CN108854968B - Elastic and repeatable oil absorption melamine sponge and preparation method thereof - Google Patents
Elastic and repeatable oil absorption melamine sponge and preparation method thereof Download PDFInfo
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- CN108854968B CN108854968B CN201810621544.8A CN201810621544A CN108854968B CN 108854968 B CN108854968 B CN 108854968B CN 201810621544 A CN201810621544 A CN 201810621544A CN 108854968 B CN108854968 B CN 108854968B
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
- A01N25/10—Macromolecular compounds
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/16—Heavy metals; Compounds thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
- B01D17/02—Separation of non-miscible liquids
- B01D17/0202—Separation of non-miscible liquids by ab- or adsorption
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0211—Compounds of Ti, Zr, Hf
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0248—Compounds of B, Al, Ga, In, Tl
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/50—Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/46—Materials comprising a mixture of inorganic and organic materials
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/04—Disinfection
Abstract
The invention relates to an elastic repeatable oil absorption melamine sponge and a preparation method thereof, wherein the sponge comprises a carbon-nitrogen-based sponge prepared from melamine sponge and a hydrophobic material loaded on the carbon-nitrogen-based sponge, the hydrophobic material is a titanium dioxide/porous single-layer titanium carbide composite material, the titanium dioxide is formed by in-situ oxidation of transition metal Ti on a titanium carbide sheet layer, part of the titanium dioxide falls off from the titanium carbide sheet layer to form micropores on the titanium carbide sheet layer, a super-hydrophobic material is prepared firstly, then the hydrophobic material and the melamine sponge are mixed in a proper proportion, and then the mixture is dried and calcined. Compared with the prior art, the sponge can repeatedly absorb oil and inhibit bacteria, can degrade oily pollutants in situ, is self-pollution-resistant and is easy to regenerate; the preparation method is simple and easy to implement, the preparation raw materials are easy to obtain, the cost is low, no pollution is caused, the reproducibility is good, the mass production can be realized, and the method is widely applied to treatment of the oil stains on the water surface.
Description
Technical Field
The invention belongs to the field of preparation of functional materials for oil-water separation and pollutant treatment technologies, and particularly relates to an elastic repeatable oil absorption melamine sponge capable of elastically and repeatedly absorbing and inhibiting bacteria and degrading adsorbed oily pollutants in situ and a preparation method thereof.
Background
Municipal wastewater is a major source of pollution to the water environment near cities. The urban wastewater is a mixture of domestic sewage and industrial wastewater in cities, the urban area has many pollution sources, wide range and high strength, water resources are easily polluted, and even if local pollution occurs, the pollution range is gradually enlarged due to the fluidity of water. At present, the concentrated treatment of the total discharge of industrial and urban sewage in China accounts for less than half of the total discharge, most of the rest sewage is directly discharged into rivers, the restriction on the discharge of sewage is not large, and a large amount of water resources are deteriorated. The water pollution formed by urban wastewater is mainly organic pollutants, and also contains organic matters which are difficult to biodegrade, toxic and harmful. Serious water pollution affects industrial and agricultural production and the health of people, and the annual loss of China caused by water pollution is estimated to be as high as 400 billion yuan.
