CN110743495B - Nano manganese oxide modified biomass charcoal, preparation method thereof and method for removing copper citrate - Google Patents
Nano manganese oxide modified biomass charcoal, preparation method thereof and method for removing copper citrate Download PDFInfo
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Abstract
The invention discloses a nano manganese oxide modified biomass charcoal and a preparation method thereof, wherein the nano manganese oxide modified biomass charcoal composite material is synthesized by combining the advantages of biomass charcoal and manganese oxide, has good stability and oxidability, is low in cost, high in efficiency and free of secondary pollution when used for treating a water body polluted by complex heavy metal. The invention also discloses a method for removing the copper citrate by adopting the nano manganese oxide modified biomass charcoal and a mechanism research. The preparation method of the nano manganese oxide modified biomass charcoal provided by the invention comprises the following steps: (11) and (3) synthesis of nano manganese oxide: adding coconut shell biomass charcoal into 0.15M potassium permanganate solution, keeping the liquid-solid ratio at 1/10, continuously stirring, filtering and drying; cooling to room temperature, soaking in anhydrous ethanol, filtering, and drying; (12) carbonizing: and (3) placing the material obtained in the step (11) into a tube furnace, roasting in an air atmosphere, and cooling to room temperature.
Description
Technical Field
The invention belongs to the field of complex heavy metal treatment, and particularly relates to nano manganese oxide modified biomass charcoal, a preparation method thereof and a method for removing copper citrate.
Background
Water pollution severity has attracted worldwide attention. Heavy metal pollution generally originates from industrial discharged wastewater, such as mining, metallurgy, electroplating, pharmacy, coating and other industries, and various heavy metals such as lead, cadmium, mercury, copper, chromium and the like directly enter a water body. Meanwhile, in the process of mining metal ores, heavy metals remained in soil can flow into a water body through rainwater washing, so that the water body is polluted. Heavy metal is migrated to the surface of the suspended matter from the water body and flows along with the water body under the adsorption action of the suspended matter in the water body, and when the load capacity of the suspended matter exceeds the transportation capacity of the suspended matter, the heavy metal is deposited and accumulated in the sediment along with the suspended matter, and at the moment, the concentration of the heavy metal in the water body is reduced. If the water environment factors, such as pH value, salinity, temperature and other conditions change, heavy metals accumulated in the bottom mud can be released again, enter the water body, and then migrate to gradually enlarge the pollution area. This is a cyclic pollution process, which causes great harm to the ecological environment. Heavy metals are not degradable in the environment, are stored for a long time and gradually accumulate, are enriched along with a food chain and have far-reaching harm to organisms.
The heavy metal pollution caused by any reason inevitably harms the health of animals, plants and human beings. Therefore, how to efficiently treat heavy metal pollution in various forms becomes urgent. A great deal of research is carried out at home and abroad aiming at the removal of metal ions, and a plurality of removal methods and different removal materials are provided. However, the form of heavy metals in water is not only in simple ionic form, but more than 90% of metal ions in aquatic or soil environments are present in complex form. In recent years, a large amount of pesticides, fertilizers, detergents, plasticizers, drugs and the like containing organic ligands are used, so that the water body components are more complex, and heavy metal ions are easily complexed with organic substances such as citric acid, Ethylene Diamine Tetraacetic Acid (EDTA), nitrilotriacetic acid (NTA), cyanide, antibiotics, Humic Acid (HA) and other ligands to form stable metal complexes with different structures and toxicity. The complex heavy metal is concerned by the ecological environment effects of difficult degradability, stable existence in a wide pH range, biological accumulation, food chain amplification and the like. Heavy metal contamination has been detrimental to human health and is very difficult to remove using existing technologies. The disposal of complex heavy metals has undoubtedly become a critical issue for environmental