阅读说明：本技术 一种具有原位破乳吸附功能的杂化泡沫及其在油水分离中的应用 (Hybrid foam with in-situ demulsification adsorption function and application thereof in oil-water separation ) 是由 刘海峰 姚理 李正全 孙一峰 于 2021-08-23 设计创作，主要内容包括：本发明公开了一种具有原位破乳吸附功能的杂化泡沫及其在油水分离中的应用。一种具有原位破乳吸附功能的杂化泡沫,由如下步骤制备得到：室温下,将破乳功能材料、疏水亲油材料、交联组分、酸性催化剂和水混合均匀后,加入溶剂,配制成固含量为5％～15％的溶液,室温搅拌5～15h；再向溶液中加入碱性催化剂,封闭条件下,50℃～80℃反应24～48h,反应完毕溶剂挥发后,即获得所述的杂化泡沫。本发明提出的具有原位破乳吸附功能的杂化泡沫具有广谱破乳性,可以对阴离子、阳离子、非离子型乳液形成破乳吸附。泡沫制备方法简单,吸附量大,水解稳定性高。(The invention discloses a hybrid foam with an in-situ demulsification adsorption function and application thereof in oil-water separation. A hybrid foam with an in-situ demulsification adsorption function is prepared by the following steps: at room temperature, uniformly mixing the demulsification functional material, the hydrophobic oleophylic material, the crosslinking component, the acidic catalyst and water, adding a solvent to prepare a solution with the solid content of 5-15%, and stirring at room temperature for 5-15 h; and adding an alkaline catalyst into the solution, reacting for 24-48 h at 50-80 ℃ under a closed condition, and volatilizing the solvent after the reaction is finished to obtain the hybrid foam. The hybrid foam with the in-situ demulsification adsorption function provided by the invention has broad-spectrum demulsification performance and can form demulsification adsorption on anionic, cationic and nonionic emulsions. The foam preparation method is simple, the adsorption capacity is large, and the hydrolytic stability is high.)

1. A hybrid foam with an in-situ demulsification adsorption function is characterized by being prepared by the following steps: at room temperature, uniformly mixing the demulsification functional material, the hydrophobic oleophylic material, the crosslinking component, the acidic catalyst and water, adding a solvent to prepare a solution with the solid content of 5-15%, and stirring at room temperature for 5-15 h; and adding an alkaline catalyst into the solution, reacting for 24-48 h at 50-80 ℃ under a closed condition, and volatilizing the solvent after the reaction is finished to obtain the hybrid foam.

2. The hybrid foam with the in-situ demulsification adsorption function as claimed in claim 1, wherein the mass ratio of the hydrophobic oleophylic material to the demulsification functional material is 1-3: 1, the mass ratio of the crosslinking component to the demulsification functional material is 3-5: 1, the mass ratio of the acidic catalyst to the demulsification functional material is 0.1-0.6: 1, and the mass ratio of water to the demulsification functional material is 0.2-0.4: 1.

3. The hybrid foam with the in-situ demulsification and adsorption function as claimed in claim 1, wherein the molar ratio of the basic catalyst to the acidic catalyst is 1.5-2: 1.

4. The hybrid foam with the in-situ demulsification adsorption function according to claim 1, wherein the demulsification functional material has the following structure: (CH)₃O)₃SiCH₂CH₂CH₂O(EO)m-(PO)n-R₁Wherein: m is 0 to 20, EO is-CH₂-CH₂-O-, PO is-CH (CH)₃)-CH₂-O-, n is 0 to 10, R₁Is dodecanoyl, hexadecanoyl or octadecanoyl.

5. The hybrid foam with the in-situ demulsification adsorption function according to claim 1, wherein the hydrophobic oleophilic material is represented by formula 1:

wherein: n/(m + n +2) is 0.15 to 0.30.

6. The hybrid foam with the in-situ demulsification adsorption function according to claim 1, wherein the crosslinking component is selected from more than one of methyltrimethoxysilane, methyltriethoxysilane, tetramethyl orthosilicate, tetraethyl orthosilicate, 1, 2-bistrimethoxysilyl ethane and 1, 2-bistiethoxysilyl ethane.

