A method for efficiently adsorbing eutectic solvent and waste dye by using MXene and CMP composite material

Abstract

The application discloses a method for efficiently adsorbing eutectic solvent and waste dye by using MXene and CMP composite material, and belongs to the field of waste liquid treatment, and solves the problem of low efficiency in the prior art. The technical scheme of the application comprises the following steps: under normal temperature and pressure, using an adsorption material to recover the waste to be treated, wherein the waste to be treated comprises non-biodegradable chemical products in wastewater, eutectic solvent and eutectic solvent of lithium cobalt-containing leaching solution; and the adsorption material is a MXene and CMP composite material. The application has the advantages of overcoming the disadvantages of the prior art, simple operation, mild conditions, low cost and environmental protection.

Description

Technical Field

[0001] This invention relates to a method for efficiently adsorbing eutectic solvents and waste dyes using a composite material of MXene and CMP, belonging to the field of water treatment. Background Technology

[0002] China is a major dye producer, ranking first in the world in annual output. However, the production process generates a large amount of wastewater, which can lead to dyes or dye intermediates being directly or indirectly discharged into aquatic bodies. Dye wastewater is difficult to biodegrade, has high color intensity, and exhibits significant variations in water quality and quantity, making it one of the most difficult types of wastewater to treat. Most dyes not only have a detrimental impact on environmental quality but also pose a serious threat to human health. Therefore, it is necessary to find a green, efficient, simple, and quick method for recycling waste dyes.

[0003] Eutectic solvents are a widely used new type of green solvent with advantages such as high designability, biodegradability, low energy consumption, and environmental friendliness. They have mature applications in electrochemistry, nanomaterial synthesis, organic synthesis, and gas absorption. However, investigations and research have revealed that the recycling process for eutectic solvents is not yet perfect, failing to form a closed-loop economic system. This results in significant resource waste, contradicting the concept of "sustainable development." Currently, no methods for recycling eutectic solvents have been reported. Summary of the Invention

[0004] This invention provides a method for efficiently adsorbing eutectic solvents and waste dyes using a composite material of MXene and CMP. The method is simple to operate, operates under mild conditions, is low in cost, and is environmentally friendly.

[0005] To solve the above-mentioned technical problems, the technical solution adopted by the present invention is a method for efficiently adsorbing eutectic solvents and waste dyes using an MXene and CMP composite material. The adsorbent material is used to recycle the waste to be treated, which includes recalcitrant chemical products in wastewater, eutectic solvents, and eutectic solvents in lithium cobalt oxide leachate; the adsorbent material is an MXene and CMP composite material.

[0006] The MXene is Ti3C2, and the raw materials for synthesizing CMP are 1,3,5-triacetylenebenzene and 1,4-diiodobenzene;

[0007] The 1,3,5-triacetylenebenzene structure is as follows: The structure of 1,4-diiodobenzene is .

[0008] The optimized method described above for efficiently adsorbing eutectic solvents and waste dyes using MXene and CMP composite materials includes the following preparation process for the adsorbent material: mixing, heating, and stirring the raw materials, followed by washing and drying; wherein the mixing, heating, and stirring process is carried out in an argon, nitrogen, or helium atmosphere.

[0009] The optimized method described above, which utilizes MXene and CMP composite materials for efficient adsorption of eutectic solvents and waste dyes, involves wastewater containing recalcitrant chemical products that is one or a mixture of two or more of the following: methyl orange solution, rhodamine B solution, aqueous iodine solution, sodium hexanitrocobaltate hydrate solution, nickel sulfate hexahydrate solution, ferric chloride solution, copper sulfate pentahydrate solution, and nickel nitrate hexahydrate solution.

[0010] The eutectic solvent is a valine:lactic acid eutectic solvent with a molar ratio of 1:12, a valine:lactic acid eutectic solvent with a molar ratio of 1:14, or a glycine:lactic acid eutectic solvent with a molar ratio of 1:12.

[0011] The eutectic solvent for lithium cobalt oxide leachate is either valine:lactic acid in a molar ratio of 1:12 or ethylene glycol:ascorbic acid in a molar ratio of 10:1.

[0012] The optimized method described above, which utilizes a composite material of MXene and CMP to efficiently adsorb eutectic solvents and waste dyes, involves the process of recycling the waste to be treated using the adsorbent material. This process is carried out in an environment of 25 degrees Celsius and 1 standard atmosphere, and the entire process lasts for at least 1 hour.