In recent years, along with the development of marine transportation and the petroleum industry, oil spilling events frequently occur, and besides, leakage and blowout accidents of offshore oil exploitation cause serious oil water body pollution. On 20/4/2010, the "deep horizon" rig in the gulf of mexico in the united states exploded and caused a fire, causing significant environmental and economic losses. Because the composition of the oil is very complex and contains toxic and harmful substances such as saturated hydrocarbon, aromatic hydrocarbon compounds, asphaltene and the like, once the oil leaks into the ocean, a series of complex changes such as evaporation, diffusion, dissolution, photochemical oxidation, microbial oxidation and the like occur immediately, so that not only is the ecological natural environment seriously affected, but also the survival and development of the human society are threatened. At present, the methods for treating and recovering the floating oil on the sea are roughly the following methods: (1) chemical treatment methods mainly including combustion methods, emulsification methods, and the like; (2) biological treatment; (3) the physical treatment method mainly comprises separation, filtration, centrifugation, adsorption and the like. Among these methods, physical adsorption is mainly used, and the adsorption recovery by selecting an oil-absorbing material is the simplest and safest method which can rapidly treat the problem of floating oil on the water surface without secondary pollution, so that the method is widely used. The traditional oil absorption material comprises organic materials such as dimethyl dimethoxy silane, magnetic melamine and the like, and the materials have poor selectivity, low oil absorption efficiency and high cost, and cannot meet the resource treatment requirement, so the research and development of a method for preparing the oil absorption material with high selectivity, high efficiency, cleanness and low cost is the most concerned subject of domestic and foreign researchers.
The melamine sponge has a three-dimensional network structure, the aperture ratio of the melamine sponge is more than ninety-five percent, and the melamine sponge has good flame retardance, namely a compact coke layer is formed on the surface of a combustion body after the melamine sponge contacts open fire, so that the melamine sponge retards combustion, has no smoke, no dripping, no combustion and self-extinguishment after leaving fire. The melamine sponge has excellent chemical stability, safety and environmental protection due to the stable chemical and crosslinking structure. However, the chemical structure of the melamine sponge has a hydrophilic effect, and the melamine sponge has no effect on the treatment of floating oil on the sea. The subject matter of this patent is therefore directed to a method for exploring an elastic, repeatable oil absorbing melamine sponge.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide an elastic repeatable oil absorption melamine sponge and a preparation method thereof.
The purpose of the invention can be realized by the following technical scheme:
the elastic and repeatable oil absorption melamine sponge comprises melamine sponge and a hydrophobic material loaded on the melamine sponge, wherein the hydrophobic material is a titanium dioxide/porous single-layer titanium carbide composite material, the titanium dioxide is formed by in-situ oxidation of transition metal Ti on a titanium carbide sheet layer, part of the titanium dioxide falls off from the titanium carbide sheet layer, and micropores are formed on the titanium carbide sheet layer.
A preparation method of elastic repeatable oil absorption melamine sponge comprises the following steps:
(1) pretreating melamine sponge;
(2) preparing a dispersion of the hydrophobic modification material:
(2-1) mixing aluminum titanium carbide powder with a hydrofluoric acid solution, stirring for reaction, centrifuging, washing and drying to obtain ML-MXene;
(2-2) dispersing ML-MXene in a solvent, stirring, adding hydrogen peroxide at room temperature, standing, and then adding the solvent for further dilution to obtain a dispersion liquid of the hydrophobic material;
(3) immersing the pretreated melamine sponge in dispersion liquid of a hydrophobic material, squeezing, and drying;
(4) and calcining the dried melamine sponge to obtain the elastic repeatable oil absorption melamine sponge.
In the step (2-2), by adding hydrogen peroxide, ML-MXene is changed into a single-layer structure, and transition metal Ti on the titanium carbide sheet layer is oxidized in situ to form titanium oxide; by dilution, the reaction is slowed down or stopped while a homogeneous system is formed.
Preferably, the pretreatment in the step (1) is to immerse the melamine sponge in the treatment liquid, extrude the liquid and dry the liquid; the treatment solution comprises methanol, ethanol or toluene, the immersion time is 10-120 min, and the drying temperature is 50-100 ℃; the drying time is 6-24 h. Further preferably, the immersion time is 30min, and the drying temperature is 60 ℃; the drying time is 12 h.