protection. The main problems faced in the treatment of complex heavy metals are how to effectively eliminate toxic heavy metal contamination and how to safely treat the complexing agent. At present, the electrolytic method, the chemical precipitation method and the membrane separation technology can not meet the requirement of removing complex metal. In recent years, the removal of complex metals by adsorption method, Fenton-like reaction, photocatalysis, photoelectrocatalysis and multi-method synergistic action is gradually the focus of research. Among them, the adsorption method is the most common method because of its advantages such as high separation efficiency, economy and simple operation, and the adsorption method is mainly an adsorption material, and the research on the adsorption material is very extensive at present. In recent years, biomass charcoal has been widely used in carbon storage, soil modification and other aspects due to its advantages of wide sources, abundant structure, biocompatibility, easy synthesis and the like, and research on metals in water treatment has been gradually increased. The biomass carbon with the multidimensional pore channel structure can efficiently separate and enrich metal ions to be treated. However, due to the large molecular structure and high stability of the complex metal, the removal effect of the complex metal is relatively poor by using the biomass charcoal only. The manganese oxide substance is widely present in the earth crust and is a stable substance. Common manganese oxides include manganese dioxide, manganic oxide and manganic oxide, which not only have good stability, but also have excellent oxidizability, and can oxidize part of large molecular weight organic matters into other low-toxic low-molecular weight organic matters and even non-toxic carbonic acid substances. The invention has the starting point that the advantages of the biomass carbon and the manganese oxide are combined to synthesize the nano manganese oxide modified biomass carbon composite material for removing the metal copper citrate, and the difficulties are complex copper which is difficult to remove and analysis of the removal mechanism of the complex copper.
Disclosure of Invention
The invention discloses a nano manganese oxide modified biomass charcoal and a preparation method thereof, wherein the nano manganese oxide modified biomass charcoal composite material is synthesized by combining the advantages of biomass charcoal and manganese oxide, has good stability and oxidability, can be used for treating a water body polluted by complex heavy metal, has low cost, high efficiency and no secondary pollution, and has wide industrial application value.
The invention also discloses a method for removing the copper citrate by adopting the nano manganese oxide modified biomass charcoal and a mechanism research.
The technical scheme of the invention is as follows:
1. the preparation method of the nano manganese oxide modified biomass charcoal is characterized by comprising the following steps:
(11) and (3) synthesis of nano manganese oxide: adding coconut shell biomass charcoal into 0.15M potassium permanganate solution, keeping the liquid-solid ratio at 1/10, continuously stirring, filtering and drying; cooling to room temperature, soaking with anhydrous ethanol, slowly reducing potassium permanganate loaded on the biomass charcoal, filtering, and drying;
(12) carbonizing: and (4) placing the material obtained in the step (11) into a tubular furnace, roasting in an air atmosphere, and cooling to room temperature to obtain the nano manganese oxide modified biomass charcoal.
2. In the step (11), 1g of coconut shell biomass charcoal is added into 10mL of 0.15M potassium permanganate, magnetic stirring is carried out at 300rpm, stirring is carried out continuously for 4h, and drying is carried out for 12h at the temperature of 90 ℃ in a constant-temperature oven after filtration; after cooling to room temperature, the mixture was immersed in 10mL of absolute ethanol for 10 minutes, slowly reduced with potassium permanganate already supported on biomass charcoal, then filtered again, and dried in a constant temperature oven at 90 ℃ for 12 hours.
3. In the step (12), the temperature of the tubular furnace is raised to 400 ℃, and the roasting is carried out for 1h in the air atmosphere.
4. The nano manganese oxide modified biomass charcoal prepared by the preparation method is characterized in that the modified biomass charcoal is obtained by adding biomass charcoal into potassium permanganate solution, drying and carbonizing; the modified biomass charcoal surface load particles are nanoparticles, and the nanoparticles are manganese oxides.