[0013] In the optimized method described above, which utilizes a composite material of MXene and CMP to efficiently adsorb eutectic solvents and waste dyes, the weight ratio of the adsorbent material to the waste to be treated is 1:500 when the adsorbent material is used to recycle the waste.

[0014] The optimized method described above, which utilizes a composite material of MXene and CMP for efficient adsorption of eutectic solvents and waste dyes, uses raw materials containing 10 mg of MXene, 100.1 mg of 1,3,5-triacetylenebenzene, and 329.9 mg of 1,4-diiodobenzene.

[0015] The optimized method described above, which utilizes a composite material of MXene and CMP for efficient adsorption of eutectic solvents and waste dyes, involves mixing, heating, and stirring the raw materials for the adsorption material, followed by washing and drying to obtain the adsorption material. The mixing, heating, and stirring process is carried out in an argon, nitrogen, or helium atmosphere, and the adsorption material is mixed with the solution to be adsorbed at room temperature and pressure for adsorption.

[0016] The optimized method described above utilizes a composite material of MXene and CMP for efficient adsorption of eutectic solvents and waste dyes. During the mixing, heating, and stirring of the raw materials for the adsorbent, the heating temperature is 100 degrees Celsius. During the washing process, a methanol solution is used for washing the adsorbent at 80 degrees Celsius for 12 hours. After washing, the material is dried in a vacuum drying oven at 80 degrees Celsius for 12 hours to obtain the adsorbent.

[0017] In the technical solution of this application, the adsorbent is easy to prepare, the adsorption reaction conditions are mild, and the adsorption efficiency is considerable. The recovery method of this application breaks through the innovation bottleneck of adsorbents. It can solve the existing problem of resource waste. The method is simple, the conditions are mild, the results are significant, it is green and efficient, the adsorption efficiency is high, and the adsorption material is easy to prepare. It has high practical value and promotion significance. Detailed Implementation

[0018] This application discloses a method for efficiently adsorbing eutectic solvents and waste dyes using a composite material of MXene and CMP. The adsorption material is used to recover the waste to be treated, which includes recalcitrant chemical products in wastewater, eutectic solvents, and eutectic solvents in lithium cobalt oxide leachate.

[0019] In this application, the wastewater containing recalcitrant chemical products is one or a mixture of two or more of the following: methyl orange solution, rhodamine B solution, aqueous solution of iodine, sodium hexanitrocobaltate hydrate 1 / 2 hydrate solution, nickel sulfate hexahydrate solution, ferric chloride solution, copper sulfate pentahydrate solution, and nickel nitrate hexahydrate solution.

[0020] The eutectic solvents are valine:lactic acid eutectic solvent with a molar ratio of 1:12, valine:lactic acid eutectic solvent with a molar ratio of 1:14, and glycine:lactic acid eutectic solvent with a molar ratio of 1:12.

[0021] The eutectic solvents for lithium cobalt oxide leachate are valine:lactic acid in a molar ratio of 1:12 and ethylene glycol:ascorbic acid in a molar ratio of 10:1.

[0022] The process of using adsorbent materials to recover recalcitrant chemical products, eutectic solvents, or eutectic solvents from lithium cobalt oxide leachates in wastewater is carried out at 25 degrees Celsius and 1 standard atmosphere, i.e., at normal temperature and pressure, and the entire process lasts for at least 1 hour.

[0023] The adsorbent is a composite material of MXene and CMP. The raw materials for the adsorbent include: 10 mg MXene, 100.1 mg 1,3,5-triacetylene, 329.9 mg 1,4-diiodobenzene, 7.5 mg tetrakis(triphenylphosphine)palladium, 12 mL N,N-dimethylformamide, and 6 mL triethylamine. Tetrakis(triphenylphosphine)palladium is used as the catalyst, and N,N-dimethylformamide and triethylamine are used as solvents. The structure of 1,3,5-triacetylene is as follows: The structure of 1,4-diiodobenzene is .

[0024] When using adsorbent materials to recover recalcitrant chemical products, eutectic solvents, or eutectic solvents from lithium cobalt oxide leachates from wastewater, the weight ratio of the adsorbent material to the waste to be treated is 1:500.

[0025] The preparation process of the adsorbent material includes: mixing, heating and stirring the raw materials of the adsorbent material, washing and drying; wherein the mixing, heating and stirring of the raw materials is carried out in an argon, nitrogen or helium environment.

