CN110575794A - super-hydrophobic cotton cellulose aerogel and preparation method and application thereof - Google Patents
super-hydrophobic cotton cellulose aerogel and preparation method and application thereof Download PDFInfo
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- CN110575794A CN110575794A CN201810588704.3A CN201810588704A CN110575794A CN 110575794 A CN110575794 A CN 110575794A CN 201810588704 A CN201810588704 A CN 201810588704A CN 110575794 A CN110575794 A CN 110575794A
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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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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/0091—Preparation of aerogels, e.g. xerogels
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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
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
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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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28047—Gels
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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
- C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
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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
- C02F1/40—Devices for separating or removing fatty or oily substances or similar floating material
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- E—FIXED CONSTRUCTIONS
- E02—HYDRAULIC ENGINEERING; FOUNDATIONS; SOIL SHIFTING
- E02B—HYDRAULIC ENGINEERING
- E02B15/00—Cleaning or keeping clear the surface of open water; Apparatus therefor
- E02B15/04—Devices for cleaning or keeping clear the surface of open water from oil or like floating materials by separating or removing these materials
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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
- B01J2220/4825—Polysaccharides or cellulose materials, e.g. starch, chitin, sawdust, wood, straw, cotton
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/20—Controlling water pollution; Waste water treatment
- Y02A20/204—Keeping clear the surface of open water from oil spills
Abstract
The invention belongs to the field of aerogels, and discloses a super-hydrophobic cotton cellulose aerogel, and a preparation method and application thereof. Super-hydrophobic cotton cellulose aerogel, it is prepared as the raw materials by the cotton fiber, super-hydrophobic cotton cellulose aerogel has three-dimensional network porous structure, and the surface has hydrophobic group, and its water contact angle is 140 ~ 155. Preparing a cotton cellulose solution by adopting cotton fibers, then sequentially obtaining cotton cellulose hydrogel and hydrophilic cotton cellulose aerogel, and carrying out hydrophobic modification on the hydrophilic cotton cellulose aerogel to obtain the super-hydrophobic cotton cellulose aerogel. Compared with an organic synthetic oil absorption material, the aerogel has the advantages of ultralight weight, super hydrophobicity, higher oil absorption multiplying power and oil retention performance. The preparation method has the characteristics of simple process, low cost, environmental protection and green, is suitable for industrial mass production, and can be widely applied to the treatment of oily wastewater discharged by industries such as chemical processing, food production, kitchens, steam repair and the like.
Description
Technical Field
The invention belongs to the field of aerogels, relates to a super-hydrophobic aerogel, and particularly relates to a super-hydrophobic cotton cellulose aerogel and a preparation method and application thereof.
Background
The petroleum leakage and the discharge of industrial and domestic waste oil cause serious pollution to the water ecological environment. If the waste oil in water can not be effectively and timely treated, immeasurable harm can be caused to the surrounding environment and human health. At present, various organic synthetic materials such as polyurethane foam and polypropylene fiber are used as adsorbing materials to selectively adsorb oil from oil-containing wastewater, and a simple mechanical extrusion method is used to recover the oil, so as to finally achieve the purpose of oil-water separation. Although the organic synthetic materials have good oleophylic and hydrophobic properties, the materials are not easy to biodegrade, and can cause secondary pollution to the environment after being discarded. Therefore, the development of environment-friendly and degradable oil absorption materials is receiving more and more attention. Cellulose materials are the most abundant natural polymers in the nature, and because of their characteristics of wide sources, renewability, degradability and the like, they have become the research focus in recent years as the matrix of oil-absorbing materials.
the cellulose aerogel is a porous material with a three-dimensional network structure, has excellent performances of good degradability, low density, high specific surface area, high porosity and the like, can be used as an ideal substitute of an organic synthetic oil absorption material, and has a wide application prospect in the field of oily wastewater treatment. However, most of the currently studied cellulose aerogels are obtained by taking separated nanocellulose as a raw material, the preparation method is complicated, and the cost is too high, which seriously limits the batch production and large-scale application of the cellulose aerogels as oil absorption materials. Therefore, there is a need to develop a cheap, simple and effective method for preparing cellulose aerogel to promote its application in oil pollution treatment of sea, river and lake water surface.
