CN110025985B - Super-hydrophilic oil-repellent treatment agent for preparing oil-water separation filter paper and using method thereof - Google Patents
Super-hydrophilic oil-repellent treatment agent for preparing oil-water separation filter paper and using method thereof Download PDFInfo
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- CN110025985B CN110025985B CN201910338280.XA CN201910338280A CN110025985B CN 110025985 B CN110025985 B CN 110025985B CN 201910338280 A CN201910338280 A CN 201910338280A CN 110025985 B CN110025985 B CN 110025985B
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Abstract
The invention relates to a super-hydrophilic oil-repellent treating agent for preparing oil-water separation filter paper and a using method thereof, wherein the treating agent consists of nano and micron organic silicon fillers, active film forming substances, penetrants and solvents; the nano and micro organic silicon filler is a diamine siloxane end-capping agent and a hydrolysate of alkoxy silane; the active film-forming substance is a reaction product of epoxy resin, a chain extender, a fluorine-containing compound and a bisphenol compound. The invention also discloses a using method of the treating agent. The treating agent is simple to use, and the obtained filter paper has super-hydrophilic and oleophobic characteristics, can be used in the fields of oil-water mixture separation, oily sewage treatment and the like, and has wide application prospects.
Description
Technical Field
The invention relates to the field of oil-water separation, and particularly relates to a super-hydrophilic oil-repellent treating agent for preparing oil-water separation filter paper and a using method thereof.
Background
The oil-in-water emulsified wastewater formed by dispersing a small amount of oil in water is a difficult problem in wastewater treatment, the particle size of oil drops in the system is less than 10 mu m, and the majority of oil drops is 0.1-2 mu m, so that the system has high stability, and the common oil-water separation technology such as gravity separation, ultrasonic separation, air flotation separation and centrifugal separation technology is difficult to realize effective separation; the adsorbent in the adsorption method is difficult to be reused; the electrochemical method has high energy consumption, needs special equipment and usually needs to add extra chemical reagents to achieve higher effect; therefore, the development of a new technology suitable for treating the oil-in-water emulsified wastewater has high market value.
The oil-water separation membrane material has two realization methods, one of which is to construct oleophilic and hydrophobic characteristics, namely oil can pass through but water can not pass through, for example, patents CN105964014A, CN107050928A, CN106868948A and CN108411707A all utilize the method to construct oil-water separation material; the other is to construct oleophobic and hydrophilic characteristics, namely water can pass but oil can not, such patents are very numerous, for example, patent CN201310575190.5 takes a red copper net as a substrate, firstly constructs a micro-nano needle structure by a solution soaking method, and then carries out surface modification by a poly dimethyl diallyl ammonium chloride-sodium perfluorooctanoate/silicon dioxide compound to obtain a material with the performance; patent CN201810754081.2 discloses a method for rapidly preparing a super-hydrophilic/underwater super-oleophobic stainless steel net, which comprises the steps of mixing 98% by mass of concentrated sulfuric acid with 2mol/L of chromium trioxide solution according to the volume ratio of 1:4, and uniformly stirring to obtain a mixed solution; ultrasonically cleaning a 350-mesh stainless steel net in absolute ethyl alcohol and deionized water respectively, and then drying, and then soaking the clean stainless steel net into the mixed solution at room temperature for 3 min; and drying the soaked stainless steel net to obtain the super-hydrophilic/underwater super-oleophobic stainless steel net. The filter paper is a common separation material, is commonly used for separating tiny particles in liquid, and can be used for oil-water separation by modifying the material. The filter paper is used for oil-water separation, and the method has the advantages of high efficiency, low energy consumption, simple equipment and the like, so the method has good application prospect. Through searching, the patent literature relevant to the application discloses the following content:
patent CN201610548449.0 provides a copolymer with pH responsiveness, which forms a mixed solution with silica nanoparticles, and then prepares a pH responsiveness two-dimensional film material (cotton cloth, filter paper) and a three-dimensional sponge material (polyurethane sponge) by means of dip coating. Patent CN201710723713.4 discloses a high-strength self-supporting oil-water separation membrane and a preparation method thereof, which comprises the following steps: dissolving a monomer, clay and a thermal initiator in water to prepare a pre-polymerization solution; pouring the obtained prepolymer solution into a filter with a water-based filter membrane for suction filtration to obtain a concentrated prepolymer; then covering a columnar array template above the filter paper with the prepolymer, putting the columnar array template into a hot press, and polymerizing under the action of certain pressure and temperature to generate a hydrogel film with a through array hole structure. Patent CN201811542523.3 provides a preparation method and application of a metal ion/Arabic gum gel modified composite membrane, which is characterized in that graphene oxide, Arabic gum and metal salt are used as raw materials, and a rough hydrophilic structure is constructed on the surfaces of substrates such as a stainless steel net, a copper net, a PVDF membrane, common filter paper and the like through a sol-gel method, so that the super-hydrophilic/underwater super-oleophobic graphene oxide/Arabic gum gel modified composite membrane is prepared. Patent CN201810603729.6 discloses a method for preparing a functional film capable of simultaneously realizing oil-water emulsion separation and dye removal, which comprises (1) preparing a polymer matrix solution, (2) combining a hydroxyl-containing base material with the polymer matrix solution, and achieving accelerated gelation and introduction of charged functional groups in one step to obtain the functional film capable of simultaneously realizing oil-water emulsion separation and dye removal. According to the invention, the polymer matrix solution endows the hydroxyl-containing base material with high specific surface energy to obtain super-hydrophilicity and super-oleophobicity under water, so that the high-efficiency separation of oil and water can be realized.