[0026] The heating temperature is 100 degrees Celsius; during the washing process of the adsorbent material, a methanol solution is used for washing at 80 degrees Celsius for 12 hours; after washing, it is dried in a vacuum drying oven at 80 degrees Celsius for 12 hours to obtain the adsorbent material.

[0027] The technical features of the present invention will be further illustrated below with reference to specific embodiments. Example 1

[0028] Weigh 7.5 mg of tetrakis(triphenylphosphine)palladium, 100.1 mg of 1,3,5-triethynylbenzene, 1 mg of MXene, and 329.9 mg of 1,4-diiodobenzene into a three-necked flask using weighing paper. Pipette 12 mL of N,N-dimethylformamide and 6 mL of triethylamine into the three-necked flask and mix well. Add a magnetic stir bar.

[0029] Apply petroleum jelly to the condenser tube and the three-necked flask connection to create a sealed environment, and tighten the other two connections with rubber stoppers. Connect the T-connector to the top of the condenser tube, and apply a suitable amount of petroleum jelly to the connection to reduce friction.

[0030] First, a vacuum pump is used to create a vacuum. Then, a gas sampling bag is used to collect an appropriate amount of argon gas and connect it to one end of a three-way tube. Finally, the three-way tube is used to perform a gas exchange operation so that the reaction takes place in pure argon gas.

[0031] The reaction apparatus was secured to the iron stand with clamps, and then the condenser was connected. The three-necked flask was placed in a magnetically stirred oil bath and reacted at 100 degrees Celsius for 24 hours. The mixture was then washed with methanol solution. After the reaction was complete, the mixture was filtered, and the resulting solid was wrapped in filter paper and placed in a Soxhlet extractor. The extractor was connected to a three-necked flask containing an appropriate amount of ethanol and to a condenser. The solid was washed at 80 degrees Celsius for 12 hours.

[0032] After washing, the material was dried in a vacuum drying oven at 80 degrees Celsius for 12 hours to obtain a composite adsorbent material of MXene and two-dimensional conjugated polymer.

[0033] The eutectic solvent to be adsorbed was diluted 200 times, and the maximum absorption wavelength and absorbance of the solution before and after adsorption were measured using instruments such as a UV spectrometer and a visible spectrophotometer. Analysis showed that the adsorption efficiency of 0.01 g of MXene and the two-dimensional conjugated polymer for the eutectic solvent valine:lactic acid (1:12) under the adsorption conditions of 25°C, ambient pressure, and magnetic stirring for 1 hour was 0.24%. Example 2

[0034] The specific implementation process is the same as in Example 1, except that valine:lactic acid (1:12) is changed to valine:lactic acid (1:14). Other conditions remain unchanged. Under the adsorption conditions of 25 degrees Celsius, normal pressure, magnetic stirring for 1 hour, the adsorption efficiency of the eutectic solvent valine:lactic acid (1:14) is 0.10%. Example 3

[0035] The specific implementation process is the same as in Example 1, except that valine:lactic acid (1:12) is replaced with glycine:lactic acid (1:12), and other conditions are not changed. Under the adsorption conditions of magnetic stirring at 25 degrees Celsius for 1 hour, the adsorption efficiency of the eutectic solvent glycine:lactic acid (1:12) is 0.10%. Example 4

[0036] The specific implementation process is the same as in Example 1, except that valine:lactic acid (1:12) is replaced with valine:lactic acid (1:12) lithium cobalt oxide leachate. Other conditions remain unchanged. Under the adsorption conditions of magnetic stirring at 25 degrees Celsius for 1 hour, the adsorption efficiency of the eutectic solvent valine:lactic acid (1:12) lithium cobalt oxide leachate is 16.51%. Example 5

[0037] The specific implementation process is the same as in Example 1, except that the valine:lactic acid (1:12) is replaced with ethylene glycol:ascorbic acid (10:1) lithium cobalt oxide leachate. Other conditions remain unchanged. Under the adsorption conditions of magnetic stirring at 25 degrees Celsius for 1 hour, the adsorption efficiency of the eutectic solvent - ethylene glycol:ascorbic acid (10:1) lithium cobalt oxide leachate is 60.13%. Example 6

[0038] The specific implementation process is the same as in Example 1, except that the valine:lactic acid (1:12) ratio is replaced with a 5 μmol / L methyl orange solution, which does not require dilution. With other conditions unchanged, the adsorption efficiency of the dye—the 5 μmol / L methyl orange solution—under adsorption conditions of 25°C, ambient pressure, and magnetic stirring for 1 hour is 27.56%. Example 7

