Method for preparing photo-thermal functional foam material based on waste printer carbon powder and application thereof

Abstract

The invention belongs to the technical field of environmental functional materials and waste resource utilization, and relates to a method for preparing a photo-thermal functional foam material based on waste printer carbon powder, which comprises the following steps: calcining and grinding the waste printer carbon powder in an inert atmosphere to obtain photo-thermal active carbon powder; the preparation method comprises the following steps: carrying out surface modification on porous polymer sponge through dopamine in-situ polymerization to obtain PDA coated sponge; mixing a PDMS prepolymer, a curing agent and the carbon powder in an organic solvent to prepare a composite dispersion liquid; finally, the PDA modified sponge is soaked in the dispersion liquid and subjected to thermocuring, and the photo-thermal functional foam material is obtained. The waste printer carbon powder is used as a raw material, the cost is low, and waste recycling is achieved. The prepared material has excellent hydrophobicity, lipophilicity, photothermal conversion performance and stability, and can be widely applied to the fields of solar seawater desalination, high-viscosity oil recovery, water pollutant adsorption and purification and the like.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of environmental functional materials and waste resource utilization, and relates to carbon powder recovery, in particular to a method for preparing a light-heat functional foam material based on waste printer toner and application thereof. BACKGROUND

[0002] With the acceleration of industrialization, various environmental pollution problems are becoming increasingly serious, especially oil leakage, water pollution and other accidents occur frequently, which has a huge impact on the ecological environment and resources. Efficient, green and low-cost adsorption and treatment materials have become a research hotspot in the field of environmental remediation.

[0003] Light-heat materials can quickly convert light energy into heat energy under sunlight, which can promote liquid evaporation, reduce oil viscosity or drive interfacial mass transfer process, and are widely used in environmental governance related technologies. For example, light-heat adsorption materials can be used to improve the flowability of high-viscosity liquids such as crude oil and improve recovery efficiency; also can promote the migration, separation and treatment of pollutants through interfacial heating. At present, biomass carbon, graphene, carbon nanotubes and other materials have been used to construct light-heat foam materials, which have achieved good results in seawater desalination, interfacial evaporation and viscous oil recovery. However, these raw materials generally have high cost and relatively complex preparation process, which makes it difficult to realize low-cost popularization.

[0004] Waste printer toner, as a kind of electronic waste, is large in quantity and contains a large amount of carbon black, magnetic oxide and other components, which has the potential of light-heat performance. Although some documents have preliminarily reported the feasibility of using such materials to construct light-heat foam and for seawater desalination, the preparation method and material structure are relatively single, and the functional application is limited. Especially in the construction of general light-heat functional foam materials with excellent mechanical stability, hydrophobic and oleophilic properties, and wide application in high-viscosity oil recovery, pollutant degradation and other environmental remediation scenarios, there is still no systematic, complete and industrialized technical solution.

[0005] Therefore, it is necessary to propose a composite foam material that systematically utilizes waste printer toner and has general light-heat function, and to clarify its application in multiple environmental functions including but not limited to seawater desalination, oil recovery, pollutant removal and other scenarios. SUMMARY

[0006] In view of the problems in the prior art that the raw materials of light-heat foam materials are high in cost and complex in preparation process, and waste printer toner is not systematically utilized to construct general light-heat functional composite foam materials and expand multiple environmental applications, the purpose of the present application is to disclose a method for preparing a light-heat functional foam material based on waste printer toner and application thereof, so as to realize waste resource utilization, reduce the cost of light-heat materials, simplify the preparation process, and expand the application scenarios in environmental governance.