Preferably, in the step (2-1), the mass-to-volume ratio of the titanium aluminum carbide powder to the hydrofluoric acid solution is 1 g: (10-20) mL, wherein the mass concentration of the HF solution is 10% -49%, the stirring condition is stirring for 12-120 h at room temperature, and the washing method comprises the steps of firstly washing with deionized water until the pH value reaches about 6 (pH value is 5-7), and then washing with absolute ethyl alcohol for 2-5 times. Further preferably, the mass volume ratio of the titanium aluminum carbide powder to the hydrofluoric acid solution is 1 g: 10mL, the mass concentration of the HF solution is 40%, the stirring condition is that the HF solution is stirred for 48 hours at room temperature, and absolute ethyl alcohol is used for washing for 3 times in the washing process. If the concentration of the hydrofluoric acid is too low, the etching is incomplete, and the lamellar structure is easy to damage if the concentration of the hydrofluoric acid is too high; the stirring time at room temperature is too short, the etching is incomplete, and the two-dimensional structure of the material can be damaged after the stirring time is too long; the invention controls the etching degree of the aluminum layer in the aluminum titanium carbide by controlling the concentration and the etching time of hydrofluoric acid.
Preferably, the drying condition in the step (2-1) is drying at room temperature for 12-72 h, and then drying at 30-120 ℃ under vacuum for 12-48 h. Further preferred drying conditions are drying at room temperature for 48h, followed by drying at 60 ℃ under vacuum for 24 h.
Preferably, the ML-MXene is dispersed in the solvent in the step (2-2) so that the mass-to-volume ratio of the ML-MXene to the solvent is 1 g: (60-200) mL; the solvent comprises deionized water, absolute ethyl alcohol, methanol or DMF; the volume-mass ratio of the diluted solvent to the ML-MXene is (500-1000) mL: 1g of the total weight of the composition. Further preferably, the ML-MXene is dispersed in the solvent so that the mass-to-volume ratio of the ML-MXene to the solvent is 1 g: 100mL, the volume mass ratio of the diluted added solvent to ML-MXene is 900 mL: 1g of the total weight of the composition.
Preferably, the stirring treatment time in the step (2-2) is 5-30 min; the standing time is 5-20 min. Further preferably, the stirring treatment time is 10min and the standing time is 10 min. If the standing time is too short, the reaction is not complete, and if the standing time is too long, titanium on the titanium carbide is completely oxidized without Ti3+And the generation of oxygen vacancies, which affect the effect of catalytic degradation.
Preferably, H is as described in step (2-2)2O2The mass concentration of the mixed solution is 10 to 50 percent, and the added H2O2The volume-mass ratio of the ML-MXene to the ML-MXene is (10-30) mL: 1g of the total weight of the composition. Further preferred is H2O2Is 50% by mass, added H2O2The volume mass ratio of the mixed solution to ML-MXene is 20 mL: 1g of the total weight of the composition.
Preferably, the immersion time in the step (3) is 0.5-5 h; the drying temperature is 50-100 ℃; the drying time is 3-36 h. Further preferably, the immersion time is 2 hours, the drying temperature is 60 ℃ and the drying time is 24 hours.
Preferably, the calcining temperature in the step (4) is 200-350 ℃; the calcination time is 1-5 h. Further preferably, the calcination temperature is 280 ℃ and the calcination time is 2 hours. The calcination is carried out under an air atmosphere.
The elastic repeatable oil absorption melamine sponge is applied to treatment of oil stains on water.
The elastic repeatable oil absorption melamine sponge prepared by the invention is uniformly loaded on the melamine sponge made of the titanium dioxide/porous single-layer titanium carbide composite material, changes the chemical structure of the melamine sponge and becomes the super-oleophylic and hydrophobic titanium dioxide/titanium carbide-based melamine sponge. The titanium dioxide is formed by in-situ oxidation of transition metal Ti on a titanium carbide sheet layer, and the particle size of the titanium dioxide is 1-3 nm. Part of titanium dioxide particles fall off from the titanium carbide sheet layer to form micropores, so that the specific surface area of the titanium dioxide/titanium carbide-based melamine sponge is further increased, and the oil absorption efficiency of the titanium dioxide/titanium carbide-based melamine sponge is enhanced. The oil absorption of the repeatable oil absorption melamine sponge reaches 20-30 times of the mass of the repeatable oil absorption melamine sponge.