5. The biomass charcoal comprises coconut shells.
6. The particle size of the nanoparticles is 25 nm.
7. The method for removing the copper citrate from the nano manganese oxide modified biomass charcoal is characterized by comprising the following steps of:
(71) determination of the optimal dosage: under the condition of room temperature, adding nano manganese oxide modified biomass carbon with different dosages into a copper citrate solution, stirring at a constant speed, sampling at different time intervals, measuring the removal rate of copper by inductively coupled plasma mass spectrometry, and determining the optimal dosage of the nano manganese oxide modified biomass carbon;
(72) influence factor investigation: the method comprises the following steps of investigating the removal effect of the copper citrate under different pH values under the condition of optimal dosage; simulating a real water body, adding cations and anions into the copper citrate solution, and inspecting the removal effect of the copper citrate;
(73) and (3) sample testing: taking out a liquid sample, carrying out ultraviolet visible spectrum and total organic carbon, and carrying out capillary electrophoresis test to analyze organic matter components; meanwhile, after a liquid sample is diluted by a nitric acid solution, the concentrations of metal copper and manganese are tested by using inductively coupled plasma mass spectrometry.
8. In the step (51), 0.01 g, 0.05 g, 0.1 g and 0.15g of the nano manganese oxide modified biomass charcoal are respectively put into a triangular flask, 100mL of a copper citrate solution with the pH value of about 7.8 is added, and the optimal dosage of the nano manganese oxide modified biomass charcoal is determined to be 1 g/L.
9. In the step (52), adjusting the pH value of the copper citrate by using 0.1M nitric acid and sodium hydroxide solution, and respectively inspecting from the pH value of 3-10; and 10mM and 50mM Na, respectively+，Ca2+And SO4 2-，CO3 2-，CH3COO-And adding copper citrate for investigation.
10. The method also comprises the step of recycling the nano manganese oxide modified biomass charcoal: the sample subjected to the removal experiment was desorbed by a nitric acid solution having a pH of 3.5, washed with ultrapure water and dried at 90 ℃, and then recycled.
The invention has the technical effects that:
1. the invention provides a nano manganese oxide modified biomass charcoal and a preparation method thereof, which are combined with the advantages of biomass charcoal and manganese oxide to synthesize a nano manganese oxide modified biomass charcoal composite material as an adsorbent, which can be used for treating a water body polluted by complex heavy metal, can effectively remove complex copper, and reduce the mobility, biological effectiveness and toxicity of the complex copper in the water body.
2. The method for removing the copper citrate by using the nano manganese oxide modified biomass carbon provided by the invention has the remarkable advantages of simple and convenient synthesis technology, easiness in repetition, low cost, good effect of removing the copper citrate, no secondary pollution and the like, has relatively wide application potential for removing complex heavy metals, and has wide industrial application value.
3. The invention provides a mechanism for removing copper citrate from nano manganese oxide modified biomass carbon, and the manganese oxide modified biomass carbon achieves the effect of removing the copper citrate by the synergistic effect between excellent adsorption performance and good oxidizability. The nano manganese oxide modified biomass charcoal prepared by the method can efficiently remove the copper citrate, and the removal rate of the copper citrate is as high as 99% in a wide pH range and a short time; the removal mechanism can be explained as the chemical adsorption of the nano manganese oxide modified biomass carbon on the copper citrate and the oxidation of the manganese oxide with strong oxidation capacity on the citric acid, so that the degradation of organic matters is synchronously realized, and the removal of complex metal is achieved under the synergistic action of oxidation and adsorption; the modified biological adsorbent has good stability and oxidability.
Drawings
FIG. 1 is a morphology chart of nano manganese oxide modified biomass charcoal prepared by the invention.
FIG. 2 is an analysis chart of the experimental process of removing copper citrate from the nano manganese oxide modified biomass charcoal.
FIG. 3 is an analysis diagram for examining the influence factors of the copper citrate removal effect.
FIG. 4 is an analysis diagram for investigating the recycling performance of the nano manganese oxide modified biomass charcoal.
Fig. 5 is a two-stage kinetic model diagram of the removal process of the nano manganese oxide modified biomass charcoal.
Fig. 6 is an X-ray diffraction spectroscopy analysis diagram of the removal process of the nano manganese oxide modified biomass charcoal.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and examples.
