CN112429799A - Method for removing cadmium in wastewater - Google Patents
Method for removing cadmium in wastewater Download PDFInfo
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- CN112429799A CN112429799A CN202011021709.1A CN202011021709A CN112429799A CN 112429799 A CN112429799 A CN 112429799A CN 202011021709 A CN202011021709 A CN 202011021709A CN 112429799 A CN112429799 A CN 112429799A
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- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
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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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/42—Materials comprising a mixture of inorganic materials
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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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
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- 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
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
Abstract
The invention discloses a method for removing cadmium in wastewater, which comprises the following steps: graphite powder is immersed in a potassium permanganate solution and heated and stirred for reaction, after the reaction is finished, the graphite powder is filtered, washed and dried for the first time, an adsorbing material can be obtained, and finally the adsorbing material is placed into cadmium-containing wastewater for oscillation adsorption treatment, wherein the adsorbing material is a manganese dioxide-loaded graphite powder composite material. According to the method for removing cadmium in wastewater provided by the invention, waste graphite products are recycled to prepare raw material graphite powder, and the adsorption material prepared from the graphite powder is used for carrying out shock adsorption treatment on cadmium-containing wastewater, so that the technical problems that the cost of the adsorbent preparation process in the prior art is too high, the adsorption efficiency of the adsorbent is low due to the low adsorption capacity of the adsorbent, and the industrialization is not facilitated can be effectively solved.
Description
Technical Field
The invention relates to the technical field of materials and environment, in particular to a method for removing cadmium in wastewater.
Background
Heavy metals have strong toxicity and nondegradable property, even trace heavy metals enter human bodies and seriously harm human health, and with the rapid development of modern industry and agriculture, the heavy metals enter water bodies in the forms of industrial pollution sources such as mining, metal processing and chemical production wastewater, artificial pollution sources such as pesticide and chemical fertilizer use and household garbage, and natural sources such as geological erosion and weathering, thereby causing serious threats to public health and ecological environment. More seriously, heavy metal pollution has the characteristics of concealment, long-term property, irreversibility, serious consequence severity and the like, and can finally enter human bodies through ecological food chains, so physiological diseases can be caused, and the human health is harmed.
Industrial development is a main cause of heavy metal pollution, and in order to ensure human health, the industrial development is required to fundamentally inhibit heavy metals from entering an ecological food chain, so that the treatment of wastewater containing heavy metals becomes a key problem.
Cadmium is one of the most harmful pollutants in heavy metal ions, cadmium is listed as a carcinogenic substance by the national toxicological project list of the United states, cadmium is difficult to volatilize in the ecological environment, cadmium which cannot volatilize is easy to enter a human body finally through an ecological food chain, cadmium is difficult to degrade after being enriched in the human body, and cadmium after being enriched in the human body can damage bones, nervous systems and organs of the human body and even influence gene diseases of offspring, so that serious human health disorder and even death are caused. The cadmium pollution problem has attracted extensive attention of researchers, and the removal of cadmium from wastewater has attracted extensive attention of researchers.
At present, a plurality of wastewater treatment technologies are available and applied to the treatment of cadmium-containing wastewater, and mainly comprise a chemical precipitation method, a membrane filtration method, an ion exchange method and an adsorption method. Compared with other methods, the adsorption method is widely used due to simple operation, economy, low price, high adsorption efficiency and strong adaptability. Because cadmium ions have higher hydration energy compared with other heavy metal ions, the adsorption capacity of adsorbing cadmium by an adsorption method is lower than that of adsorbing other heavy metal ions, and the adsorption efficiency is low due to the lower adsorption capacity, so how to improve the adsorption capacity of an adsorbent is a key factor for improving the adsorption efficiency of the adsorbent.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a method for removing cadmium in wastewater.
In order to achieve the purpose, the invention adopts the following technical scheme.
The invention provides a method for removing cadmium in wastewater, which comprises the following steps: graphite powder is immersed in a potassium permanganate solution and heated and stirred for reaction, after the reaction is finished, the graphite powder is filtered, washed and dried for the first time, an adsorbing material can be obtained, and finally the adsorbing material is placed into cadmium-containing wastewater for oscillation adsorption treatment, wherein the adsorbing material is a manganese dioxide-loaded graphite powder composite material.
As a further improvement of the method, in the process of oscillating adsorption treatment, the pH of the solution is controlled to be 2-6.
As a further improvement of the invention, in the process of the oscillating adsorption treatment, the temperature of oscillating adsorption is 15-35 ℃ and the time of oscillating adsorption is 10-30 h.
As a further improvement of the invention, in the process of the oscillating adsorption treatment, the oscillating adsorption temperature is 25 ℃, and the oscillating adsorption time is 24 hours.
As a further improvement of the method, the graphite powder is immersed in the potassium permanganate solution and heated at the temperature of 30-70 ℃, and the stirring reaction lasts for 2-6 hours.
As a further improvement of the invention, the graphite powder is immersed in the potassium permanganate solution and heated at the temperature of 50 ℃, and the duration of the stirring reaction is 4 hours.
As a further improvement of the invention, the solute mass fraction of the potassium permanganate solution is 0.01-0.05%.
As a further improvement of the invention, the graphite powder is prepared by recycling waste graphite products.
As a further improvement of the invention, the method for preparing graphite powder by recycling the waste graphite product comprises the following steps:
s1: cleaning and airing the waste graphite product, crushing the waste graphite product by a crusher, and performing first ball milling by a ball mill to obtain first intermediate graphite powder;
s2: soaking the first intermediate graphite powder in a sulfuric acid solution, performing ultrasonic treatment, performing secondary filtration, washing and drying after the ultrasonic treatment is finished, and obtaining second intermediate graphite powder after the secondary filtration, washing and drying is finished;
s3: placing the second intermediate graphite powder into a hydrochloric acid solution containing hydrogen peroxide to be heated and stirred for reaction, carrying out third filtration, washing and drying after the reaction is finished, and obtaining third intermediate graphite powder after the third filtration, washing and drying is finished;
s4: calcining the third intermediate graphite powder to obtain fourth intermediate graphite powder;
s5: and performing secondary ball milling on the fourth intermediate graphite powder by using a ball mill to obtain graphite powder.
According to the further improvement of the method, the particle size range of the graphite powder obtained from the graphite powder after the fourth intermediate graphite powder is subjected to secondary ball milling by the ball mill is 10-50 mu m.