Disclosure of Invention
The invention aims to provide a cotton cellulose aerogel and a preparation method and application thereof, wherein the aerogel has low density, high hydrophobicity, high oil absorption multiplying power and excellent oil retention performance; the preparation method is simple and effective, easy to operate and low in cost, can realize the mass production of the aerogel, and solves the problems that the existing cellulose aerogel has high preparation cost and complicated preparation process, and the preparation method limits the use of the cellulose aerogel as an oil-water separation material.
In a first aspect, the invention provides a super-hydrophobic cotton cellulose aerogel, which is prepared from cotton fibers as a raw material, wherein the super-hydrophobic cotton cellulose aerogel has a three-dimensional network porous structure, hydrophobic groups are arranged on the surface of the super-hydrophobic cotton cellulose aerogel, and the water contact angle of the super-hydrophobic cotton cellulose aerogel is 140-155 degrees (preferably 150-155 degrees).
According to the invention, the hydrophobic groups are introduced by a hydrophobic modifier selected from organosilanes; for example, the organosilane is selected from R1SiR2 3Or polysiloxane, wherein R1selected from alkyl or halogen, R2identical or different, independently of one another, from alkoxy, halogen or alkyl; preferably, R1Selected from methyl or chlorine, R2Selected from methoxy, methyl or chlorine. For example, the hydrophobic modifier is selected from at least one of methyltrimethoxysilane, polydimethylsiloxane, trimethylchlorosilane, or methyltrichlorosilane; illustratively, the hydrophobic modifier is methyltrimethoxysilane.
According to the invention, the cellulose content of the cotton fibres is greater than or equal to 90 wt%, for example greater than or equal to 93 wt%, greater than or equal to 95 wt%, greater than or equal to 97 wt%.
according to the invention, the density of the super-hydrophobic cotton cellulose aerogel is 0.01-0.1 g/cm3Preferably, the density is 0.02 to 0.08g/cm3for example, a density of 0.025g/cm3、0.041g/cm3、0.062g/cm3、0.064g/cm3。
In a second aspect, the present invention also provides a preparation method of a hydrophilic cotton cellulose aerogel, which comprises the following steps:
(1) Selecting an alkaline solvent system, adding cotton fibers into the alkaline solvent system to obtain a cotton fiber dispersion liquid, and preparing the cotton fiber dispersion liquid into a cotton cellulose solution;
(2) Standing and gelatinizing the cotton cellulose solution to obtain cotton cellulose hydrogel;
(3) and (3) after the cotton cellulose hydrogel forms jelly, freezing and drying to obtain the hydrophilic cotton cellulose aerogel.
In a third aspect, the invention further provides a preparation method of the super-hydrophobic cotton cellulose aerogel, which comprises the following steps:
(1) Selecting an alkaline solvent system, adding cotton fibers into the alkaline solvent system to obtain a cotton fiber dispersion liquid, and preparing the cotton fiber dispersion liquid into a cotton cellulose solution;
(2) Standing and gelatinizing the cotton cellulose solution to obtain cotton cellulose hydrogel;
(3) After the cotton cellulose hydrogel forms jelly, freezing and drying to obtain hydrophilic cotton cellulose aerogel;
(4) and (3) carrying out hydrophobic modification on the hydrophilic cotton cellulose aerogel to obtain the super-hydrophobic cotton cellulose aerogel.
Preferably, the basic solvent system requires a pre-cooling before use. The pre-cooling temperature is-10 to-30 ℃, and the pre-cooling time is 5 to 40min, for example, the pre-cooling time is 25min at-20 ℃.
According to the preparation method, before the cotton fiber is added into the alkaline solvent system in the step (1), the preparation method further comprises a pretreatment step, namely, the cotton fiber is added into a sodium hydroxide solution, treated for a period of time at a certain temperature, cleaned and dried to obtain the pretreated cotton fiber. Wherein the concentration of the sodium hydroxide solution is 2 to 18 wt%, for example 6 to 16 wt%, further 8 to 12 wt%. In addition, the treatment temperature is 40-100 ℃, for example, 40-80 ℃; the treatment time is 0.5-6 h, for example 0.5-4 h. The cleaning agent is distilled water, deionized water or secondary water.