[0007] Technical solution

[0008] A method for preparing a light-heat functional foam material based on waste printer toner, comprising the following steps:

[0009] S1. Carbon powder activation: printer toner obtained by disassembling a waste printer selenium drum is calcined at 400-800 DEG C for 0.5-4h in an inert atmosphere, and then ground to obtain light-heat active carbon powder;

[0010] S2. Sponge substrate modification: a porous polymer sponge is immersed in a Tris buffer solution containing dopamine, and is subjected to magnetic stirring for 6-24h, so that a polydopamine (PDA) coating layer is formed on the surface by in-situ polymerization, and a PDA-coated sponge material is obtained;

[0011] S3. Preparation of dispersion liquid: polydimethylsiloxane (PDMS) prepolymer and a curing agent are uniformly mixed in an organic solvent, the mass concentration of PDMS is controlled to be 0.5-2 mg / mL, the light-heat active carbon powder is added, and the mass concentration of the carbon powder is controlled to be 0.5-5 mg / mL, and then the mixture is subjected to ultrasonic dispersion to obtain a uniform PDMS / carbon powder composite dispersion liquid;

[0012] S4. Compounding and curing: the PDA-coated sponge material is immersed in the PDMS / carbon powder composite dispersion liquid, and is subjected to repeated extrusion-release for several times, so as to ensure that the dispersion liquid penetrates and adheres to the sponge skeleton; then, the mixture is heated at 80-150 DEG C for 1-5h, so that the PDMS is crosslinked and cured to form a coating layer, and a light-heat functional foam material uniformly coated with PDMS / carbon powder on the surface is obtained.

[0013] In the preferred disclosure of the present application, in step S1, the inert atmosphere is nitrogen or argon.

[0014] In the preferred disclosure of the present application, in step S1, the particle size of the light-heat active carbon powder is 2-20 μm.

[0015] In the preferred disclosure of the present application, in step S2, the porous polymer sponge is at least one of melamine foam, polyurethane foam or polyolefin foam.

[0016] In the preferred disclosure of the present application, in step S2, the concentration of the Tris buffer solution is 5-20 mM, and the pH value is 7.5-9.

[0017] In the preferred disclosure of the present application, in step S2, the concentration of dopamine in the Tris buffer solution is 1-10 mg / mL.

[0018] In the preferred disclosure of the present application, in step S3, the organic solvent is at least one of methanol, ethanol, acetone, n-hexane, cyclohexane or toluene.

[0019] In the step S3, the mass ratio of the polydimethylsiloxane (PDMS) prepolymer and the curing agent is 10:1.

[0020] In the step S4, the extrusion-releasing is repeated 3-6 times.

[0021] The light-heat functional foam material with the surface uniformly coated with PDMS / carbon powder prepared by the method has hydrophobic and oleophilic properties, with a water contact angle greater than 130° and an oil contact angle less than 5°.

[0022] Under the condition of 1 kW / m 2 Under the condition of solar irradiation, the surface temperature of the light-heat functional foam material reaches 60-90 ℃, showing excellent light-heat conversion performance, and after 10 cycles of light-heat test, the surface temperature decreases by less than 5%, showing good light-heat stability.

[0023] The light-heat functional foam material with the surface uniformly coated with PDMS / carbon powder prepared by the method has hydrophobic and oleophilic properties, with a water contact angle greater than 130° and an oil contact angle less than 5°.

[0024] Advantages

[0025] The present application uses waste printer carbon powder as a light-heat component, and through high-temperature calcination, the light absorption and heat conversion activity of the waste printer carbon powder is excited, the waste is given a new environmental function, and the resource recycling is realized, which has important environmental protection and economic value. The method uses conventional calcination, solution immersion and heat curing technologies, and does not need expensive equipment and high energy consumption treatment. The raw materials are easy to obtain, the preparation path is clear and easy to realize, and the industrial transformation feasibility is remarkable. The PDMS coating used has multiple functional synergies. First, PDMS acts as an adhesive between carbon powder and sponge substrate, and also plays a protective role for carbon powder particles, improving the fixation of light-heat carbon powder particles in the foam structure and improving its durability. Second, PDMS itself has excellent hydrophobicity, giving the foam material a hydrophobic / oleophilic surface, making it feasible to adsorb oil or evaporate water. The foam sponge substrate is modified by PDA to improve the synergistic adhesion of carbon powder and PDMS, and a composite material with mechanical flexibility, stable structure and continuous light-heat interface can be constructed. The light-heat functional foam material constructed has excellent light-heat conversion, adsorption, mechanical flexibility and hydrophobicity, and is suitable for solar seawater desalination, high-viscosity oil recovery, oil spill removal, interfacial evaporation sterilization and purification, etc. It has high functional integration capability. BRIEF DESCRIPTION OF DRAWINGS

