CN109847722B - In-situ assembled polyvinyl alcohol composite carbon-based hydrophobic oil absorption material and preparation method thereof - Google Patents
In-situ assembled polyvinyl alcohol composite carbon-based hydrophobic oil absorption material and preparation method thereof Download PDFInfo
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- CN109847722B CN109847722B CN201910067027.5A CN201910067027A CN109847722B CN 109847722 B CN109847722 B CN 109847722B CN 201910067027 A CN201910067027 A CN 201910067027A CN 109847722 B CN109847722 B CN 109847722B
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Abstract
The invention relates to an in-situ assembled polyvinyl alcohol composite carbon-based hydrophobic oil absorption material and a preparation method thereof, wherein the in-situ assembled polyvinyl alcohol composite carbon-based hydrophobic oil absorption material has good hydrophobic oleophylic property (the water contact angle is up to 146 degrees), higher adsorption rate and mechanical strength, and can be recycled through simple extrusion.
Description
Technical Field
The invention relates to an in-situ assembled polyvinyl alcohol composite carbon-based hydrophobic oil absorption material and a preparation method thereof.
Background
Water quality in some regions of the world is contaminated by frequently occurring water contamination events, including oil and chemical spills and resulting accidents and disasters. Methods for removing oil from water generally include physical, chemical and biological methods, and among these, physical adsorption is considered to be the most environmentally friendly, efficient and low-cost method for dealing with oil leakage accidents. However, the traditional inorganic adsorption materials (activated carbon, expanded graphite, clay and the like), synthetic polymer adsorption materials (polyurethane foam, melamine sponge, macroporous rubber gel and the like) and natural organic adsorption materials (kapok fiber, cotton, straw and the like) have various defects such as low adsorption quantity, poor oil-water selectivity, poor recycling capability and the like. Therefore, the development of the adsorption material which has high adsorption rate, good oil-water selectivity, recycling and lower cost is of great significance.
Novel carbon materials represented by graphene have a number of excellent properties. Such as high specific surface area, hydrophobic oleophilic characteristics and good chemical stability, make it a potential adsorbent material for the treatment of contaminated water bodies. Various carbon-based three-dimensional structures with different microstructures can be prepared by a CVD (chemical vapor deposition) method, a freeze-drying method, a hydrothermal method or a 3D (three-dimensional) printing method and the like, and the aerogel three-dimensional structures show good oil and organic solvent adsorption performances, such as high adsorption rate, high adsorption speed and the like. For example, for three-dimensional graphene aerogels, the very high oil adsorption capacity results from the porous structure of the material and the very low density (typically less than 5 mg/cm)3). However, the material has low strength, so that the macroscopic structure of the material cannot be well maintained after adsorbing oil liquid, and the material is difficult to recycle by adopting a conventional mechanical extrusion mode. In the past reports, the recycling of the carbon-based aerogel oil absorption material is generally realized by adopting a heating distillation or combustion regeneration mode, and the modes have the problems of low efficiency or secondary pollution in practical application. Meanwhile, the carbon-based aerogel materials are difficult to be applied in a large scale in practice due to the high cost of raw materials and the complex preparation process.
No matter the traditional adsorption material or the novel carbon-based aerogel with high adsorption rate, different problems exist in the practical application process. Therefore, it is a very challenging subject to simultaneously realize the characteristics of high hydrophobicity, high oil absorption rate, high mechanical property, reusability and the like of the adsorbing material.
Disclosure of Invention
The invention aims to solve the problems of poor hydrophobicity, low oil absorption multiplying power, less recycling times, low mechanical strength and the like of the existing adsorbing material, and provides an excellent adsorbing material for removing oil products overflowing from water or other organic matters by using a physical method. Therefore, the invention aims to provide an in-situ assembled polyvinyl alcohol composite carbon-based hydrophobic oil absorption material and a preparation method thereof.
