Method for preparing carbon black from waste wind power lubricating oil and obtained carbon black

Abstract

The invention provides a method for preparing carbon black by using waste wind power lubricating oil and the carbon black prepared by the method. The method comprises the following steps: 1) preliminary purification: standing and settling the waste wind power lubricating oil, and then filtering; (2) distilling and deoiling: transferring the waste wind power lubricating oil primarily purified in the step (1) into a distilling device, and carrying out reduced pressure distillation to obtain carbon-containing residues; 3) pickling treatment: reacting the carbon-containing residues with a strong acid aqueous solution, and then washing and filtering; 4) carbonizing treatment: transferring the carbon-containing residues subjected to acid pickling into a carbonizing furnace, and carbonizing in an inert atmosphere; according to the method, impurities in the waste wind power lubricating oil can be effectively removed, the purity and the quality of carbon black are improved, meanwhile, the energy consumption and the cost in the production process are reduced, and efficient resource utilization of the waste wind power lubricating oil is achieved.

Description

Technical Field

[0001] This invention relates to the field of waste resource recycling, specifically to a method for preparing carbon black from waste wind power lubricating oil, aiming to realize the resource utilization of waste wind power lubricating oil, reduce environmental pollution, and obtain high-value-added carbon black products. Background Technology

[0002] With the rapid development of the wind power industry, the amount of waste wind turbine lubricating oil generated is increasing day by day. Waste wind turbine lubricating oil contains a large amount of mineral oil, additives, and metallic impurities. If it is directly discharged or simply treated, it will not only cause serious environmental pollution, but also waste the resources it contains. Carbon black is an important industrial raw material, widely used in rubber, plastics, inks, coatings, and other fields. Traditional carbon black production methods primarily use petroleum hydrocarbons as raw materials, prepared through incomplete combustion or thermal cracking. This method not only consumes large amounts of fossil resources but also generates significant amounts of waste gas, residue, and other pollutants during production. Therefore, developing a method for producing carbon black using waste wind turbine lubricating oil has significant economic and environmental implications. Currently, although there are some studies on the treatment of waste lubricating oil and the preparation of carbon black, the existing treatment methods for waste wind power lubricating oil have problems such as low carbon black purity, low production efficiency, and high energy consumption due to the special composition of the oil (such as containing metal additives unique to wind power equipment and complex polymers), making it difficult to achieve large-scale industrial application. Summary of the Invention

[0003] Technical issues The purpose of this invention is to provide a method for preparing carbon black from waste wind power lubricating oil. This method can effectively remove impurities from waste wind power lubricating oil, improve the purity and quality of carbon black, and reduce energy consumption and costs in the production process, thereby achieving efficient resource utilization of waste wind power lubricating oil. Technical solution According to a first aspect of the present invention, a method for preparing carbon black using waste wind power lubricating oil is provided, the method comprising the following steps: (1) Preliminary purification: Waste wind power lubricating oil is allowed to settle and then filtered; (2) Distillation and deoiling: The waste wind power lubricating oil after preliminary purification in step (1) is transferred to a distillation device for vacuum distillation to obtain carbon-containing residue; (3) Acid washing treatment: react the carbon-containing residue with a strong acid aqueous solution, then wash and filter; (4) Carbonization treatment: The carbon-containing residue after pickling is transferred to a carbonization furnace and carbonized in an inert atmosphere; (5) Activation treatment: The product obtained in step (4) is thoroughly mixed with the activator and reacted; and (6) Wash and dry.

[0004] Preferably, in step (1), the settling time is 12~48h.

[0005] Preferably, in step (1), impurities with a particle size of 5 μm or larger are removed by filtration.

[0006] Preferably, in step (1), a plate and frame filter press is used for filtration.

[0007] Preferably, in step (2), the distillation and deoiling conditions are as follows: pressure of 5~20 kPa, temperature of 250~350℃, preferably 250~300℃, and distillation until no fractions remain.

[0008] Preferably, in step (3), the strong acid aqueous solution is an aqueous solution of nitric acid, hydrochloric acid, or sulfuric acid.

[0009] Preferably, the concentration of the strong acid aqueous solution is 4~8 mol / L.

[0010] Preferably, the reaction time between the carbon-containing residue and the strong acid aqueous solution is 1 to 90 hours, more preferably 2 to 12 hours.

[0011] Preferably, the temperature at which the carbon-containing residue reacts with the strong acid aqueous solution is 60~90℃.

[0012] Preferably, the liquid-to-solid ratio of the strong acid aqueous solution to the carbon-containing residue is 10 or higher.

