaves are taken, 500mL of deionized water at 80 ℃ is added to be soaked for 2 hours, the tea leaves are washed three times by deionized water and then drained, the tea leaves are put into a vacuum drying oven to be dried at 60 ℃ overnight, and then the tea leaves are ground into powder by a mortar and sieved by a 70-mesh screen to obtain waste tea powder.
(3) Preparing 0.1g of manganese dioxide nano particles and 0.5g of waste tea powder, mixing the manganese dioxide nano particles and the waste tea powder into 6mL of deionized water (namely, the mass ratio of the manganese dioxide nano particles to the waste tea powder is 1:5), carrying out ultrasonic treatment for 60 minutes (working power: 40kHz, 200W), placing the mixture in a water bath kettle at 80 ℃ to be dried by evaporation in a water bath, then feeding the mixture into a tubular furnace for calcination, wherein the calcination condition is that the temperature is raised to 450 ℃ at 3 ℃/min under the protection of high-purity argon, and naturally cooling to room temperature after calcination for 3h, so as to obtain the Mn-5WT composite material, wherein manganese oxide comprises MnO and Mn 3 O 4 。
The HRTEM diagram of the Mn-5WT composite material obtained in the embodiment is shown in FIG. 1; as can be seen from FIG. 1, the Mn-5WT composite material was prepared in this example, and the manganese oxide particles were uniformly dispersed on the biochar material and had a distinct lattice, indicating that the crystallinity was high.
Example 2
The preparation method of Mn-1WT composite catalytic material is different from that of example 1 in that: in the step (3), the mass ratio of the manganese dioxide nano particles to the waste tea powder is 1:1, and 0.1g of manganese dioxide nano particles and 0.1g of waste tea powder are mixed into 2mL of deionized water. The Mn-1WT composite catalytic material is obtained, wherein the manganese oxide comprises MnO 2 And Mn of 2 O 3 。
Example 3
The preparation method of Mn-3WT composite catalytic material is different from example 1 in that: the mass ratio of the manganese dioxide nano particles to the waste tea powder in the step (3) is 1:3, and 0.1g of manganese dioxide nano particles and0.3g of waste tea leaf powder was mixed into 4mL of deionized water. The Mn-3WT composite catalytic material is obtained, wherein the manganese oxide comprises MnO, mn 3 O 4 And Mn of 2 O 3 。
Example 4
The preparation method of Mn-7WT composite catalytic material is different from example 1 in that: in the step (3), the mass ratio of the manganese dioxide nano particles to the waste tea powder is 1:7, and 0.1g of manganese dioxide nano particles and 0.7g of waste tea powder are mixed into 8mL of deionized water. The Mn-7WT composite catalytic material is obtained, wherein the manganese oxide is MnO.
Comparative example 1
The preparation method of the wood chip derived biochar supported manganese oxide composite (Mn-5 WW) composite catalytic material is characterized in that the difference between the embodiment and the embodiment 1 is that: in the step (2), the waste Longjing green tea leaves were replaced with commercially available sawdust powder, 10g of the sawdust powder was uniformly mixed with manganese dioxide nanoparticles in a mass ratio of 1:5 by the same treatment step as in the step (2) of example 1,0.1g of manganese dioxide nanoparticles and 0.5g of sawdust powder were mixed into 6mL of deionized water and the subsequent treatment step was the same as in the step (3) of example 1. The Mn-5WW composite catalytic material is obtained, wherein manganese oxide is MnO 2 。
For the catalytic effect of the composite catalytic materials provided in comparative examples 1 to 4 and comparative example 1 in the ozone catalytic advanced oxidation of organic pollutants, the following comparative experiments were performed. The degraded organic pollutant is odorous organic pollutant 2,3, 5-trimethyl pyrazine (TrMP). The test process is specifically as follows:
(1) TrMP was dissolved in 1L deionized water to give a simulated wastewater with a TrMP concentration of 5 μm/L.