The invention provides an in-situ assembled polyvinyl alcohol composite carbon-based hydrophobic oil absorption material, which is prepared by performing hydrothermal crosslinking, cleaning and drying on polyvinyl alcohol and a carbon-based nano material in an acid environment; the dosage of the carbon-based nano material is 2-10% of the mass of the polyvinyl alcohol, and the concentration of the polyvinyl alcohol aqueous solution is 3-10%.
In the invention, the carbon-based nano material comprises one or more of graphene oxide, graphene, carbon nano tubes, carbon black or carbon microspheres.
In the invention, the graphene, the carbon nano tube, the carbon black or the carbon microsphere is subjected to acidification treatment before use, so that the graphene, the carbon nano tube, the carbon black or the carbon microsphere is uniformly dispersed in a water system.
In the invention, the acid environment in the hydrothermal process of the hydrophobic oil absorption material is provided by a 98% sulfuric acid solution, and the addition amount of 98% sulfuric acid in the system is 10-40% of the mass of polyvinyl alcohol.
In the invention, the hydrothermal crosslinking is controlled to be 150-240 ℃ and the hydrothermal time is 12-48 h.
In the present invention, the drying method includes any one of supercritical drying, freeze drying, vacuum drying and natural drying.
The invention provides a preparation method of an in-situ assembled polyvinyl alcohol composite carbon-based hydrophobic oil absorption material, which comprises the following specific steps:
(1) dissolving PVA particles in water at the temperature of 95 ℃ to form a transparent dispersion solution, cooling, adding a graphene oxide solution or an acidification modified graphene, a carbon nano tube, carbon black or a carbon microsphere solution, mechanically stirring and mixing uniformly, adding a sulfuric acid aqueous solution, and further mechanically stirring and mixing uniformly to obtain a mixed solution;
(2) placing the mixed solution obtained in the step (1) in a hydrothermal reaction kettle, and performing hydrothermal cross-linking at a set reaction temperature to obtain an in-situ assembled polyvinyl alcohol composite carbon-based material;
(3) and (3) immersing the in-situ assembled polyvinyl alcohol composite carbon-based material prepared in the step (2) in a pure water environment, removing unreacted raw material components, and further drying to obtain the polyvinyl alcohol composite carbon-based hydrophobic oil absorption material.
In the invention, the amount of the graphene oxide solution or the acidified and modified graphene, the carbon nano tube, the carbon black or the carbon microsphere solution in the step (1) is 2-10% of the mass of the polyvinyl alcohol, and the concentration of the polyvinyl alcohol aqueous solution is 3-10%.
In the invention, in the step (2), hydrothermal crosslinking is carried out to control the hydrothermal temperature to be 150-.
The invention has the beneficial effects that: the method disclosed by the invention is simple to operate, and the prepared polyvinyl alcohol composite carbon-based hydrophobic oil absorption material is excellent in comprehensive performance and has the potential to be widely applied to the environment-friendly fields of adsorption of oils and organic solvents and the like.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention without limiting the invention. In the drawings:
fig. 1 shows a flow chart of a preparation scheme of the polyvinyl alcohol composite carbon-based hydrophobic oil absorption material assembled in situ according to the invention.
Fig. 2 shows the hydrophobic characteristics (water contact angle of material is 146 °) of the in-situ assembled polyvinyl alcohol composite carbon-based hydrophobic oil absorption material according to the present invention.
Fig. 3 shows a bar graph of adsorption rates of polyvinyl alcohol composite graphene carbon-based hydrophobic oil absorption material for adsorbing different organic solvents according to the in-situ assembly method.
Fig. 4 shows an experiment of rapidly adsorbing underwater chloroform droplets by the polyvinyl alcohol composite graphene carbon-based hydrophobic oil absorption material assembled in situ according to the invention.