According to the preparation method of the invention, the step (1) is specifically as follows: and (2) selecting an alkaline solvent system, adding the cotton fibers into the alkaline solvent system, and violently stirring to obtain the cotton fiber dispersion liquid. Preferably, the conditions of the vigorous stirring treatment are as follows: stirring at 500-2000 rpm for 2-15 min, such as 800rpm for 5 min. Preferably, the basic solvent system is selected from a basic solution. Preferably, the alkali solution is selected from an aqueous solution of sodium hydroxide or potassium hydroxide, for example from an aqueous sodium hydroxide solution; preferably, the aqueous sodium hydroxide solution has a concentration of 4 to 20 wt%, such as 4 to 15 wt%, illustratively 4 wt%, 10 wt%, 14 wt%.
According to the preparation method, in the step (1), the operation of preparing the cotton cellulose solution is as follows: and adding the mixed solution of urea/thiourea into the cotton fiber dispersion solution to prepare a cotton cellulose solution. Preferably, the volume ratio of the alkaline solvent system to the mixed solution of urea/thiourea is (1-2): 1-2, for example 1: 1. Preferably, the concentration of urea in the mixed solution of urea/thiourea is 1.5-8 wt%, such as 1.5-5 wt%, and exemplarily 1.5 wt%, 3 wt%, 4.5 wt%. Preferably, the concentration of thiourea in the urea/thiourea mixture solution is 0.5 to 8.0 wt%, such as 1.5 to 5.0 wt%, exemplarily 0.5 wt%, 1.0 wt%, 4.0 wt%. Preferably, the content of cotton fiber in the cotton cellulose solution is 0.5-4.0 wt%, such as 1.5 wt%, 2.5 wt%, 3.5 wt%.
Preferably, the cellulose content of the cotton fibers is more than 90 wt%, such as more than 93 wt%, more than 95 wt%, more than 97 wt%.
According to the preparation method, the standing in the step (2) is standing for 2-36 h (e.g. 10-30 h) at 50-100 ℃ (e.g. 50-80 ℃), for example, standing for 3h or 30h at 80 ℃, and standing for 36h at 50 ℃.
Preferably, after standing and gelling, the gel is soaked in an acid solution and then repeatedly replaced to be neutral by distilled water, so as to obtain the cotton cellulose hydrogel. Preferably, the acid solution may be at least one of hydrochloric acid, sulfuric acid, and nitric acid, preferably hydrochloric acid; the acid solution has a concentration of 2 to 24 wt%, such as 2 to 10 wt%, illustratively 2 wt%, 6 wt%, 10 wt%. Preferably, the soaking time is 12-48 h, such as 24-48 h, and exemplarily 48 h. Preferably, the operation of repeatedly replacing the distilled water is as follows: soaking in distilled water for 6-48 h, and replacing for 3-10 times; for example, soaking in distilled water for 12-36 h, and replacing for 5-10 times.
According to the preparation method of the invention, the conditions for forming the jelly in the step (3) are as follows: freezing at-5 to-60 ℃ for 18 to 64h, such as-5 to-20 ℃ for 18 to 40h, and illustratively at-15 ℃ for 24h or 32 h. Preferably, the freeze drying condition is-40 to-80 ℃ freeze drying for 40 to 50 hours, for example-40 ℃ freeze drying for 48 hours and-80 ℃ freeze drying for 48 hours.
According to the preparation method of the present invention, the hydrophobic modification in the step (4) includes the following operations: carrying out a sealing reaction on the hydrophilic cotton cellulose aerogel obtained in the step (3) with a hydrophobic modifier and distilled water; preferably, the mass ratio of the cotton cellulose aerogel, the hydrophobic modifier and the distilled water is (0.5-4): (0.2-1.5): 0.1-1, for example, (1-3): 0.5-1.5): 0.4-1, and exemplarily, the mass ratio is 2:0.5:0.5, 4:1.5:1, 4:1: 1.
Preferably, the hydrophobic modifier is as previously defined.
preferably, the reaction conditions are: reacting for 1-24 h at 40-100 ℃; for example, reacting for 4-24 h at 50-80 ℃; illustratively, the reaction is carried out at 80 ℃ for 4h, at 50 ℃ for 24h and at 70 ℃ for 8 h.
Preferably, step (4) further comprises, after the hydrophobic modification is completed, placing the aerogel in a vacuum environment to extract residual modifying agent from the aerogel.
Further, the super-hydrophobic cotton cellulose aerogel according to the first aspect of the invention is prepared by the preparation method according to the third aspect.