The invention provides a research on removing copper citrate by using nano manganese oxide modified biomass charcoal, which specifically comprises the following two steps:
the method comprises the following steps: preparing the nano manganese oxide modified biomass charcoal: a preparation method of nano manganese oxide modified biomass charcoal comprises the following steps:
(11) and (3) synthesis of nano manganese oxide: adding coconut shell biomass charcoal into 0.15M potassium permanganate solution, keeping the liquid-solid ratio at 1/10, continuously stirring, filtering and drying; cooling to room temperature, soaking with absolute ethyl alcohol, slowly reducing potassium permanganate loaded on the biomass charcoal, filtering, and drying;
(12) carbonizing: and (2) placing the material obtained in the step (1) into a tubular furnace, roasting at high temperature in air atmosphere, and cooling to room temperature to obtain the nano manganese oxide modified biomass charcoal.
Example 1:
the embodiment provides a preparation method of nano manganese oxide modified biomass charcoal, which comprises the following steps:
(1) preparing materials: coconut shell biomass charcoal, 0.15M potassium permanganate solution and absolute ethyl alcohol;
(2) synthesizing: adding 1g of coconut shell biomass charcoal into 10mL of 0.15M potassium permanganate, magnetically stirring at 300rpm for 4 hours, filtering, and drying in a constant-temperature oven at 90 ℃ for 12 hours; cooling to room temperature, soaking in 10mL of absolute ethanol for 10min, filtering, and drying in a constant-temperature oven at 90 ℃ for 12 h;
(3) carbonizing: placing the material obtained in the step (2) in a tubular furnace, and roasting for 1h at 400 ℃ in air atmosphere; cooling to room temperature and taking out for later use.
As shown in fig. 1, is a morphology diagram of the nano manganese oxide modified biomass charcoal prepared by the invention. In FIG. 1, a is a scanning electron microscope image, manganese oxide with the particle size of about 25nm is loaded on the surface of the modified biomass carbon, and the modified biomass carbon is uniformly dispersed and has uniform particle size and no agglomeration of particles; b is a transmission electron microscope image, and the analysis of the transmission electron microscope shows that the existing manganese oxide is manganous oxide or manganous manganic oxide; and c is a Fourier infrared spectrum characterization diagram, wherein the change of the functional groups of the biomass charcoal before and after modification is illustrated, a manganese-oxygen functional group exists after modification, a new peak appears on the surface of the modified biomass charcoal after the experiment is removed, and the modified biomass charcoal belongs to a citric acid functional group, and the copper citrate can be successfully removed by the nano manganese oxide modified biomass charcoal.
Therefore, the nano manganese oxide modified biomass charcoal prepared by the invention is characterized in that the modified biomass charcoal is obtained by adding biomass charcoal into potassium permanganate solution, drying and carbonizing; the modified biomass charcoal surface load particles are nanoparticles, and the nanoparticles are manganese oxides. Wherein the biomass charcoal is coconut shell. The particle size of the nanoparticles was 25 nm.
Step two: research on removal of copper citrate by using nano manganese oxide modified biomass charcoal:
the method for removing the copper citrate from the nano manganese oxide modified biomass charcoal comprises the following steps:
(71) determination of the optimal dosage: under the condition of room temperature, adding nano manganese oxide modified biomass carbon with different dosages into a copper citrate solution, stirring at a constant speed, sampling at different time intervals, measuring the removal rate of copper by inductively coupled plasma mass spectrometry, and determining the optimal dosage of the nano manganese oxide modified biomass carbon;
(72) influence factor investigation: the method comprises the following steps of investigating the removal effect of the copper citrate under different pH values under the condition of optimal dosage; simulating a real water body, adding cations and anions into the copper citrate solution, and inspecting the removal effect of the copper citrate;
(73) and (3) sample testing: taking out a liquid sample, carrying out ultraviolet visible spectrum and total organic carbon, and carrying out capillary electrophoresis test to analyze organic matter components; meanwhile, after a liquid sample is diluted by a nitric acid solution, the concentrations of metal copper and manganese are tested by using inductively coupled plasma mass spectrometry.