Detailed Description
The following detailed description of embodiments of the invention refers to the accompanying drawings. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
Example 1
Weighing 5g of PVA, placing the PVA in 100mL of graphene oxide solution (the concentration of the graphene oxide is 0.5 mg/mL), magnetically stirring and dissolving at 95 ℃, further adding 5mL of 4 mol/L sulfuric acid aqueous solution into the solution after uniform mixing, placing the mixture in a hydrothermal kettle after uniform mixing and defoaming, carrying out hydrothermal treatment at 180 ℃ for 24 hours, then placing foams obtained by the hydrothermal treatment in clear water for soaking for 3 days, changing water once every 24 hours, and then placing the materials in a freeze dryer for freeze drying for 72 hours to obtain the polyvinyl alcohol composite carbon-based hydrophobic oil absorption material 1.
Example 2
Weighing 8g of PVA, placing the PVA in 100ml of aqueous solution in which 120 mg of acidized carbon nano tubes are dispersed, magnetically stirring and dissolving the PVA at 95 ℃, further adding 10ml of 3 mol/L sulfuric acid aqueous solution into the mixed solution after uniform mixing, placing the mixture in a hydrothermal kettle after uniform mixing, carrying out hydrothermal treatment for 12 hours at 200 ℃, then placing foams obtained by the hydrothermal treatment in clear water for 3 days, changing water once every 24 hours, and then carrying out supercritical drying on the materials to obtain the polyvinyl alcohol composite carbon-based hydrophobic oil absorption material 2.
Example 3
Weighing 10g of PVA, placing the PVA in 100ml of aqueous solution in which 200 mg of acidified graphene nanosheets are dispersed, magnetically stirring and dissolving the PVA at 95 ℃, further adding 5ml of 5 mol/L sulfuric acid aqueous solution into the mixed solution after uniformly mixing, mixing and defoaming the mixture, placing the uniformly mixed components in a hydrothermal kettle, carrying out hydrothermal treatment at 200 ℃ for 24 hours, placing foams obtained by the hydrothermal treatment in clear water for 3 days, changing water once every 24 hours, and then carrying out freeze drying on the materials to obtain the polyvinyl alcohol composite carbon-based hydrophobic oil absorption material 3.
Comparative example 1
100g of high-activity polyether polyol, 3g of triethanolamine serving as a catalyst, 1.5g of dibutyltin dilaurate, 9g of an organic silicon surfactant, 22.2g of trifluorotrichloroethane serving as a physical foaming agent and 1g of deionized water are placed in a reaction container, the materials are fully stirred and uniformly mixed, a mixed solution is placed in a vacuum drying box, bubbles in a mixed system are removed by vacuumizing twice, diisocyanate is added into the components, the mixed system is mechanically and uniformly stirred, the mixture is rapidly poured into a mold, the mixture is placed in a 60 ℃ drying oven for foaming, and after 120 minutes, a polyurethane foaming material is taken out of the mold, so that the polyurethane foam oil absorption material is obtained.
Comparative example 2
Weighing 1g of PVA and 4g of nanocellulose, placing the PVA and the nanocellulose in 100ml of deionized water, mixing the mixture for 1 hour at the temperature of 90 ℃, adding 250 microliters of glutaraldehyde aqueous solution with the mass fraction of 25%, further adding 1% of dilute sulfuric acid solution to adjust the pH value of the system to 4-6, pouring the obtained gel solution into a curing mold, and placing the curing mold in a vacuum oven at the temperature of 75 ℃ to cure and crosslink the gel solution for 3 hours to obtain the cellulose-polyvinyl alcohol hydrophobic oil absorption foam material.
TABLE 1 Performance test data sheet of experiment sample of hydrophobic oil absorption material
| Apparent Density (mg/cm)3） | Oil absorption multiplying power% (chloroform) | Water contact Angle (hydrophobicity) | |
| Example 1 | 77 mg/cm3 | 47 | 148 |
| Example 2 | 84 mg/cm3 | 45 | 145 |
| Example 3 | 101 mg/cm3 | 41 | 144 |
| Comparative example 1 | 95 mg/cm3 | 18 | 89 |
| Comparative example 2 | 117 mg/cm3 | 14 | 102 |
From the table, it is obvious that the in-situ assembled polyvinyl alcohol composite carbon-based hydrophobic oil absorption material has good hydrophobic oleophylic property, and the oil absorption multiplying power of the chloroform case is far higher than that of other oil absorption materials.