According to the method for removing cadmium in wastewater provided by the invention, waste graphite products are recycled to prepare raw material graphite powder, and the adsorption material prepared from the graphite powder is used for carrying out shock adsorption treatment on cadmium-containing wastewater, so that the technical problems that the cost of the adsorbent preparation process in the prior art is too high, the adsorption efficiency of the adsorbent is low due to the low adsorption capacity of the adsorbent, and the industrialization is not facilitated can be effectively solved.
Drawings
Fig. 1 is a scanning electron microscope image of the adsorbent prepared in example 1 of the present invention at 1000 times magnification.
Fig. 2 is a comparison graph of XRD spectra of the graphite powder and the adsorbing material prepared in example 1 of the present invention.
FIG. 3 is a graph showing adsorption capacity data of the adsorbents in examples 1 to 15 of the present invention in wastewater containing cadmium at different concentrations.
Detailed Description
The technical solutions will be described clearly and completely in the following with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a method for removing cadmium in wastewater, which comprises the following steps: graphite powder is immersed in a potassium permanganate solution to be heated and stirred for reaction, the graphite powder is prepared by recovering waste graphite products, the graphite products comprise at least one of a graphite crucible, a graphite spoon, a graphite shovel and a graphite electrode, the mass fraction of a solute of the potassium permanganate solution is 0.01-0.05%, and the mass fraction of the solute of the potassium permanganate solution is preferably 0.025%.
The main reaction of potassium permanganate and graphite powder in the solution is as follows: MnO4 -+4H++3e-→MnO2+2H2In the process that potassium permanganate and graphite powder react in a solution, manganese acid radicals obtain electrons on the surface of the graphite powder and are reduced into manganese dioxide, and the delocalized pi electrons similar to graphene on the surface of the graphite powder lose the electrons and are oxidized into carbonyl or carboxyl by potassium permanganate in the solution.
In the reaction process of potassium permanganate and graphite powder in the solution, the reaction heating temperature is 30-70 ℃, the heating temperature is preferably 50 ℃, the stirring reaction duration is 2-6 hours, and the stirring reaction duration is preferably 4 hours.
After the reaction of potassium permanganate and graphite powder in the solution is finished, the solution after the reaction is filtered, washed and dried for the first time, and washed by ultrapure water with neutral pH value, so that an adsorbing material can be obtained, and finally the adsorbing material is placed into cadmium-containing wastewater to be subjected to oscillation adsorption treatment, wherein the adsorbing material is a manganese dioxide-loaded graphite powder composite material.
The oscillation adsorption principle of the invention is as follows:
1. manganese acid radicals obtain electrons on the surface of graphite powder and are reduced into manganese dioxide, one end of manganese atoms and delocalized pi electrons on the surface of the graphite powder are attracted under the action of static electricity, and one end of oxygen atoms are exposed outside to assist the graphite powder in absorbing cadmium ions in solution.
2. After delocalized pi electrons on the surface of the graphite powder similar to graphene lose electrons, the electrons are oxidized into carbonyl or carboxyl by potassium permanganate in a solution, and the capacity of adsorbing cadmium ions in the solution by the graphite powder is enhanced.
In the process of oscillating adsorption treatment, the pH value of the solution is required to be kept at 2-6, when the pH value is lower than 2, the pH value is too low, so that hydrogen ions are adsorbed on the surface of the adsorption material, the adsorption of the adsorption material on cadmium ions is prevented, and when the pH value is higher than 6.5, the pH value is too high, so that cadmium ions form precipitation.
In the process of oscillating adsorption treatment, the oscillating adsorption temperature is 15-35 ℃, the oscillating adsorption temperature is preferably 25 ℃, the oscillating adsorption time is 10-30 h, and the oscillating adsorption time is preferably 24 h.
The method for preparing graphite powder by recycling waste graphite products comprises the following steps:
s1: the waste graphite product is cleaned and dried, and is crushed by a crusher and then is subjected to first ball milling by a ball mill to obtain first intermediate graphite powder.
S2: and (3) soaking the first intermediate graphite powder in a sulfuric acid solution, performing ultrasonic treatment, performing secondary filtration, washing and drying after the ultrasonic treatment is finished, and obtaining second intermediate graphite powder after the secondary filtration, washing and drying is finished.
In some embodiments of the invention, the mass fraction of the solute in the sulfuric acid solution is 0.02-2%, the duration of ultrasonic treatment is 20-40 min, and the drying temperature in the second filtration, washing and drying process is 60-100 ℃.
S3: and (3) placing the second intermediate graphite powder into a hydrochloric acid solution containing hydrogen peroxide to be heated and stirred for reaction, carrying out third filtration, washing and drying after the reaction is finished, and obtaining third intermediate graphite powder after the third filtration, washing and drying is finished.
In some embodiments of the invention, in the hydrochloric acid solution containing hydrogen peroxide, the mass concentration of hydrogen peroxide is 1-5%, the mass concentration of hydrochloric acid is 6-12%, in the heating and stirring reaction process, the heating temperature is 30-90 ℃, the heating temperature is preferably 70 ℃, the duration of the heating and stirring reaction is 3-8 hours, and the duration of the heating and stirring reaction is preferably 4 hours.
S4: and calcining the third intermediate graphite powder to obtain fourth intermediate graphite powder.
In some embodiments of the present invention, the calcination temperature is 300 to 500 ℃, the calcination temperature is preferably 400 ℃, the calcination duration is 2 to 8 hours, the calcination duration is preferably 4 hours, and the calcination is to remove organic compounds in the graphite.
S5: and performing secondary ball milling on the fourth intermediate graphite powder by using a ball mill to obtain graphite powder.
In some embodiments of the invention, during the second ball milling, the weight ratio of the graphite powder to the zirconium balls is 1: (12-36), the duration time of the second ball milling is 4-12 h, graphite powder with the particle size range of 10-50 mu m can be obtained after the second ball milling is finished, the graphite powder obtained after the second ball milling has a large specific surface area, and meanwhile, the delocalized pi-shaped electronic structure similar to graphene is kept in graphite.
For further understanding of the present invention, the method and effects of the present invention will be described in further detail with reference to specific examples. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Example 1.
(1) The waste graphite product is cleaned and dried, and is crushed by a crusher and then is subjected to first ball milling by a ball mill to obtain first intermediate graphite powder.