Compared with the prior art, the invention has the following beneficial effects:
(1) the elastic repeatable oil absorption melamine sponge (elastic hydrophobic melamine sponge) prepared by the invention has the functions of bacteriostasis and sterilization; the used hydrophobic modification material is cheap and has small dosage.
(2) The elastic repeatable oil absorption melamine sponge prepared by the invention has trivalent titanium and oxygen vacancies, and can generate ROS (reactive oxygen species) under illumination, so that the sponge has an in-situ degradation function on adsorbed oily pollutants under the illumination condition, and the sponge prepared by the invention is self anti-pollution and easy to regenerate.
(3) The preparation method is simple and easy to implement, the preparation raw materials are easy to obtain, the cost is low, no pollution is caused, the reproducibility is good, the mass production can be realized, and the method is widely applied to treatment of the oil stains on the water surface.
Drawings
FIG. 1 is an SEM image of a resilient, repeatable oil absorption melamine sponge of the present invention;
fig. 2 shows the contact angle of a common melamine sponge with water (a) and the contact angle of an elastic repeatable oil absorption melamine sponge with water (b).
Detailed Description
The elastic and repeatable oil absorption melamine sponge comprises melamine sponge and a hydrophobic material loaded on the melamine sponge, wherein the hydrophobic material is a titanium dioxide/porous single-layer titanium carbide composite material, the titanium dioxide is formed by in-situ oxidation of transition metal Ti on a titanium carbide sheet layer, part of the titanium dioxide falls off from the titanium carbide sheet layer, and micropores are formed on the titanium carbide sheet layer.
The preparation method of the elastic repeatable oil absorption melamine sponge comprises the following steps:
(1) pretreating melamine sponge;
(2) preparing a dispersion of the hydrophobic modification material:
(2-1) mixing aluminum titanium carbide powder with a hydrofluoric acid solution, stirring for reaction, centrifuging, washing and drying to obtain ML-MXene;
(2-2) dispersing ML-MXene in a solvent, stirring, adding hydrogen peroxide at room temperature, standing, and then adding the solvent for further dilution to obtain a dispersion liquid of the hydrophobic material;
(3) immersing the pretreated melamine sponge in dispersion liquid of a hydrophobic material, squeezing, and drying;
(4) and calcining the dried melamine sponge to obtain the elastic repeatable oil absorption melamine sponge.
Preferably, the pretreatment in the step (1) is to immerse the melamine sponge in the treatment liquid, extrude the liquid and dry the liquid; the treatment solution comprises methanol, ethanol or toluene, the immersion time is 10-120 min, and the drying temperature is 50-100 ℃; the drying time is 6-24 h. Further preferably, the immersion time is 30min, and the drying temperature is 60 ℃; the drying time is 12 h.
Preferably, in the step (2-1), the mass-to-volume ratio of the titanium aluminum carbide powder to the hydrofluoric acid solution is 1 g: (10-20) mL, wherein the mass concentration of the HF solution is 10% -49%, the stirring condition is stirring for 12-120 h at room temperature, and the washing method comprises the steps of firstly washing with deionized water until the pH value reaches about 6 (pH value is 5-7), and then washing with absolute ethyl alcohol for 2-5 times. Further preferably, the mass volume ratio of the titanium aluminum carbide powder to the hydrofluoric acid solution is 1 g: 10mL, the mass concentration of the HF solution is 40%, the stirring condition is that the HF solution is stirred for 48 hours at room temperature, and absolute ethyl alcohol is used for washing for 3 times in the washing process.
Preferably, the drying condition in the step (2-1) is drying at room temperature for 12-72 h, and then drying at 30-120 ℃ under vacuum for 12-48 h. Further preferred drying conditions are drying at room temperature for 48h, followed by drying at 60 ℃ under vacuum for 24 h.