In a fourth aspect, the invention also provides application of the super-hydrophobic cotton cellulose aerogel in the field of oil adsorption, preferably, the field of oil adsorption comprises industrial and domestic oily wastewater treatment, marine oil contamination leakage treatment and other oil-water separation.
in a fifth aspect, the invention further provides a method for regenerating the super-hydrophobic cotton cellulose aerogel after oil absorption, which comprises the following steps: the super-hydrophobic cotton cellulose aerogel after oil absorption is subjected to extrusion or vacuum filtration and other modes, so that the regeneration of the super-hydrophobic cotton cellulose aerogel and the recovery of the adsorption oil are realized.
The invention has the beneficial effects that:
1. The main raw material adopted by the invention is cotton fiber which is one of natural macromolecules with high cellulose content and has the characteristics of easy mass acquisition, regeneration, easy degradation and the like. Therefore, the super-hydrophobic cotton cellulose aerogel material provided by the invention belongs to the category of green environment-friendly materials, and has a wide application prospect due to good performance.
2. The preparation method provided by the invention has the advantages of simple process, low preparation cost and no need of expensive equipment, and can realize large-scale industrial production of products.
3. Compared with an organic synthetic oil absorption material, the super-hydrophobic cotton cellulose aerogel prepared by the invention has higher oil absorption multiplying power (the absorption multiplying power can reach 19.8-41.5 times of the self weight) and oil retention performance (after oil absorption, the gel can bear the pressure of about 50 times of the self weight and no oil is extruded). Compared with the nano-cellulose aerogel, the carbon nano-tube aerogel and the like reported in the literature, the nano-cellulose aerogel and the carbon nano-tube aerogel have the advantages of economy, practicability, environmental friendliness and the like.
4. compared with other cellulose aerogels, the cotton fiber aerogel provided by the invention has lower density (the density can reach 0.025g/cm at the lowest)3) And the hydrophobic degree is higher, the oil can float on the water surface after the oil absorption is saturated, the adsorbed oil can be recovered through simple vacuum filtration, and the oil absorption is not obviously reduced after the oil absorption is recycled for multiple times.
Drawings
Fig. 1 is a digital photograph of the superhydrophobic cotton cellulose aerogel prepared in example 1.
Fig. 2 is a scanning electron micrograph of the superhydrophobic cotton cellulose aerogel prepared in example 1.
Fig. 3 is a graph showing the hydrophobic effect of the superhydrophobic cotton cellulose aerogel prepared in example 1.
Detailed Description
The materials of the present invention, methods of making the same, and uses thereof, are described in further detail below with reference to specific examples. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
unless otherwise indicated, the raw materials and reagents used in the following examples are all commercially available products or can be prepared by known methods.
The cellulose content of the cotton fibers used in examples 1-4 was 90 wt% or more.
Example 1
1. Adding cotton fiber into 12 wt% sodium hydroxide solution, pretreating at 80 deg.C for 1 hr, washing with distilled water, and drying thoroughly. 3.0g of the pretreated cotton fibers were added to 98.5mL of NaOH solution (14 wt%) pre-cooled at-20 ℃ for 25 min. Stirring at 800rpm for 5min, adding a mixed solution (98.5mL) containing 3.0 wt% of urea and 1.0 wt% of thiourea into the cotton fiber dispersion, and stirring uniformly to obtain a cotton cellulose solution. Subsequently, the resulting cotton cellulose solution is transferred to the desired mold.
2. Placing the cotton cellulose solution at 80 ℃ for standing for 3h, after complete gelation, placing the solution in 6 wt% hydrochloric acid solution for soaking for 24h, and finally repeatedly replacing the solution with distilled water until the solution is neutral to obtain the cotton cellulose hydrogel.
3. And (3) freezing the obtained cotton cellulose hydrogel at-15 ℃ for 32h to obtain cotton cellulose gel, and freeze-drying the sample at-80 ℃ for 48h to obtain the hydrophilic cotton cellulose aerogel.
4. Placing hydrophilic cotton cellulose aerogel, methyltrimethoxysilane and distilled water in a mass ratio of 2:0.5:0.5 in a sealed container, reacting for 4 hours at 80 ℃, taking out the cotton cellulose aerogel, placing in a vacuum environment, and pumping out residual methyltrimethoxysilane from the cotton cellulose aerogel to finally obtain the super-hydrophobic cotton cellulose aerogel.