Example 2:
the embodiment provides a method for removing copper citrate by extracting nano manganese oxide modified biomass charcoal, which comprises the following steps:
(1) determination of the optimal dosage: under the condition of room temperature, firstly, respectively taking 0.01 g, 0.05 g, 0.1 g and 0.15g of the nano manganese oxide modified biomass charcoal obtained in the example 1 and filling the mixture into a triangular flask; adding 100mL of copper citrate solution with the pH value of about 7.8, stirring at a constant speed, shaking at room temperature for 24h to achieve sufficient adsorption balance, sampling at different time intervals, filtering with a 0.45-micron filter membrane, and refrigerating at 4 ℃ in a refrigerator to be tested. The removal rate of the metallic copper is analyzed by inductively coupled plasma mass spectrometry, the optimal dosage is determined to be 1g/L, and the optimal dosage is applied to subsequent research.
(2) Influence factor investigation: because the copper citrate exists stably in a wide pH range and has different forms under different pH values, the pH value is an important influence factor, and under the condition that the optimal dosage is 1g/L, the pH value is adjusted by using 0.1M nitric acid and sodium hydroxide solution and is respectively investigated from 3 to 10; secondly, simulating a real water body, investigating the interference of cations and anions in the water body, and adding 10mM Na and 50mM Na respectively+，Ca2+And SO4 2-，CO3 2-，CH3COO-Carrying out research; finally, carrying out a cyclic experiment on the experiment sample after desorption, washing and drying; all the above experimental conditions were as described in (1). Samples were tested by refrigeration at 4 ℃.
(3) And (3) sample testing: all the liquid samples are taken out to carry out ultraviolet visible spectrum, total organic carbon and capillary electrophoresis test to analyze organic matter components; meanwhile, after a liquid sample is diluted by 2% nitric acid solution, the concentrations of metal copper and manganese are tested by using inductively coupled plasma mass spectrometry.
FIG. 2 is an analysis chart of the experimental process of removing copper citrate from the nano manganese oxide modified biomass charcoal.
In FIG. 2, a is a diagram of UV spectroscopy, and after the removal experiment, the absorption peak of copper citrate at 240nm disappears, which indirectly indicates that the solution has no copper citrate; b is a capillary electrophoresis analysis chart, and after the removal experiment is also carried out, the copper citrate peak positioned about 7 minutes disappears, and a new small peak appears at 6.6 minutes, so that the partial oxidation of the copper citrate by the nano manganese oxide into the small molecular weight organic acid can be illustrated. Through the ultraviolet-visible spectrum and capillary electrophoresis analysis of the removed solution, the copper citrate is successfully removed, and the copper citrate is partially oxidized into other small molecular organic matters under the action of manganese oxide, and the process of removing the copper citrate is completed through adsorption and oxidation reaction.
FIG. 3 is an analysis diagram for examining the influence factors of the copper citrate removal effect.
In FIG. 3, a is a study on the amount of different manganese oxide modified biomass charcoals, and it is found that the removal rate can reach 99% when the amount is 1g/L, and it can be determined thatThe optimum amount is 1 g/L. And b is the influence of different pH values, the nano manganese oxide modified biomass carbon can efficiently remove the copper citrate within a wider pH range (4-10), the removal rate of the copper citrate can reach more than 95%, the elution amount of manganese is 0.3mg/L, the copper and manganese contents meet the drinking water standard, and the nano manganese oxide modified biomass carbon has excellent stability. c and d are simulated real water bodies, and the addition of cation Na is investigated+，Ca2+And anion SO4 2-，CO3 2-，CH3COO-Except for 50mM Na+When cations coexist, almost no influence is caused on the removal, which shows that the addition of sodium influences the removal effect, but the presence of calcium almost has no influence on the removal effect, while the presence of anions at a lower concentration has a smaller influence on the removal, and when anions at a higher concentration exist, the removal effect of copper citrate is inhibited. Possible reasons are the presence of active sites and similar structural competition.
(4) And (3) cycle experiment: the modified material can be recycled after being desorbed and washed by dilute nitric acid. The sample subjected to the removal experiment was desorbed by a nitric acid solution having a pH of 3.5, washed with ultrapure water and dried at 90 ℃, and then recycled.
