CN115999604A - Method for preparing efficient core-shell structure catalyst by taking tail end waste residue recovered from waste ternary lithium battery as raw material, product and application - Google Patents
Method for preparing efficient core-shell structure catalyst by taking tail end waste residue recovered from waste ternary lithium battery as raw material, product and application Download PDFInfo
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Images
Abstract
The invention discloses a method for preparing a high-efficiency core-shell structure catalyst by taking tail end waste residues recovered from waste ternary lithium batteries as raw materials, a product and application thereof. The invention takes the tail end waste residue recovered by the waste ternary lithium battery as a raw material, mixes the raw material with a nitrogen source, heats up, calcines under inert gas, and cools to obtain the core-shell structure catalyst. The catalyst with the core-shell structure can efficiently activate monopersulfate to degrade organic pollutants, is little influenced by environmental conditions in the degradation process, has little metal dissolution compared with untreated waste residues, and can fix toxic metal elements in the waste residues. Therefore, the core-shell structured catalyst is applied to the degradation of organic pollutants by activating monopersulfate.
Description
Technical Field
The invention belongs to the technical fields of chemical materials and pollutant treatment, and particularly relates to a method for preparing a high-efficiency core-shell structure catalyst by taking tail end waste residues recovered from waste ternary lithium batteries as raw materials, a product and application thereof.
Background
With the popularization of electric automobiles and the fact that 3C products become living necessities of people, the recovery treatment of waste lithium batteries becomes an urgent problem to be solved. New energy automobiles are brought into strategic industry planning in 2010 in China, the production rate is over 50% in 2015-2018, and the sales of the new energy automobiles in 2019 reaches 120.6 ten thousand. The service life of the lithium battery is about 3-5 years, and by 2025 years, the waste lithium ion battery is expected to reach 64 ten thousand tons. Ternary material Li (NixCoyMn 1-x-y) O 2 Because of the high specific mass capacity, high specific mass energy and high specific volume energy, and the high rate performance and low temperature performance of the material, the material becomes a pet of a new energy passenger car, and the loading capacity is increased year by year. The positive electrode material of the ternary lithium battery mainly comprises lithium, nickel, cobalt and manganese, and the negative electrode material is conductive graphite. The current lithium battery recovery process mainly comprises the steps of recovering a metal shell and recovering organic metals such as lithium, nickel, cobalt and the like in a positive electrode material. According to the current recovery process, the recovery efficiency cannot reach 100%, so that part of metal elements such as nickel, cobalt, manganese and the like can exist in the recovered waste residues, and the random discarding can cause heavy metal dissolution, thereby causing environmental risks. In addition, nickel, cobalt, manganese and other elements are transition metal elements with better catalytic activity.
Advanced oxidation technology is a common technology for organically polluting wastewater. Compared with H used in the traditional advanced oxidation 2 O 2 The persulfate oxidizer has the advantages of low storage and transportation cost, wide activation technology, little influence of environmental conditions in the oxidation process, and the like. Monopersulfate (PMS) is a highly effective stabilizing oxidant commonly used in persulfate oxidation technology. The activation technology of PMS includes thermal activation, transition metal ion activation, alkali activation, ultraviolet light activation, etc. However, existing living organismsThe method has the defects of high energy consumption, secondary pollution of heavy metal ions and the like. The development of efficient and safe catalysts is a precondition for the wide application of persulfate oxidizer-based degradation technologies. Therefore, the development of the carbon catalyst with simple synthesis method, good effect and low cost has very important significance.
Disclosure of Invention
The invention aims at overcoming the defects and shortcomings of the prior art and providing a method for preparing a high-efficiency core-shell structure catalyst by taking terminal waste residue recovered from a waste ternary lithium battery as a raw material. The method is a one-step synthesis method, wherein the waste residue at the tail end of the waste ternary lithium battery after Li, ni, co, mn and other magnetic metals are extracted is used as a raw material, melamine is added as a nitrogen source, and the catalyst with a core-shell structure is prepared through a simple one-step synthesis method, so that organic pollutants can be efficiently activated by monopersulfate to degrade, heavy metal ions can be fixed, and the heavy metal pollution risk caused by metal ion dissolution is reduced.
It is another object of the present invention to provide a highly efficient core-shell structured catalyst obtained by the above method.
It is still another object of the present invention to provide the use of the above-described high efficiency core-shell structured catalyst.
The aim of the invention is achieved by the following technical scheme:
a method for preparing a high-efficiency core-shell structure catalyst by taking tail end waste residues recovered from waste ternary lithium batteries as raw materials comprises the following steps: and mixing the raw materials with a nitrogen source, heating, calcining under inert gas, and cooling to obtain the core-shell catalyst.