[0013] Preferably, the washing in step (3) is: washing with a mixed solution of ethanol and water for more than 20 minutes.

[0014] Preferably, the volume percentage of ethanol in the ethanol-water mixture is 10% or more.

[0015] Preferably, in step (4), the carbonization temperature is 600~800℃ and the time is more than 2 hours.

[0016] Preferably, in step (4), the inert atmosphere is a nitrogen atmosphere.

[0017] Preferably, in step (5), the activator is an alkaline aqueous solution, more preferably a 4% to 20% mass concentration potassium hydroxide or sodium hydroxide aqueous solution.

[0018] Preferably, in step (5), the amount of activator used is more than 5 times the weight of the product obtained in step (4), more preferably 10 to 40 times.

[0019] Preferably, in step (5), the activation treatment reaction temperature is 90~150℃ and the reaction time is 30~240 minutes.

[0020] Preferably, in step (6), the solution is washed sequentially with distilled water and ethanol until the pH of the solution is 7.

[0021] Preferably, in step (6), drying is performed at a temperature above 80°C.

[0022] According to a second aspect of the present invention, a carbon black is provided, which is prepared by the method for preparing carbon black using waste wind power lubricating oil according to the present invention.

[0023] Preferably, the specific surface area of ​​the carbon black is 150 m² / g or more, and more preferably 160 m² / g or more.

[0024] Preferably, the carbon black has an iodine absorption value of 100 mg / g or higher, more preferably 105 mg / g or higher.

[0025] Preferably, the coloring rate of the carbon black is 85% or more, and more preferably 90% or more.

[0026] Beneficial effects Efficient utilization of resources: This method converts waste wind power lubricating oil into high-value-added carbon black products, realizing efficient recycling of waste resources and reducing dependence on traditional fossil resources. Excellent product quality: Through unique distillation, degreasing, carbonization, and activation processes, impurities in waste wind power lubricating oil are effectively removed, improving the purity and quality of carbon black. The resulting carbon black has a large specific surface area and rich pore structure, exhibiting excellent adsorption performance and reactivity, and can meet the application needs of multiple fields such as rubber and plastics. Environmentally friendly and energy-saving: The entire production process takes place in a closed system, reducing the emission of pollutants such as waste gas and waste residue, and lowering environmental pollution. At the same time, the use of technologies such as vacuum distillation and reasonable temperature control reduces energy consumption during production, meeting the requirements of sustainable development. The process is simple and feasible: the process flow of this method is relatively simple and easy to operate. The required equipment is all conventional chemical equipment, which is easy to realize large-scale industrial production. Detailed Implementation

[0027] The present invention will now be described in detail with reference to the embodiments. It should be noted that the following embodiments are only used to illustrate the purpose of the present invention and are not intended to limit the scope of the present invention.

[0028] Test methods Specific surface area: BET specific surface area analyzer Iodine uptake value: GB / T 3780.1-2017 Coloring rate: GB / T 14624.2-2021 Example 1 Preliminary purification: Collect 100L of waste wind power lubricating oil, place it in a settling tank, let it stand at room temperature for 24 hours, and then perform preliminary filtration through a plate and frame filter press (filtration accuracy of 5μm) to obtain preliminarily purified waste wind power lubricating oil. Distillation and deoiling: The preliminarily purified waste wind turbine lubricating oil is transferred to a distillation apparatus and distilled under reduced pressure of 5 kPa. The temperature is raised to 250°C at a heating rate of 5°C / min, and distillation is carried out for 3 hours. The distilled mineral oil is collected to obtain carbon-containing residue. Acid washing: The carbon-containing residue was reacted with a 6 mol / L nitric acid aqueous solution for a period of time at a temperature of 80℃ for 7 hours, with a liquid-to-solid ratio of 10:1. After the reaction was completed, it was washed with a mixed solution of ethanol and water (volume ratio 1:1) for 30 minutes, and then filtered.

[0029] Carbonization treatment: The product obtained from acid washing is transferred to a carbonization furnace. Under the protection of nitrogen flow rate of 5L / min, the temperature is raised to 600℃ at a heating rate of 10℃ / min and held at this temperature for 2 hours to obtain the primary carbon black product. Activation treatment: The obtained primary carbon black product is added to a 10% potassium hydroxide solution as an activator and activated at a reaction temperature of 120℃ for 60 minutes. The weight of the potassium hydroxide solution is 10 times the weight of the primary carbon black product.

