CN108147566A - A kind of method using waste lithium ion cell anode material catalytic degradation organic wastewater - Google Patents

Abstract

The invention discloses a method for catalytically degrading organic waste water by using the anode material of a waste lithium ion battery; the method comprises: dismantling the waste lithium ion battery, taking out the anode material, collecting the powder of the anode material after heat treatment, and putting it into organic waste In the aqueous solution, it acts as a catalyst for adsorption for a period of time. Then put tetravalent sulfur (S ( )) Salt or monopersulfate (PMS) solution, after a certain period of degradation reaction, purified wastewater can be obtained. The mass ratio of the positive electrode material powder and the total organic matter in the organic wastewater is 1:10~1:100; the present invention is characterized in that it is carried out under normal temperature and pressure, the reaction conditions are mild, the reaction speed is fast, easy to operate, and the catalyst can be reused . The purpose of degrading organic wastewater is achieved while recycling waste lithium-ion batteries as resources.

Description

A method for catalytically degrading organic wastewater using waste lithium-ion battery cathode materials

technical field

The invention belongs to the technical field of electronic waste recycling and organic wastewater treatment, and in particular relates to an advanced oxidation technology using tetravalent sulfur salt or monopersulfate (PMS) solution as an oxidant.

Background technique

In recent years, advanced oxidation processes (Advanced Oxidation Processes, AOPs) based on free radical reactions, because of their strong oxidation ability, fast reaction rate, small selectivity, mild reaction conditions, high flexibility and high mineralization rate of organic pollutants, etc. Advantages, it has developed rapidly in the field of organic wastewater treatment. These free radicals include sulfate radicals (SO ₄ ^•- ), hydroxyl radicals (•OH), superoxide anion radicals (O ₂ ^•- ), etc. They decompose macromolecular organic matter into small molecular organic matter through electron transfer, and then decompose small molecular organic matter into carbon dioxide and water.

Lithium-ion battery has become the battery system with the best comprehensive performance due to its unique advantages such as high specific energy, small size, light weight, wide application temperature range, low self-discharge rate, long cycle life, and good safety performance. Volume and scrap are in a stage of rapid growth.

Contents of the invention

The technical problem to be solved by the present invention is to provide a method for catalytically degrading organic wastewater by using the anode material of waste lithium-ion batteries. The present invention is carried out at normal temperature and pressure, with mild reaction conditions, fast reaction speed, easy operation, and reusable catalyst. It has great application potential in the field of recycling electronic waste and treating organic wastewater.

The technical solution of the present invention is specifically introduced as follows.

The invention provides a method for catalytically degrading organic wastewater by using the anode material of a waste lithium ion battery, comprising the following steps:

(1) Disassemble the used lithium-ion battery, take out the positive electrode material, and collect the positive electrode material powder with a particle size of 10 ~ 100 µm after heat treatment;

(2) Put the positive electrode material powder in the organic wastewater solution for normal temperature adsorption, the adsorption time is 0.5~1h, and then add an oxidant to catalytically degrade the organic wastewater at normal temperature; wherein: the oxidant is selected from sulfite, sulfurous acid One or more of hydrogen salt or monopersulfate PMS.

In the above step (1), the waste lithium ion battery is a lithium cobalt oxide battery or a lithium iron phosphate battery.

In the above step (2), the organic wastewater solution contains one or more of rhodamine, methylene blue or 2,4,6-trichlorophenol.

In the above step (2), the initial pH value of the organic wastewater solution is between 2 and 9; the total molar concentration of organic matter in the organic wastewater solution is between 0.01 mM and 1 mM.

In the above step (1), the mass ratio of the cathode material powder to the total organic matter in the organic wastewater is 1:10-1:100; the adsorption time is 0.5-1h.

In the above step (2), the molar ratio of the oxidant to the total organic matter in the organic wastewater is 2:1 to 100:1. Preferably, the molar ratio is 20:1-80:1.

In the above step (2), the degradation reaction time is 1-30 min.

In the above step (2), the degradation reaction time is 1-20 min.

Compared with the prior art, the present invention has the following advantages:

1. The present invention uses waste lithium-ion batteries as a catalyst to degrade organic waste water to achieve the purpose of treating waste with waste.

2. The present invention has mild reaction conditions, fast reaction speed, wide reaction pH range and easy operation.

3. The catalyst of the present invention can be recycled and reused, and is environmentally friendly.

4. The present invention has a good effect in degrading organic pollutants, and has great application potential in the field of environmental governance.

Detailed ways

Below in conjunction with specific embodiment, further illustrate the present invention. It should be understood that these examples are only for illustrating the present invention and are not intended to limit the scope of the present invention. In addition, it should be understood that those skilled in the art may make various changes or modifications to the present invention after reading the teachings of the present invention, and these equivalent forms also fall within the scope defined by the appended claims of the present application.

Example 1

In this example, the method for degrading rhodamine B (RhB) with waste lithium cobalt oxide battery positive electrode materials includes the following steps:

1. Disassemble the lithium cobalt oxide battery, and collect the heat-treated lithium cobalt oxide waste battery cathode material powder (average particle size, 10 μm).

2. Take three reaction vessels and add 0.01 mmol/L RhB solution to each of them. Adjust the initial pH to 3.

3. Put 0.12 g/L positive electrode material powder into reaction vessels No. 1 and No. 3 respectively, and start timing adsorption for 1 hour.

4. Afterwards, take two sets of sodium bisulfite stock solution with a certain concentration and put them into No. 2 and No. 3 reaction containers respectively, so that the concentration of sodium bisulfite reaches 1mmol/L, and the degradation reaction starts.