(2) And (3) soaking the first intermediate graphite powder in a sulfuric acid solution with solute mass fraction of 0.02%, ultrasonically treating for 30min by using ultrasonic waves, and performing secondary filtration, washing and drying after the ultrasonic treatment is finished, wherein the drying temperature in the secondary filtration, washing and drying is 80 ℃, and the second intermediate graphite powder can be obtained after the secondary filtration, washing and drying is finished.
(3) And (3) placing the second intermediate graphite powder into a hydrochloric acid solution containing hydrogen peroxide (the mass concentration of the hydrogen peroxide is 3% and the mass concentration of the hydrochloric acid is 9%), heating and stirring for reaction, wherein the heating temperature is 50 ℃, the duration of the heating and stirring reaction is 5 hours, after the reaction is finished, filtering, washing and drying for the third time are carried out, and after the filtering, washing and drying for the third time are finished, the third intermediate graphite powder can be obtained.
(4) And calcining the third intermediate graphite powder, wherein the calcining temperature is 350 ℃, the calcining duration is 3 hours, and the fourth intermediate graphite powder can be obtained after the calcining is finished.
(5) And carrying out secondary ball milling on the fourth intermediate graphite powder by using a ball mill to obtain graphite powder with the particle size range of 10-50 mu m, wherein the weight ratio of the fourth intermediate graphite powder to zirconium balls is 1: and 24, the duration time of the second ball milling is 8 h.
(6) Immersing graphite powder in an aqueous solution of potassium permanganate with solute mass fraction of 0.03%, heating to 50 ℃, stirring for reaction for 3 hours, filtering after the reaction is finished, washing with ultrapure water with neutral pH value, drying to obtain an adsorbing material, FIG. 1 is a scanning electron microscope image of the adsorbent prepared in this example at 1000 times magnification, FIG. 2 is a scanning electron microscope image of the adsorbent prepared in this example at 100 times magnification, figure 3 is a comparison graph of XRD spectra of the graphite powder and the adsorbing material prepared in this example, wherein GP and GP-MnO2 represent graphite powder and graphite powder loaded with manganese dioxide respectively, in an XRD diffraction pattern of GP-MnO2, two small peaks marked by arrows in the ranges of 30-40 degrees and 60-70 degrees are characteristic absorption peaks of manganese dioxide, and a comparison graph of XRD shows that manganese dioxide is successfully loaded on graphite powder.
(7) Adding 0.1g of adsorbing material into every 100ml of cadmium-containing wastewater (the cadmium content is 20 mg/L), placing the adsorbing material into the cadmium-containing wastewater at the temperature of 25 ℃, and carrying out oscillation adsorption treatment for 24 hours, wherein the pH value of the solution is kept to be 4 in the oscillation adsorption treatment process.
Example 2.
(1) The waste graphite product is cleaned and dried, and is crushed by a crusher and then is subjected to first ball milling by a ball mill to obtain first intermediate graphite powder.
(2) And (3) soaking the first intermediate graphite powder in a sulfuric acid solution with solute mass fraction of 0.02%, ultrasonically treating for 30min by using ultrasonic waves, and performing secondary filtration, washing and drying after the ultrasonic treatment is finished, wherein the drying temperature in the secondary filtration, washing and drying is 80 ℃, and the second intermediate graphite powder can be obtained after the secondary filtration, washing and drying is finished.
(3) And (3) placing the second intermediate graphite powder into a hydrochloric acid solution containing hydrogen peroxide (the mass concentration of the hydrogen peroxide is 3% and the mass concentration of the hydrochloric acid is 9%), heating and stirring for reaction, wherein the heating temperature is 50 ℃, the duration of the heating and stirring reaction is 5 hours, after the reaction is finished, filtering, washing and drying for the third time are carried out, and after the filtering, washing and drying for the third time are finished, the third intermediate graphite powder can be obtained.
(4) And calcining the third intermediate graphite powder, wherein the calcining temperature is 350 ℃, the calcining duration is 3 hours, and the fourth intermediate graphite powder can be obtained after the calcining is finished.
(5) And carrying out secondary ball milling on the fourth intermediate graphite powder by using a ball mill to obtain graphite powder with the particle size range of 10-50 mu m, wherein the weight ratio of the fourth intermediate graphite powder to zirconium balls is 1: and 24, the duration time of the second ball milling is 8 h.
(6) Immersing graphite powder in an aqueous solution of potassium permanganate with solute mass fraction of 0.03%, heating to 50 ℃, stirring for reaction for 3 hours, filtering after the reaction is finished, washing with ultrapure water with neutral pH value, and drying to obtain the adsorbing material.
(7) Adding 0.1g of adsorbing material into every 100ml of cadmium-containing wastewater (the cadmium content is 80 mg/L), placing the adsorbing material into the cadmium-containing wastewater at the temperature of 25 ℃, and carrying out oscillation adsorption treatment for 24 hours, wherein the pH value of the solution is kept to be 4 in the oscillation adsorption treatment process.
Example 3.
(1) The waste graphite product is cleaned and dried, and is crushed by a crusher and then is subjected to first ball milling by a ball mill to obtain first intermediate graphite powder.
(2) And (3) soaking the first intermediate graphite powder in a sulfuric acid solution with solute mass fraction of 0.02%, ultrasonically treating for 30min by using ultrasonic waves, and performing secondary filtration, washing and drying after the ultrasonic treatment is finished, wherein the drying temperature in the secondary filtration, washing and drying is 80 ℃, and the second intermediate graphite powder can be obtained after the secondary filtration, washing and drying is finished.
(3) And (3) placing the second intermediate graphite powder into a hydrochloric acid solution containing hydrogen peroxide (the mass concentration of the hydrogen peroxide is 3% and the mass concentration of the hydrochloric acid is 9%), heating and stirring for reaction, wherein the heating temperature is 50 ℃, the duration of the heating and stirring reaction is 5 hours, after the reaction is finished, filtering, washing and drying for the third time are carried out, and after the filtering, washing and drying for the third time are finished, the third intermediate graphite powder can be obtained.
(4) And calcining the third intermediate graphite powder, wherein the calcining temperature is 350 ℃, the calcining duration is 3 hours, and the fourth intermediate graphite powder can be obtained after the calcining is finished.
(5) And carrying out secondary ball milling on the fourth intermediate graphite powder by using a ball mill to obtain graphite powder with the particle size range of 10-50 mu m, wherein the weight ratio of the fourth intermediate graphite powder to zirconium balls is 1: and 24, the duration time of the second ball milling is 8 h.
