Surface-hydrophobically-modified SiO2 whisker with high length-diameter ratio as well as preparation method and application of surface-hydrophobically-modified SiO2 whisker
The high aspect ratio SiO2 whiskers modified by the surface hydrophobic modification solve the problem of complex and high cost in the preparation process of chemical demulsification method, and achieve efficient and stable oil-water separation, reduce production costs, and in extreme environments Shows good stability and cyclability.
Patent Information
- Application Number
- CN202411168319.5
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-08-23
- Publication Date
- 2024-12-17
AI Technical Summary
In the existing oil-water separation methods, the preparation process of the copolymer by chemical demulsification method is complex, resulting in high production costs, limiting its widespread application, and the traditional methods are unstable in extreme environments.
The base metal catalyst was prepared by in-situ catalytic synthesis using surface hydrophobic modified high-even-diameter ratio SiO2 whiskers, using Fe salt and Co salt as catalyst precursors, and the base metal catalyst was prepared by vacuum impregnation of stearic acid alcohol solution. , SiO2 whiskers with oleophilic and hydrophobic properties were prepared.
It achieves efficient oil-water separation, reduces production costs, and shows good stability and recyclability in extreme environments, making it suitable for industrial large-scale production.
Smart Images
Figure CN119145033A_ABST
Abstract
Description
Technical Field
[0001] The invention relates to the technical field of oil-water separation and sewage treatment, and in particular to a surface hydrophobically modified SiO2 whisker with a high aspect ratio, and a preparation method and application thereof. Background Art
[0002] At present, the methods used for oil-water separation mainly include gravity separation, filtration, membrane separation, electrical aggregation, adsorption, chemical demulsification and biological methods. Among them, chemical demulsification is the most widely used method at present. It mainly changes the interfacial properties of the emulsion system by adding demulsifiers, making it unstable from relatively stable, so as to achieve the purpose of demulsification. For the demulsification of O / W emulsions, cationic organic demulsifiers are usually used, and commonly used ones are polyacrylamide graft copolymers, quaternary ammonium salts, imines, etc. Among them, polyacrylamide flocculants have been widely used in industries such as petroleum industry, environmental protection and papermaking. However, the preparation process of its copolymer is complicated, which leads to increased production costs and limits its further application. Compared with traditional methods, the method of using modified whisker demulsification not only has the advantages of high separation efficiency, low environmental pollution and fast separation efficiency, but also has the advantages of good recyclability and stable use in extreme environments, and is expected to be widely used in the treatment of oil and water pollutants. Summary of the invention
[0003] The present invention aims to overcome the defects of the prior art and provide a surface hydrophobically modified SiO2 whisker with a high aspect ratio and a preparation method and application thereof.
[0004] In order to achieve the above object, the technical solution of the present invention is as follows:
[0005] On the one hand, the present invention provides a method for preparing a surface hydrophobically modified SiO2 whisker with a high aspect ratio, the method comprising the following steps:
[0006] Step 1: adding a protective agent to deionized water to obtain a protective agent solution, and then adding an Fe salt solution and a Co salt solution respectively to obtain a catalyst precursor solution;
[0007] Step 2: adding SiO2 particles to the catalyst precursor solution obtained in step 1, filtering, drying, and obtaining powder;
[0008] Step 3, the powder obtained in step 2 is kept at 850-1400° C. in an atmosphere furnace for 1.5-3 hours to obtain SiO2 whiskers with a high aspect ratio;
[0009] Step 4: Vacuum-immerse the SiO2 whiskers obtained in step 3 in an alcohol solution of stearic acid, filter and dry them to obtain surface hydrophobically modified SiO2 whiskers with a high aspect ratio.
[0010] In the above technical solution, further, in the catalyst precursor solution, the concentration of the protective agent is 0.5wt% to 5wt%.
[0011] In the above technical solution, further, in the catalyst precursor solution, the total concentration of Fe salt and Co salt is 0.05wt% to 1wt%. When the added amount is greater than 1wt%, the excess Fe and Co nanoparticles will agglomerate after reduction, thereby affecting the activity of the catalyst.
[0012] In the above technical solution, further, the mass ratio of the Fe salt in the Fe salt solution to the Co salt in the Co salt solution is 1:1.
[0013] In the above technical solution, further, in step 1, the protective agent is any one of polyvinyl pyrrolidone, isobutylene-maleic anhydride copolymer, and sodium carboxymethyl cellulose.
[0014] In the above technical solution, further, in step 2, the mass volume ratio of the SiO2 particles to the catalyst precursor solution is 5-10g:100ml.
[0015] In the above technical solution, further, in step three, the vacuum degree of the vacuum impregnation is 0.01-0.05Mpa, and the impregnation time is 5-30min.