Disclosure of Invention
The invention provides a super-hydrophilic oil-repellent treatment agent for preparing oil-water separation filter paper, aiming at the problem that the preparation process of a super-hydrophilic oil-repellent oil-water separation material is complex, and the treatment agent has an obvious effect and is simple and convenient to use.
The technical scheme adopted by the invention is as follows: the super-hydrophilic oil-repellent treating agent for preparing the oil-water separation filter paper is characterized by comprising the following components in parts by weight:
0.5-5% of nano organic silicon filler and micron organic silicon filler;
1-8% of active film forming substance;
0.1-2% of a penetrating agent;
the balance of solvent;
the nano organic silicon filler and the micron organic silicon filler are hydrolysate of diamine siloxane end-capping agent and alkoxy silane, and a large number of amino groups are carried on the surfaces of the nano organic silicon filler and the micron organic silicon filler;
the active film-forming substance is a reaction product of epoxy resin, a chain extender, a fluorine-containing compound and a bisphenol compound;
the penetrating agent is fatty alcohol polyoxyethylene ether surfactant;
the solvent is at least one of water, ethanol, propanol, isopropanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 1,3 dioxolane and dioxane, and can well disperse the nano and micron organosilicon fillers, active film forming substances and penetrants.
Wherein the structure of the bisaminosiloxane end-capping agent is as follows:
Wherein the chain extender is ethylamine, propylamine, butylamine, ethanolamine, amino acid or a mixture thereof; the fluorine-containing compound is CF3(CF2CF2)n-(CH2CH2O)m-R2-NH2Wherein n is 2 to 9, m is 2 to 9, R2Is a linking group-CH2-，-CH2CH2-or-COCH2CH2-; the structure of the bisphenol compound is shown below
Wherein R is3Is a linking group such as-CH2-，-CH2CH2-or-CH2CH2CH2-; the chain extender improves the molecular weight of the resin on one hand and adjusts the hydrophilic property on the other hand; the fluorine-containing compound endows the material with oleophobic performance; the bisphenol compound can perform coupling reaction with the amino group, so that the active film-forming substance is crosslinked to improve the strength, and the nano-sized and micro-sized organic silicon fillers can be fixed to form a stable micro-nano structure.
Furthermore, the particle size of the nano organic silicon filler is 10-50 nm, the particle size of the micron organic silicon filler is 0.5-3 mu m, and the dosage of the nano filler is 0.3-1 of that of the micron filler by weight.
Furthermore, the active film forming substance comprises the chain extender, the fluorine-containing compound and the bisphenol compound in a molar ratio of (0.5-0.7) to (0.2-0.3).
The invention also provides a using method of the super-hydrophilic and oil-repellent treating agent for preparing the oil-water separation filter paper, which comprises the following steps:
(1) diluting the solid part of the treating agent to 1%;
(2) placing the filter paper in a Buchner funnel, and pouring the treating agent into the Buchner funnel;
(3) carrying out suction filtration by using a vacuum pump;
(4) and drying the treated filter paper at 50-90 ℃.
Compared with the prior art, the invention has the beneficial effects that: (1) the treating agent is convenient to use, does not need complex equipment and is simple to operate; (2) the super-hydrophilic oleophobic effect is obvious, and the prepared oil-water separation filter paper can be used for oil-water separation, effectively removes oil stains in oil-containing wastewater, and has wide application prospects in the fields of chemical separation and water pollution control.
Drawings
FIG. 1 is a topographical view of untreated filter paper according to the present invention.
FIG. 2 is a topographical view of filter paper in example 1 of the present invention.
Detailed Description
The present invention is described in further detail below with reference to examples, which are intended to facilitate the understanding of the present invention and are not intended to limit the present invention in any way. The experimental methods in the following examples, which are not specified under specific conditions, are generally performed under conventional conditions. Unless otherwise indicated, all parts are parts by weight and all percentages are percentages by weight.