(6) Immersing graphite powder in an aqueous solution of potassium permanganate with solute mass fraction of 0.03%, heating to 50 ℃, stirring for reaction for 3 hours, filtering after the reaction is finished, washing with ultrapure water with neutral pH value, and drying to obtain the adsorbing material.
(7) Adding 0.1g of adsorbing material into every 100ml of cadmium-containing wastewater (the cadmium content is 100 mg/L), placing the adsorbing material into the cadmium-containing wastewater at the temperature of 25 ℃, and carrying out oscillation adsorption treatment for 24 hours, wherein the pH value of the solution is kept to be 4 in the oscillation adsorption treatment process.
Example 4.
(1) The waste graphite product is cleaned and dried, and is crushed by a crusher and then is subjected to first ball milling by a ball mill to obtain first intermediate graphite powder.
(2) And (3) soaking the first intermediate graphite powder in a sulfuric acid solution with solute mass fraction of 0.02%, ultrasonically treating for 30min by using ultrasonic waves, and performing secondary filtration, washing and drying after the ultrasonic treatment is finished, wherein the drying temperature in the secondary filtration, washing and drying is 80 ℃, and the second intermediate graphite powder can be obtained after the secondary filtration, washing and drying is finished.
(3) And (3) placing the second intermediate graphite powder into a hydrochloric acid solution containing hydrogen peroxide (the mass concentration of the hydrogen peroxide is 3% and the mass concentration of the hydrochloric acid is 9%), heating and stirring for reaction, wherein the heating temperature is 50 ℃, the duration of the heating and stirring reaction is 5 hours, after the reaction is finished, filtering, washing and drying for the third time are carried out, and after the filtering, washing and drying for the third time are finished, the third intermediate graphite powder can be obtained.
(4) And calcining the third intermediate graphite powder, wherein the calcining temperature is 350 ℃, the calcining duration is 3 hours, and the fourth intermediate graphite powder can be obtained after the calcining is finished.
(5) And carrying out secondary ball milling on the fourth intermediate graphite powder by using a ball mill to obtain graphite powder with the particle size range of 10-50 mu m, wherein the weight ratio of the fourth intermediate graphite powder to zirconium balls is 1: and 24, the duration time of the second ball milling is 8 h.
(6) Immersing graphite powder in an aqueous solution of potassium permanganate with solute mass fraction of 0.03%, heating to 50 ℃, stirring for reaction for 3 hours, filtering after the reaction is finished, washing with ultrapure water with neutral pH value, and drying to obtain the adsorbing material.
(7) Adding 0.1g of adsorbing material into every 100ml of cadmium-containing wastewater (the cadmium content is 120 mg/L), placing the adsorbing material into the cadmium-containing wastewater at the temperature of 25 ℃, and carrying out oscillation adsorption treatment for 24 hours, wherein the pH value of the solution is kept to be 4 in the oscillation adsorption treatment process.
Example 5.
(1) The waste graphite product is cleaned and dried, and is crushed by a crusher and then is subjected to first ball milling by a ball mill to obtain first intermediate graphite powder.
(2) And (3) soaking the first intermediate graphite powder in a sulfuric acid solution with solute mass fraction of 0.02%, ultrasonically treating for 30min by using ultrasonic waves, and performing secondary filtration, washing and drying after the ultrasonic treatment is finished, wherein the drying temperature in the secondary filtration, washing and drying is 80 ℃, and the second intermediate graphite powder can be obtained after the secondary filtration, washing and drying is finished.
(3) And (3) placing the second intermediate graphite powder into a hydrochloric acid solution containing hydrogen peroxide (the mass concentration of the hydrogen peroxide is 3% and the mass concentration of the hydrochloric acid is 9%), heating and stirring for reaction, wherein the heating temperature is 50 ℃, the duration of the heating and stirring reaction is 5 hours, after the reaction is finished, filtering, washing and drying for the third time are carried out, and after the filtering, washing and drying for the third time are finished, the third intermediate graphite powder can be obtained.
(4) And calcining the third intermediate graphite powder, wherein the calcining temperature is 350 ℃, the calcining duration is 3 hours, and the fourth intermediate graphite powder can be obtained after the calcining is finished.
(5) And carrying out secondary ball milling on the fourth intermediate graphite powder by using a ball mill to obtain graphite powder with the particle size range of 10-50 mu m, wherein the weight ratio of the fourth intermediate graphite powder to zirconium balls is 1: and 24, the duration time of the second ball milling is 8 h.
(6) Immersing graphite powder in an aqueous solution of potassium permanganate with solute mass fraction of 0.03%, heating to 50 ℃, stirring for reaction for 3 hours, filtering after the reaction is finished, washing with ultrapure water with neutral pH value, and drying to obtain the adsorbing material.
(7) Adding 0.1g of adsorbing material into every 100ml of cadmium-containing wastewater (the cadmium content is 180 mg/L), placing the adsorbing material into the cadmium-containing wastewater at the temperature of 25 ℃, and carrying out oscillation adsorption treatment for 24 hours, wherein the pH value of the solution is kept to be 4 in the oscillation adsorption treatment process.
Example 6.
(1) The waste graphite product is cleaned and dried, and is crushed by a crusher and then is subjected to first ball milling by a ball mill to obtain first intermediate graphite powder.
(2) And (3) soaking the first intermediate graphite powder in a sulfuric acid solution with solute mass fraction of 0.01%, ultrasonically treating for 20min by using ultrasonic waves, and performing secondary filtration, washing and drying after the ultrasonic treatment is finished, wherein the drying temperature in the secondary filtration, washing and drying is 60 ℃, and the second intermediate graphite powder can be obtained after the secondary filtration, washing and drying is finished.
(3) And (3) placing the second intermediate graphite powder into a hydrochloric acid solution containing hydrogen peroxide (the mass concentration of the hydrogen peroxide is 1% and the mass concentration of the hydrochloric acid is 6%), heating and stirring for reaction, wherein the heating temperature is 30 ℃, the duration of the heating and stirring reaction is 3 hours, after the reaction is finished, filtering, washing and drying for the third time are carried out, and after the filtering, washing and drying for the third time are finished, the third intermediate graphite powder can be obtained.
(4) And calcining the third intermediate graphite powder, wherein the calcining temperature is 300 ℃, the calcining duration is 2 hours, and the fourth intermediate graphite powder can be obtained after the calcining is finished.