7. The hybrid foam with the in-situ demulsification adsorption function as claimed in claim 1, wherein the solvent is one selected from tetrahydrofuran, dioxane and acetonitrile.

8. The hybrid foam with the in-situ demulsification adsorption function according to claim 1, wherein the acidic catalyst is concentrated hydrochloric acid or glacial acetic acid; the alkaline catalyst is tetramethyl ammonium hydroxide solution with the mass fraction of 5-20%, trimethyl benzyl ammonium hydroxide solution with the mass fraction of 5-20% or tetrabutyl ammonium hydroxide solution with the mass fraction of 5-20%.

9. The use of the hybrid foam with in-situ demulsification and adsorption functions as claimed in claim 1 in oil-water separation.

Technical Field

The invention relates to the technical field of oil-water separation, in particular to a hybrid foam with an in-situ demulsification adsorption function and application thereof in oil-water separation.

Background

The pollution of the oil-containing emulsion can slowly release oil in natural water, so that the oxygen content of the water is reduced, the content of toxic and harmful substances is increased, and a large amount of death of aquatic organisms is caused, even ecological disasters are caused. The treatment method generally adopts a fence collection or adsorption material adsorption method, and the oil recovery efficiency is very low due to the slow release characteristic of the treatment method.

In recent years, with the development of the biomimetic technology, a series of novel oil-water separation technologies based on a membrane method and a foam adsorption material are emerging. For example, Guojun Liu et al disclose Janus process membrane materials, which are capable of separating O/W type emulsions by connecting poly (dimethylaminoethyl methacrylate) dimethylamine ethyl ester or polyether with a demulsification function to one side of the membrane material and modifying polysiloxane on the other side of the membrane material, but the method of separating the O/W type emulsions in the form of the membrane material has great limitations in treating oil-water pollution of natural water areas with aquatic organisms. The adsorption material based on foam has little influence on aquatic organisms when treating oil pollution in natural water areas, but has only single oleophylic and hydrophobic functions and has no effect on O/W type emulsion pollution. The Shengyu Feng et al disclose an oil-water separation material based on foam, which has a demulsification function on O/W type emulsion, but needs to extrude the foam to absorb the emulsion to realize oil absorption, and is obviously not suitable for steady-state oil pollution treatment of natural water areas. There is a need to propose a new adsorbent material to solve this problem.

Disclosure of Invention

The invention solves the problems in the prior art, and aims to provide the hybrid foam with the in-situ demulsification adsorption function and the application thereof in oil-water separation.

In order to achieve the purpose, the invention adopts the technical scheme that: a hybrid foam with an in-situ demulsification adsorption function is prepared by the following steps: at room temperature, uniformly mixing the demulsification functional material, the hydrophobic oleophylic material, the crosslinking component, the acidic catalyst and water, adding a solvent to prepare a solution with the solid content of 5-15%, and stirring at room temperature for 5-15 h; and adding an alkaline catalyst into the solution, reacting for 24-48 h at 50-80 ℃ under a closed condition, and volatilizing the solvent after the reaction is finished to obtain the hybrid foam.

The invention takes the hydrolysis-crosslinking of the silane coupling agent as a reaction mechanism, gradually crosslinks in the solution to form a porous network structure, and has simple preparation method. The hybrid foam (3D foam) with the in-situ demulsification adsorption function provided by the invention has no influence on aquatic organisms, and can solve the problem of stable oil in an in-situ demulsification adsorption mode. When the emulsion breaking agent is contacted with the O/W type emulsion, the responsive surface has an emulsion breaking function, the inner layer of the hybrid foam (3D foam) still maintains hydrophobic and oleophylic characteristics because the inner layer is not contacted with water, and oil drops agglomerated on the interface are absorbed by the inner layer of the 3D foam through Laplace pressure, so that in-situ emulsion breaking-adsorption of the emulsion is realized, and the aim of oil-water separation is fulfilled.