Active film-forming Material A
Dissolving epoxy resin E4451 g in 105ml ethylene glycol monoethyl ether, adding ethanolamine 4g and fluorine-containing compound 8.5g (CF)3(CF2CF2)2(CH2CH2O)2CH2CH2NH2) And 6.5g of 4- (2-ethylamino) benzene-1, 2-diol, and the mixture is heated to 80 ℃ for reaction for 1 hour under the protection of nitrogen by mechanical stirring.
Active film-forming material B
Dissolving epoxy resin E4451 g in 101ml ethylene glycol monoethyl ether, adding ethanolamine 2g, butylamine 3.2g, and fluorine-containing compound 4.4g (CF)3(CF2CF2)2(CH2CH2O)2CH2CH2NH2) And 6.7g of 4- (2-ethylamino) benzene-1, 2-diol, mechanically stirred, and heated to 80 ℃ for reaction for 1 hour under the protection of nitrogen.
Example 1
Taking 175g of the active film-forming substance A solution, 10g of nano organosilicon filler (with average diameter of 30nm), 20g of micro organosilicon filler (with average diameter of 2 mu m) and 3g of penetrating agent, and adding 970g of ethylene glycol monoethyl ether for dilution, wherein the solid content is 10%.
Adding ethylene glycol monoethyl ether into the treating agent, further diluting to 1%, placing medium-speed filter paper with the diameter of 20cm into a Buchner funnel, placing 50ml of treating agent with the concentration of 1% into the Buchner funnel, performing suction filtration by using a vacuum circulating water pump, and placing the filter paper at 60 ℃ for drying for one hour.
The filter paper was measured to have a contact angle of 3 ° with water and a contact angle of 89 ° with petroleum ether. The filter paper was folded into a funnel shape and placed in the filter funnel. Mixing petroleum ether (with a boiling point of 60-90 ℃) and deionized water according to a volume ratio of 1:50, stirring the mixture into an oil-water mixture by a high-speed dispersion machine, pouring the oil-water mixture into filter paper, and effectively separating the oil-water mixture, wherein the separation efficiency can reach more than 99.7%. The filter paper has good stability and can be repeatedly used.
Example 2
Otherwise, as in example 1, only medium-speed filter paper having a diameter of 20cm was changed to fast-speed filter paper.
The filter paper was measured to have a contact angle of water of 15 DEG and a contact angle of petroleum ether of 78 DEG and was folded in a funnel shape and placed in a filter funnel. Mixing petroleum ether (with a boiling point of 60-90 ℃) and deionized water according to a volume ratio of 1:50, stirring the mixture into an oil-water mixture by a high-speed dispersion machine, pouring the oil-water mixture into filter paper, and effectively separating the oil-water mixture, wherein the separation efficiency can reach more than 95.7%. The filter paper has good stability and can be repeatedly used.
Example 3
Taking 175g of the active film forming substance A solution and 3g of penetrating agent, and adding 657g of ethylene glycol monoethyl ether for dilution, wherein the solid content is 10%.
Adding ethylene glycol monoethyl ether into the treating agent, further diluting to 1%, placing medium-speed filter paper with the diameter of 20cm into a Buchner funnel, placing 50ml of treating agent with the concentration of 1% into the Buchner funnel, performing suction filtration by using a vacuum circulating water pump, and placing the filter paper at 60 ℃ for drying for one hour.
The filter paper was measured to have a contact angle of 40 ° with water and a contact angle of 65 ° with petroleum ether. The filter paper is folded into a funnel shape and placed in the filter funnel. Mixing petroleum ether (with a boiling point of 60-90 ℃) and deionized water according to a volume ratio of 1:50, stirring the mixture into an oil-water mixture by a high-speed dispersion machine, pouring the oil-water mixture into filter paper, and effectively separating the oil-water mixture, wherein the separation efficiency can reach more than 50.1%. The filter paper has good stability and can be repeatedly used.
Example 4
Taking 168g of active film forming matter B solution, 15g of nano organic silicon filler (with the average diameter of 30nm), 35g of micro organic silicon filler (with the average diameter of 2 mu m) and 3g of penetrating agent, and adding 650g of ethylene glycol monoethyl ether for dilution, wherein the solid content is 15%.
Adding ethylene glycol monoethyl ether into the treating agent, further diluting to 1.5%, placing medium-speed filter paper with the diameter of 20cm into a Buchner funnel, placing 50ml of treating agent with the concentration of 1% into the Buchner funnel, performing suction filtration by using a vacuum circulating water pump, and placing the filter paper at 60 ℃ for drying for one hour.
The filter paper was measured to have a contact angle of 20 ° with water and a contact angle of 75 ° with petroleum ether. The filter paper is folded into a funnel shape and placed in the filter funnel. Mixing petroleum ether (with a boiling point of 60-90 ℃) and deionized water according to a volume ratio of 1:50, stirring the mixture into an oil-water mixture by a high-speed dispersion machine, pouring the oil-water mixture into filter paper, and effectively separating the oil-water mixture, wherein the separation efficiency can reach more than 70.7%.