The super-hydrophobic cotton cellulose aerogel obtained in the embodiment has the density of 0.025g/cm3。
Fig. 1 is a digital photograph of the superhydrophobic cotton cellulose aerogel prepared in this embodiment, and it can be seen that the aerogel has a loose porous structure and is white. Fig. 2 is a scanning electron microscope image of the superhydrophobic cotton cellulose aerogel prepared in the embodiment, and a three-dimensional network porous structure inside the aerogel can be seen.
Fig. 3 is a graph of the hydrophobic effect of the superhydrophobic cotton cellulose aerogel prepared in this embodiment, in which a water droplet does not penetrate into the aerogel, is spherical on the surface, and the measured value of the contact angle is 154 °.
The super-hydrophobic cotton cellulose aerogel prepared in the example has oil absorption multiplying power of 19.8, 25.7, 41.5, 23.2, 24.8 and 24.1g/g for n-hexane, toluene, chloroform, gasoline, diesel oil and kerosene respectively. After oil absorption, the fishing net can be directly used for fishing by using a net or other appliances, and oil leakage is avoided in the fishing process. Moreover, the super-hydrophobic cotton cellulose aerogel material after oil absorption can recover adsorbed oil through extrusion or vacuum filtration and other modes, the aerogel material can be regenerated, and the oil absorption multiplying power of n-hexane, toluene, chloroform, gasoline, diesel oil and kerosene is respectively 17.2, 22.4, 37.3, 21.0, 22.1 and 21.0g/g after the aerogel material is repeatedly utilized for 12 times.
example 2
1. adding cotton fiber into 6 wt% sodium hydroxide solution, pretreating at 80 deg.C for 4 hr, washing with distilled water, and drying thoroughly. 5.0g of the pretreated cotton fibers were added to 97.5mL of NaOH solution (10 wt%) pre-cooled at-20 ℃ for 25 min. Stirring at 800rpm for 5min, adding a mixed solution (97.5mL) containing 4.5 wt% of urea and 0.5 wt% of thiourea into the cotton fiber dispersion, and stirring uniformly to obtain a cotton cellulose solution. Subsequently, the resulting cotton cellulose solution is transferred to the desired mold.
2. Placing the cotton cellulose solution at 50 ℃ for standing for 36h, after complete gelation, placing the solution in 2 wt% hydrochloric acid solution for soaking for 48h, and finally repeatedly replacing the solution with distilled water until the solution is neutral to obtain the cotton cellulose hydrogel.
3. and (3) freezing the obtained cotton cellulose hydrogel at-15 ℃ for 32h to obtain cotton cellulose gel, and freeze-drying the sample at-80 ℃ for 48h to obtain the hydrophilic cotton cellulose aerogel.
4. Placing the hydrophilic cotton cellulose aerogel, methyltrimethoxysilane and distilled water in a mass ratio of 4:1.5:1 in a sealed container, reacting at 50 ℃ for 24 hours, taking out the cotton cellulose aerogel, placing in a vacuum environment, and pumping out residual methyltrimethoxysilane from the cotton cellulose aerogel to finally obtain the super-hydrophobic cotton cellulose aerogel.
The density of the super-hydrophobic cotton cellulose aerogel obtained in the embodiment is 0.041g/cm3the water contact angle was 148 degrees, and the oil absorption magnifications for chloroform and kerosene were 30.6 and 18.7g/g, respectively.
Example 3
1. Adding cotton fiber into 16 wt% sodium hydroxide solution, pretreating at 40 deg.C for 0.5 hr, washing with distilled water, and drying thoroughly. 7.0g of the pretreated cotton fibers were added to 96.5mL of NaOH solution (14 wt%) pre-cooled at-20 ℃ for 25 min. Stirring at 800rpm for 5min, adding a mixed solution (96.5mL) containing 3.0 wt% of urea and 1.0 wt% of thiourea into the cotton fiber dispersion, and stirring uniformly to obtain a cotton cellulose solution. Subsequently, the resulting cotton cellulose solution is transferred to the desired mold.
2. Placing the cotton cellulose solution at 80 ℃ and standing for 30h, after complete gelation, placing the solution in 10 wt% hydrochloric acid solution for soaking for 48h, and finally repeatedly replacing the solution with distilled water until the solution is neutral to obtain the cotton cellulose hydrogel.
3. And (3) freezing the obtained cotton cellulose hydrogel at-15 ℃ for 24h to obtain cotton cellulose gel, and freeze-drying the sample at-40 ℃ for 48h to obtain the hydrophilic cotton cellulose aerogel.
