Formulation and method of making a high surface area glass fiber support

Abstract

The application discloses a glass fiber carrier with high specific surface area and a preparation method thereof, and belongs to the technical field of formula and preparation of the glass fiber carrier. The formula of the glass fiber carrier is as follows: 50-70 parts of SiO2, 10-20 parts of Al2O3, 5-10 parts of B2O3, 5-15 parts of CaO and / or MgO, 1-5 parts of Na2O and / or K2O, 10-20 parts of a pore forming agent, 1-3 parts of a surface activation stabilizer and 1-2 parts of a mineralizer. The structure of the surface activation stabilizer is shown in the drawing, the deuterium group of which improves the thermal stability, the aromatic ring structure of which enhances the pi-pi interaction with the surface of the fiber, and the uniform nanoparticle loading sites are formed through directional arrangement. The application solves the problems of low porosity and insufficient surface activity of the traditional glass fiber carrier, and has significant application value in the fields of catalysis and adsorption.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of glass fiber carrier formulation and preparation, and particularly relates to a high specific surface area glass fiber carrier formulation and preparation method. BACKGROUND

[0002] With the continuous development of industrial technology, glass fiber carriers are increasingly widely used in catalysis, adsorption, filtration and other fields. However, due to the low specific surface area of traditional glass fiber carriers, their application potential in high-precision adsorption, high-efficiency catalysis and other fields is limited. In the prior art, glass fiber carriers are usually prepared by a melt drawing method, but this process has problems such as low porosity and uneven pore structure, making it difficult to significantly improve the specific surface area. In addition, the surface activity of traditional glass fiber carriers is insufficient, making it difficult to load highly dispersed active components, further limiting their application in functional materials.

[0003] In the formulation of existing glass fiber carriers, although attempts have been made to improve the pore structure by adding pore-forming agents and mineralizers, the selection and use ratio of pore-forming agents are often not precise enough, resulting in uneven pore distribution, and the addition of mineralizers has not effectively optimized the surface chemical properties of the carrier. In addition, in the preparation process of traditional glass fiber carriers, the surface treatment steps of glass fibers are relatively simple, and functional nanoparticles such as metal oxides cannot be effectively loaded, making it difficult for the carrier to meet the high-end application requirements in terms of catalytic activity and adsorption performance.

[0004] In the field of catalyst carriers, high specific surface area and uniform pore structure are key factors to improve catalytic efficiency. However, in the preparation method of existing glass fiber carriers, the temperature control and forming speed in the melt drawing process are difficult to accurately adjust, resulting in uneven distribution of glass fiber diameter, which further affects the specific surface area and pore structure of the carrier. In addition, in the existing technology, the use of surface activation stabilizers is mostly single component, without fully considering the interaction with the glass fiber carrier matrix, resulting in limited surface treatment effect.

[0005] In summary, existing glass fiber carriers have obvious deficiencies in specific surface area, pore structure uniformity, surface activity and functional loading capacity. Therefore, developing a glass fiber carrier with high specific surface area, uniform pore structure and high surface activity and its preparation method is of great significance to promote the development of catalyst carriers, adsorbent materials and filtration materials and other fields. The present application proposes a technical solution that significantly improves the specific surface area and functionality of glass fiber carriers by optimizing the formulation and preparation process. SUMMARY

[0006] The present application aims to solve the problems existing in the prior art and provides a high specific surface area glass fiber carrier and its preparation method, which significantly improves the specific surface area, pore structure uniformity and surface activity of the glass fiber carrier by optimizing the formulation and preparation process.

[0007] To achieve the above object, the technical scheme adopted by the present application is: a high specific surface area glass fiber carrier, comprising the following components in mass percentage: 50-70 parts of SiO2, 10-20 parts of Al2O3, 5-10 parts of B2O3, 5-15 parts of CaO and / or MgO, 1-5 parts of Na2O and / or K2O, 10-20 parts of pore forming agent, 1-3 parts of surface activation stabilizer, and 1-2 parts of mineralizer.

[0008] The structure of the surface activation stabilizer is shown in formula 1:

[0009] Formula 1;

[0010] The D represents deuterium;

[0011] The R1 is selected from: H, D, alkyl with carbon atom number 1-5, aryl with carbon atom number 6-15, alkoxy with carbon atom number 1-5, deuterated alkyl with carbon atom number 1-5, deuterated aryl with carbon atom number 6-15;

[0012] Or the R1 is selected from: aryl with carbon atom number 6-15 substituted by alkoxy with carbon atom number 1-5, deuterated alkyl with carbon atom number 1-5, alkyl with carbon atom number 1-5, deuterated aryl with carbon atom number 6-15;

[0013] The R2 is selected from: H or D;

[0014] The n is selected from: 1, 2, 3, 4;

[0015] The m is selected from: 2.

[0016] Further, the structure of formula 1 is selected from formula 2 or formula 3;

[0017] Formula 2; Formula 3.

[0018] Further, the alkyl with carbon atom number 1-5 is selected from: methyl, ethyl, propyl, tert-butyl; the deuterated alkyl with carbon atom number 1-5 is selected from: deuterated methyl, deuterated ethyl, deuterated propyl, deuterated tert-butyl.