Preferably, the ML-MXene is dispersed in the solvent in the step (2-2) so that the mass-to-volume ratio of the ML-MXene to the solvent is 1 g: (60-200) mL; the solvent comprises deionized water, absolute ethyl alcohol, methanol or DMF; the volume-mass ratio of the diluted solvent to the ML-MXene is (500-1000) mL: 1g of the total weight of the composition. Further preferably, the ML-MXene is dispersed in the solvent so that the mass-to-volume ratio of the ML-MXene to the solvent is 1 g: 100mL, the volume mass ratio of the diluted added solvent to ML-MXene is 900 mL: 1g of the total weight of the composition.
Preferably, the stirring treatment time in the step (2-2) is 5-30 min; the standing time is 5-20 min. Further preferably, the stirring treatment time is 10min and the standing time is 10 min.
Preferably, H is as described in step (2-2)2O2The mass concentration of the mixed solution is 10 to 50 percent, and the added H2O2The volume-mass ratio of the ML-MXene to the ML-MXene is (10-30) mL: 1g of the total weight of the composition. Further preferred is H2O2Is 50% by mass, added H2O2The volume mass ratio of the mixed solution to ML-MXene is 20 mL: 1g of the total weight of the composition.
Preferably, the immersion time in the step (3) is 0.5-5 h; the drying temperature is 50-100 ℃; the drying time is 3-36 h. Further preferably, the immersion time is 2 hours, the drying temperature is 60 ℃ and the drying time is 24 hours.
Preferably, the calcining temperature in the step (4) is 200-350 ℃; the calcination time is 1-5 h. Further preferably, the calcination temperature is 280 ℃ and the calcination time is 2 hours. The calcination is carried out under an air atmosphere.
The elastic repeatable oil absorption melamine sponge can be applied to treatment of oil stains on water.
The invention is described in detail below with reference to the figures and specific embodiments.
Example 1
A preparation method of an elastic repeatable oil absorption melamine sponge comprises the following steps:
(1) 0.5g (length × width × height ═ 6cm × 5cm × 2cm) of melamine sponge was immersed in methanol for 30min, taken out, the solvent was extruded, and the resultant mixture was put in an oven at 60 ℃ for 12h and taken out for use.
(2) Mixing 1g of Ti3AlC2Mixing the powder with 10ml of HF solution with the mass concentration of 40%, stirring for 48h at room temperature, centrifuging, repeatedly washing with deionized water until the pH value of supernatant is about 6, washing with absolute ethyl alcohol for three times, drying for 48h at room temperature, and then vacuum-drying for 24 h. Obtaining the multilayer titanium carbide. 50mg of titanium carbide powder was redispersed in 5mL of ethanolStirring for 10min at room temperature until the mixture is uniformly dispersed, and adding 1mL of H with the mass fraction of 30%2O2The solution was allowed to stand for 10min, and diluted to 50mL with ethanol to obtain a dispersion of the hydrophobic material.
(3) Immersing the melamine sponge treated in the method (1) in a dispersion liquid of a hydrophobic material for 2 hours, squeezing, and drying in an oven at 60 ℃ for 24 hours;
(4) and taking out the dried melamine sponge, and calcining for 2h at 280 ℃ to obtain the elastic repeatable oil absorption melamine sponge.
The SEM image of the elastic repeatable oil absorption melamine sponge prepared in this example is shown in fig. 1, and it can be seen from fig. 1 that the loose porous skeleton of the original melamine sponge is retained after the treatment, and at the same time, the hydrophobic material is successfully loaded on the melamine sponge.
The contact angle of the common melamine sponge and water and the contact angle of the elastic repeatable oil absorption melamine sponge and water are shown in figure 2, and as can be seen from figure 2, by comparing the contact angles of water, the elastic repeatable oil absorption melamine sponge has good hydrophobic oleophilic property, and actually, the oil absorption of the repeatable oil absorption melamine sponge reaches 20-30 times of the self mass.