[0016] In the above technical solution, further, in step three, the mass fraction of stearic acid in the alcohol solution of stearic acid is 2wt% to 10wt%.
[0017] Another aspect of the present invention provides an application of the SiO2 whisker prepared by the above preparation method in oil-water separation.
[0018] The beneficial effects of the present invention are:
[0019] 1. The present invention adopts an in-situ catalytic synthesis method to prepare SiO2 whiskers. The prepared SiO2 whiskers have demulsification ability and a high aspect ratio. The preparation method has high output and is suitable for industrial large-scale production.
[0020] 2. The preparation process of the present invention is simple, the number and aspect ratio of the whiskers on the surface of the SiO2 particles are controllable, and the whiskers have oleophilic and hydrophobic properties.
[0021] 3. The present invention uses Fe salt and Co salt as catalyst precursors. The base metal catalyst prepared after reduction has the advantage of being inexpensive compared to conventional precious metal catalysts. Using it for whisker preparation has a significant cost advantage. BRIEF DESCRIPTION OF THE DRAWINGS
[0022] Figure 1 The water contact angle test result of the SiO2 whisker prepared in Example 1;
[0023] Figure 2 The oil wetting angle test results of the SiO2 whisker prepared in Example 1 are shown in FIG. DETAILED DESCRIPTION
[0024] The following examples may enable those skilled in the art to more fully understand the present invention, but are not intended to limit the present invention in any way.
[0025] Unless otherwise specified, the materials used in the embodiments of the present invention can be obtained through commercial channels or prepared according to conventional methods well known to those skilled in the art.
[0026] Example 1
[0027] A method for preparing a surface hydrophobically modified SiO2 whisker with a high aspect ratio comprises the following steps:
[0028] Step 1, adding polyvinylpyrrolidone (PVP) to deionized water to obtain a protective agent solution, and then adding Fe salt solution and Co salt solution with a mass ratio of Fe salt to Co salt of 1:1 respectively to obtain a catalyst precursor solution, wherein the concentration of PVP in the catalyst precursor solution is 0.5wt%, and the total concentration of Fe salt and Co salt is 0.05%;
[0029] Step 2: Add 5 g of SiO2 particles to 100 ml of the catalyst precursor solution obtained in step 1, filter, and dry to obtain a powder;
[0030] Step 3: The powder obtained in step 2 is placed in an atmosphere furnace under N2 protection at 850°C for 2 hours to obtain SiO2 whiskers with an aspect ratio of 60 to 80;
[0031] Step 4: Vacuum impregnate the SiO2 whiskers obtained in step 3 into a 2 wt% stearic acid alcohol solution, filter and dry to obtain surface hydrophobically modified SiO2 whiskers with a high aspect ratio.
[0032] Figure 1 , 2 The test results of the water contact angle and oil wetting angle of the SiO2 whisker prepared in Example 1 show that the water wetting angle of the sample surface is 143 degrees and the oil wetting angle is 0 degrees. The SiO2 whisker prepared in the present invention has oleophilic and hydrophobic properties.
[0033] Example 2
[0034] A method for preparing a surface hydrophobically modified SiO2 whisker with a high aspect ratio comprises the following steps:
[0035] Step 1, adding isobutylene-maleic anhydride copolymer (ISOBAM-104) into deionized water to obtain a protective agent solution, and then adding Fe salt solution and Co salt solution with a mass ratio of Fe salt to Co salt of 1:1 respectively to obtain a catalyst precursor solution, wherein the concentration of ISOBAM-104 in the catalyst precursor solution is 2wt%, and the total concentration of Fe salt and Co salt is 0.5%;
[0036] Step 2: Add 5 g of SiO2 particles to 100 ml of the catalyst precursor solution obtained in step 1, filter, and dry to obtain a powder;
[0037] Step 3, the powder obtained in step 2 is placed in an atmosphere furnace, under Ar protection, at 1300° C. for 2 hours to obtain SiO2 whiskers with an aspect ratio of 75 to 90;
[0038] Step 4: Vacuum-immerse the SiO2 whiskers obtained in step 3 into a 6 wt % stearic acid alcohol solution, filter and dry to obtain surface hydrophobically modified SiO2 whiskers with a high aspect ratio.