[0030] Washing and drying: Wash with water until the pH of the washing solution is close to 7, then place in a drying oven and dry at 100°C for 2 hours to obtain the final carbon black product. Product testing: The carbon black product was tested and found to have a specific surface area of ​​180.39 m² / g, an iodine absorption value of 110.44 mg / g, and a tinting strength of 90.34%. Example 2 Preliminary purification: Collect 100L of waste wind power lubricating oil, place it in a settling tank, let it stand at room temperature for 24 hours, and then perform preliminary filtration through a plate and frame filter press (filtration accuracy of 5μm) to obtain preliminarily purified waste wind power lubricating oil. Distillation and deoiling: The preliminarily purified waste wind turbine lubricating oil is transferred to a distillation apparatus and distilled under reduced pressure of 5 kPa. The temperature is raised to 300℃ at a heating rate of 5℃ / min, and distillation is carried out for 3 hours. The distilled mineral oil is collected to obtain carbon-containing residue. Acid washing: The carbon-containing residue is reacted with a 6 mol / L sulfuric acid aqueous solution for a period of time at a temperature of 80℃ for 7 hours, with a liquid-to-solid ratio of 10:1. After the reaction is completed, it is washed with a mixed solution of ethanol and water (volume ratio 1:1) for 30 minutes, and then filtered.

[0031] Carbonization treatment: The product obtained from acid washing is transferred to a carbonization furnace. Under the protection of nitrogen flow rate of 5L / min, the temperature is raised to 600℃ at a heating rate of 10℃ / min and held at this temperature for 2 hours to obtain the primary carbon black product. Activation treatment: The obtained primary carbon black product is added to a 10% potassium hydroxide solution as an activator and activated at a reaction temperature of 120℃ for 60 minutes. The weight of the potassium hydroxide solution is 10 times the weight of the primary carbon black product.

[0032] Washing and drying: Wash with water until the pH of the washing solution is close to 7, then place in a drying oven and dry at 100°C for 2 hours to obtain the final carbon black product. Product testing results: its specific surface area is 178.21 m² / g, its iodine uptake value is 116.30 mg / g, and its tinting strength is 95.34%. Example 3 Preliminary purification: Collect 100L of waste wind power lubricating oil, place it in a settling tank, let it stand at room temperature for 24 hours, and then perform preliminary filtration through a plate and frame filter press (filtration accuracy of 5μm) to obtain preliminarily purified waste wind power lubricating oil. Distillation and deoiling: The preliminarily purified waste wind turbine lubricating oil is transferred to a distillation apparatus and distilled under reduced pressure of 5 kPa. The temperature is raised to 250°C at a heating rate of 5°C / min, and distillation is carried out for 3 hours. The distilled mineral oil is collected to obtain carbon-containing residue. Acid washing: The carbon-containing residue was reacted with a 6 mol / L nitric acid aqueous solution for a period of time at a temperature of 80℃ for 7 hours, with a liquid-to-solid ratio of 10:1. After the reaction was completed, it was washed with a mixed solution of ethanol and water (volume ratio 1:1) for 30 minutes and then filtered.

[0033] Carbonization treatment: The product obtained from acid washing is transferred to a carbonization furnace. Under the protection of nitrogen flow rate of 5L / min, the temperature is raised to 800℃ at a heating rate of 10℃ / min and held at this temperature for 2 hours to obtain the primary carbon black product. Activation treatment: The obtained primary carbon black product is added to a 10% potassium hydroxide solution as an activator and activated at a reaction temperature of 120℃ for 60 minutes. The weight of the potassium hydroxide solution is 10 times the weight of the primary carbon black product.

[0034] Washing and drying: Wash with water until the pH of the washing solution is close to 7, then place in a drying oven and dry at 100°C for 2 hours to obtain the final carbon black product. Product testing: Its specific surface area is 192.03 m². 2 / g, iodine uptake value is 112.45mg / g, and tinting strength is 93.22%. Comparative Example 1 Distillation and deoiling: The preliminarily purified waste wind turbine lubricating oil is transferred to a distillation apparatus and distilled under reduced pressure of 5 kPa. The temperature is raised to 250°C at a heating rate of 5°C / min, and distillation is carried out for 3 hours. The distilled mineral oil is collected to obtain carbon-containing residue. Acid washing: The carbon-containing residue was reacted with a 6 mol / L nitric acid aqueous solution for a period of time at a temperature of 80℃ for 7 hours, with a liquid-to-solid ratio of 10:1. After the reaction was completed, it was washed with a mixed solution of ethanol and water (volume ratio 1:1) for 30 minutes, and then filtered.