4. Placing the hydrophilic cotton cellulose aerogel, methyltrimethoxysilane and distilled water in a mass ratio of 4:1:1 in a sealed container, reacting for 8 hours at 70 ℃, taking out the cotton cellulose aerogel, placing in a vacuum environment, and pumping out residual methyltrimethoxysilane from the cotton cellulose aerogel to finally obtain the super-hydrophobic cotton cellulose aerogel.
The super-hydrophobic cotton cellulose aerogel obtained in the embodiment has the density of 0.062g/cm3The water contact angle was 149 °, and the oil absorption magnifications for chloroform and kerosene were 28 and 17.1g/g, respectively.
example 4
1. Adding cotton fiber into 12 wt% sodium hydroxide solution, pretreating at 80 deg.C for 2 hr, washing with distilled water, and drying thoroughly. 7.0g of the pretreated cotton fibers were added to 96.5mL of NaOH solution (4 wt%) pre-cooled at-20 ℃ for 25 min. Stirring at 800rpm for 5min, adding a mixed solution (96.5mL) containing 1.5 wt% of urea and 4.0 wt% of thiourea into the cotton fiber dispersion, and stirring uniformly to obtain a cotton cellulose solution. Subsequently, the resulting cotton cellulose solution is transferred to the desired mold.
2. Placing the cotton cellulose solution at 80 ℃ and standing for 30h, after complete gelation, placing the solution in 10 wt% hydrochloric acid solution for soaking for 48h, and finally repeatedly replacing the solution with distilled water until the solution is neutral to obtain the cotton cellulose hydrogel.
3. and (3) freezing the obtained cotton cellulose hydrogel at-15 ℃ for 24h to obtain cotton cellulose gel, and freeze-drying the sample at-40 ℃ for 48h to obtain the hydrophilic cotton cellulose aerogel.
4. Placing the hydrophilic cotton cellulose aerogel, methyltrimethoxysilane and distilled water in a mass ratio of 4:1:1 in a sealed container, reacting for 8 hours at 70 ℃, taking out the cotton cellulose aerogel, placing in a vacuum environment, and pumping out residual methyltrimethoxysilane from the cotton cellulose aerogel to finally obtain the super-hydrophobic cotton cellulose aerogel.
The super-hydrophobic cotton cellulose aerogel obtained in the embodiment has the density of 0.064g/cm3the water contact angle was 148 degrees, and the oil absorption magnifications for chloroform and kerosene were 27 and 16.4g/g, respectively.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The super-hydrophobic cotton cellulose aerogel is characterized in that the super-hydrophobic cotton cellulose aerogel is prepared by taking cotton fibers as raw materials, and has a three-dimensional network porous structure, hydrophobic groups are arranged on the surface of the super-hydrophobic cotton cellulose aerogel, and the water contact angle of the super-hydrophobic cotton cellulose aerogel is 140-155 degrees.
2. The aerogel of claim 1, wherein the hydrophobic groups are introduced by a hydrophobic modifier selected from the group consisting of organosilanes;
Preferably, the organosilane is selected from R1SiR2 3Or polysiloxane, wherein R1Selected from alkyl or halogen, R2Identical or different, independently of one another, from alkoxy, halogen or alkyl;
Preferably, R1Selected from methyl or chlorine, R2Selected from methoxy, methyl or chlorine;
preferably, the hydrophobic modifier is selected from at least one of methyltrimethoxysilane, polydimethylsiloxane, trimethylchlorosilane or methyltrichlorosilane;
Preferably, the cellulose content of the cotton fibers is greater than or equal to 90 wt%.
3. The aerogel according to claim 1 or 2, wherein the super-hydrophobic cotton cellulose aerogel has a density of 0.01 to 0.1g/cm3。
4. The preparation method of the hydrophilic cotton cellulose aerogel is characterized by comprising the following steps:
(1) Selecting an alkaline solvent system, adding cotton fibers into the alkaline solvent system to obtain a cotton fiber dispersion liquid, and preparing the cotton fiber dispersion liquid into a cotton cellulose solution;
(2) Standing and gelatinizing the cotton cellulose solution to obtain cotton cellulose hydrogel;
(3) And (3) after the cotton cellulose hydrogel forms jelly, freezing and drying to obtain the hydrophilic cotton cellulose aerogel.