[0019] Further, the alkoxy with carbon atom number 1-5 is selected from: methoxy, ethoxy.

[0020] Further, the aryl with carbon atom number 6-15 is selected from: phenyl, biphenyl, naphthyl, anthryl; the deuterated aryl with carbon atom number 6-15 is selected from: deuterated phenyl, deuterated biphenyl, deuterated naphthyl, deuterated anthryl.

[0021] Further, the structure of the surface-activating stabilizer is selected from any one of the following compounds:

[0022] ;

[0023] ;

[0024] ;

[0025] ;

[0026] ;

[0027] ;

[0028] ;

[0029] ;

[0030] ;

[0031] .

[0032] Further, the pore-forming agent is selected from polymethyl methacrylate or ammonium carbonate; and the mineralizing agent is sodium fluoride.

[0033] Further, the glass fiber carrier has a diameter of 5-20 μm, and the surface is loaded with metal oxide nanoparticles, the metal oxide being selected from TiO2 or ZrO2.

[0034] A method for preparing a glass fiber carrier with high specific surface area, comprising the following steps:

[0035] S1. The SiO2, Al2O3, B2O3, CaO and / or MgO, Na2O and / or K2O are mixed in a predetermined ratio, the pore-forming agent and the mineralizing agent are added, and ball milling is performed for 2-4 hours to obtain a mixture;

[0036] S2. The mixture obtained in S1 is melted at 1400-1600 ℃ for 4-6 hours, and is then drawn into a glass fiber with a diameter of 5-20 μm;

[0037] S3. The surface-activating stabilizer is prepared into an ethanol solution with a concentration of 0.5-2 wt%, and the glass fiber is subjected to surface treatment;

[0038] S4. The surface-treated glass fiber is immersed in a precursor solution of the metal oxide, and is then calcined at 500-600 ℃ for 2-4 hours to obtain a glass fiber carrier loaded with metal oxide nanoparticles on the surface.

[0039] Further, the drawing forming in S2 adopts the way of roller drawing, the roller rotating speed is 800-1200 rpm, and the drawing speed is 50-80 m / min.

[0040] Further, the precursor solution of the metal oxide in S4 is the ethanol solution of tetrabutyl titanate or the aqueous solution of zirconium oxychloride, and the metal oxide loading is 3-8% of the total mass of the glass fiber carrier.

[0041] Further, the preparation method of the surface activation stabilizer is as follows:

[0042] ;

[0043] Under the protection of nitrogen, the raw material 1 and the raw material 2 are added into a flask; then 5-15 times of the mass of the raw material 1 of acetonitrile is added; the reaction is stirred at room temperature for 25-35 hours; then the solvent is removed by rotary evaporation, and the product is collected after being washed with excess ethyl acetate and dried to obtain the surface activation stabilizer.

[0044] Further, the deuterium group (C-D bond) is introduced into the molecule of the surface activation stabilizer, which has higher bond energy than the traditional C-H bond, significantly enhances the thermal stability of the molecule in high-temperature treatment (such as the calcination step), avoids premature decomposition, and ensures the durability of the surface treatment effect. The surface activation stabilizer promotes the formation of an ordered monolayer arrangement of molecules on the fiber surface, providing uniform nucleation sites for subsequent metal oxide nanoparticles. The untreated glass fiber surface has high surface energy, which easily leads to uneven infiltration of the precursor solution. The surface activation stabilizer reduces the surface tension and avoids local aggregation. There are Si-O - defect sites on the surface of the glass fiber, and the polar end group of the surface activation stabilizer covers the defects through coordination, reduces the non-specific adsorption of metal ions, and realizes the narrowing of the size distribution of the nanoparticles. During the calcination process, the carbon chain part of the surface activation stabilizer decomposes to produce CO2 / H2O, forming a micro-gas flow disturbance, inhibiting the sintering of the nanoparticles, and making the specific surface area increase to more than 200 m 2 / g.

[0045] In the ethanol solution, the surface activation stabilizer forms reverse micelles through the critical micelle concentration, and the tetrabutyl titanate precursor is wrapped in the core of the micelles. The size of the micelles determines the final size of the TiO2 nanoparticles during calcination. The deuterated phenyl group of the surface activation stabilizer limits the preferential growth of ZrO2 grains along the crystal plane through the steric hindrance effect, promoting the formation of a tetragonal phase structure with high exposure of active surfaces.

[0046] In the melting stage F - ions react with Si-O bonds in the SiO2 network to form [SiF6] 2-Complex, reducing the glass melt viscosity, allowing the drawing speed to increase to 80 m / min while maintaining fiber diameter uniformity. Residual trace amounts of F - Hydrogen bonding network with surface-activated stabilizer groups, enhancing the adhesion of the organic layer to the glass substrate. Pore-forming agent PMMA decomposes at 300-400°C to produce CO2 and H2O, while the surface-activated stabilizer decomposes at 500°C. The stepwise decomposition of both forms a hierarchical pore structure. The directional alignment of surface-activated stabilizer molecules on the fiber surface guides the escape path of PMMA decomposition gas, resulting in tubular channels aligned along the fiber axis, improving gas diffusion efficiency. The isotopic effect of deuterated groups in the surface-activated stabilizer reduces the C-D vibrational frequency, promoting the deposition of ZrO2 in an amorphous phase with high specific surface area.