(5) And carrying out secondary ball milling on the fourth intermediate graphite powder by using a ball mill to obtain graphite powder with the particle size range of 10-50 mu m, wherein the weight ratio of the fourth intermediate graphite powder to zirconium balls is 1: and 12, the duration of the second ball milling is 4 h.
(6) Immersing graphite powder in an aqueous solution of potassium permanganate with solute mass fraction of 0.01%, heating to 30 ℃, stirring for reaction for 2 hours, filtering after the reaction is finished, washing with ultrapure water with neutral pH value, and drying to obtain the adsorbing material.
(7) Adding 0.1g of adsorbing material into every 100ml of cadmium-containing wastewater (the cadmium content is 40 mg/L), placing the adsorbing material into the cadmium-containing wastewater at the temperature of 15 ℃, and carrying out oscillation adsorption treatment for 10 hours, wherein the pH value of the solution is kept to be 2 in the oscillation adsorption treatment process.
Example 7.
(1) The waste graphite product is cleaned and dried, and is crushed by a crusher and then is subjected to first ball milling by a ball mill to obtain first intermediate graphite powder.
(2) And (3) soaking the first intermediate graphite powder in a sulfuric acid solution with solute mass fraction of 0.01%, ultrasonically treating for 20min by using ultrasonic waves, and performing secondary filtration, washing and drying after the ultrasonic treatment is finished, wherein the drying temperature in the secondary filtration, washing and drying is 60 ℃, and the second intermediate graphite powder can be obtained after the secondary filtration, washing and drying is finished.
(3) And (3) placing the second intermediate graphite powder into a hydrochloric acid solution containing hydrogen peroxide (the mass concentration of the hydrogen peroxide is 1% and the mass concentration of the hydrochloric acid is 6%), heating and stirring for reaction, wherein the heating temperature is 30 ℃, the duration of the heating and stirring reaction is 3 hours, after the reaction is finished, filtering, washing and drying for the third time are carried out, and after the filtering, washing and drying for the third time are finished, the third intermediate graphite powder can be obtained.
(4) And calcining the third intermediate graphite powder, wherein the calcining temperature is 300 ℃, the calcining duration is 2 hours, and the fourth intermediate graphite powder can be obtained after the calcining is finished.
(5) And carrying out secondary ball milling on the fourth intermediate graphite powder by using a ball mill to obtain graphite powder with the particle size range of 10-50 mu m, wherein the weight ratio of the fourth intermediate graphite powder to zirconium balls is 1: and 12, the duration of the second ball milling is 4 h.
(6) Immersing graphite powder in an aqueous solution of potassium permanganate with solute mass fraction of 0.01%, heating to 30 ℃, stirring for reaction for 2 hours, filtering after the reaction is finished, washing with ultrapure water with neutral pH value, and drying to obtain the adsorbing material.
(7) Adding 0.1g of adsorbing material into every 100ml of cadmium-containing wastewater (the cadmium content is 60 mg/L), placing the adsorbing material into the cadmium-containing wastewater at the temperature of 15 ℃, and carrying out oscillation adsorption treatment for 10 hours, wherein the pH value of the solution is kept to be 2 in the oscillation adsorption treatment process.
Example 8.
(1) The waste graphite product is cleaned and dried, and is crushed by a crusher and then is subjected to first ball milling by a ball mill to obtain first intermediate graphite powder.
(2) And (3) soaking the first intermediate graphite powder in a sulfuric acid solution with solute mass fraction of 0.01%, ultrasonically treating for 20min by using ultrasonic waves, and performing secondary filtration, washing and drying after the ultrasonic treatment is finished, wherein the drying temperature in the secondary filtration, washing and drying is 60 ℃, and the second intermediate graphite powder can be obtained after the secondary filtration, washing and drying is finished.
(3) And (3) placing the second intermediate graphite powder into a hydrochloric acid solution containing hydrogen peroxide (the mass concentration of the hydrogen peroxide is 1% and the mass concentration of the hydrochloric acid is 6%), heating and stirring for reaction, wherein the heating temperature is 30 ℃, the duration of the heating and stirring reaction is 3 hours, after the reaction is finished, filtering, washing and drying for the third time are carried out, and after the filtering, washing and drying for the third time are finished, the third intermediate graphite powder can be obtained.
(4) And calcining the third intermediate graphite powder, wherein the calcining temperature is 300 ℃, the calcining duration is 2 hours, and the fourth intermediate graphite powder can be obtained after the calcining is finished.
(5) And carrying out secondary ball milling on the fourth intermediate graphite powder by using a ball mill to obtain graphite powder with the particle size range of 10-50 mu m, wherein the weight ratio of the fourth intermediate graphite powder to zirconium balls is 1: and 12, the duration of the second ball milling is 4 h.
(6) Immersing graphite powder in an aqueous solution of potassium permanganate with solute mass fraction of 0.01%, heating to 30 ℃, stirring for reaction for 2 hours, filtering after the reaction is finished, washing with ultrapure water with neutral pH value, and drying to obtain the adsorbing material.
(7) Adding 0.1g of adsorbing material into every 100ml of cadmium-containing wastewater (the cadmium content is 110 mg/L), placing the adsorbing material into the cadmium-containing wastewater at the temperature of 15 ℃, and carrying out oscillation adsorption treatment for 10 hours, wherein the pH value of the solution is kept to be 2 in the oscillation adsorption treatment process.
Example 9.
(1) The waste graphite product is cleaned and dried, and is crushed by a crusher and then is subjected to first ball milling by a ball mill to obtain first intermediate graphite powder.
(2) And (3) soaking the first intermediate graphite powder in a sulfuric acid solution with solute mass fraction of 0.01%, ultrasonically treating for 20min by using ultrasonic waves, and performing secondary filtration, washing and drying after the ultrasonic treatment is finished, wherein the drying temperature in the secondary filtration, washing and drying is 60 ℃, and the second intermediate graphite powder can be obtained after the secondary filtration, washing and drying is finished.
(3) And (3) placing the second intermediate graphite powder into a hydrochloric acid solution containing hydrogen peroxide (the mass concentration of the hydrogen peroxide is 1% and the mass concentration of the hydrochloric acid is 6%), heating and stirring for reaction, wherein the heating temperature is 30 ℃, the duration of the heating and stirring reaction is 3 hours, after the reaction is finished, filtering, washing and drying for the third time are carried out, and after the filtering, washing and drying for the third time are finished, the third intermediate graphite powder can be obtained.
