Super-hydrophobic photothermal sponge for fast adsorption of high viscosity petroleum and preparation and application thereof

Abstract

The present application relates to the field of super-hydrophobic adsorption material, and relates to a super-hydrophobic photo-thermal sponge for quickly adsorbing high-viscosity petroleum and preparation and application thereof, comprising the following steps: soaking a sponge in a dopamine solution, carrying out in-situ oxidative polymerization, washing and drying after the reaction is completed to obtain a PDA sponge; soaking the PDA sponge obtained in step S1 in a cobalt solution to react, then taking out and washing to obtain an intermediate, then putting the intermediate into a hexahydroxytriphenylamine solution to react, then taking out, washing and drying to obtain a Co-HHTP / PDA sponge; immersing the Co-HHTP / PDA sponge obtained in step S2 in a polydimethylsiloxane solution, then solidifying and drying to obtain a PDMS / Co-HHTP / PDA sponge. Compared with the prior art, the present application has the advantages of low price, excellent mechanical stability, easy availability of raw materials, suitability for large-scale production and the like.

Description

Technical Field

[0001] This invention relates to the field of superhydrophobic adsorption materials, and in particular to a superhydrophobic photothermal sponge that rapidly adsorbs high-viscosity petroleum, its preparation and application. Background Technology

[0002] Frequent crude oil spills and the discharge of oily wastewater have caused serious harm to marine ecosystems and human health. Currently used superhydrophobic materials are mainly designed for low-viscosity oils, while high-viscosity oil is difficult to flow at room temperature and cannot penetrate the pores of materials, severely affecting adsorption and separation efficiency. Typically, the viscosity of oil decreases with increasing temperature. Therefore, introducing photothermal materials onto a hydrophobic surface to convert solar energy into heat energy to heat the surrounding viscous crude oil, reducing its viscosity and increasing its fluidity, thereby promoting oil adsorption, is an energy-efficient, green, and environmentally friendly new oil removal strategy that has received widespread attention in recent years. Three-dimensional porous materials, such as sponges, possess a highly porous mesh structure. By modifying sponges with photothermal materials, such as carbon-based, polymer-based, metal-based, and semiconductor materials, three-dimensional oil-absorbing materials with good photothermal conversion capabilities can be prepared.

[0003] In the prior art, Chinese patent CN113321846A discloses a method for preparing a photothermal superhydrophobic adsorbent material, which uses polyaniline as the photothermal material and melamine sponge as the substrate. Under light, it can increase the surface temperature and reduce the viscosity of crude oil. However, it uses perfluorooctanoic acid (PFOA) in its preparation, and the use of fluorides can easily cause secondary pollution. Therefore, preparing adsorbent materials with good photothermal effects using a simple, low-cost, and environmentally friendly method is a problem that urgently needs to be solved in the existing technology. Summary of the Invention

[0004] The purpose of this invention is to overcome the defects of the existing technology and provide a superhydrophobic photothermal sponge that can rapidly adsorb high-viscosity petroleum, as well as its preparation and application. Melamine sponge is used as the substrate, polydopamine (PDA) is polymerized in situ, Co-HHTP is used as the photothermal material, and polydimethylsiloxane (PDMS) is coated for surface modification. The superhydrophobic photothermal sponge is constructed by layer-by-layer assembly and coating adhesive, which realizes the rapid increase of surface temperature under sunlight and the rapid adsorption of high-viscosity petroleum, and has good prospects for practical application.

[0005] The objective of this invention can be achieved through the following technical solutions:

[0006] The preparation of a superhydrophobic photothermal sponge includes the following steps:

[0007] S1: The sponge is soaked in a dopamine solution to undergo an in-situ oxidative polymerization reaction. After the reaction is complete, it is washed and dried to obtain a PDA sponge.

[0008] S2: The PDA sponge obtained in step S1 is immersed in a cobalt solution for reaction, then taken out and washed to obtain an intermediate. The intermediate is then placed in a hexahydroxytriphenylene solution for reaction, then taken out, washed, and dried to obtain a Co-HHTP / PDA sponge.