Preferably, the mass ratio of the hydrophobic oleophylic material to the demulsification functional material is 1-3: 1, the mass ratio of the crosslinking component to the demulsification functional material is 3-5: 1, the mass ratio of the acidic catalyst to the demulsification functional material is 0.1-0.6: 1, and the mass ratio of the water to the demulsification functional material is 0.2-0.4: 1.

Preferably, the molar ratio of the basic catalyst to the acidic catalyst is 1.5-2: 1.

Preferably, the demulsification functional material has the following structure: (CH)₃O)₃SiCH₂CH₂CH₂O(EO)m-(PO)n-R₁Wherein: m is 0 to 20, EO is-CH₂-CH₂-O-, PO is-CH (CH)₃)-CH₂-O-, n is 0 to 10,R₁is dodecanoyl, hexadecanoyl or octadecanoyl.

Preferably, the hydrophobic oleophilic material is represented by formula 1:

wherein: n/(m + n +2) is 0.15 to 0.30.

Preferably, the crosslinking component is selected from more than one of methyltrimethoxysilane, methyltriethoxysilane, tetramethyl orthosilicate, tetraethyl orthosilicate, 1, 2-bistrimethoxysilyl ethane and 1, 2-bistiethoxysilyl ethane.

Preferably, the solvent is selected from one of tetrahydrofuran, dioxane and acetonitrile.

Preferably, the acidic catalyst is concentrated hydrochloric acid or glacial acetic acid; the alkaline catalyst is tetramethyl ammonium hydroxide solution with the mass fraction of 5-20%, trimethyl benzyl ammonium hydroxide solution with the mass fraction of 5-20% or tetrabutyl ammonium hydroxide solution with the mass fraction of 5-20%.

The invention also protects the application of the hybrid foam with the in-situ demulsification adsorption function in oil-water separation. The hybrid foam for in-situ demulsification and adsorption provided by the invention has broad-spectrum demulsification performance and can form demulsification and adsorption on anionic, cationic and nonionic emulsions. The oil removal rate of the cationic emulsion removed by the foam for 12 hours is up to 98.8 percent, the oil removal rate of the anionic emulsion is up to 97.9 percent, the oil removal rate of the nonionic emulsion is up to 98.0 percent, the oil removal rate of the cationic emulsion removed by the foam for 24 hours is up to 99.9 percent, the oil removal rate of the anionic emulsion is up to 99.9 percent, and the oil removal rate of the nonionic emulsion is up to 99.9 percent. The foam density is 60-165 mg/cm³。

Compared with the prior art, the invention has the beneficial effects that:

1. the preparation method of the hybrid foam with the in-situ demulsification adsorption function provided by the invention is simple, the hybrid foam can be obtained only by hydrolyzing and polycondensing the reaction raw materials in one pot and volatilizing the solvent, and the utilization rate of the reaction monomers is high.

2. The hybrid foam provided by the invention has large adsorption capacity, and the foam framework contains a polysiloxane structure, so that swelling can occur; the weather resistance is strong, and the foam components are polysiloxane and polyether, so that the foam is anti-aging and hydrolysis-resistant.

3. The organosilicon foam with the in-situ demulsification adsorption function has broad-spectrum demulsification performance and can form demulsification adsorption on anionic, cationic and nonionic emulsions; when the method is applied to oil pollution environment treatment, the demulsifier is not involved, and the method is environment-friendly.

4. The hybrid foam with the in-situ demulsification adsorption function provided by the invention has uniformity, can be normally used after being cut at will, and has strong practicability.

Detailed Description

The following examples are further illustrative of the present invention and are not intended to be limiting thereof. The equipment and reagents used in the present invention are, unless otherwise specified, conventional commercial products in the art. The room temperature proposed by the present invention means 25 ℃.

The oil removal rate calculation formula referred to in the following examples is as follows:

the model emulsion preparation referred to in the following examples was as follows:

anionic emulsion: dissolving 10mg of sodium dodecyl sulfate in 80g of water, mechanically stirring and dissolving in a flask, adding 20g of n-hexadecane, mechanically stirring at 1300r/min for 5min, and ultrasonically homogenizing for 3min by using an ultrasonic cell crusher to obtain emulsion with centrifugal stability (4000 r/min).