[0039] The specific implementation process is the same as in Example 1, except that the valine:lactic acid (1:12) ratio is replaced with a 5 μmol / L Rhodamine B solution, which does not require dilution. With other conditions unchanged, the adsorption efficiency of the dye—the 5 μmol / L Rhodamine B solution—was 26.92% under the adsorption conditions of 25°C, ambient pressure, magnetic stirring for 1 hour. Example 8

[0040] The specific implementation process is the same as in Example 1, except that the valine:lactic acid (1:12) ratio is replaced with an aqueous solution of 0.792 μmol / L iodine, without dilution. With other conditions unchanged, the adsorption efficiency of the dye—an aqueous solution of 0.792 μmol / L iodine—was 75.13% under the adsorption conditions of 25°C, ambient pressure, magnetic stirring for 1 hour. Example 9

[0041] The specific implementation process is the same as in Example 1, except that the valine:lactic acid (1:12) ratio is replaced with a 50 mmol / L 1 / 2 hydrate sodium hexanitrocobaltate solution, without dilution. Other conditions remain unchanged. Under adsorption conditions of 25°C, normal pressure, and magnetic stirring for 1 hour, the adsorption efficiency of the dye—the 50 mmol / L 1 / 2 hydrate sodium hexanitrocobaltate solution—is 36.39%. Example 10

[0042] The specific implementation process is the same as in Example 1, except that the valine:lactic acid (1:12) ratio is replaced with a 50 mmol / L nickel sulfate hexahydrate solution, without dilution. Other conditions remain unchanged. Under adsorption conditions of 25°C, ambient pressure, magnetic stirring for 1 hour, the adsorption efficiency of the dye—the 50 mmol / L nickel sulfate hexahydrate solution—is 68.90%. Example 11

[0043] The specific implementation process is the same as in Example 1, except that the valine:lactic acid (1:12) ratio is replaced with a 50 mmol / L ferric chloride solution, which does not require dilution. With other conditions unchanged, the adsorption efficiency of the dye—the 50 mmol / L ferric chloride solution—was 76.53% under the adsorption conditions of 25°C, normal pressure, magnetic stirring for 1 hour. Example 12

[0044] The specific implementation process is the same as in Example 1, except that the valine:lactic acid (1:12) ratio is replaced with a 50 mmol / L copper sulfate pentahydrate solution, without dilution. Other conditions remain unchanged. Under adsorption conditions of 25°C, normal pressure, and magnetic stirring for 1 hour, the adsorption efficiency of the dye—the 50 mmol / L copper sulfate pentahydrate solution—is 90.77%. Example 13

[0045] The specific implementation process is the same as in Example 1, except that the valine:lactic acid (1:12) ratio is replaced with a 50 mmol / L nickel nitrate hexahydrate solution, without dilution. Other conditions remain unchanged. Under adsorption conditions of 25°C, ambient pressure, and magnetic stirring for 1 hour, the adsorption efficiency of the dye—the 50 mmol / L nickel nitrate hexahydrate solution—is 84.44%.

[0046] Of course, the above description is not intended to limit the present invention, and the present invention is not limited to the examples given above. Any changes, modifications, additions or substitutions made by those skilled in the art within the scope of the present invention should be protected by the present invention.

Claims

1. A method for efficient adsorption of eutectic solvent and waste dyes by MXene and CMP composite material, using adsorption material to recover the waste to be treated, the waste to be treated including refractory chemical products in wastewater; characterized in that: The adsorption material is a composite material of MXene and CMP; ​ The MXene is Ti3C2, and the raw material for synthesizing the CMP is 1, 3, 5-triethynylbenzene and 1, 4-diiodobenzene; wherein the 1,3,5-triethynylbenzene structure is , and the 1,4-diiodobenzene structure is ; The preparation process of the adsorption material includes: after the raw materials of the adsorption material are mixed, heated and stirred, the adsorption material is prepared by washing and drying; wherein, the process of mixing, heating and stirring of the raw materials is carried out in an argon, nitrogen or helium environment; In the process of mixing, heating and stirring of the raw materials of the adsorption material, the heating temperature is 100 degrees Celsius; in the washing process of the adsorption material, methanol solution is used for washing operation, and the washing is carried out at 80 degrees Celsius for 12 hours; after washing is completed, the adsorption material is dried in a vacuum drying oven at 80 degrees Celsius for 12 hours; The process of recycling the waste to be treated using the adsorption material is carried out in an environment of 25 degrees Celsius and 1 standard atmosphere, and the whole process lasts at least 1 hour; When the adsorption material is used to recycle the waste to be treated, the weight ratio of the adsorption material to the waste to be treated is 1:

500.