[0035] Carbonization treatment: The product obtained from acid washing is transferred to a carbonization furnace. Under the protection of nitrogen flow rate of 5L / min, the temperature is raised to 600℃ at a heating rate of 10℃ / min and held at this temperature for 2 hours to obtain the primary carbon black product. Activation treatment: The obtained primary carbon black product is added to a 10% potassium hydroxide solution as an activator and activated at a reaction temperature of 120℃ for 60 minutes. The weight of the potassium hydroxide solution is 10 times the weight of the primary carbon black product.

[0036] Washing and drying: Wash with water until the pH of the washing solution is close to 7, then place in a drying oven and dry at 100°C for 2 hours to obtain the final carbon black product. Product testing: The carbon black product was tested and found to have a specific surface area of ​​87.67 m² / g, an iodine absorption value of 56.5 mg / g, and a tinting strength of 70.2%. Comparative Example 2 Preliminary purification: Collect 100L of waste wind power lubricating oil, place it in a settling tank, let it stand at room temperature for 24 hours, and then perform preliminary filtration through a plate and frame filter press (filtration accuracy of 5μm) to obtain preliminarily purified waste wind power lubricating oil. Distillation and deoiling: The preliminarily purified waste wind turbine lubricating oil is transferred to a distillation apparatus and distilled under reduced pressure of 5 kPa. The temperature is raised to 250°C at a heating rate of 5°C / min, and distillation is carried out for 3 hours. The distilled mineral oil is collected to obtain carbon-containing residue. Carbonization treatment: The carbon-containing residue is transferred to a carbonization furnace. Under the protection of nitrogen flow rate of 5L / min, the temperature is raised to 600℃ at a heating rate of 10℃ / min, and held at this temperature for 2 hours to obtain the primary carbon black product. Activation treatment: The obtained primary carbon black product is added to a 10% potassium hydroxide solution as an activator and activated at a reaction temperature of 120℃ for 60 minutes. The weight of the potassium hydroxide solution is 10 times the weight of the primary carbon black product.

[0037] Washing and drying: Wash with water until the pH of the washing solution is close to 7, then place in a drying oven and dry at 100°C for 2 hours to obtain the final carbon black product. Product testing: The carbon black product was tested and found to have a specific surface area of ​​110.56 m² / g, an iodine absorption value of 72.67 mg / g, and a tinting strength of 79.22%. Comparative Example 3 Preliminary purification: Collect 100L of waste wind power lubricating oil, place it in a settling tank, let it stand at room temperature for 24 hours, and then perform preliminary filtration through a plate and frame filter press (filtration accuracy of 5μm) to obtain preliminarily purified waste wind power lubricating oil. Distillation and deoiling: The preliminarily purified waste wind turbine lubricating oil is transferred to a distillation apparatus and distilled under reduced pressure of 5 kPa. The temperature is raised to 250°C at a heating rate of 5°C / min, and distillation is carried out for 3 hours. The distilled mineral oil is collected to obtain carbon-containing residue. Acid washing: The carbon-containing residue was reacted with a 6 mol / L nitric acid aqueous solution for a period of time at a temperature of 80℃ for 7 hours, with a liquid-to-solid ratio of 10:1. After the reaction was completed, it was washed with a mixed solution of ethanol and water (volume ratio 1:1) for 30 minutes, and then filtered.

[0038] Activation treatment: The product obtained by acid washing is added to a 10% potassium hydroxide solution as an activator and activated at a reaction temperature of 120℃ for 60 min. The weight of the potassium hydroxide solution is 10 times the weight of the primary carbon black product.

[0039] Washing and drying: Wash with water until the pH of the washing solution is close to 7, then place in a drying oven and dry at 100°C for 2 hours to obtain the final carbon black product. Product testing: The carbon black product was tested and found to have a specific surface area of ​​97.13 m² / g, an iodine absorption value of 65.67 mg / g, and a tinting strength of 74.31%. Comparative Example 4 Preliminary purification: Collect 100L of waste wind power lubricating oil, place it in a settling tank, let it stand at room temperature for 24 hours, and then perform preliminary filtration through a plate and frame filter press (filtration accuracy of 5μm) to obtain preliminarily purified waste wind power lubricating oil. Distillation and deoiling: The preliminarily purified waste wind turbine lubricating oil is transferred to a distillation apparatus and distilled under reduced pressure of 5 kPa. The temperature is raised to 250°C at a heating rate of 5°C / min, and distillation is carried out for 3 hours. The distilled mineral oil is collected to obtain carbon-containing residue. Acid washing: The carbon-containing residue was reacted with a 6 mol / L nitric acid aqueous solution for a period of time at a temperature of 80℃ for 7 hours, with a liquid-to-solid ratio of 10:1. After the reaction was completed, it was washed with a mixed solution of ethanol and water (volume ratio 1:1) for 30 minutes, and then filtered.