Example 2
A preparation method of an elastic repeatable oil absorption melamine sponge comprises the following steps:
(1) immersing melamine sponge in ethanol for 20min, taking out, extruding the solvent, putting the solvent in an oven at 60 ℃ for 12h, and taking out for later use.
(2) Mixing 1g of Ti3AlC2Mixing the powder with 10ml of HF solution with the mass concentration of 40%, stirring for 48h at room temperature, centrifuging, repeatedly washing with deionized water until the pH value of supernatant is about 6, washing with absolute ethyl alcohol for three times, drying for 48h at room temperature, and vacuum drying for 24h at 60 ℃. Obtaining the multilayer titanium carbide. Re-dispersing 50mg of titanium carbide powder in 5mL of ethanol, stirring at room temperature for 10min until the titanium carbide powder is uniformly dispersed, and adding 1mL of 30 mass percent H2O2The solution was allowed to stand for 10min, and diluted to 50mL with ethanol to obtain a dispersion of the hydrophobic material.
(3) Immersing the melamine sponge treated in the method (1) in a dispersion liquid of a hydrophobic material for 3h, squeezing, and drying in an oven at 60 ℃ for 18 h;
(4) and taking out the dried melamine sponge, and calcining the melamine sponge at 260 ℃ for 2h to obtain the elastic repeatable oil absorption melamine sponge.
Example 3
A preparation method of an elastic repeatable oil absorption melamine sponge comprises the following steps:
(1) immersing melamine sponge in a toluene solution for 30min, taking out, extruding the solvent, putting the solvent in an oven at 60 ℃ for 24h, and taking out for later use.
(2) Mixing 1g of Ti3AlC2Mixing the powder with 10ml of HF solution with the mass concentration of 40%, stirring for 48h at room temperature, centrifuging, repeatedly washing with deionized water until the pH value of supernatant is about 6, washing with absolute ethyl alcohol for three times, drying for 48h at room temperature, and then vacuum-drying for 24 h. Obtaining the multilayer titanium carbide. Re-dispersing 50mg of titanium carbide powder in 5mL of toluene, stirring at room temperature for 30min until the titanium carbide powder is uniformly dispersed, and adding 1mL of 30 mass percent H2O2The solution was allowed to stand for 30min, and diluted to 50mL with a toluene solution to obtain a dispersion of the hydrophobic material.
(3) Immersing the melamine sponge treated in the method (1) in a dispersion liquid of a hydrophobic material for 3h, squeezing, and drying in an oven at 60 ℃ for 24 h;
(4) and taking out the dried melamine sponge, and calcining for 2h at 300 ℃ to obtain the elastic repeatable oil absorption melamine sponge.
Example 4
A preparation method of an elastic repeatable oil absorption melamine sponge comprises the following steps:
(1) immersing melamine sponge in methanol for 30min, taking out, extruding the solvent, putting the solvent in an oven at 60 ℃ for 12h, and taking out for later use.
(2) Mixing 1g of Ti3AlC2Mixing the powder with 10ml of HF solution with the mass concentration of 40%, stirring for 48h at room temperature, centrifuging, repeatedly washing with deionized water until the pH value of supernatant is about 6, washing with absolute ethyl alcohol for three times, drying for 48h at room temperature, and then vacuum-drying for 24 h. Obtaining the multilayer titanium carbide. 50mg of titanium carbide powder was redispersed in 5mL of toluene solutionStirring at room temperature for 30min until the mixture is uniformly dispersed, and adding 1mL of 30% H2O2The solution was allowed to stand for 30min, and diluted to 50mL with toluene to obtain a dispersion of the hydrophobic material.
(3) Immersing the melamine sponge treated in the method (1) in a dispersion liquid of a hydrophobic material for 3h, squeezing, and drying in an oven at 60 ℃ for 24 h;
(4) and taking out the dried melamine sponge, and calcining for 2h at 300 ℃ to obtain the elastic repeatable oil absorption melamine sponge.