[0026] Figure 1SEM images of the original printer carbon powder and the carbon powder after calcination prepared in Example 1;

[0027] Figure 2 FTIR spectra of the original printer carbon powder and the carbon powder after calcination prepared in Example 1;

[0028] Figure 3 SEM images of the photothermal functional foam material prepared in Example 1;

[0029] Figure 4 Photothermal performance of the photothermal functional foam material prepared in Example 1;

[0030] Figure 5 Photothermal functional foam material prepared in Example 1 for strengthening the heavy oil recovery process;

[0031] Figure 6 Photothermal performance of the photothermal functional foam material prepared in Examples 2-4. DETAILED DESCRIPTION

[0032] The application will be described in detail below with reference to examples, so that those skilled in the art can better understand the application, but the application is not limited to the following examples.

[0033] Example 1

[0034] A method for preparing a photothermal functional foam material based on waste printer carbon powder, comprising the following steps:

[0035] ① Disassemble the waste printer selenium drum, and take out the printer carbon powder;

[0036] ② Calcine the printer carbon powder obtained in step ① at 650 ℃ for 2 h in a nitrogen atmosphere, and after grinding treatment, obtain a photothermally active carbon powder;

[0037] ③ Immerse the elastic melamine polymer sponge in a Tris buffer solution (10 mM, pH=8.5) containing dopamine, and magnetically stir at room temperature for 12 h, so that a polydopamine (PDA) coating layer is formed on the surface in situ, and obtain a PDA-coated sponge material;

[0038] ④ Add polydimethylsiloxane (PDMS) prepolymer and curing agent (mass ratio of 10:1) in an ethanol solvent and mix uniformly, control the PDMS concentration at 1 mg / mL, then add the carbon powder obtained in step ②, control the carbon powder concentration at 2 mg / mL, and after ultrasonic dispersion, obtain a uniform PDMS / carbon powder dispersion liquid;

[0039] ⑤ Immerse the PDA-coated sponge material obtained in step ③ into the dispersion liquid described in step ④, and repeatedly squeeze and release it 4 times at room temperature to ensure that the dispersion liquid fully penetrates and covers the sponge skeleton; then heat it at 120 ℃ for 2 h to complete the PDMS crosslinking and curing, and obtain a photothermal functional foam material with a uniformly coated PDMS / carbon powder layer on the surface.

[0040] Such as SEM images ( Figure 1 As shown in the figure, the original printer toner has a uniform granular morphology with a particle size of approximately 10 μm. Figure 1 a); After calcination at 650℃, the particle size is significantly reduced, the morphology changes to irregular slag particles, and it exhibits a relatively rough surface characteristic. Figure 1 b).

[0041] Such as FTIR spectra ( Figure 2 As shown in the figure, compared with the original carbon powder, the infrared absorption peaks of the sample after calcination (e.g., 3025–3060 cm⁻¹) are significantly different. -1 2900 cm -1 1720 cm -1 1184 cm -1 The significant reduction in organic components (such as polystyrene (PS) and polymethyl methacrylate (PMMA) in the original toner is due to the pyrolysis of these components at high temperatures. FTIR results indicate that the organic polymer matrix in the sample has been largely removed during calcination, and the heat treatment effectively transformed the material from an organic phase to carbonized inorganic residue.