(2) Loading the simulated wastewater into an ozone catalytic reaction device to serve as an experimental group and a control group; five experimental groups and a control group are arranged in total; the composite catalytic materials prepared in examples 1 to 4 and comparative example 1 were respectively added to the ozone catalytic reaction devices of experimental groups 1 to 5; the catalyst dosage in each experimental group was 50mg so that the catalyst concentration in the simulated wastewater was 0.05g/L.
(3) Ozone was continuously aerated into the reactors of all experimental and control groups, and the ozone concentration was detected at the reactor outlet. Samples were taken at intervals to monitor the concentration of TrMP in the simulated wastewater.
The results of the comparative experiments are shown in figures 2 and 3, in figure 2, +.s represent the residual concentration of TrMP for the control group without catalyst; represents the residual concentration of TrMP added to experimental group 1 (catalyst prepared in addition example 1); represents the residual concentration of TrMP added to experimental group 2 (catalyst prepared in example 2 was added);
represents the residual concentration of TrMP added to experimental group 3 (catalyst prepared in addition example 3); />
Represents the residual concentration of TrMP added to experimental group 4 (catalyst prepared in addition example 4); ■ Represents the residual concentration of TrMP added to experimental group 5 (catalyst prepared in comparative example 1).
The results in figure 2 show that ozone alone degraded 53.8% of TrMP after 20 minutes of reaction time without catalyst; the Mn-5WT composite material prepared in the embodiment 1 is added to catalyze and degrade 84.7% of TrMP within 1 minute, and the TrMP can reach 97.8% after 20 minutes; the Mn-1WT composite material prepared in example 2 was added to degrade 91.2% of TrMP after 20 minutes of reaction time; the Mn-3WT composite material prepared in example 3 was added to degrade 88.3% of TrMP after 20 minutes of reaction time; the Mn-7WT composite material prepared in example 4 was added to degrade 86.8% of TrMP after 20 minutes of reaction time; the Mn-5WW composite material prepared in comparative example 1 was added to degrade 58.6% of TrMP after 20 minutes of reaction time. A series of Mn-nWT shows the performance of efficiently degrading pollutants, but the biochar-supported manganese oxide composite material (Mn-5 WW) derived from wood dust powder cannot promote the degradation of pollutants, which shows that the catalytic performance of the obtained catalyst can be effectively improved by using waste tea leaves as a biochar source, namely the invention has excellent performance by using the waste tea leaves as the biochar-supported manganese oxide composite material (Mn-nWT).
In FIG. 3, +.Ozone outlet concentration of the control group with catalyst added; represents the ozone outlet concentration added to experimental group 1 (catalyst prepared in addition example 1); represents the ozone outlet concentration added to experimental group 2 (catalyst prepared in example 2 was added);
represents the ozone outlet concentration added to experimental group 3 (catalyst prepared in addition example 3); />
Represents the ozone outlet concentration added to experimental group 4 (catalyst prepared in addition example 4); ■ Represents the ozone outlet concentration added to experimental group 5 (addition of the catalyst prepared in comparative example 1). .
The results in FIG. 3 show that the Mn-5WT, mn-1WT, mn-3WT and Mn-7WT composites prepared in examples 1-4 can function to catalyze the decomposition of ozone to generate free radicals. The Mn-5WW prepared in comparative example 1 was poor in ozone catalytic decomposition ability, which is consistent with the results in FIG. 2.
Through ICP-OES test, the leaching amount of manganese ions in the simulated wastewater after the reaction of the experimental group 1 is only 0.024mg/L, and the leaching amount is extremely low, which indicates that the Mn-5WT composite catalytic material has high stability. FIG. 4 shows that the Mn-5WT composite material can efficiently catalyze ozone to degrade organic pollutants TrMP after four cycle experiments. FIG. 5 shows that the X-ray diffraction lines of the Mn-5WT composite material before and after the reaction of catalyzing ozone to degrade organic pollutant TrMP are basically consistent, and the original MnO and Mn 3 O 4 And CaCO (CaCO) 3 The diffraction peak exists and no new diffraction peak is generated, which indicates that the Mn-5WT composite material has high stability, and the valence state of manganese is basically kept stable before and after the reaction.