[0009] S3: Immerse the Co-HHTP / PDA sponge obtained in step S2 in a polydimethylsiloxane solution, and then cure and dry to obtain PDMS / Co-HHTP / PDA sponge.

[0010] Furthermore, in step S1, the sponge includes one or more of polyurethane sponge, melamine sponge, and melamine sponge.

[0011] Furthermore, in step S1, the concentration of the dopamine solution is 1-5 g / L, and the feeding ratio of the sponge to the dopamine solution is 0.1-0.2 g: 50-200 mL.

[0012] Furthermore, in step S1, the in-situ oxidative polymerization reaction takes 24-48 hours and the reaction temperature is 50-80°C.

[0013] Furthermore, in step S2, the concentration of the cobalt solution is 1-5 mmol / L, and the feeding ratio of the PDA sponge to the cobalt solution is 2-4:1.

[0014] Furthermore, in step S2, the concentration of the hexahydroxytriphenylene solution is 0.1-0.5 mmol / L.

[0015] Furthermore, in step S3, the polydimethylsiloxane solution includes PDMS, a curing agent, and an ethyl acetate solution, and the ratio of the amount of Co-HHTP / PDA sponge, PDMS, curing agent, and ethyl acetate is 0.1-0.5g: 1-5g: 0.1-0.5g: 50-200mL.

[0016] Furthermore, in step S3, the curing time is 2-6 hours and the curing temperature is 70-100℃.

[0017] A superhydrophobic photothermal sponge was prepared using the above-described preparation method.

[0018] An application of a superhydrophobic photothermal sponge, wherein the superhydrophobic photothermal sponge is used to adsorb petroleum.

[0019] Compared with the prior art, the present invention has the following advantages and beneficial effects:

[0020] 1. The sponge in this invention is inexpensive, has excellent mechanical stability, and the raw materials are readily available, making it suitable for large-scale production.

[0021] 2. The Co-HHTP metal-organic framework in this invention is assembled using a layer-by-layer method, which is simple to operate; and it uses environmentally friendly PDMS instead of fluorine-containing compounds as a low surface energy modifier for the hydrophobic surface of the material, making it more green and environmentally friendly.

[0022] 3. The PDMS / Co-HHTP / PDA sponge in this invention has a water contact angle of up to 160.2°, exhibiting excellent hydrophobic and oleophilic properties.

[0023] 4. The Co-HHTP in this invention has good photothermal conversion efficiency. The PDMS / Co-HHTP / PDA sponge can reach 109°C within 300 seconds under one solar intensity. It can absorb 43.8g of petroleum within 5 minutes through a peristaltic pump, thus achieving a good effect of photothermal adsorption of high-viscosity petroleum. Attached Figure Description

[0024] Figure 1 A schematic diagram of the preparation process for a superhydrophobic photothermal sponge;

[0025] Figure 2 These are scanning electron microscope images of the sponges prepared at each stage in Example 1;

[0026] Figure 3 The image shows the contact angle test results of the PDMS / Co-HHTP / PDA sponge obtained in Example 1.

[0027] Figure 4 This is a graph showing the temperature changes of the sponge obtained from each step of the modification in Example 1 under sunlight irradiation.

[0028] Figure 5 The graph shows the cyclic adsorption performance of the modified PDMS / Co-HHTP / PDA sponge obtained in Example 1 on petroleum under simulated sunlight.

[0029] Figure 2 The accompanying figures are labeled as follows: (a) original sponge, (b) PDA sponge, (c) Co-HHTP / PDA sponge, and (d) PDMS / Co-HHTP / PDA sponge. Detailed Implementation

[0030] The present invention will now be described in detail with reference to the accompanying drawings and specific embodiments.