Comparative example 1
The contact angle of the medium-speed filter paper with water is 1 degree, and the contact angle of the petroleum ether is 0 degree. The filter paper is folded into a funnel shape and placed in the filter funnel. Mixing petroleum ether (with a boiling point of 60-90 ℃) and deionized water according to a volume ratio of 1:50, stirring the mixture into an oil-water mixture by a high-speed dispersion machine, and pouring the oil-water mixture into filter paper, wherein oil and water cannot be separated.
The embodiments described above are intended to illustrate the technical solutions of the present invention, and it should be understood that the above-mentioned embodiments are only specific embodiments of the present invention, and are not intended to limit the present invention, and any modifications, additions, or equivalents made within the scope of the principles of the present invention should be included in the scope of the present invention.
Claims (6)
1. The super-hydrophilic oil-repellent treating agent for preparing the oil-water separation filter paper is characterized by comprising the following components in parts by weight:
0.5-5% of nano organic silicon filler and micron organic silicon filler;
1-8% of active film forming substance;
0.1-2% of a penetrating agent;
the balance of solvent;
the nano organic silicon filler and the micron organic silicon filler are hydrolysate of diamine siloxane end-capping agent and alkoxy silane, and a large number of amino groups are carried on the surfaces of the nano organic silicon filler and the micron organic silicon filler;
the active film-forming substance is a reaction product of epoxy resin, a chain extender, a fluorine-containing compound and a bisphenol compound;
the penetrating agent is fatty alcohol polyoxyethylene ether surfactant;
the solvent is at least one of water, ethanol, propanol, isopropanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 1, 3-dioxolane and dioxane.
2. The super-hydrophilic and oil-repellent treatment agent for preparing oil-water separation filter paper according to claim 1, wherein the super-hydrophilic and oil-repellent treatment agent comprises: wherein the structure of the bisaminosiloxane end-capping agent is as follows:
3. The super-hydrophilic and oil-repellent treatment agent for preparing oil-water separation filter paper according to claim 1, wherein the super-hydrophilic and oil-repellent treatment agent comprises: wherein the chain extender is ethylamine, propylamine, butylamine, ethanolamine, amino acid or a mixture thereof; the fluorine-containing compound is CF3(CF2CF2)n-(CH2CH2O)m-R2-NH2Wherein n is 2 to 9, m is 2 to 9, R2Is a linking group-CH2-，-CH2CH2-or-COCH2CH2-; the structure of the bisphenol compound is shown below
Wherein R is3Is a linking group-CH2-，-CH2CH2-or-CH2CH2CH2-。
4. The super-hydrophilic and oil-repellent treatment agent for preparing oil-water separation filter paper according to claim 1, wherein the super-hydrophilic and oil-repellent treatment agent comprises: the particle size of the nano organic silicon filler is 10-50 nm, the particle size of the micron organic silicon filler is 0.5-3 mu m, and the dosage of the nano filler is 0.3-1 of that of the micron filler by weight.
5. The super-hydrophilic and oil-repellent treatment agent for preparing oil-water separation filter paper according to claim 1, wherein the super-hydrophilic and oil-repellent treatment agent comprises: in the active film forming substance, the ratio of the chain extender to the fluorine-containing compound to the bisphenol compound is (0.5-0.7) to (0.2-0.3) calculated by molar weight.
6. The use method of the super-hydrophilic and oil-repellent treatment agent for preparing oil-water separation filter paper according to claim 1, comprising the following steps:
(1) diluting the solid part of the treating agent to 1%;
(2) placing the filter paper in a Buchner funnel, and pouring the treating agent into the Buchner funnel;
(3) carrying out suction filtration by using a vacuum pump;
(4) and drying the treated filter paper at 50-90 ℃.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1580397A (en) * | 2003-08-11 | 2005-02-16 | 王剑光 | Chemical Modifying method of filter paper core for oil-water separating filter |
| CN105771322A (en) * | 2016-05-19 | 2016-07-20 | 山东交通学院 | Super hydrophilic oil-water separation filter paper and preparation method thereof |
| CN109603302A (en) * | 2018-12-20 | 2019-04-12 | 东南大学 | Antifouling modified walnut shell filtering material of one kind and its preparation method and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1580397A (en) * | 2003-08-11 | 2005-02-16 | 王剑光 | Chemical Modifying method of filter paper core for oil-water separating filter |
| CN105771322A (en) * | 2016-05-19 | 2016-07-20 | 山东交通学院 | Super hydrophilic oil-water separation filter paper and preparation method thereof |
| CN109603302A (en) * | 2018-12-20 | 2019-04-12 | 东南大学 | Antifouling modified walnut shell filtering material of one kind and its preparation method and application |
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