阅读说明：本技术 一种超亲水性及水下超疏油性材料及其制备方法与应用 (Super-hydrophilic and underwater super-oleophobic material and preparation method and application thereof ) 是由 蔡建国 石洪雁 刘锐 于 2020-11-19 设计创作，主要内容包括：本发明公开了一种超亲水性及水下超疏油性材料及其制备方法与应用,该材料的制备方法包括：采用酸液对介孔SiO-2纳米材料进行酸化处理；将酸化后的介孔SiO-2纳米材料与壳寡糖溶液混合,搅拌以发生反应,得到偶联壳寡糖的介孔SiO-2纳米材料；将偶联壳寡糖的介孔SiO-2纳米材料与去水卫矛醇于有机溶剂中混合,80～130℃下回流5～10小时；反应结束后,收集并纯化产物,得到超亲水性及水下超疏油性材料。本发明的超亲水性及水下超疏油性材料,可用于油水分离,能够提高油/水分离效率。(The invention discloses a super-hydrophilic and underwater super-oleophobic material, a preparation method and application thereof, wherein the preparation method of the material comprises the following steps: acid liquor is adopted to treat mesoporous SiO 2 Acidizing the nano material; acidized mesoporous SiO 2 Mixing the nano material with the chitosan oligosaccharide solution, stirring for reaction to obtain mesoporous SiO coupled with the chitosan oligosaccharide 2 A nanomaterial; coupling mesoporous SiO of chitosan oligosaccharide 2 Mixing the nano material and dianhydrogalactitol in an organic solvent, and refluxing for 5-10 hours at 80-130 ℃; and after the reaction is finished, collecting and purifying the product to obtain the super-hydrophilic and underwater super-oleophobic material. The super-hydrophilic and underwater super-oleophobic material can be used for oil-water separation, and can improve the oil-water separation efficiency.)

1. A super-hydrophilic and underwater super-oleophobic material is characterized by having a structural formula as shown in the following formula:

wherein the content of the first and second substances,represents mesoporous SiO₂And (3) nano materials, wherein n is 2-10.

2. The method of claim 1, comprising the steps of:

(i) acid liquor is adopted to treat mesoporous SiO₂Acidizing the nano material;

(ii) acidized mesoporous SiO₂Mixing the nano material with the chitosan oligosaccharide solution, stirring for reaction to obtain mesoporous SiO coupled with the chitosan oligosaccharide₂A nanomaterial; removing excessive chitosan oligosaccharide after the reaction is finished;

(iii) coupling the mesoporous SiO of the chitosan oligosaccharide₂Mixing the nano material and dianhydrogalactitol in an organic solvent, and refluxing for 5-10 hours at 80-130 ℃; and after the reaction is finished, collecting and purifying the product to obtain the super-hydrophilic and underwater super-oleophobic material.

3. The method for preparing super hydrophilic and underwater super oleophobic material of claim 2, wherein in step (i), the acid solution is hydrochloric acid, acetic acid, sulfuric acid or oxalic acid.

4. The method for preparing the super-hydrophilic and underwater super-oleophobic material of claim 2, wherein in step (i), the mesoporous SiO is₂The mesh number of the nano material is 35-200 meshes.

5. The method for preparing the super-hydrophilic and underwater super-oleophobic material of claim 2, wherein in step (i), the time for the acidification treatment is 5-12 hours.

6. The method for preparing super hydrophilic and underwater super oleophobic material of claim 2, wherein in step (ii), the chitosan oligosaccharide solution is obtained by dissolving chitosan oligosaccharide in water or hydrochloric acid, acetic acid, sulfuric acid, oxalic acid.

7. The method for preparing the super-hydrophilic and underwater super-oleophobic material of claim 2, wherein in step (ii), the stirring time is 4-8 hours.

8. The method according to claim 2, wherein in step (iii), the organic solvent is DMF, DMSO, THF, ethanol, toluene, 1, 4-dioxane or acetonitrile.