Example 6
A method for degrading organic pollutants in tap water or town sewage by ozone advanced oxidation technology comprises the following specific processes: after the composite material prepared in any one of the embodiments 1-4 is added into the water body to be treated, ozone is introduced into the water body to be treated.
Claims (10)
1. A tea biochar loaded manganese oxide composite material is characterized in that: the manganese dioxide nano particles and tea powder are fully mixed according to the mass ratio of 1 (1) - (7) and then calcined.
2. The tea biochar-supported manganese oxide composite material according to claim 1, wherein: the mass ratio of the manganese dioxide nano particles to the tea powder is 1:5.
3. The tea biochar-supported manganese oxide composite material according to claim 1, wherein: the calcination temperature of the manganese dioxide nano particles and tea powder after mixing is 450 ℃.
4. The method for preparing the tea biochar-supported manganese oxide composite material according to claim 1, which is characterized by comprising the following steps: the method comprises the following steps:
step one, grinding the dried tea leaves to obtain tea leaf powder;
step two, mixing manganese dioxide nano particles and tea powder according to the mass ratio of 1 (1) to 7), adding deionized water, uniformly mixing under the ultrasonic condition, and drying;
and thirdly, grinding the solid product obtained in the second step, and calcining to obtain the tea biochar-loaded manganese oxide composite material.
5. The method of manufacturing according to claim 4, wherein: the tea leaves in the first step are soaked and washed for a plurality of times before being ground; the brewing is specifically to brew tea leaves by using deionized water at 80 ℃, and the dosage of the deionized water is 50 times of the mass of the tea leaves; the drying conditions were oven dried overnight at 60 ℃ in a vacuum oven and sieved with a 70 mesh screen.
6. The method of manufacturing according to claim 4, wherein: the preparation process of the manganese dioxide nano-particles in the second step is as follows:
a. respectively dissolving sodium thiosulfate and potassium permanganate in deionized water, heating the obtained solutions in an ultrasonic cleaning bath at 60 ℃, dripping the sodium thiosulfate solution into the potassium permanganate solution magnetically stirred in a water bath at 60 ℃ until dripping is complete, and aging in the water bath at 60 ℃ for 2 hours;
b. taking out the suspension after the water bath aging, naturally cooling to room temperature, and carrying out solid-liquid separation in a centrifugal or filtering mode;
c. and (3) drying the separated solid components, and then sending the solid components into a tube furnace for calcination.
7. The method of manufacturing according to claim 6, wherein: in the step a, the concentration of the sodium thiosulfate solution and the potassium permanganate solution are respectively 0.376mol/L and 0.2mol/L; the volume ratio of the sodium thiosulfate solution to the potassium permanganate solution is 1:5;
in the step b, the centrifugal separation condition is 10000 revolutions per minute, 3 minutes, and the washing is carried out for a plurality of times; the conditions of filtration and separation are that a filter membrane with the specification of 0.45 μm is used for vacuum filtration and water washing is carried out for a plurality of times;
in the step c, the drying conditions are as follows: drying in an oven at 110 ℃ for 12 hours; the conditions for calcination are: adding the mixture into a tube furnace under the protection of high-purity nitrogen, heating to 400 ℃ per minute at 5 ℃, calcining for 4 hours, and naturally cooling.
8. The method of manufacturing according to claim 4, wherein: in the second step, the dosage of deionized water is 10 times of the total mass of the manganese dioxide nano particles and the tea powder.
9. The method of manufacturing according to claim 4, wherein: in the third step, the calcining conditions are as follows: and (3) adding the solid product obtained in the step (II) into a tube furnace, heating to 450 ℃ per minute at 3 ℃ under the protection of high-purity argon, calcining for 3 hours, and naturally cooling.
10. Use of a tea biochar-supported manganese oxide composite material according to any one of claims 1-3 as a catalyst in the oxidative degradation of organic pollutants by ozone.
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