2. A method for efficiently adsorbing a deep eutectic solvent and a waste dye using a MXene and CMP composite material, wherein the adsorption material is used to recover the waste to be treated, and the waste to be treated includes a deep eutectic solvent; characterized in that: The adsorption material is a composite material of MXene and CMP; The MXene is Ti3C2, and the raw material for synthesizing the CMP is 1, 3, 5-triethynylbenzene and 1, 4-diiodobenzene; wherein the 1,3,5-triethynylbenzene structure is , and the 1,4-diiodobenzene structure is ; The preparation process of the adsorption material includes: after the raw materials of the adsorption material are mixed, heated and stirred, the adsorption material is prepared by washing and drying; wherein, the process of mixing, heating and stirring of the raw materials is carried out in an argon, nitrogen or helium environment; In the process of mixing, heating and stirring of the raw materials of the adsorption material, the heating temperature is 100 degrees Celsius; in the washing process of the adsorption material, methanol solution is used for washing operation, and the washing is carried out at 80 degrees Celsius for 12 hours; after washing is completed, the adsorption material is dried in a vacuum drying oven at 80 degrees Celsius for 12 hours; The process of recycling the waste to be treated using the adsorption material is carried out in an environment of 25 degrees Celsius and 1 standard atmosphere, and the whole process lasts at least 1 hour; When the adsorption material is used to recycle the waste to be treated, the weight ratio of the adsorption material to the waste to be treated is 1:

500.

3. A method for efficiently adsorbing a eutectic solvent and waste dyes using a MXene and CMP composite material, using an adsorption material to recover the waste to be treated, the waste to be treated including a eutectic solvent containing a lithium cobalt acid leaching solution; characterized in that: The adsorption material is a composite material of MXene and CMP; The MXene is Ti3C2, and the raw material for synthesizing the CMP is 1, 3, 5-triethynylbenzene and 1, 4-diiodobenzene; wherein the 1,3,5-triethynylbenzene structure is , and the 1,4-diiodobenzene structure is ; The preparation process of the adsorption material includes: after the raw materials of the adsorption material are mixed, heated and stirred, the adsorption material is prepared by washing and drying; wherein, the process of mixing, heating and stirring of the raw materials is carried out in an argon, nitrogen or helium environment; In the process of mixing, heating and stirring of the raw materials of the adsorption material, the heating temperature is 100 degrees Celsius; in the washing process of the adsorption material, methanol solution is used for washing operation, and the washing is carried out at 80 degrees Celsius for 12 hours; after washing is completed, the adsorption material is dried in a vacuum drying oven at 80 degrees Celsius for 12 hours; The process of recycling the waste to be treated using the adsorption material is carried out in an environment of 25 degrees Celsius and 1 standard atmosphere, and the whole process lasts at least 1 hour; When the adsorption material is used to recycle the waste to be treated, the weight ratio of the adsorption material to the waste to be treated is 1:

500.

4. The method for high-efficiency adsorption of eutectic solvent and waste dye by using MXene and CMP composite material according to claim 1, 2 or 3, characterized in that: The refractory chemical product in the wastewater containing the refractory chemical product is one of methyl orange solution, rhodamine B solution, aqueous iodine solution, 1 / 2 hydrated sodium cobalt hexanitrate solution, nickel sulfate hexahydrate solution, ferric chloride solution, copper sulfate pentahydrate solution, nickel nitrate hexahydrate solution, or a mixture of two or more thereof; The eutectic solvent is a valine:lactic acid eutectic solvent with a molar ratio of 1:12, a valine:lactic acid eutectic solvent with a molar ratio of 1:14, or a glycine:lactic acid eutectic solvent with a molar ratio of 1:12; The eutectic solvent of the lithium cobalt-containing leaching solution is a valine:lactic acid eutectic solvent with a molar ratio of 1:12 and containing the lithium cobalt-containing leaching solution, or a ethylene glycol:ascorbic acid eutectic solvent with a molar ratio of 10:1 and containing the lithium cobalt-containing leaching solution.

5. The method of claim 1, 2 or 3, wherein the MXene and CMP composite material efficiently adsorbs the deep eutectic solvent and the waste dye. The raw material of the adsorption material comprises 10 milligrams of MXene, 100.1 milligrams of 1, 3, 5-triethynylbenzene and 329.9 milligrams of 1, 4-diiodobenzene.

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