The tail end waste residue is obtained by recycling metal shells of waste ternary lithium batteries and recycling organic metals such as lithium, nickel, cobalt and the like in positive electrode materials.
The nitrogen source is preferably melamine powder.
The raw materials and the nitrogen source are preferably mixed according to the mass ratio of 1: 3-3: 1, proportioning; more preferably in a mass ratio of 1:1 proportion.
The inert gas is used for ensuring that the reaction environment is free of oxygen and does not participate in the reaction; preferably nitrogen or argon.
The heating rate is preferably 4-6 ℃/min; more preferably 5 deg.c/min.
The calcination conditions are preferably 750-850 ℃ for 1 hour; more preferably calcined at 800 c for 1 hour.
The calcination equipment is preferably a tube furnace.
The cooling is preferably natural cooling.
The method further comprises the following steps: and (5) cleaning and drying the obtained core-shell catalyst.
The cleaning solvent is preferably ultrapure water.
The drying temperature is preferably 100-110 ℃; more preferably 105 ℃.
The high-efficiency core-shell structure catalyst is prepared by the method.
The high-efficiency core-shell catalyst can efficiently activate monopersulfate to degrade organic pollutants, the degradation process is little affected by environmental conditions, and compared with untreated waste residues, the catalyst has the advantages that only a very small amount of metal is dissolved out, and toxic metal elements in the waste residues can be fixed. Therefore, the high-efficiency core-shell structure catalyst is applied to the degradation of organic pollutants by activating monopersulfate.
Such organic contaminants include, but are not limited to, 2, 4-dichlorophenol, phenol, carbamazepine, benzoic acid, 1-naphthol, and the like.
The organic pollutant is preferably the organic pollutant in the water body, so that the high-efficiency core-shell catalyst can be used for organic wastewater treatment.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) The catalyst developed by the invention has a core-shell structure, the nano-scale graphite shell wraps metal nitrogen oxides, transition metals are fixed, the transition metals are prevented from being dissolved out in the reaction process, and the environmental risk of heavy metal dissolution is avoided.
(2) The core-shell structure material prepared by the invention can efficiently activate PMS to degrade organic pollutants, the dosage is small, and the effect of environmental conditions on degradation is less.
(3) The material provided by the invention has the advantages of simple preparation method, the raw material is dangerous industrial waste, the dangerous waste is changed into a high-value catalyst through a one-step synthesis method, and the material has the condition of large-scale industrial production and high economic value.
Drawings
FIG. 1 is a scanning electron microscope image and element distribution diagram of the original waste residue and the catalyst with a core-shell structure.
FIG. 2 is a transmission electron microscope and element distribution diagram of the original slag and the core-shell catalyst.
FIG. 3 is a graph showing the kinetic results of a core-shell catalyst for catalyzing monopersulfate to degrade organic pollutants.
FIG. 4 is a graph showing the results of the catalytic degradation of 2, 4-dichlorophenol by a core-shell catalyst at different pH conditions.
FIG. 5 is a graph showing the effect of anions on the catalytic degradation of 2, 4-dichlorophenol by monopersulfate with a core-shell catalyst.
FIG. 6 is a graph showing the results of the degradation of 2, 4-dichlorophenol by a core-shell structured catalyst under the condition of different concentrations of humic acid.
FIG. 7 is a graph showing the results of water washing of a core-shell catalyst.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but embodiments of the present invention are not limited thereto.
Example 1
The preparation method of the core-shell structure catalyst in the embodiment comprises the following specific steps:
adding the tail end waste residue recovered from the powdery 1g waste ternary lithium battery and 1g melamine into a corundum ark, fully and uniformly mixing by using a spoon, putting into a tubular furnace, and introducing high-purity N 2 Ensuring that the air outlet valve is unblocked, then raising the temperature from room temperature to 800 ℃ at a heating rate of 5 ℃/min, keeping the temperature for one hour, naturally cooling to room temperature, cleaning with ultrapure water for three times, and drying in a blast drying oven at 105 ℃.
The results of scanning electron microscopy and transmission electron microscopy of the virgin slag (NCM 0) and the core-shell structured catalyst (NCM 1) are shown in FIG. 1. Fig. 1 (a) and 1 (b) are scanning electron microscope images of the raw waste residue (NCM 0) and the core-shell catalyst (NCM 1), respectively. As can be seen from fig. 1, the morphology of both materials is that the composite metal is attached to the surface of the bulk graphite in the form of particles, but the particles of NCM0 are irregular, and the particles of NCM1 are more nearly regular spheres. Fig. 2 is a transmission electron microscope image and an element distribution surface scanning image of a core-shell structure catalyst (NCM 1), and the result shows that the material is of a core-shell structure, the shell is a carbon layer, and the core is nitrogen oxide of various metal elements.