9. The method according to claim 2, wherein in step (iii), the collected and purified product is: and filtering the solution, washing the obtained product for 2-5 times by using deionized water or absolute ethyl alcohol, and drying at 60-100 ℃.

10. The use of the superhydrophilic and underwater superoleophobic material of claim 1 in the field of oil-water separation.

Technical Field

The invention relates to the technical field of oil-water separation materials, in particular to a super-hydrophilic and underwater super-oleophobic material and a preparation method and application thereof.

Background

In recent years, the production of industrial oily wastewater has been greatly increased under the drive of environmental and economic demands, and thus there is a strong demand for materials capable of effectively separating oil and water. Oil/water separation has been a global challenge, and designing novel materials with specific wettability is an efficient and easy process. However, the types of materials that are currently called "oil-removing" materials, such as kapok, carbon-based materials, hydrophobic aerogels, Polytetrafluoroethylene (PTFE) coated screens, Polydimethylsiloxane (PDMS) coated nanowire films, nanoporous polydivinylbenzene materials, crosslinked oil-absorbing polymer gels, and the like, are not amenable to gravity-driven separation due to their inherent oleophilicity, and are easily contaminated, clogged, and even destroyed by some high viscosity oils. Especially, the oil adhered to the coal chemical industry/petroleum industry, especially the oil with high viscosity, can seriously affect the separation efficiency of the material after being used for a limited time. In addition, the adhered or absorbed oil is difficult to remove, which results in secondary pollution of the oleophilic material during the post-treatment process, resulting in waste. Therefore, it is very important to develop a material having high separation ability for the separation of petroleum-based wastewater.

At present, functional oil removing materials with stable super-hydrophilicity and underwater super-lipophobicity appear in the prior art, a water layer can be formed on the surface of the materials, when only gravity is a driving force, only water is allowed to freely pass through, and oil is reserved, so that oil and harsh oil can be separated. However, the super oleophobic interface of the oil removing material is highly dependent on the modification of the fluorinated material, but the introduced fluorine is easy to cause secondary pollution of water.

Disclosure of Invention

The invention aims to provide a fluoride-free super-hydrophilic and underwater super-oleophobic material.

In order to solve the technical problems, the invention provides the following technical scheme:

the invention provides a super-hydrophilic and underwater super-oleophobic material, which has the following structural formula:

wherein the content of the first and second substances,represents mesoporous SiO₂And (3) nano materials, wherein n is 2-10.

The second aspect of the invention provides a preparation method of the super-hydrophilic and underwater super-oleophobic material, which comprises the following steps:

(i) acid liquor is adopted to treat mesoporous SiO₂Acidizing the nano material;

(ii) acidized mesoporous SiO₂Mixing the nanometer material with Chitosan Oligosaccharide (COS) solution, stirring for reaction to obtain mesoporous SiO coupled with chitosan oligosaccharide₂A nanomaterial; removing excessive chitosan oligosaccharide after the reaction is finished;

(iii) coupling the mesoporous SiO of the chitosan oligosaccharide₂Mixing the nano material and dianhydrogalactitol (VAL-083) in an organic solvent, and refluxing for 5-10 hours at the temperature of 80-130 ℃; and after the reaction is finished, collecting and purifying the product to obtain the super-hydrophilic and underwater super-oleophobic material.

In the invention, mesoporous SiO is used₂The nano material is a carrier, has large surface area, low relative density, light weight, good permeability and high chemical stability, and has more hydroxyl groups on the surface, and-OH belongs to a polar chemical bond, so that SiO₂Has hydrophilic and oleophobic properties; the chitosan oligosaccharide is used as a raw material, contains amino and hydroxyl hydrophilic groups, is easy to dissolve in water, is non-toxic and is biodegradable. The synthesized material has the characteristics of super-hydrophilicity and super-lipophobicity under water, and can be used for oil-water separation.