5. A method for preparing the superhydrophobic cotton cellulose aerogel according to any one of claims 1 to 3, comprising the steps of:
(1) Selecting an alkaline solvent system, adding cotton fibers into the alkaline solvent system to obtain a cotton fiber dispersion liquid, and preparing the cotton fiber dispersion liquid into a cotton cellulose solution;
(2) Standing and gelatinizing the cotton cellulose solution to obtain cotton cellulose hydrogel;
(3) After the cotton cellulose hydrogel forms jelly, freezing and drying to obtain hydrophilic cotton cellulose aerogel;
(4) And (3) carrying out hydrophobic modification on the hydrophilic cotton cellulose aerogel to obtain the super-hydrophobic cotton cellulose aerogel.
6. The method according to claim 4 or 5, wherein the alkaline solvent system is pre-cooled before use;
In the step (1), before the cotton fiber is added into the alkaline solvent system, the method further comprises a pretreatment step, namely adding the cotton fiber into a sodium hydroxide solution, treating for a period of time at a certain temperature, cleaning and drying to obtain pretreated cotton fiber;
the step (1) is specifically as follows: selecting an alkaline solvent system, adding cotton fibers into the alkaline solvent system, and violently stirring to obtain a cotton fiber dispersion liquid; preferably, the alkali solution is selected from a sodium hydroxide or potassium hydroxide aqueous solution, and the concentration of the sodium hydroxide aqueous solution is 4-20 wt%;
Preferably, the operation of preparing the cotton cellulose solution is as follows: adding a urea/thiourea mixed solution into the cotton fiber dispersion solution to prepare a cotton cellulose solution; preferably, the volume ratio of the alkaline solvent system to the mixed solution of urea/thiourea is (1-2) to (1-2); preferably, the concentration of urea in the urea/thiourea mixed solution is 1.5-8 wt%, and the concentration of thiourea in the urea/thiourea mixed solution is 0.5-8.0 wt%; preferably, the content of the cotton fibers in the cotton cellulose solution is 0.5-4.0 wt%; preferably, the cellulose content of the cotton fibers is greater than 90 wt%.
7. The preparation method according to any one of claims 4 to 6, wherein the standing in the step (2) is standing at 50 to 100 ℃ for 2 to 36 hours; preferably, after standing and gelling, soaking the gel in an acid solution, and repeatedly replacing the gel with distilled water until the gel is neutral to obtain the cotton cellulose hydrogel;
Preferably, the acid solution may be at least one of hydrochloric acid, sulfuric acid, and nitric acid; the concentration of the acid solution is 2-24 wt%, the soaking time is 12-48 h, and the operation of repeatedly replacing the distilled water is as follows: soaking in distilled water for 6-48 h, and replacing for 3-10 times;
preferably, the conditions for forming the jelly in the step (3) are as follows: freezing for 18-64 h at the temperature of-5 to-60 ℃; preferably, the freeze drying condition is-40 to-80 ℃ for 40 to 50 hours.
8. The method according to any one of claims 5 to 7, wherein the hydrophobic modification in the step (4) comprises the following operations: carrying out a sealing reaction on the hydrophilic cotton cellulose aerogel obtained in the step (3) with a hydrophobic modifier and distilled water; preferably, the mass ratio of the cotton cellulose aerogel to the hydrophobic modifier to the distilled water is (0.5-4): (0.2-1.5): 0.1-1);
Preferably, the hydrophobic modifier is as defined in claim 2;
preferably, the reaction conditions are: reacting for 1-24 h at 40-100 ℃;
Preferably, step (4) further comprises, after the hydrophobic modification is completed, placing the aerogel in a vacuum environment to extract residual modifying agent from the aerogel.
9. the application of the super-hydrophobic cotton cellulose aerogel according to any one of claims 1 to 3 in the field of oil adsorption, wherein the field of oil adsorption comprises industrial and domestic oily wastewater treatment, marine oil contamination leakage treatment and other oil-water separation.
10. the method for regenerating the super-hydrophobic cotton cellulose aerogel according to any one of claims 1 to 3 after oil absorption, which comprises the following steps: and the super-hydrophobic cotton cellulose aerogel after oil absorption is subjected to extrusion or vacuum filtration to realize the regeneration of the super-hydrophobic cotton cellulose aerogel and the recovery of the adsorbed oil.
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