[0042] From SEM images ( Figure 3 It can be seen that the original porous melamine sponge has a porous skeleton structure and a smooth skeleton surface. Figure 3 (a) This porous structure enhances light absorption and promotes liquid flow. After in-situ polymerization modification with PDA, the surface of the sponge skeleton changes from smooth to a wrinkled or granular coating. Figure 3 b). Because PDA is rich in amine and catechol functional groups, it provides abundant anchoring sites for the fixation of micro / nanoparticle functional materials. Therefore, the PDA layer on the PDA-coated sponge can act as an adhesive between the toner particles and the substrate sponge. When the PDA-coated sponge is impregnated with a PDMS / toner dispersion, a dense layer of toner particles can be formed on its surface and fixed by the cured PDMS coating. Figure 3 c), thereby significantly improving the adhesion and structural stability of the photothermal coating.

[0043] Example 2

[0044] The preparation method in this embodiment differs from that in Example 1 in that:

[0045] In step ②, the printer carbon powder obtained in step ① is calcined at 500 ℃ for 2 h under a nitrogen atmosphere, and after grinding treatment, a photo-thermal active carbon powder is obtained;

[0046] ③The elastic polyurethane sponge is immersed in a Tris buffer solution (10 mM, pH=8.5) containing dopamine, and is magnetically stirred at room temperature for 12 h to form a polydopamine (PDA) coating layer on the surface by in-situ polymerization, thereby obtaining a PDA-coated sponge material;

[0047] ④A polydimethylsiloxane (PDMS) prepolymer and a curing agent (mass ratio of 10:1) are uniformly mixed in an organic solvent, and the PDMS concentration is controlled at 1 mg / mL, then the carbon powder obtained in step ② is added, and the carbon powder concentration is controlled at 2 mg / mL, and after ultrasonic dispersion, a uniform PDMS / carbon powder dispersion liquid is obtained;

[0048] ⑤The PDA-coated sponge material obtained in step ③ is immersed in the dispersion liquid in step ④, and is repeatedly squeezed and released 4 times at room temperature to ensure that the dispersion liquid fully penetrates and covers the sponge skeleton; then, PDMS cross-linking and curing are completed at 120 ℃ for 2 h, thereby obtaining a photo-thermal functional foam material with a uniform PDMS / carbon powder layer on the surface.

[0049] Example 3

[0050] The difference between the preparation method of this example and Example 1 is that:

[0051] In step ②, the printer carbon powder obtained in step ① is calcined at 500 ℃ for 2 h under a nitrogen atmosphere, and after grinding treatment, a photo-thermal active carbon powder is obtained;

[0052] ③The elastic polyurethane sponge is immersed in a Tris buffer solution (10 mM, pH=8.5) containing dopamine, and is magnetically stirred at room temperature for 12 h to form a polydopamine (PDA) coating layer on the surface by in-situ polymerization, thereby obtaining a PDA-coated sponge material;

[0053] ④A polydimethylsiloxane (PDMS) prepolymer and a curing agent (mass ratio of 10:1) are uniformly mixed in an organic solvent, and the PDMS concentration is controlled at 1 mg / mL, then the carbon powder obtained in step ② is added, and the carbon powder concentration is controlled at 1 mg / mL, and after ultrasonic dispersion, a uniform PDMS / carbon powder dispersion liquid is obtained;

[0054] ⑤The PDA-coated sponge material obtained in step ③ is immersed in the dispersion liquid in step ④, and is repeatedly squeezed and released 4 times at room temperature to ensure that the dispersion liquid fully penetrates and covers the sponge skeleton; then, PDMS cross-linking and curing are completed at 120 ℃ for 2 h, thereby obtaining a photo-thermal functional foam material with a uniform PDMS / carbon powder layer on the surface.

[0055] Example 4

[0056] The preparation method of this example is different from that of Example 1 in that:

[0057] In step ②, the printer toner obtained in step ① is calcined at 500 ℃ for 2 h under a nitrogen atmosphere, and after grinding treatment, a photo-thermal active carbon powder is obtained;

[0058] ③The elastic melamine sponge is immersed in a Tris buffer solution (10 mM, pH=8.5) containing dopamine and magnetically stirred at room temperature for 12 h to form a polydopamine (PDA) coating layer in situ on the surface, thereby obtaining a PDA-coated sponge material;