[0031] The following embodiments are implemented based on the above-described technical solution of the present invention, and provide detailed implementation methods and specific operation processes. However, the scope of protection of the present invention is not limited to the following embodiments.

[0032] The following are more detailed implementation examples, which further illustrate the technical solution of the present invention and the technical effects that can be obtained.

[0033] In the following embodiments, unless otherwise specified, the raw materials, reagents or processing techniques are all conventional commercial products or conventional processing techniques in the art.

[0034] In the following examples, melamine foam was selected and purchased from Shanghai Xuxian Sound Insulation and Thermal Insulation Building Materials Co., Ltd.

[0035] Dopamine hydrochloride (DA) was purchased from Titan Reagents platform;

[0036] Hexahydroxytriphenylene (HHTP) was purchased from the Aladdin Reagent Platform;

[0037] Both PDMS and curing agent were purchased from Titan Reagents platform;

[0038] Example 1

[0039] This embodiment provides a superhydrophobic photothermal sponge that rapidly adsorbs high-viscosity petroleum and its preparation method, such as... Figure 1 As shown, it includes the following steps:

[0040] S1: Cut the melamine sponge into 3cm×3cm×2cm pieces, each weighing about 0.15g. Wash it three times each with ethanol and deionized water, and dry it for 1.5h. Then soak it in 100mL of dopamine hydrochloride (DA) solution with a concentration of 2g / L. React it at 60℃ for 24h. After the reaction is complete, wash and dry it for 2h to obtain the PDA sponge.

[0041] S2: The polydopamine-modified sponge obtained in step S1 was immersed in 100 mL of 4 mmol / L cobalt ion aqueous solution and reacted at 25 °C for 10 min. Then it was taken out and washed with deionized water, and then placed in 100 mL of 4 mmol / L hexahydroxytriphenylene (HHTP) ligand aqueous solution. After taking it out, it was washed with deionized water. The above steps were repeated ten times and then dried to obtain Co-HHTP / PDA sponge.

[0042] S3: Immerse the Co-HHTP / PDA sponge obtained in step S2 in 200 mL of hydrophobic polydimethylsiloxane solution for 20 min, then cure at 80 °C for 4 h, finally wash the unreacted PDMS with ethyl acetate, and dry at 60 °C to obtain a superhydrophobic PDMS / Co-HHTP / PDA sponge with photothermal effect.

[0043] When preparing the hydrophobic polydimethylsiloxane solution, the ratio of PDMS:curing agent:ethyl acetate solution is 5g:0.5g:200mL. After mixing, the solution is sonicated at room temperature for 30 minutes to make it homogeneous.

[0044] The sponges prepared in the above steps were subjected to scanning electron microscopy (SEM) tests, such as... Figure 2As shown, (a) is a scanning electron microscope (SEM) image of the original sponge; (b) is a scanning electron microscope (SEM) image of the PDA sponge in S1; (c) is a scanning electron microscope (SEM) image of the Co-HHTP / PDA sponge synthesized in S2; and (d) is a scanning electron microscope (SEM) image of the modified PDMS / Co-HHTP / PDA sponge obtained in S3. Figure 2 It can be observed that the original sponge has a very smooth surface and large pore size, while the modified sponge has many nano-protrusions on its surface, with PDMS evenly covering the surface, which enhances the hydrophobic effect.

[0045] To verify the excellent hydrophobicity of the PDMS / Co-HHTP / PDA sponge, contact angle tests were performed to characterize the sponge. Figure 3 As shown in the figure. The results show that the static water contact angle of the modified PDMS / Co-HHTP / PDA sponge surface is 160.2°, achieving a superhydrophobic effect.