5. After about 30 minutes, the reaction was basically complete, and the results are shown in Table 1.

Table 1 Degradation of rhodamine B by cathode materials of spent lithium cobalt oxide batteries

project Reaction Vessel (No. 1) Reaction Vessel (No. 2) Reaction Vessel (No. 3) Additives Lithium cobaltate sodium bisulfite Lithium cobaltate + sodium bisulfite RhB degradation rate% 5.1 5.9 99.8

The results show that only 5.1% of the degradation effect of lithium cobaltate alone is put into the RhB solution; only 5.9% of the degradation effect of the single sodium bisulfite solution is put into the RhB solution; and the combination of lithium cobaltate and sodium bisulfite , the degradation rate of RhB reached 99.8%. It shows that lithium cobaltate can activate sodium bisulfite to make RhB fade rapidly, and its treatment effect is obviously better than that of lithium cobaltate or sodium bisulfite alone.

Example 2

In this example, the method for degrading methylene blue (MB) with waste lithium iron phosphate battery cathode material includes the following steps:

1. Disassemble the lithium iron phosphate battery, and collect the heat-treated positive electrode material powder (average particle size, 10 μm ) in the lithium iron phosphate waste battery.

2. Take three reaction vessels and add 0.03 mmol/LMB solution to each of them. Adjust the initial pH to 7.

3. Put 0.12 g/L cathode material powder into reaction containers No. 1 and No. 3, and start timing adsorption for 30 min.

4. After that, take a certain concentration of PMS stock solution and put it into No. 2 and No. 3 reaction containers, so that the concentration of PMS reaches 1mM, and the degradation reaction starts.

After 5.5 min, the reaction was basically complete, and the results are shown in Table 2.

Table 2 Degradation of methylene blue with waste lithium iron phosphate battery cathode materials

project Reaction Vessel (No. 1) Reaction Vessel (No. 2) Reaction Vessel (No. 3) Additives Lithium iron phosphate PMS Lithium iron phosphate+PMS MB degradation rate% 4.5 20.5 99.9

The results show that only 4.5% of the degradation effect of lithium iron phosphate is put into the MB solution; only 20.5% of the degradation effect of the single PMS solution is put into the MB solution; while the combination of lithium iron phosphate and PMS, the degradation rate of MB reaches 99.9% . It shows that lithium iron phosphate can activate PMS and make MB fade rapidly, and its treatment effect is obviously better than that of lithium iron phosphate or PMS alone.

Example 3

In this example, the method for degrading 2,4,6-trichlorophenol (2,4,6-TCP) with the positive electrode material of waste lithium cobalt oxide battery includes the following steps:

1. Disassemble the lithium cobalt oxide battery, and collect the heat-treated lithium cobalt oxide waste battery cathode material powder (average particle size, 10 μm).

2. Take three reaction vessels and add 0.05 mM 2,4,6-TCP solution to each of them. Adjust the initial pH to 8.

3. Put 0.12 g/L cathode material powder into reaction containers No. 1 and No. 3, and start timing for 1 hour.

4. After that, take a certain concentration of PMS stock solution and put it into No. 2 and No. 3 reaction containers, so that the concentration of PMS reaches 1mM, and the degradation reaction starts.

5. After 20 min, the reaction was basically complete, and the results are shown in Table 3.

Table 3 Degradation of 2,4,6-trichlorophenol with waste lithium cobalt oxide battery cathode materials

project Reaction Vessel (No. 1) Reaction Vessel (No. 2) Reaction Vessel (No. 3) Additives Lithium cobaltate PMS Lithium cobalt oxide+PMS 2,4,6-TCP degradation rate% 1.7 29.3 99.9

The results show that only 1.7% of the degradation effect of lithium cobalt oxide is put into 2,4,6-TCP solution alone; Lithium acid and PMS are used, and the degradation rate of 2,4,6-TCP reaches 99.9%. It shows that lithium cobaltate can activate PMS to rapidly degrade 2,4,6-TCP, and its treatment effect is obviously better than that of lithium cobaltate or PMS alone.

Claims (9)

1. A method for catalytically degrading organic waste water using waste lithium-ion battery anode material, is characterized in that, comprises the following steps: (1) Disassemble the used lithium-ion battery, take out the positive electrode material, and collect the positive electrode material powder with a particle size of 10 ~ 100 µm after heat treatment; (2) Pour the positive electrode material powder into the organic wastewater solution placed on a magnetic stirrer for stirring and adsorption. The adsorption time is 0.5~1h, and then add an oxidant to catalytically degrade the organic wastewater at room temperature; wherein: the oxidant is selected from One or more of sulfite, bisulfite or monopersulfate PMS. 2. The method according to claim 1, characterized in that: in step (1), the used lithium ion battery is a lithium cobalt oxide battery or a lithium iron phosphate battery. 3. The method according to claim 1, characterized in that, in step (2), the organic wastewater solution contains one or more of rhodamine, methylene blue or 2,4,6-trichlorophenol. 4. The method according to claim 1, characterized in that, in step (2), the initial pH value of the organic wastewater solution is between 2 and 9; the total molar concentration of organic matter in the organic wastewater solution is 0.01 mmol/ Between L~ 1 mmol/L. 5. The method according to claim 1, characterized in that, in step (1), the mass ratio of the positive electrode material powder to the total organic matter in the organic wastewater is 1:10~1:100; the adsorption time is 0.5~1h . 6. The method according to claim 1, characterized in that, in step (2), the molar ratio of the oxidant to the total organic matter in the organic wastewater is 2:1 to 100:1. 7. The method according to claim 1, characterized in that, in step (2), the molar ratio of the oxidant to the total organic matter in the organic wastewater is 20:1-80:1. 8. The method according to claim 1, characterized in that, in step (2), the degradation reaction time is 1-30 min. 9. The method according to claim 1, characterized in that, in step (2), the degradation reaction time is 1-20 min.