[0039] Example 3
[0040] A method for preparing a surface hydrophobically modified SiO2 whisker with a high aspect ratio comprises the following steps:
[0041] Step 1, adding sodium carboxymethyl cellulose (CMC) to deionized water to obtain a protective agent solution, and then adding Fe salt solution and Co salt solution with a mass ratio of Fe salt to Co salt of 1:1 respectively to obtain a catalyst precursor solution, wherein the concentration of CMC in the catalyst precursor solution is 5wt%, and the total concentration of Fe salt and Co salt is 0.9%;
[0042] Step 2: Add 5 g of SiO2 particles to 100 ml of the catalyst precursor solution obtained in step 1, filter, and dry to obtain a powder;
[0043] Step 3, the powder obtained in step 2 is placed in an atmosphere furnace, under the protection of Ar / 5% H2 (volume fraction) mixed gas, at 1400°C for 2 hours to obtain SiO2 whiskers with an aspect ratio of 70 to 100;
[0044] Step 4: Vacuum-immerse the SiO2 whiskers obtained in step 3 into a 12 wt% stearic acid alcohol solution, filter and dry to obtain surface hydrophobically modified SiO2 whiskers with a high aspect ratio.
[0045] Example 4
[0046] A method for preparing a surface hydrophobically modified SiO2 whisker with a high aspect ratio comprises the following steps:
[0047] Step 1, adding polyvinylpyrrolidone (PVP) to deionized water to obtain a protective agent solution, and then adding Fe salt solution and Co salt solution with a mass ratio of Fe salt to Co salt of 1:1 respectively to obtain a catalyst precursor solution, wherein the concentration of PVP in the catalyst precursor solution is 3wt%, and the total concentration of Fe salt and Co salt is 0.7%;
[0048] Step 2: Add 5 g of SiO2 particles to 100 ml of the catalyst precursor solution obtained in step 1, filter, and dry to obtain a powder;
[0049] Step 3: The powder obtained in step 2 is placed in an atmosphere furnace under N2 protection at 1350°C for 2 hours to obtain SiO2 whiskers with an aspect ratio of 70 to 100;
[0050] Step 4: Vacuum-immerse the SiO2 whiskers obtained in step 3 into an 8 wt % stearic acid alcohol solution, filter and dry to obtain surface hydrophobically modified SiO2 whiskers with a high aspect ratio.
[0051] The above embodiments are only preferred embodiments of the present invention and are not intended to limit the implementation methods. The protection scope of the present invention shall be subject to the scope defined in the claims. Other different forms of changes or modifications may be made based on the above description. Obvious changes or modifications derived therefrom are still within the protection scope of the present invention.
Claims
1. A method for preparing a surface hydrophobically modified SiO2 whisker with a high aspect ratio, characterized in that: The method comprises the following steps: Step 1: adding a protective agent to deionized water to obtain a protective agent solution, and then adding an Fe salt solution and a Co salt solution respectively to obtain a catalyst precursor solution; Step 2: adding SiO2 particles to the catalyst precursor solution obtained in step 1, filtering, drying, and obtaining powder; Step 3, the powder obtained in step 2 is kept at 850-1400° C. in an atmosphere furnace for 1.5-3 hours to obtain SiO2 whiskers with a high aspect ratio; Step 4: Vacuum-immerse the SiO2 whiskers obtained in step 3 in an alcohol solution of stearic acid, filter and dry them to obtain surface hydrophobically modified SiO2 whiskers with a high aspect ratio.
2. The method for preparing the surface hydrophobically modified high aspect ratio SiO2 whisker according to claim 1, characterized in that: In the catalyst precursor solution, the concentration of the protective agent is 0.5wt% to 5wt%, and the total concentration of the Fe salt and the Co salt is 0.05wt% to 1wt%.
3. The method for preparing the surface hydrophobically modified high aspect ratio SiO2 whisker according to claim 1, characterized in that: The mass ratio of the Fe salt in the Fe salt solution to the Co salt in the Co salt solution is 1:
1.
4. The method for preparing the surface hydrophobically modified SiO2 whisker with high aspect ratio according to claim 1, characterized in that: In step 1, the protective agent is any one of polyvinyl pyrrolidone, isobutylene-maleic anhydride copolymer, and sodium carboxymethyl cellulose.
5. The method for preparing the surface hydrophobically modified high aspect ratio SiO2 whisker according to claim 1, characterized in that: In step 2, the mass volume ratio of the SiO2 particles to the catalyst precursor solution is 5-10g:100ml.
6. The method for preparing the surface hydrophobically modified SiO2 whisker with high aspect ratio according to claim 1, characterized in that: In step three, the vacuum degree of the vacuum impregnation is 0.01-0.05 MPa, and the impregnation time is 5-30 min.
7. The method for preparing the surface hydrophobically modified SiO2 whisker with high aspect ratio according to claim 1, characterized in that: In step 3, the mass fraction of stearic acid in the alcohol solution of stearic acid is 2wt% to 10wt%.
8. Use of SiO2 whiskers prepared by the preparation method according to any one of claims 1 to 7 in oil-water separation.