Cationic emulsion: dissolving 10mg of hexadecyl trimethyl ammonium chloride in 80g of water, mechanically stirring and dissolving in a flask, adding 20g of n-hexadecane, mechanically stirring at 1300r/min for 5min, and ultrasonically homogenizing for 3min by using an ultrasonic cell pulverizer to obtain emulsion with centrifugal stability (4000 r/min).

Non-ionic emulsion: 10mg of fatty alcohol-polyoxyethylene ether (peregal O) is dissolved in 80g of water, the mixture is mechanically stirred and dissolved in a flask, 20g of n-hexadecane is added, the mixture is mechanically stirred for 5min at 1300r/min, and then ultrasonic homogenization is carried out for 3min by using an ultrasonic cell disruptor, so as to obtain emulsion with centrifugal stability (4000 r/min).

The oil-water separation experiment and quantitative experiment involved in the following examples were as follows: putting 1g of foam into 10mL of emulsion, stirring for a certain time, and taking out the foam; during this time, the emulsion was taken up and dissolved in tetrahydrofuran, and the n-hexadecane content was measured by gas chromatography.

The preparation method of the demulsification functional material comprises the following steps: reacting trimethoxy silane with CH₂＝CH-CH₂-O(EO)m-(PO)n-R₁Mixing according to the molar ratio of 1:1.1, adding chloroplatinic acid hexahydrate with the mass fraction of 0.1%, reacting for 1h at 80 ℃, heating to 100 ℃, and reacting for 2h to obtain the demulsification functional material.

The preparation method of the hydrophobic oleophylic material comprises the following steps: mixing vinyl silicone oil and trimethoxy silane according to the molar ratio of 1:1 of vinyl to trimethoxy silane, adding chloroplatinic acid hexahydrate with the molar weight of 0.02 percent of vinyl, reacting at 80 ℃ for 1h, heating to 100 ℃, and reacting for 2h to obtain the demulsification functional material.

Example 1

At room temperature, the molecular formula is (CH)₃O)₃SiCH₂CH₂CH₂O(EO)₁₀-(PO)₅-CO(CH₂)₁₀CH₃5g of demulsification functional material, 5g of hydrophobic oleophylic material with the concentration of n/(m + n +2) being 0.15, 15g of methyltrimethoxysilane, 0.5g of concentrated hydrochloric acid and 1g of water are uniformly mixed, tetrahydrofuran is added to prepare a solution with the solid content of 5%, and the solution is stirred for 5 hours at room temperature; adding a tetramethylammonium hydroxide solution with the mass fraction of 20% and the molar weight of 1.5 times of concentrated hydrochloric acid, uniformly stirring, reacting for 48 hours at 50 ℃ under a closed condition, and volatilizing the solvent after the reaction is finished to obtain the hybrid foam.

The oil removal rate of the 12h foam is as follows: 84.3 percent of cationic, 85.2 percent of anionic and 84.4 percent of nonionic.

The oil removal rate of the 24h foam is as follows: 99.9 percent of cationic, 99.9 percent of anionic and 99.9 percent of nonionic.

Example 2

At room temperature, the molecular formula is (CH)₃O)₃SiCH₂CH₂CH₂O(EO)₁₀-(PO)₅-CO(CH₂)₁₀CH₃5g of demulsification functional material, 15g of hydrophobic oleophylic material with n/(m + n +2) ═ 0.15, 25g of methyltrimethoxysilane, 2g of concentrated hydrochloric acid and 2g of water, uniformly mixing, adding tetrahydrofuran to prepare a solution with the solid content of 15%, and stirring for 15 hours at room temperature; adding a tetramethylammonium hydroxide solution with the mass fraction of 20% and the molar weight of 2 times of concentrated hydrochloric acid, uniformly stirring, reacting at 80 ℃ for 24 hours under a closed condition, and volatilizing the solvent after the reaction is finished to obtain the hybrid foam.

The oil removal rate of the 12h foam is as follows: cationic type 85.5%, anionic type 84.1%, and nonionic type 86.2%.