(4) And calcining the third intermediate graphite powder, wherein the calcining temperature is 300 ℃, the calcining duration is 2 hours, and the fourth intermediate graphite powder can be obtained after the calcining is finished.
(5) And carrying out secondary ball milling on the fourth intermediate graphite powder by using a ball mill to obtain graphite powder with the particle size range of 10-50 mu m, wherein the weight ratio of the fourth intermediate graphite powder to zirconium balls is 1: and 12, the duration of the second ball milling is 4 h.
(6) Immersing graphite powder in an aqueous solution of potassium permanganate with solute mass fraction of 0.01%, heating to 30 ℃, stirring for reaction for 2 hours, filtering after the reaction is finished, washing with ultrapure water with neutral pH value, and drying to obtain the adsorbing material.
(7) Adding 0.1g of adsorbing material into every 100ml of cadmium-containing wastewater (the cadmium content is 140 mg/L), placing the adsorbing material into the cadmium-containing wastewater at the temperature of 15 ℃, and carrying out oscillation adsorption treatment for 10 hours, wherein the pH value of the solution is kept to be 2 in the oscillation adsorption treatment process.
Example 10.
(1) The waste graphite product is cleaned and dried, and is crushed by a crusher and then is subjected to first ball milling by a ball mill to obtain first intermediate graphite powder.
(2) And (3) soaking the first intermediate graphite powder in a sulfuric acid solution with solute mass fraction of 0.01%, ultrasonically treating for 20min by using ultrasonic waves, and performing secondary filtration, washing and drying after the ultrasonic treatment is finished, wherein the drying temperature in the secondary filtration, washing and drying is 60 ℃, and the second intermediate graphite powder can be obtained after the secondary filtration, washing and drying is finished.
(3) And (3) placing the second intermediate graphite powder into a hydrochloric acid solution containing hydrogen peroxide (the mass concentration of the hydrogen peroxide is 1% and the mass concentration of the hydrochloric acid is 6%), heating and stirring for reaction, wherein the heating temperature is 30 ℃, the duration of the heating and stirring reaction is 3 hours, after the reaction is finished, filtering, washing and drying for the third time are carried out, and after the filtering, washing and drying for the third time are finished, the third intermediate graphite powder can be obtained.
(4) And calcining the third intermediate graphite powder, wherein the calcining temperature is 300 ℃, the calcining duration is 2 hours, and the fourth intermediate graphite powder can be obtained after the calcining is finished.
(5) And carrying out secondary ball milling on the fourth intermediate graphite powder by using a ball mill to obtain graphite powder with the particle size range of 10-50 mu m, wherein the weight ratio of the fourth intermediate graphite powder to zirconium balls is 1: and 12, the duration of the second ball milling is 4 h.
(6) Immersing graphite powder in an aqueous solution of potassium permanganate with solute mass fraction of 0.01%, heating to 30 ℃, stirring for reaction for 2 hours, filtering after the reaction is finished, washing with ultrapure water with neutral pH value, and drying to obtain the adsorbing material.
(7) Adding 0.1g of adsorbing material into every 100ml of cadmium-containing wastewater (the cadmium content is 160 mg/L), placing the adsorbing material into the cadmium-containing wastewater at the temperature of 15 ℃, and carrying out oscillation adsorption treatment for 10 hours, wherein the pH value of the solution is kept to be 2 in the oscillation adsorption treatment process.
Example 11.
(1) The waste graphite product is cleaned and dried, and is crushed by a crusher and then is subjected to first ball milling by a ball mill to obtain first intermediate graphite powder.
(2) And (3) soaking the first intermediate graphite powder in a sulfuric acid solution with solute mass fraction of 0.05%, ultrasonically treating for 40min by using ultrasonic waves, and performing secondary filtration, washing and drying after the ultrasonic treatment is finished, wherein the drying temperature in the secondary filtration, washing and drying is 100 ℃, and the second intermediate graphite powder can be obtained after the secondary filtration, washing and drying is finished.
(3) And (3) placing the second intermediate graphite powder into a hydrochloric acid solution containing hydrogen peroxide (the mass concentration of the hydrogen peroxide is 5% and the mass concentration of the hydrochloric acid is 12%), heating and stirring for reaction, wherein the heating temperature is 90 ℃, the duration of the heating and stirring reaction is 8 hours, after the reaction is finished, filtering, washing and drying for the third time are carried out, and after the filtering, washing and drying for the third time are finished, the third intermediate graphite powder can be obtained.
(4) And calcining the third intermediate graphite powder, wherein the calcining temperature is 500 ℃, the calcining duration is 8 hours, and the fourth intermediate graphite powder can be obtained after the calcining is finished.
(5) And carrying out secondary ball milling on the fourth intermediate graphite powder by using a ball mill to obtain graphite powder with the particle size range of 10-50 mu m, wherein the weight ratio of the fourth intermediate graphite powder to zirconium balls is 1: and 36, the duration of the second ball milling is 12 h.
(6) Immersing graphite powder in an aqueous solution of potassium permanganate with solute mass fraction of 0.05%, heating to 70 ℃, stirring for reaction for 5 hours, filtering after the reaction is finished, washing with ultrapure water with neutral pH value, and drying to obtain the adsorbing material.
(7) Adding 0.1g of adsorbing material into every 100ml of cadmium-containing wastewater (the cadmium content is 50 mg/L), placing the adsorbing material into the cadmium-containing wastewater at the temperature of 35 ℃, and carrying out oscillation adsorption treatment for 30 hours, wherein the pH value of the solution is kept to be 6 in the oscillation adsorption treatment process.
Example 12.
(1) The waste graphite product is cleaned and dried, and is crushed by a crusher and then is subjected to first ball milling by a ball mill to obtain first intermediate graphite powder.
(2) And (3) soaking the first intermediate graphite powder in a sulfuric acid solution with solute mass fraction of 0.05%, ultrasonically treating for 40min by using ultrasonic waves, and performing secondary filtration, washing and drying after the ultrasonic treatment is finished, wherein the drying temperature in the secondary filtration, washing and drying is 100 ℃, and the second intermediate graphite powder can be obtained after the secondary filtration, washing and drying is finished.
(3) And (3) placing the second intermediate graphite powder into a hydrochloric acid solution containing hydrogen peroxide (the mass concentration of the hydrogen peroxide is 5% and the mass concentration of the hydrochloric acid is 12%), heating and stirring for reaction, wherein the heating temperature is 90 ℃, the duration of the heating and stirring reaction is 8 hours, after the reaction is finished, filtering, washing and drying for the third time are carried out, and after the filtering, washing and drying for the third time are finished, the third intermediate graphite powder can be obtained.