Further, in the step (i), the acid solution is hydrochloric acid, acetic acid, sulfuric acid or oxalic acid, and the concentration of the acid solution is preferably 2% -10%.

Further, in step (i), the mesoporous SiO₂The mesh number of the nano material is 35-200 meshes.

Further, in the step (i), the time of the acidification treatment is 5-12 hours.

Further, in the step (ii), the chitosan oligosaccharide solution is obtained by dissolving chitosan oligosaccharide in water or hydrochloric acid, acetic acid, sulfuric acid, oxalic acid.

Further, in the step (ii), the stirring time is 4-8 hours.

Further, in step (iii), the organic solvent is DMF, DMSO, THF, ethanol, toluene, 1, 4-dioxane, or acetonitrile.

Further, in step (iii), the collected and purified product is specifically: and filtering the solution, washing the obtained product for 2-5 times by using deionized water or absolute ethyl alcohol, and drying at 60-100 ℃.

The third aspect of the invention provides the application of the super-hydrophilic and underwater super-oleophobic material in the first aspect in the field of oil-water separation.

The invention has the beneficial effects that:

1. the invention uses dianhydrogalactitol to crosslink chitosan oligosaccharide and mesoporous SiO₂The nano material is modified, so that the super-hydrophilic and underwater super-oleophobic material suitable for oil-water separation is successfully prepared; the preparation method is simple and adopts a one-step solution soaking method; the raw materials are cheap and easy to obtain, and the paint is non-toxic, harmless, green and pollution-free.

2. The super-hydrophilic and underwater super-oleophobic material disclosed by the invention has low adhesion to oil drops underwater and strong anti-fouling capability, can be used for oil-water separation, and particularly has high separation efficiency in the aspect of being used for coal tar wastewater.

Drawings

FIG. 1 is a schematic of the synthetic route for the superhydrophilic and underwater superoleophobic material of the invention;

FIG. 2 is a stability test chart (inlet water 1000ppm) of the degreasing material synthesized in example 5;

FIG. 3 is a comparison of the effluent of the deoiled material synthesized in example 5: the left picture is the original emulsified oil, and the right picture is the effluent after being treated by the oil removing material.

Detailed Description

The present invention is further described below in conjunction with the following figures and specific examples so that those skilled in the art may better understand the present invention and practice it, but the examples are not intended to limit the present invention.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.

Preparation of super-hydrophilic and underwater super-oleophobic material

Example 1

1.2 g of SiO₂The mesoporous nano material (40 meshes) is soaked in 60ml of 2% hydrochloric acid for 6 hours and then is acidified and hydrolyzed.

2. 5g of chitosan oligosaccharide was dissolved in 100ml of deionized water, and stirred for 6 hours to obtain a chitosan oligosaccharide solution.

3. The acidified SiO₂And adding the mesoporous nano material into the chitosan oligosaccharide solution, stirring for 5 hours at room temperature, and filtering to remove the redundant chitosan oligosaccharide solution.

4. 30ml of 1M dianhydrogalactitol (solvent used: DMF) was added thereto and refluxed at 80 ℃ for 5 hours.

5. Filtering to remove excessive mixed solution, washing the product with anhydrous ethanol for 3 times, and drying in an oven at 60 deg.C.

Example 2

1. 4g of SiO₂The mesoporous nano material (100 meshes) is soaked in 80ml of 6% acetic acid for 8 hours and then is acidified and hydrolyzed.

2. 7g of chitosan oligosaccharide was dissolved in 150ml of deionized water and stirred for 6 hours.

3. The acidified SiO₂And adding the mesoporous nano material into the chitosan oligosaccharide solution, stirring for 6 hours at room temperature, and filtering to remove the redundant chitosan oligosaccharide solution.

4. 80ml of 1.5M dianhydrogalactitol (solvent used: DMSO) was added thereto and refluxed at 130 ℃ for 6 hours.