Example 5
A preparation method of an elastic repeatable oil absorption melamine sponge comprises the following steps:
(1) immersing melamine sponge in ethanol for 20min, taking out, extruding the solvent, putting the solvent in an oven at 60 ℃ for 12h, and taking out for later use.
(2) Mixing 1g of Ti3AlC2Mixing the powder with 10ml of HF solution with the mass concentration of 40%, stirring for 48h at room temperature, centrifuging, repeatedly washing with deionized water until the pH value of supernatant is about 6, washing with absolute ethyl alcohol for three times, drying for 48h at room temperature, and then vacuum-drying for 24 h. Obtaining the multilayer titanium carbide. Re-dispersing 50mg of titanium carbide powder in 5mL of toluene solution, stirring at room temperature for 30min until the titanium carbide powder is uniformly dispersed, and adding 1mL of 30 mass percent H2O2The solution was allowed to stand for 30min, and diluted to 50mL with toluene to obtain a dispersion of the hydrophobic material.
(3) Immersing the melamine sponge treated in the method (1) in a dispersion liquid of a hydrophobic material for 3h, squeezing, and drying in an oven at 60 ℃ for 24 h;
(4) and taking out the dried melamine sponge, and calcining for 2h at 300 ℃ to obtain the elastic repeatable oil absorption melamine sponge.
Example 6
A preparation method of an elastic repeatable oil absorption melamine sponge comprises the following steps:
(2) immersing melamine sponge in methanol for 120min, taking out, extruding the solvent, putting the solvent in an oven at 100 ℃ for 6h, and taking out for later use.
(2) Mixing 1g of Ti3AlC2The powder and 20ml of the powder have mass concentration ofMixing 10% HF solution, stirring at room temperature for 120h, centrifuging, repeatedly washing with deionized water until the pH value of the supernatant is about 6, washing with anhydrous ethanol for 2 times, drying at room temperature for 12h, and vacuum drying at 30 deg.C for 48 h. Obtaining the multilayer titanium carbide. Re-dispersing 50mg of titanium carbide powder in 3mL of ethanol, stirring at room temperature for 30min until the titanium carbide powder is uniformly dispersed, and adding 0.5mL of H with the mass fraction of 50%2O2Standing the solution for 20min, and adding ethanol to dilute the solution to 30mL to obtain a dispersion of the hydrophobic material.
(3) Immersing the melamine sponge treated in the method (1) in a dispersion liquid of a hydrophobic material for 5 hours, squeezing, and drying in an oven at 100 ℃ for 3 hours;
(4) and taking out the dried melamine sponge, and calcining the melamine sponge at 350 ℃ for 1h to obtain the elastic repeatable oil absorption melamine sponge.
Example 7
A preparation method of an elastic repeatable oil absorption melamine sponge comprises the following steps:
(3) immersing melamine sponge in methanol for 10min, taking out, extruding the solvent, putting the solvent in an oven at 50 ℃ for 24h, and taking out for later use.
(2) Mixing 1g of Ti3AlC2Mixing the powder with 15ml of HF solution with the mass concentration of 49%, stirring for 12h at room temperature, centrifuging, repeatedly washing with deionized water until the pH value of the supernatant is about 6, washing with absolute ethyl alcohol for 5 times, drying for 72h at room temperature, and vacuum drying for 12h at 120 ℃. Obtaining the multilayer titanium carbide. Re-dispersing 50mg of titanium carbide powder in 10mL of ethanol, stirring at room temperature for 30min until the titanium carbide powder is uniformly dispersed, and adding 1.5mL of 10 mass percent H2O2Standing the solution for 5min, and adding ethanol to dilute the solution to 60mL to obtain a dispersion of the hydrophobic material.
(3) Immersing the melamine sponge treated in the method (1) in a dispersion liquid of a hydrophobic material for 0.5h, squeezing, and drying in an oven at 50 ℃ for 36 h;
(4) and taking out the dried melamine sponge, and calcining for 5 hours at 200 ℃ to obtain the elastic repeatable oil absorption melamine sponge.