(4) And calcining the third intermediate graphite powder, wherein the calcining temperature is 500 ℃, the calcining duration is 8 hours, and the fourth intermediate graphite powder can be obtained after the calcining is finished.
(5) And carrying out secondary ball milling on the fourth intermediate graphite powder by using a ball mill to obtain graphite powder with the particle size range of 10-50 mu m, wherein the weight ratio of the fourth intermediate graphite powder to zirconium balls is 1: and 36, the duration of the second ball milling is 12 h.
(6) Immersing graphite powder in an aqueous solution of potassium permanganate with solute mass fraction of 0.05%, heating to 70 ℃, stirring for reaction for 5 hours, filtering after the reaction is finished, washing with ultrapure water with neutral pH value, and drying to obtain the adsorbing material.
(7) Adding 0.1g of adsorbing material into every 100ml of cadmium-containing wastewater (the cadmium content is 70 mg/L), placing the adsorbing material into the cadmium-containing wastewater at the temperature of 35 ℃, and carrying out oscillation adsorption treatment for 30 hours, wherein the pH value of the solution is kept to be 6 in the oscillation adsorption treatment process.
Example 13.
(1) The waste graphite product is cleaned and dried, and is crushed by a crusher and then is subjected to first ball milling by a ball mill to obtain first intermediate graphite powder.
(2) And (3) soaking the first intermediate graphite powder in a sulfuric acid solution with solute mass fraction of 0.05%, ultrasonically treating for 40min by using ultrasonic waves, and performing secondary filtration, washing and drying after the ultrasonic treatment is finished, wherein the drying temperature in the secondary filtration, washing and drying is 100 ℃, and the second intermediate graphite powder can be obtained after the secondary filtration, washing and drying is finished.
(3) And (3) placing the second intermediate graphite powder into a hydrochloric acid solution containing hydrogen peroxide (the mass concentration of the hydrogen peroxide is 5% and the mass concentration of the hydrochloric acid is 12%), heating and stirring for reaction, wherein the heating temperature is 90 ℃, the duration of the heating and stirring reaction is 8 hours, after the reaction is finished, filtering, washing and drying for the third time are carried out, and after the filtering, washing and drying for the third time are finished, the third intermediate graphite powder can be obtained.
(4) And calcining the third intermediate graphite powder, wherein the calcining temperature is 500 ℃, the calcining duration is 8 hours, and the fourth intermediate graphite powder can be obtained after the calcining is finished.
(5) And carrying out secondary ball milling on the fourth intermediate graphite powder by using a ball mill to obtain graphite powder with the particle size range of 10-50 mu m, wherein the weight ratio of the fourth intermediate graphite powder to zirconium balls is 1: and 36, the duration of the second ball milling is 12 h.
(6) Immersing graphite powder in an aqueous solution of potassium permanganate with solute mass fraction of 0.05%, heating to 70 ℃, stirring for reaction for 5 hours, filtering after the reaction is finished, washing with ultrapure water with neutral pH value, and drying to obtain the adsorbing material.
(7) Adding 0.1g of adsorbing material into every 100ml of cadmium-containing wastewater (the cadmium content is 90 mg/L), placing the adsorbing material into the cadmium-containing wastewater at the temperature of 35 ℃, and carrying out oscillation adsorption treatment for 30 hours, wherein the pH value of the solution is kept to be 6 in the oscillation adsorption treatment process.
Example 14.
(1) The waste graphite product is cleaned and dried, and is crushed by a crusher and then is subjected to first ball milling by a ball mill to obtain first intermediate graphite powder.
(2) And (3) soaking the first intermediate graphite powder in a sulfuric acid solution with solute mass fraction of 0.05%, ultrasonically treating for 40min by using ultrasonic waves, and performing secondary filtration, washing and drying after the ultrasonic treatment is finished, wherein the drying temperature in the secondary filtration, washing and drying is 100 ℃, and the second intermediate graphite powder can be obtained after the secondary filtration, washing and drying is finished.
(3) And (3) placing the second intermediate graphite powder into a hydrochloric acid solution containing hydrogen peroxide (the mass concentration of the hydrogen peroxide is 5% and the mass concentration of the hydrochloric acid is 12%), heating and stirring for reaction, wherein the heating temperature is 90 ℃, the duration of the heating and stirring reaction is 8 hours, after the reaction is finished, filtering, washing and drying for the third time are carried out, and after the filtering, washing and drying for the third time are finished, the third intermediate graphite powder can be obtained.
(4) And calcining the third intermediate graphite powder, wherein the calcining temperature is 500 ℃, the calcining duration is 8 hours, and the fourth intermediate graphite powder can be obtained after the calcining is finished.
(5) And carrying out secondary ball milling on the fourth intermediate graphite powder by using a ball mill to obtain graphite powder with the particle size range of 10-50 mu m, wherein the weight ratio of the fourth intermediate graphite powder to zirconium balls is 1: and 36, the duration of the second ball milling is 12 h.
(6) Immersing graphite powder in an aqueous solution of potassium permanganate with solute mass fraction of 0.05%, heating to 70 ℃, stirring for reaction for 5 hours, filtering after the reaction is finished, washing with ultrapure water with neutral pH value, and drying to obtain the adsorbing material.
(7) Adding 0.1g of adsorbing material into every 100ml of cadmium-containing wastewater (the cadmium content is 130 mg/L), placing the adsorbing material into the cadmium-containing wastewater at the temperature of 35 ℃, and carrying out oscillation adsorption treatment for 30 hours, wherein the pH value of the solution is kept to be 6 in the oscillation adsorption treatment process.
Example 15.
(1) The waste graphite product is cleaned and dried, and is crushed by a crusher and then is subjected to first ball milling by a ball mill to obtain first intermediate graphite powder.
(2) And (3) soaking the first intermediate graphite powder in a sulfuric acid solution with solute mass fraction of 0.05%, ultrasonically treating for 40min by using ultrasonic waves, and performing secondary filtration, washing and drying after the ultrasonic treatment is finished, wherein the drying temperature in the secondary filtration, washing and drying is 100 ℃, and the second intermediate graphite powder can be obtained after the secondary filtration, washing and drying is finished.