FIG. 4 is an analysis diagram for investigating the recycling performance of the nano manganese oxide modified biomass charcoal. The results of fig. 4 show that after three times of recycling, although the manganese is dissolved out obviously (1mg/L) after the third cycle, the removal effect of the nano manganese oxide modified biomass charcoal can still reach 90%, which indicates that the nano manganese oxide modified biomass charcoal has better stability.
(5) Research on a kinetic model: under the optimal experimental conditions, namely 1g/L of modified material, the nano manganese oxide modified biomass charcoal material is subjected to pH adjustment of a copper citrate solution at room temperature, continuously stirred, sampled at certain time intervals, filtered, diluted and analyzed for metal concentration by using inductively coupled plasma mass spectrometry.
Fig. 5 is a kinetic model diagram of the removal process of the nano manganese oxide modified biomass charcoal. The original biomass carbon or the nano manganese oxide modified biomass carbon is proved to accord with a quasi-second-order kinetic model, and the removal process is mainly chemical adsorption and has a composite effect. There is electron transfer or formation of chemical bonds.
(6) Explanation of the removal mechanism: and characterizing the samples before and after adsorption, wherein the characterization mainly comprises the characteristic analysis of a field emission scanning electron microscope, a transmission electron microscope, X-ray diffraction, X-ray photoelectron spectroscopy, Fourier infrared spectroscopy and the like, and various characterization results are integrated, so that the nano manganese oxide modified biomass carbon is successfully applied to the removal of the copper citrate. Fig. 6 is an X-ray diffraction spectroscopy analysis diagram of the removal process of the nano manganese oxide modified biomass charcoal. In fig. 6, a is a manganese oxide-modified biomass char Mn 2p, and b is a manganese oxide-modified biomass char Mn 2p after a removal experiment. The change in manganese valence state is reduced from a higher valence state of manganese oxide (trivalent manganese) to a lower valence state of divalent manganese, there being an electron transfer between the modifying material and the copper citrate.
The removal mechanism can be explained in two steps: 1. in the adsorption process, the copper citrate and the manganese sesquioxide loaded on the biomass carbon act to form a new chemical bond, so that the removal effect is achieved; the nanometer manganese oxide modified biomass charcoal mainly adsorbs the copper citrate by forming a new chemical bond-Cu-O-Mn-O-in a chemical adsorption mode, 2. the manganous oxide with stronger oxidation capability oxidizes the citric acid into low molecular weight organic acid substances, and simultaneously the valence state is reduced; manganese oxide (manganese sesquioxide) loaded on the biomass charcoal has stronger oxidability, and can oxidize citric acid to degrade the citric acid into organic matters with low molecular weight and break the copper citrate structure, and the released copper is removed by the manganese oxide modified biomass charcoal, so that the aim of simultaneously removing metal copper and the organic matters is fulfilled.
Claims (11)
1. The application of the nano manganese oxide modified biomass charcoal for removing the copper citrate is characterized in that uniformly dispersed nano particles with uniform particle size and no agglomeration are loaded on the nano manganese oxide modified biomass charcoal, the nano particles are manganese oxide, the manganese oxide is manganese sesquioxide, and the manganese oxide breaks the complex structure of complex copper and degrades the complex structure into organic matters with low molecular weight at the same time, so that the purpose of simultaneously removing released copper and the organic matters with low molecular weight is achieved.
2. The application of the nano manganese oxide modified biomass charcoal to the removal of copper citrate according to claim 1, wherein the preparation method of the nano manganese oxide modified biomass charcoal comprises the following steps:
(21) and (3) synthesis of nano manganese oxide: adding coconut shell biomass charcoal into 0.15M potassium permanganate solution, keeping the liquid-solid ratio at 1/10, continuously stirring, filtering and drying; cooling to room temperature, soaking with anhydrous ethanol, slowly reducing potassium permanganate loaded on the biomass charcoal, filtering, and drying;
(22) carbonizing: and (4) placing the material obtained in the step (21) in a tubular furnace, roasting in an air atmosphere, and cooling to room temperature to obtain the nano manganese oxide modified biomass charcoal.