The embodiments described above are intended to facilitate the understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (10)
1. The elastic and repeatable oil absorption melamine sponge is characterized by comprising melamine sponge and a hydrophobic material loaded on the melamine sponge, wherein the hydrophobic material is a titanium dioxide/porous single-layer titanium carbide composite material, the titanium dioxide is formed by in-situ oxidation of transition metal Ti on a titanium carbide sheet layer, part of the titanium dioxide falls off from the titanium carbide sheet layer, and micropores are formed on the titanium carbide sheet layer.
2. The method of making an elastic, repeatable oil absorbing melamine sponge according to claim 1 comprising the steps of:
(1) pretreating melamine sponge;
(2) preparing a dispersion of the hydrophobic modification material:
(2-1) mixing aluminum titanium carbide powder with a hydrofluoric acid solution, stirring for reaction, centrifuging, washing and drying to obtain ML-MXene;
(2-2) dispersing ML-MXene in a solvent, stirring, adding hydrogen peroxide at room temperature, standing, and then adding the solvent for further dilution to obtain a dispersion liquid of the hydrophobic material;
(3) immersing the pretreated melamine sponge in dispersion liquid of a hydrophobic material, squeezing, and drying;
(4) and calcining the dried melamine sponge to obtain the elastic repeatable oil absorption melamine sponge.
3. The method for preparing the elastic repeatable oil absorption melamine sponge according to the claim 2, wherein the pretreatment in the step (1) is immersing the melamine sponge in the treatment liquid, extruding the liquid and drying; the treatment solution comprises methanol, ethanol or toluene, the immersion time is 10-120 min, and the drying temperature is 50-100 ℃; the drying time is 6-24 h.
4. The method for preparing an elastic repeatable oil absorption melamine sponge according to claim 2, wherein in the step (2-1), the mass volume ratio of the titanium aluminum carbide powder to the hydrofluoric acid solution is 1 g: (10-20) mL, wherein the mass concentration of the HF solution is 10% -49%, stirring is carried out at room temperature for 12-120 h, and the washing method comprises the steps of firstly washing with deionized water until the pH value reaches 5-7, and then washing with absolute ethyl alcohol for 2-5 times.
5. The method for preparing the elastic repeatable oil absorption melamine sponge according to the claim 2, wherein the drying condition in the step (2-1) is drying at room temperature for 12-72 h, and then drying at 30-120 ℃ under vacuum for 12-48 h.
6. The method for preparing the elastic repeatable oil absorption melamine sponge according to the claim 2, wherein in the step (2-2), ML-MXene is dispersed in the solvent so that the mass-to-volume ratio of ML-MXene to solvent is 1 g: (60-200) mL; the solvent comprises deionized water, absolute ethyl alcohol, methanol or DMF; the volume-mass ratio of the diluted solvent to the ML-MXene is (500-1000) mL: 1g of the total weight of the composition.
7. The method for preparing the elastic repeatable oil absorption melamine sponge according to the claim 2, wherein the stirring treatment time in the step (2-2) is 5-30 min; the standing time is 5-20 min.
8. The method for preparing an elastic repeatable oil absorption melamine sponge according to claim 2, wherein the H in step (2-2)2O2The mass concentration of the mixed solution is 10 to 50 percent, and the added H2O2The volume-mass ratio of the ML-MXene to the ML-MXene is (10-30) mL: 1g of the total weight of the composition.
9. The method for preparing the elastic repeatable oil absorption melamine sponge according to the claim 2, wherein the immersion time in the step (3) is 0.5-5 h; the drying temperature is 50-100 ℃; the drying time is 3-36 h.
10. The method for preparing the elastic repeatable oil absorption melamine sponge according to the claim 2, wherein the calcining temperature in the step (4) is 200-350 ℃; the calcination time is 1-5 h.
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