(3) And (3) placing the second intermediate graphite powder into a hydrochloric acid solution containing hydrogen peroxide (the mass concentration of the hydrogen peroxide is 5% and the mass concentration of the hydrochloric acid is 12%), heating and stirring for reaction, wherein the heating temperature is 90 ℃, the duration of the heating and stirring reaction is 8 hours, after the reaction is finished, filtering, washing and drying for the third time are carried out, and after the filtering, washing and drying for the third time are finished, the third intermediate graphite powder can be obtained.
(4) And calcining the third intermediate graphite powder, wherein the calcining temperature is 500 ℃, the calcining duration is 8 hours, and the fourth intermediate graphite powder can be obtained after the calcining is finished.
(5) And carrying out secondary ball milling on the fourth intermediate graphite powder by using a ball mill to obtain graphite powder with the particle size range of 10-50 mu m, wherein the weight ratio of the fourth intermediate graphite powder to zirconium balls is 1: and 36, the duration of the second ball milling is 12 h.
(6) Immersing graphite powder in an aqueous solution of potassium permanganate with solute mass fraction of 0.05%, heating to 70 ℃, stirring for reaction for 5 hours, filtering after the reaction is finished, washing with ultrapure water with neutral pH value, and drying to obtain the adsorbing material.
(7) Adding 0.1g of adsorbing material into every 100ml of cadmium-containing wastewater (the cadmium content is 200 mg/L), placing the adsorbing material into the cadmium-containing wastewater at the temperature of 35 ℃, and carrying out oscillation adsorption treatment for 30h, wherein the pH value of the solution is kept to be 6 in the oscillation adsorption treatment process.
Referring to FIG. 3, which is a graph showing the adsorption capacity data of the adsorbent in the wastewater containing cadmium of different concentrations in examples 1 to 15 of the present invention, it can be seen from FIG. 3 that the maximum adsorption capacity of the adsorbent provided by the present invention is 84 mg/g.
According to the method for removing cadmium in wastewater provided by the invention, waste graphite products are recycled to prepare raw material graphite powder, and the adsorption material prepared from the graphite powder is used for carrying out shock adsorption treatment on cadmium-containing wastewater, so that the technical problems that the cost of the adsorbent preparation process in the prior art is too high, the adsorption efficiency of the adsorbent is low due to the low adsorption capacity of the adsorbent, and the industrialization is not facilitated can be effectively solved.
Although the preferred embodiments of the present invention have been disclosed for illustrative purposes, those skilled in the art will appreciate that various modifications, additions and substitutions are possible, without departing from the scope and spirit of the invention as disclosed in the accompanying claims.
Claims (10)
1. A method for removing cadmium in wastewater is characterized by comprising the following steps: graphite powder is immersed in a potassium permanganate solution and heated and stirred for reaction, after the reaction is finished, the graphite powder is filtered, washed and dried for the first time, an adsorbing material can be obtained, and finally the adsorbing material is placed into cadmium-containing wastewater for oscillation adsorption treatment, wherein the adsorbing material is a manganese dioxide-loaded graphite powder composite material.
2. The method according to claim 1, wherein the pH of the solution is controlled to be 2-6 during the oscillating adsorption treatment.
3. The method according to claim 1, wherein during the oscillating adsorption treatment, the oscillating adsorption temperature is 15-35 ℃ and the oscillating adsorption time is 10-30 h.
4. The method according to claim 3, wherein during the oscillating adsorption treatment, the oscillating adsorption temperature is 25 ℃ and the oscillating adsorption time is 24 hours.
5. The method according to claim 1, wherein the graphite powder is immersed in the potassium permanganate solution and heated at the temperature of 30-70 ℃, and the stirring reaction lasts for 2-6 hours.
6. The method according to claim 5, wherein the graphite powder is immersed in the potassium permanganate solution and heated at 50 ℃, and the stirring reaction lasts for 4 hours.
7. The method according to claim 1, wherein the solute mass fraction of the potassium permanganate solution is 0.01-0.05%.
8. The method of claim 1, wherein the graphite powder is prepared by recycling waste graphite products.
9. The method as claimed in claim 8, wherein the method for preparing graphite powder by recycling waste graphite products comprises the following steps:
s1: cleaning and airing the waste graphite product, crushing the waste graphite product by a crusher, and performing first ball milling by a ball mill to obtain first intermediate graphite powder;
s2: soaking the first intermediate graphite powder in a sulfuric acid solution, performing ultrasonic treatment, performing secondary filtration, washing and drying after the ultrasonic treatment is finished, and obtaining second intermediate graphite powder after the secondary filtration, washing and drying is finished;
s3: placing the second intermediate graphite powder into a hydrochloric acid solution containing hydrogen peroxide to be heated and stirred for reaction, carrying out third filtration, washing and drying after the reaction is finished, and obtaining third intermediate graphite powder after the third filtration, washing and drying is finished;
s4: calcining the third intermediate graphite powder to obtain fourth intermediate graphite powder;
s5: and performing secondary ball milling on the fourth intermediate graphite powder by using a ball mill to obtain graphite powder.
10. The method according to claim 9, characterized in that the particle size of the graphite powder obtained in the step S5 is 10-50 μm.
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| US20140081067A1 (en) * | 2011-02-25 | 2014-03-20 | William Marsh Rice University | Sorption and separation of various materials by graphene oxides |
| CN109745948A (en) * | 2019-03-07 | 2019-05-14 | 中国科学院过程工程研究所 | One kind except cadmium adsorbent, and its preparation method and application |
| CN110396598A (en) * | 2019-07-22 | 2019-11-01 | 广东环境保护工程职业学院 | A kind of method that waste and old lithium ion battery manganate cathode material for lithium recycles |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US20140081067A1 (en) * | 2011-02-25 | 2014-03-20 | William Marsh Rice University | Sorption and separation of various materials by graphene oxides |
| CN109745948A (en) * | 2019-03-07 | 2019-05-14 | 中国科学院过程工程研究所 | One kind except cadmium adsorbent, and its preparation method and application |
| CN110396598A (en) * | 2019-07-22 | 2019-11-01 | 广东环境保护工程职业学院 | A kind of method that waste and old lithium ion battery manganate cathode material for lithium recycles |
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| CN114950361A (en) * | 2022-04-29 | 2022-08-30 | 上海交通大学 | Method for preparing composite adsorbent by waste lithium batteries |
| CN114950361B (en) * | 2022-04-29 | 2023-09-29 | 上海交通大学 | Method for preparing composite adsorbent through waste lithium batteries |
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