The oil removal rate of the 24h foam is as follows: 99.9 percent of cationic, 99.9 percent of anionic and 99.9 percent of nonionic.

Example 3

The molecular formula is (CH)₃O)₃SiCH₂CH₂CH₂O(EO)₁₀-(PO)₅-CO(CH₂)₁₀CH₃5g of demulsification functional material, 7.5g of hydrophobic oleophylic material with n/(m + n +2) ═ 0.15, 20g of methyltrimethoxysilane, 1.5g of concentrated hydrochloric acid and 1.5g of water, adding tetrahydrofuran after uniformly mixing to prepare a solution with the solid content of 10%, and stirring for 10 hours at room temperature; adding a 10 mass percent trimethyl benzyl ammonium hydroxide solution with the molar weight 2 times that of concentrated hydrochloric acid, uniformly stirring, reacting for 36 hours at 65 ℃ under a closed condition, and volatilizing the solvent after the reaction is finished to obtain the hybrid foam.

The oil removal rate of the 12h foam is as follows: 98.8 percent of cationic, 97.9 percent of anionic and 98.0 percent of nonionic.

The oil removal rate of the 24h foam is as follows: 99.9 percent of cationic, 99.9 percent of anionic and 99.9 percent of nonionic.

Comparative example 1

Uniformly mixing 7.5g of hydrophobic oleophilic material with the n/(m + n +2) ═ 0.15, 20g of methyltrimethoxysilane, 1.5g of concentrated hydrochloric acid and 1.5g of water, adding tetrahydrofuran to prepare a solution with the solid content of 10%, and stirring at room temperature for 10 hours; adding a 10 mass percent trimethyl benzyl ammonium hydroxide solution with the molar weight 2 times that of concentrated hydrochloric acid, uniformly stirring, reacting for 36 hours at 65 ℃ under a closed condition, and volatilizing the solvent after the reaction is finished to obtain the hybrid foam.

The oil removal rate of the 12h foam is as follows: 2.4 percent of cationic, 3.9 percent of anionic and 3.3 percent of nonionic.

The oil removal rate of the 24h foam is as follows: 3.9 percent of cationic, 5.5 percent of anionic and 4.7 percent of nonionic.

Comparative example 2

The molecular formula is (CH)₃O)₃SiCH₂CH₂CH₂O(EO)₁₀-(PO)₅-CO(CH₂)₁₀CH₃5g of demulsification functional material, 20g of methyltrimethoxysilane, 1.5g of concentrated hydrochloric acid and 1.5g of water are uniformly mixed, tetrahydrofuran is added to prepare a solution with the solid content of 10%, and the solution is stirred for 10 hours at room temperature; adding a 10 mass percent trimethyl benzyl ammonium hydroxide solution with the molar weight 2 times that of concentrated hydrochloric acid, uniformly stirring, reacting for 36 hours at 65 ℃ under a closed condition, and volatilizing the solvent after the reaction is finished to obtain the hybrid foam.

The oil removal rate of the 12h foam is as follows: 11.9 percent of cationic, 10.7 percent of anionic and 9.5 percent of nonionic.

The oil removal rate of the 24h foam is as follows: 14.7 percent of cationic, 13.9 percent of anionic and 12.5 percent of nonionic.

Example 4

The molecular formula is (CH)₃O)₃SiCH₂CH₂CH₂O(EO)₁₅-CO-(CH₂)₁₄CH₃5g of demulsification functional material, 7.5g of hydrophobic oleophylic material with n/(m + n +2) ═ 0.30, 20g of methyltrimethoxysilane, 1.5g of concentrated hydrochloric acid and 1.5g of water, adding tetrahydrofuran after uniformly mixing to prepare a solution with the solid content of 10%, and stirring for 10 hours at room temperature; adding a 10 mass percent trimethyl benzyl ammonium hydroxide solution with the molar weight 2 times that of concentrated hydrochloric acid, uniformly stirring, reacting at 65 ℃ for 36 hours under a closed condition, and volatilizing the solvent after the reaction is finished to obtain the catalystHybrid foams.

The oil removal rate of the 12h foam is as follows: 96.8 percent of cationic type, 94.9 percent of anionic type and 96.0 percent of nonionic type.