It should be noted that the above-mentioned description is given for illustrating the present invention in more detail with reference to specific preferred embodiments, and it should not be considered that the present invention is limited to the specific embodiments, but rather that several simple deductions or substitutions can be made by those skilled in the art without departing from the spirit of the present invention, which should be regarded as belonging to the patent protection scope defined by the claims filed with the present invention.
Claims (3)
1. The in-situ assembled polyvinyl alcohol composite carbon-based hydrophobic oil absorption material is characterized in that the hydrophobic oil absorption material consists of polyvinyl alcohol and a carbon-based nano material, and is obtained by hydrothermal crosslinking, cleaning and drying in an acidic environment; the dosage of the carbon-based nano material is 2-10% of the mass of the polyvinyl alcohol, and the concentration of the polyvinyl alcohol aqueous solution is 3-10%; the carbon-based nano material comprises one or more of graphene oxide, graphene, carbon nano tubes, carbon black or carbon microspheres; the graphene, the carbon nano tube, the carbon black or the carbon microsphere are subjected to acidification treatment before use, so that the graphene, the carbon nano tube, the carbon black or the carbon microsphere is uniformly dispersed in a water system; the acid environment in the hydrothermal process of the hydrophobic oil absorption material is provided by a 98% sulfuric acid solution, and the addition amount of 98% sulfuric acid in the system is 10-40% of the mass of polyvinyl alcohol; the hydrothermal temperature is controlled to be 150-240 ℃ in the hydrothermal crosslinking process, and the hydrothermal time is 12-48 h.
2. The in-situ assembled polyvinyl alcohol composite carbon-based hydrophobic oil absorption material as claimed in claim 1, wherein the drying manner comprises any one of supercritical drying, freeze drying, vacuum drying or natural drying.
3. The preparation method of the in-situ assembled polyvinyl alcohol composite carbon-based hydrophobic oil absorption material as claimed in claim 1, which is characterized by comprising the following specific steps:
(1) dissolving PVA particles in water at the temperature of 95 ℃ to form a transparent dispersion solution, cooling, adding a graphene oxide solution or an acidification modified graphene, a carbon nano tube, carbon black or a carbon microsphere solution, mechanically stirring and mixing uniformly, adding a sulfuric acid aqueous solution, and further mechanically stirring and mixing uniformly to obtain a mixed solution;
(2) placing the mixed solution obtained in the step (1) in a hydrothermal reaction kettle, and performing hydrothermal cross-linking at a set reaction temperature to obtain an in-situ assembled polyvinyl alcohol composite carbon-based material;
(3) immersing the in-situ assembled polyvinyl alcohol composite carbon-based material prepared in the step (2) in a pure water environment, removing unreacted raw material components, and further drying to obtain a polyvinyl alcohol composite carbon-based hydrophobic oil absorption material;
in the step (1), the amount of the graphene oxide solution or the acidified and modified graphene, the carbon nano tube, the carbon black or the carbon microsphere solution is 2-10% of the mass of the polyvinyl alcohol, and the concentration of the polyvinyl alcohol aqueous solution is 3-10%; in the step (2), hydrothermal crosslinking is carried out to control the hydrothermal temperature to be 150-.
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| CN113083251A (en) * | 2021-03-30 | 2021-07-09 | 安徽光特新材料科技有限公司 | Preparation method and application of boron nitride modified polyvinyl alcohol composite material |
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| CN101993056A (en) * | 2010-12-01 | 2011-03-30 | 天津大学 | Graphene-based porous macroscopic carbon material and preparation method thereof |
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| CN108745290A (en) * | 2018-07-12 | 2018-11-06 | 山东佳星环保科技有限公司 | The preparation method of graphene/carbon nano-tube composite aerogel with efficient oil absorbency |
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