[0059] ④A polydimethylsiloxane (PDMS) prepolymer and a curing agent (mass ratio of 10:1) are added to an organic solvent and uniformly mixed, and the PDMS concentration is controlled at 1 mg / mL. Then, the carbon powder obtained in step ② is added, and the carbon powder concentration is controlled at 3 mg / mL. After ultrasonic dispersion, a uniform PDMS / carbon powder dispersion liquid is obtained;

[0060] ⑤The PDA-coated sponge material obtained in step ③ is immersed in the dispersion liquid described in step ④, and is repeatedly squeezed and released 4 times at room temperature to ensure that the dispersion liquid penetrates and covers the sponge skeleton; then, PDMS cross-linking and curing are completed at 120 ℃ for 2 h, thereby obtaining a photo-thermal functional foam material uniformly coated with a PDMS / carbon powder layer on the surface.

[0061] Application Example

[0062] The photo-thermal functional foam material prepared in Example 1 is subjected to photo-thermal performance and high-viscosity oil stain recovery performance tests.

[0063] Photo-thermal performance test

[0064] The photo-thermal functional foam material is placed below a xenon lamp solar light simulation light source, the light intensity is controlled by adjusting the voltage, and a light power density meter is used for calibration (1 sun = 1.0 kW / m 2 ). After the light source is turned on, the temperature of the material increases with time under the simulation of sunlight, and the surface temperature change is recorded in real time by a contact thermocouple.

[0065] As Figure 4 shown, the simulation of sunlight test results show that the prepared photo-thermal functional foam material exhibits excellent photo-thermal conversion performance under the condition of a simulated light intensity of one sun (1 sun = 1.0 kW / m 2 ). The equilibrium temperature can reach 82 ℃ in about 50 s.

[0066] High-viscosity oil stain recovery performance test

[0067] To evaluate the absorption behavior of the photothermal functional foam material to high viscosity oil, a certain mass of simulated oil spill droplet was added to the surface of the foam material for static absorption experiment. The penetration and absorption process of the oil droplet on the material surface was investigated under the conditions of closing and opening the simulated sunlight irradiation. The whole process was recorded in real time by a camera to compare the influence of light conditions on the oil absorption rate and absorption behavior.

[0068] The results are shown in Figure 5 Under the condition of no sunlight irradiation, 0.1 g of high viscosity oil droplet needs 710 s to be absorbed by the absorption material; while under the condition of 1 sun intensity of simulated sunlight irradiation, the absorption and penetration time of the same mass of high viscosity oil droplet is significantly shortened to 75 s, and the penetration rate is increased by nearly 10 times. This is mainly due to the rapid temperature rise of the foam material caused by the photothermal effect, which heats and reduces the viscosity of the high viscosity oil at the interface, thereby significantly improving the penetration and absorption rate.

[0069] The photothermal performance of the photothermal functional foam material samples prepared in Examples 2-4 was also tested to evaluate its rationality and the influence of different preparation conditions on the photothermal performance, and the results are shown in Figure 6 The results show that the calcination temperature of carbon powder and its concentration in the dispersion liquid are the key factors affecting the photothermal performance of the material. Specifically, under the condition of 1 sun intensity (1.0 kW / m 2 ) of simulated light irradiation, the sample prepared by using carbon powder calcined at 500 ℃ in Example 2 can reach an equilibrium temperature of 77 ℃ in about 50 s, which is slightly lower than that of the sample prepared by using carbon powder calcined at 650 ℃ in Example 1. This shows that the calcination temperature of carbon powder has a certain influence on its photothermal performance. Further, when the addition concentration of carbon powder calcined is reduced from 2 mg / mL to 1 mg / mL (Example 3), the equilibrium temperature of the sample is reduced to about 68 ℃; on the contrary, when the carbon powder concentration is increased from 2 mg / mL to 3 mg / mL (Example 4), the equilibrium temperature is increased to about 89 ℃. It can be seen that the content of the photothermal additive has a significant influence on the photothermal performance of the composite foam material, and the photothermal response ability of the material is obviously enhanced with the increase of the content of carbon powder.