The oil removal rate of the 24h foam is as follows: 99.9 percent of cationic, 99.9 percent of anionic and 99.9 percent of nonionic.

Example 5

The molecular formula is (CH)₃O)₃SiCH₂CH₂CH₂O(EO)₁₀-(PO)₅-CO(CH₂)₁₀CH₃5g of demulsification functional material, 7.5g of hydrophobic oleophylic material with n/(m + n +2) ═ 0.15, 15g of tetramethyl orthosilicate, 1.5g of concentrated hydrochloric acid and 1.5g of water, adding dioxane after uniformly mixing to prepare solution with the solid content of 10%, and stirring for 10 hours at room temperature; adding a 20 mass percent trimethyl benzyl ammonium hydroxide solution with the molar weight 2 times that of concentrated hydrochloric acid, uniformly stirring, reacting for 36 hours at 65 ℃ under a closed condition, and volatilizing the solvent after the reaction is finished to obtain the hybrid foam.

The oil removal rate of the 12h foam is as follows: cationic type 93.8%, anionic type 92.9%, and nonionic type 90.0%.

The oil removal rate of the 24h foam is as follows: 99.9 percent of cationic, 99.9 percent of anionic and 99.9 percent of nonionic.

Example 6

The molecular formula is (CH)₃O)₃SiCH₂CH₂CH₂O(EO)₂₀-(PO)_10-CO(CH₂)₁₆CH₃5g of demulsification functional material, 7.5g of hydrophobic oleophylic material with n/(m + n +2) ═ 0.15, 20g of tetraethyl orthosilicate, 3.0g of glacial acetic acid and 3.0g of water, adding acetonitrile after uniformly mixing to prepare a solution with the solid content of 10%, and stirring for 10 hours at room temperature; adding a tetramethylammonium hydroxide solution with the mass fraction of 10% and the molar weight of glacial acetic acid of 2 times, uniformly stirring, reacting for 36 hours at 65 ℃ under a closed condition, and volatilizing the solvent after the reaction is finished to obtain the hybrid foam.

The oil removal rate of the 12h foam is as follows: 96.3 percent of cationic, 96.3 percent of anionic and 94.7 percent of nonionic.

The oil removal rate of the 24h foam is as follows: 99.9 percent of cationic, 99.9 percent of anionic and 99.9 percent of nonionic.

Comparative example 1 comparison of the ability of the foam to oil

1g of the foam obtained in example 6 disclosed in CN112691649A was taken out after being immersed in n-hexadecane for 2 hours, and the weight of the foam was increased to 2.5 g.

1g of the hybrid foam prepared in the embodiment 3 of the invention is taken out after being immersed in n-hexadecane for 2h, and the weight of the foam is increased by 4.2 g. The oil absorption of the foam prepared in example 3 of the present invention was increased by 68% over the foam of example 6 disclosed in CN 112691649A. In the actual oil-water separation application, the foam with the same quality can adsorb oil with higher quality.

Comparative example 2 hydrolysis resistance

1g of the foam obtained in example 6 disclosed in CN112691649A and 1g of the foam obtained in example 3 of the present invention were put in a hydrochloric acid solution having pH of 1 and stirred at 30 ℃ for 24 hours, respectively. Taking out, washing with water and drying.

The 12h oil absorption of the example 6 foam disclosed in CN112691649A was: cationic 43.7% (unhydrolyzed 95.6%); anionic 39.6% (unhydrolyzed 94.9%); non-ionic 36.2% (unhydrolyzed 93.1%); the 12h oil absorption of the foam prepared in example 3 of the invention was: cationic 89.4% (unhydrolyzed 98.8%), anionic 86.9% (unhydrolyzed 97.9%), and nonionic 84.5% (unhydrolyzed 98.0%).

The above is only a preferred embodiment of the present invention, and it should be noted that the above preferred embodiment should not be considered as limiting the present invention, and the protection scope of the present invention should be subject to the scope defined by the claims. It will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the spirit and scope of the invention, and these modifications and adaptations should be considered within the scope of the invention.