[0040] Carbonization treatment: The product obtained from acid washing is transferred to a carbonization furnace. Under the protection of nitrogen flow rate of 5L / min, the temperature is raised to 600℃ at a heating rate of 10℃ / min and held at this temperature for 2 hours to obtain carbon black. Washing and drying: The carbon black obtained is washed with water until the pH value of the washing solution is close to 7, and then placed in a drying oven and dried at 100°C for 2 hours to obtain the final carbon black product. Product testing: The carbon black product was tested and found to have a specific surface area of ​​94.69 m² / g, an iodine absorption value of 58.83 mg / g, and a tinting strength of 68.56%.

Claims

1. A method for preparing carbon black using waste wind turbine lubricating oil, the method comprising the following steps: (1) Preliminary purification: Waste wind power lubricating oil is allowed to settle and then filtered; (2) Distillation and deoiling: The waste wind power lubricating oil after preliminary purification in step (1) is transferred to a distillation device for vacuum distillation to obtain carbon-containing residue; (3) Acid washing treatment: react the carbon-containing residue with a strong acid aqueous solution, then wash and filter; (4) Carbonization treatment: The carbon-containing residue after pickling is transferred to a carbonization furnace and carbonized in an inert atmosphere; (5) Activation treatment: The product obtained in step (4) is thoroughly mixed with the activator and reacted; and (6) Wash and dry.

2. The method for preparing carbon black using waste wind power lubricating oil according to claim 1, wherein, In step (1), the settling time is 12~48h; and / or In step (1), impurities with a particle size of 5 μm or larger are removed by filtration; and / or In step (1), a plate and frame filter press is used for filtration.

3. The method for preparing carbon black using waste wind power lubricating oil according to claim 1 or 2, wherein, In step (2), the distillation deoiling conditions are as follows: pressure of 5~20 kPa, temperature of 250~350℃, preferably 250~300℃, distillation until no fractions remain; and / or In step (3), the strong acid aqueous solution is an aqueous solution of nitric acid, hydrochloric acid, or sulfuric acid.

4. The method for preparing carbon black using waste wind power lubricating oil according to any one of claims 1 to 3, wherein, The concentration of the strong acid aqueous solution is 4~8 mol / L; and / or The reaction time between the carbonaceous residue and the strong acid aqueous solution is 1-90 h; and / or The temperature at which the carbonaceous residue reacts with the strong acid aqueous solution is 60-90°C; and / or The liquid-to-solid ratio of the strong acid aqueous solution to the carbonaceous residue is greater than 10; and / or The washing in step (3) is to wash with a mixed solution of ethanol and water for more than 20 minutes.

5. The method for preparing carbon black using waste wind power lubricating oil according to claim 4, wherein, The reaction time between the carbonaceous residue and the strong acid aqueous solution is 2-12 hours; and / or The volume percentage of ethanol in a mixed solution of ethanol and water is more than 10%.

6. The method for preparing carbon black using waste wind power lubricating oil according to any one of claims 1 to 5, wherein, In step (4), the carbonization temperature is 600~800℃, and the time is more than 2 hours; and / or In step (4), the inert atmosphere is a nitrogen atmosphere.

7. The method for preparing carbon black using waste wind power lubricating oil according to any one of claims 1 to 6, wherein, In step (5), the activator is an alkaline aqueous solution; and / or In step (5), the amount of activator used is more than 5 times the weight of the product obtained in step (4), more preferably 10 to 40 times.

8. The method for preparing carbon black using waste wind power lubricating oil according to any one of claims 1 to 7, wherein, In step (5), the activator is a 4%~20% (w / w) aqueous solution of potassium hydroxide or sodium hydroxide; and / or In step (5), the activation treatment reaction temperature is 90~150℃, and the reaction time is 30~240 minutes; and / or In step (6), the solution is washed sequentially with distilled water and ethanol until the pH reaches 7; and / or In step (6), the product is dried at a temperature above 80°C.

9. A carbon black prepared by the method for preparing carbon black using waste wind power lubricating oil according to any one of claims 1 to 8.

10. The carbon black according to claim 9, wherein, The specific surface area of ​​the carbon black is 150 m² / g or more; and / or The carbon black has an iodine uptake value of 100 mg / g or higher; and / or The carbon black has a coloring rate of 85% or higher, preferably 90% or higher.