3. The application of the nano manganese oxide modified biomass charcoal to removal of copper citrate according to claim 2, wherein in the step (21), 1g of coconut shell biomass charcoal is added into 10mL of 0.15M potassium permanganate, the mixture is magnetically stirred at 300rpm for 4 hours, and the mixture is filtered and dried in a constant temperature oven at 90 ℃ for 12 hours; after cooling to room temperature, the mixture was immersed in 10mL of absolute ethanol for 10 minutes, slowly reduced with potassium permanganate already supported on biomass charcoal, then filtered again, and dried in a constant temperature oven at 90 ℃ for 12 hours.
4. The application of the nano manganese oxide modified biomass charcoal to the removal of the copper citrate according to claim 3, wherein in the step (22), the temperature of the tube furnace is raised to 400 ℃, and the baking is carried out in an air atmosphere for 1 h.
5. The application of the nano manganese oxide modified biomass charcoal to the removal of copper citrate according to any one of claims 1 to 4, wherein the modified biomass charcoal is obtained by adding biomass charcoal into a potassium permanganate solution, drying and then carbonizing; the modified biomass charcoal surface load particles are nanoparticles, and the nanoparticles are manganese oxides.
6. The application of the nano manganese oxide modified biomass charcoal in removing the copper citrate according to claim 5, wherein the biomass charcoal is coconut shell.
7. The application of the nano manganese oxide modified biomass charcoal in removing the copper citrate according to claim 5, wherein the particle size of the nano particles is 25 nm.
8. A method for removing copper citrate by using nano manganese oxide modified biomass charcoal is characterized by comprising the following steps:
(81) determination of the optimal dosage: under the condition of room temperature, adding different doses of the nano manganese oxide modified biomass charcoal of one of claims 1 to 7 into a copper citrate solution, stirring at a constant speed, sampling at different time intervals, measuring the removal rate of copper by inductively coupled plasma mass spectrometry, and determining the optimal dosage of the nano manganese oxide modified biomass charcoal;
(82) influence factor investigation: the method comprises the following steps of investigating the removal effect of the copper citrate under different pH values under the condition of optimal dosage; simulating a real water body, adding cations and anions into the copper citrate solution, and inspecting the removal effect of the copper citrate;
(83) and (3) sample testing: taking out a liquid sample, carrying out ultraviolet visible spectrum and total organic carbon, and carrying out capillary electrophoresis test to analyze organic matter components; meanwhile, after a liquid sample is diluted by a nitric acid solution, the concentrations of metal copper and manganese are tested by using inductively coupled plasma mass spectrometry.
9. The method for removing copper citrate from nano manganese oxide modified biomass charcoal according to claim 8, wherein in the step (81), 0.01,0.05,0.1 and 0.15 g/L of nano manganese oxide modified biomass charcoal is respectively loaded into an Erlenmeyer flask, 100mL of a copper citrate solution with a pH value of about 7.8 is added, and the optimal dosage of the nano manganese oxide modified biomass charcoal is determined to be 1 g/L.
10. The method for removing the copper citrate from the nano manganese oxide modified biomass charcoal according to claim 9, wherein in the step (82), the pH value of the copper citrate is adjusted by using 0.1M nitric acid and sodium hydroxide solution, and the pH values are respectively considered from 3 to 10; and 10mM and 50mM Na, respectively+，Ca2+And SO4 2-，CO3 2-，CH3COO-The cationic as well as anionic effects were investigated in the addition of copper citrate.
11. The method for removing the copper citrate from the nano manganese oxide modified biomass charcoal according to any one of claims 8 to 10, further comprising the step of recycling the nano manganese oxide modified biomass charcoal: the sample subjected to the removal experiment was desorbed by a nitric acid solution having a pH of 3.5, washed with ultrapure water and dried at 90 ℃, and then recycled.
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