The 0.31g waste residue is put into a digestion tank to be digested by aqua regia, and the basic information of metal in the material can be obtained by conversion after the concentration is measured: ni 0.103g/g; co 0.008g/g; mn 0.012g/g.
Application example 1:
to analyze the performance of the core-shell structured catalyst (NCM 1) in example 1 to activate PMS for degradation of organic contaminants, NCM 1-activated PMS degradation experiments on 2, 4-dichlorophenol, 1-naphthol, phenol, benzoic acid, and carbamazepine at 20 ℃ were performed in 150mL Erlenmeyer flasks.
Which comprises the following steps:
3mg of the core-shell structured catalyst (NCM 1) prepared in example 1 was added to 100mL of the target contaminant solution (initial concentration 0.05 mM), and after adsorption equilibrium was reached, the degradation kinetics experiment was started by adding PMS solution. In the experimental system, the pH is controlled to be 7 by preparing phosphate buffer solution with deionized water, the concentration of the phosphate buffer solution is 5.67mM/L, the initial concentration of PMS is 1mM, and the reaction temperature is 20 ℃. The reaction process is that 99mL buffer solution is firstly put into a conical flask, 1mL of organic matter mother solution with the concentration of 5mM is added, a magnetic stirrer is started, the amount of organic matters removed by adsorption is sampled and measured at 30min and 60min, and the adsorption balance is achieved after 60 min. As a result, as shown in FIG. 3A, the adsorption removal rates of NCM1 for 2, 4-dichlorophenol, 1-naphthol, phenol, benzoic acid, and carbamazepine were 11%, 10%, 2%, 1%, and 3%, respectively, and the adsorption removal tendencies showed large adsorption amounts for the hydrophobic organic matters and the anionic organic matters. Then 1mL of PMS mother liquor at a concentration of 100mM was added to start degradation. At fixed time points 1mL of the teflon filter head was sampled with a syringe into a chromatographic bottle containing 20 μl of 2M sodium thiosulfate solution to quench the residual PMS in the sample. After 2 hours of degradation, the residual rates of 2, 4-dichlorophenol, 1-naphthol, phenol, benzoic acid and carbamazepine in the NCM system solution were 0, 50%, 35% and 48%, respectively.
In addition, metal elution of NCM0 and NCM1 after degradation of phenol and benzoic acid in the same degradation system was measured by ICP-OES to give the results shown in FIG. 3B. The NCM0 system has high concentration of Ni, co and Mn dissolved out, and the metal dissolved out in the system for degrading phenol is higher than that in the system for degrading benzoic acid. However, after the reaction is completed, ni and Co of the catalyst prepared by the method are below the detection limit of ICP-OES, and are not detected, and only a trace amount of Mn is detected. Compared with NCM0 system, the metal dissolution of NCM1 is greatly reduced, which shows that the method can effectively fix toxic metal elements in waste residues and prevent the toxic metal elements from dissolution in the catalytic reaction process.
Application example 2:
to further verify the effect of environmental factors on the performance of the catalyst NCM 1-activated PMS in example 1 to degrade organic contaminants, NCM 1-activated PMS degradation experiments on 2, 4-dichlorophenol under different environmental conditions including pH, common anions, and humic acid were performed in 125mL Erlenmeyer flasks.
To verify the effect of pH, 100mL of 2, 4-dichlorophenol solution (initial concentration of 0.05 mM) and PMS solution (initial concentration of 1 mM) were used to adjust the pH of the system to 3, 5, 7 and 9 with perchloric acid and sodium hydroxide, respectively, and 3mg of the catalyst of example 1 was added to start the degradation kinetics experiment, the reaction temperature was 20℃and the results were shown in FIG. 4. As can be seen from FIG. 4, the degradation system can effectively remove 2, 4-dichlorophenol in the pH range of 3-9, and the system pH has less influence on the degradation rate. But relatively neutral conditions (ph=5 to 7) are more advantageous for the removal of 2, 4-dichlorophenol by the system.