[0046] Example 2

[0047] The PDMS / Co-HHTP / PDA sponge modified in Example 1 was applied to petroleum photothermal adsorption, and its effectiveness was tested. The specific testing process is as follows:

[0048] A xenon lamp was used to simulate the intensity of a solar light source (1 kW / m²). 2 The temperature changes on the sample surface are recorded using an infrared camera, such as... Figure 4 As shown, the modified sponge reached 109℃ after 300 seconds of light exposure, significantly better than the untreated original sponge. The sponge was then placed in viscous petroleum, and the light source was turned on to test its adsorption effect on the petroleum. Figure 5 As shown, the PDMS / Co-HHTP / PDA sponge has an absorption capacity of 52.6-62.5 g / g for petroleum, and the absorbed petroleum can be recovered through a simple mechanical extrusion process. After 10 cycles (each cycle is defined as the sponge absorbing petroleum under light and then mechanically extruding it), the recovery rate exceeds 92%, demonstrating good durability. The excellent photothermal conversion effect of Co-HHTP enables the adsorption of high-viscosity petroleum. Furthermore, the operation method of this invention is simple, the process is time-saving, environmentally friendly, and low-cost, showing broad application prospects.

[0049] The above description of the embodiments is provided to enable those skilled in the art to understand and use the invention. It will be apparent to those skilled in the art that various modifications can be made to these embodiments, and the general principles described herein can be applied to other embodiments without inventive effort. Therefore, the present invention is not limited to the above embodiments, and any improvements and modifications made by those skilled in the art based on the disclosure of the present invention without departing from the scope of the invention should be within the protection scope of the present invention.

Claims

1. A method for preparing a superhydrophobic photothermal sponge, characterized in that, Includes the following steps: S1: The sponge is soaked in a dopamine solution to undergo an in-situ oxidative polymerization reaction. After the reaction is complete, it is washed and dried to obtain a PDA sponge. S2: The PDA sponge obtained in step S1 is immersed in a cobalt solution for reaction, then taken out and washed to obtain an intermediate. The intermediate is then placed in a hexahydroxytriphenylene solution for reaction, then taken out, washed, and dried to obtain a Co-HHTP / PDA sponge. S3: Immerse the Co-HHTP / PDA sponge obtained in step S2 in a polydimethylsiloxane solution, then cure and dry to obtain PDMS / Co-HHTP / PDA sponge; In step S1, the sponge includes one or more of polyurethane sponge, melamine sponge, and melamine sponge.

2. The method for preparing the superhydrophobic photothermal sponge according to claim 1, characterized in that, In step S1, the concentration of the dopamine solution is 1-5 g / L, and the feeding ratio of the sponge to the dopamine solution is 0.1-0.2 g: 50-200 ml.

3. The method for preparing the superhydrophobic photothermal sponge according to claim 1, characterized in that, In step S1, the in-situ oxidative polymerization reaction takes 24-48 hours and the reaction temperature is 50-80℃.

4. The method for preparing the superhydrophobic photothermal sponge according to claim 1, characterized in that, In step S2, the concentration of cobalt ions in the cobalt solution is 1-5 mmol / L, and the feeding ratio of the PDA sponge to the cobalt solution is 2-4:

1.

5. The method for preparing the superhydrophobic photothermal sponge according to claim 1, characterized in that, In step S2, the concentration of the hexahydroxytriphenylene solution is 0.1-0.5 mmol / L.

6. The method for preparing the superhydrophobic photothermal sponge according to claim 1, characterized in that, In step S3, the polydimethylsiloxane solution includes polydimethylsiloxane, a curing agent, and an ethyl acetate solution. The ratio of the amount of Co-HHTP / PDA sponge, polydimethylsiloxane, curing agent, and ethyl acetate is 0.1-0.5g: 1-5g: 0.1-0.5g: 50-200 mL.

7. The method for preparing the superhydrophobic photothermal sponge according to claim 1, characterized in that, In step S3, the curing time is 2-6 hours and the curing temperature is 70-100℃.

8. A superhydrophobic photothermal sponge, characterized in that, It is prepared by any of the preparation methods described in claims 1-7.

9. An application of the superhydrophobic photothermal sponge as described in claim 8, characterized in that, The superhydrophobic photothermal sponge is used to adsorb petroleum.

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