5. The excess mixed solution was removed by filtration, and the product was washed 4 times with deionized water and dried in an oven at 80 ℃.

Example 3

1. 4g of SiO₂The mesoporous nano material is soaked in 80ml of 8 percent oxalic acid for 12 hours and then is acidified and hydrolyzed.

2. 4g of chitosan oligosaccharide was dissolved in 100ml of deionized water and stirred for 6 hours.

3. The acidified SiO₂And adding the mesoporous nano material into the chitosan oligosaccharide solution, stirring for 5 hours at room temperature, and filtering to remove the redundant chitosan oligosaccharide solution.

4. 50ml of 0.9M dianhydrogalactitol (solvent used: ethanol) was added thereto and refluxed at 100 ℃ for 5 hours.

5. Filtering to remove excessive mixed solution, washing the product with anhydrous ethanol for 3 times, and drying in an oven at 50 deg.C.

Example 4

1. Mixing 8g of SiO₂The mesoporous nano material (200 meshes) is soaked in 100ml of 4% sulfuric acid for 12 hours and then is acidified and hydrolyzed.

2. 9g of chitosan oligosaccharide was dissolved in 200ml of deionized water and stirred for 5 hours.

3. The acidified SiO₂And adding the mesoporous nano material into the chitosan oligosaccharide solution, stirring for 8 hours at room temperature, and filtering to remove the redundant chitosan oligosaccharide solution.

4. 100ml of 3M dianhydrogalactitol (solvent used: acetonitrile) was added thereto and refluxed at 120 ℃ for 8 hours.

5. The excess mixed solution was removed by filtration, and the product was washed 3 times with deionized water and dried in an oven at 80 ℃.

Example 5

1. 3g of SiO₂The mesoporous nano material (70 mesh) is soaked in 80ml of 2% acetic acid for 6 hours and then is acidified and hydrolyzed.

2. 2g of chitosan oligosaccharide was dissolved in 100ml of deionized water and stirred for 6 hours.

3. The acidified SiO₂And adding the mesoporous nano material into the chitosan oligosaccharide solution, stirring for 7 hours at room temperature, and filtering to remove the redundant chitosan oligosaccharide solution.

4. 40ml of 1.2M dianhydrogalactitol (solvent used: DMF) was added thereto and refluxed at 90 ℃ for 10 hours.

5. Filtering to remove excessive mixed solution, washing the product with anhydrous ethanol for 4 times, and drying in an oven at 70 deg.C.

Performance testing

The deoiling performance of the deoiling materials synthesized in examples 1 to 5 was tested by using an OIL480 type infrared spectroscopic OIL meter, wherein the evaluation parameters of the deoiling materials were as follows: selecting a column with the height-diameter ratio of 6: 1, 10ml of filler and 5BV/H of flow rate; raw water (oil-water mixture): emulsified oil (raw water containing oil 1000-. The results obtained are shown in table 1.

Table 1 results of oil removing performance test of oil removing materials synthesized in examples 1 to 5

From the results of Table 1, it is understood that the content of the raw water after the treatment of the degreasing materials of examples 1-5 was reduced from 1000-2000ppm to 30ppm or less, indicating that the degreasing material of the present invention has excellent degreasing ability. Wherein the oil content of the effluent after treatment with the degreasing material of example 5 was only 4.6ppm, which is consistent with the results of fig. 3, and the effluent became clear after treatment with the degreasing material.

Referring to fig. 2, the oil content of the effluent of the oil removing material of example 5 is still only about 6ppm after the oil removing treatment for 30d, which shows that the oil removing material of the present invention has good oil removing stability.

The above-mentioned embodiments are merely preferred embodiments for fully illustrating the present invention, and the scope of the present invention is not limited thereto. The equivalent substitution or change made by the technical personnel in the technical field on the basis of the invention is all within the protection scope of the invention. The protection scope of the invention is subject to the claims.