When verifying the effect of anions and humic acid, 3mg of the core-shell catalyst (NCM 1) prepared in example 1 was added to 100mL of 2, 4-dichlorophenol solution to ensure the initial 2, 4-dichlorophenolThe concentration was 0.05mM, respectively, with KNO added 3 NaHCO (100 mM concentration) 3 (concentration 100 mM) and humic acid (concentration 10mg/L, 25mg/L and 50 mg/L) were added to the solution after 30min to reach adsorption equilibrium, and then the experiment of degradation kinetics was started by adding PMS solution (initial concentration 1 mM). In the experimental system, the pH is controlled to be 7 by preparing phosphate buffer solution by deionized water, and the reaction temperature is 20 ℃. The results are shown in FIGS. 5 and 6. FIG. 5 is the effect of high concentrations (100 mM) of common anions on degradation. The results showed that HCO 3 - Inhibiting degradation of 2, 4-dichlorophenol, NO 3 - Can promote the degradation of 2, 4-dichlorophenol. FIG. 6 shows the effect of humic acid of different concentrations on degradation. 10mg/L and 25mg/L of humic acid slightly inhibited 2, 4-dichlorophenol, and when the humic acid concentration was raised to 50mg/L, 2, 4-dichlorophenol was significantly inhibited. Overall, the system is less affected by environmental conditions.
Application example 3:
to further analyze the effect of the core-shell catalyst prepared in example 1 on the repeated use, a water washing cycle use experiment was added on the basis of the experiment of application example 1.
In detail, 30mg of the core-shell structured catalyst (NCM 1) prepared in example 1 was added to 1000mL of the target contaminant solution (initial concentration of 0.05 mM), and the degradation kinetics experiments were started by adding PMS solution at an initial concentration of 1mM for PMS, while 2 experiments were carried out in the same setting. After degradation for 2 hours, the materials in the degradation system are all collected on filter paper by vacuum suction filtration, the filter paper is washed 3 times with 500mL of ultrapure water, and then the filter paper is transferred into a glass culture dish for drying. A similar procedure was used for the subsequent 4 cycles. The degradation kinetics data of 2, 4-dichlorophenol in each experiment were determined and the results are shown in FIG. 7.
FIG. 7 shows that the degradation rate of NCM1,2, 4-dichlorophenol after each degradation by washing with pure water decreases with the increase of the number of cycles, and the residual rate of 2, 4-dichlorophenol after 2 hours was about 20.0% by the fifth cycle. Illustrating that the materials prepared by the method of example 1 have good stability. The 5-time metal elution data are shown in table 1. The metal ions are obviously reduced along with the increase of the cycle times, wherein the highest nickel concentration of the first cycle is 0.179mg/L, which is lower than 1mg/L specified by the integrated wastewater discharge Standard (GB 8978-1996) and is also lower than the standard of 0.5mg/L specified by the copper-nickel-cobalt industrial pollutant discharge Standard (GB 25467-2010). In combination with NCM1 as a catalyst to degrade phenol and benzoic acid, it can be seen that the extent of metal dissolution is different for different contaminants of degradation (FIG. 3B).
TABLE 1 concentration of Metal ions in System after five cycle degradation experiments
Note that: ND represents a detection limit below ICP-OES.
In addition, the mass ratio of the tail end waste residue and the melamine which are recovered by the waste ternary lithium battery is 1:3 and 3:1, the mass ratio is 1:3 is also better but the cost is relatively higher, so the preferred technical scheme is as shown in example 1, the mass ratio is 1:1.
the above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (10)
1. The method for preparing the high-efficiency core-shell structure catalyst by taking the tail end waste residue recovered by the waste ternary lithium battery as the raw material is characterized by comprising the following steps: and mixing the raw materials with a nitrogen source, heating, calcining under inert gas, and cooling to obtain the core-shell catalyst.
2. The method of claim 1, further comprising the step of: and (5) cleaning and drying the obtained core-shell catalyst.
3. The method according to claim 1 or 2, characterized in that:
the nitrogen source is melamine powder;
the raw materials and the nitrogen source are mixed according to the mass ratio of 1: 3-3: 1 proportion.
4. The method according to claim 1 or 2, characterized in that:
the inert gas is nitrogen or argon.
5. The method according to claim 1 or 2, characterized in that:
the heating rate is 4-6 ℃/min;
the calcining condition is that the calcining is carried out for 1 hour at 750-850 ℃;
the calcining equipment is a tube furnace;
the cooling is natural cooling.
6. The method according to claim 2, characterized in that:
the cleaning solvent is ultrapure water;
the drying temperature is 100-110 ℃.
7. A high-efficiency core-shell structure catalyst is characterized in that: is prepared by the method of any one of claims 1 to 6.
8. The use of the high-efficiency core-shell structured catalyst of claim 7 for activating monopersulfate to degrade organic pollutants.
9. The use according to claim 8, characterized in that: the organic contaminants include, but are not limited to, 2, 4-dichlorophenol, phenol, carbamazepine, benzoic acid, 1-naphthol.
10. Use according to claim 8 or 9, characterized in that: the organic pollutant is the organic pollutant in the water body.
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