[0070] Overall, the samples obtained according to the preparation conditions of Examples 1-4 all exhibit excellent photothermal response performance, which provides a reliable performance basis for their application in the fields of high viscosity oil recovery, floating oil removal and interfacial evaporation and other environmental management.

[0071] The above examples are merely specific embodiments of the present application, and do not limit the patent scope of the present application, and any equivalent structure or equivalent process transformation made by the present application specification, or direct or indirect application in other related technical fields, are also included in the patent protection scope of the present application.

Claims

1. A method for preparing photothermal functional foam materials based on waste printer toner, characterized in that, Includes the following steps: S1. Toner activation: Printer toner obtained from dismantling waste printer drums is calcined at 400-800℃ for 0.5-4 hours in an inert atmosphere and then ground to obtain photothermal activated toner. S2. Sponge substrate modification: The porous polymer sponge is immersed in a Tris buffer solution containing dopamine and magnetically stirred for 6 to 24 hours to allow in-situ polymerization on its surface to form a polydopamine PDA coating, thereby obtaining a PDA-coated sponge material. S3. Dispersion preparation: Polydimethylsiloxane (PDMS) prepolymer and curing agent are added to an organic solvent and mixed evenly. The PDMS mass concentration is controlled at 0.5–2 mg / mL. Then, the photothermal activated carbon powder is added and the carbon powder mass concentration is controlled at 0.5–5 mg / mL. After ultrasonic dispersion, a uniform PDMS / carbon powder composite dispersion is obtained. S4. Composite and curing: The PDA-coated sponge material is immersed in the PDMS / carbon powder composite dispersion, and the compression-release is repeated several times to ensure that the dispersion fully penetrates and adheres to the sponge skeleton; then it is heated at 80-150 ℃ for 1-5 hours to allow the PDMS to crosslink and cure to form a coating, thereby obtaining a photothermal functional foam material with a uniformly coated surface of PDMS / carbon powder.

2. The method for preparing photothermal functional foam materials based on waste printer toner according to claim 1, characterized in that: In step S1, the inert atmosphere is nitrogen or argon; the particle size of the photothermal activated carbon powder is 2–20 μm.

3. The method for preparing photothermal functional foam materials based on waste printer toner according to claim 1, characterized in that: In step S2, the porous polymer sponge is at least one of melamine foam, polyurethane foam, or polyolefin foam; the concentration of the Tris buffer solution is 5–20 mM, and the pH value is 7.5–9; the concentration of dopamine in the Tris buffer solution is 1–10 mg / mL.

4. The method for preparing photothermal functional foam materials based on waste printer toner according to claim 1, characterized in that: In step S3, the organic solvent is at least one of methanol, ethanol, acetone, n-hexane, cyclohexane, or toluene; the mass ratio of polydimethylsiloxane PDMS prepolymer to curing agent is 10:

1.

5. The method for preparing photothermal functional foam materials based on waste printer toner according to claim 1, characterized in that: In step S4, the squeezing-releasing process is repeated 3 to 6 times.

6. A photothermal functional foam material prepared by the method of any one of claims 1-5.

7. The photothermal functional foam material according to claim 6, characterized in that: The material has hydrophobic and oleophilic properties, with a water contact angle greater than 130° and an oil contact angle less than 5°.

8. The photothermal functional foam material according to claim 6, characterized in that: The material is at 1 kW / m 2 Under sunlight, its surface temperature rises to 60-90 ℃, exhibiting excellent photothermal conversion performance. After 10 cycles of photothermal testing, the surface temperature rise decreases by less than 5%.

9. The application of the photothermal functional foam material according to any one of claims 6-8 in environmental remediation.

10. The application of the photothermal functional foam material according to claim 9 in environmental remediation, characterized in that: The applications include solar-driven seawater desalination or interfacial evaporation; solar-assisted heating, adsorption, and recovery of high-viscosity oils; and solar-assisted adsorption, sterilization, and disinfection of organic pollutants in water.

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