[0047] Compared with the prior art, the beneficial effects of the present application are:

[0048] 1. Significant increase in specific surface area: The present application significantly increases the specific surface area of the glass fiber carrier by optimizing the formulation and preparation process. As shown in Table 2, the specific surface areas of Examples 1-10 are much higher than those of Comparative Examples 1 and 2, with Examples 4 and 7 reaching 248 m 2 / g and 252 m 2 / g, respectively. This is mainly due to the use of surface-activated stabilizers, whose molecular structure is designed to enhance interaction with the glass fiber surface, reduce surface tension, and optimize wettability, allowing the precursor solution to more uniformly impregnate the fiber surface, resulting in a more abundant pore structure and higher specific surface area during calcination.

[0049] 2. Optimizing pore structure uniformity: The present application precisely selects pore-forming agents (such as polymethyl methacrylate or ammonium carbonate) and mineralizers (sodium fluoride), and controls process parameters such as melting temperature and drawing speed during preparation, resulting in a more uniform pore structure of the glass fiber carrier. Pore-forming agents decompose at a specific temperature to produce gas, forming micro-gas flow disturbances that synergize with the decomposition of surface-activated stabilizers to produce tubular channels aligned along the fiber axis, creating a hierarchical pore structure. This not only increases porosity but also makes the pore distribution more uniform, improving gas diffusion efficiency and providing superior mass transfer conditions for catalysis, adsorption, and other applications.

[0050] 3. Enhanced functional loading capacity: The glass fiber carrier of the present application is loaded with metal oxide nanoparticles (such as TiO2 or ZrO2) on the surface, and the loading amount can be accurately controlled at 3-8%. The surface activation stabilizer covers the defect sites on the glass fiber surface through coordination, reduces the non-specific adsorption of metal ions, and provides uniform nucleation sites for nanoparticles. During calcination, the micro-gas flow generated by the decomposition of the carbon chain part of the surface activation stabilizer further inhibits the sintering of the nanoparticles, making the particle size distribution narrower and the active surface more fully exposed. This significantly improves the functional loading capacity of the glass fiber carrier, enhances its catalytic activity and adsorption performance, and meets the demand for high-performance carriers in high-end application fields. BRIEF DESCRIPTION OF DRAWINGS

[0051] Figure 1 Preparation method of the surface activation stabilizer described in the present application. DETAILED DESCRIPTION

[0052] The technical solutions of the present application will be described below in conjunction with the drawings in the present application. Obviously, the described embodiments are only a part of the embodiments of the present application, not all embodiments. Based on the embodiments in the present application, all other embodiments obtained by those of ordinary skill in the art without creative labor fall within the scope of protection of the present application.

[0053] Example 1

[0054] ;

[0055] Under nitrogen protection, 20 raw material 1 and 43.65g of raw material 2 were added to a flask; then 220g of acetonitrile was added; the reaction was stirred at room temperature for 32 hours; then the solvent was removed by rotary evaporation, and the product was collected and dried after washing with excess ethyl acetate to obtain 12.67g of surface activation stabilizer 1.1H NMR (deuterated chloroform) δ 8.02 (d, 2H), 7.70(d, 2H), 7.15-7.04 (m, 8H), 3.89 (s, 12H), 2.32 (d, 6H). MS [MS+H + ]: 431.

[0056] The synthesis method of Examples 2-10 refers to the synthesis method in Example 1, the raw material 2 is different, the rest of the feeding equivalent ratio, post-processing are the same as Example 1, the specific structure of the synthesized compounds of Examples 2-10, the structure of raw material 2, MS [MS+H + ] values are shown in Table 1.

[0057] Table 1.

[0058] Examples Structure of raw material 2 Structure of synthesized compounds MS [MS+H + ]]]> Example 2 CAS No. 156028-00-1 555 Example 3 CAS No: 3056617-52-5 487 Example 4 CAS No. 35656-93-0 413 Example 5 CAS No. 35693-16-4 463 Example 6 CAS No. 104-81-4 585 Example 7 CAS No. 2567-29-5 551 Example 8 CAS No. 73789-86-3 483 Example 9 CAS No. 71258-22-5 409 Example 10 CAS No. 2746-25-0 459

[0059] Note: The CAS number is the number of the compound in the SciFinder (https: / / scifinder-n.cas.org / ) database.

[0060] Application Example 1

[0061] A formula of a glass fiber carrier with high specific surface area: 70 parts of SiO2, 10 parts of Al2O3, 10 parts of B2O3, 15 parts of CaO, 5 parts of Na2O, 20 parts of a pore-forming agent, 3 parts of a surface activation stabilizer 1, and 2 parts of a mineralizer;

[0062] The pore-forming agent is selected from ammonium carbonate; and the mineralizer is selected from sodium fluoride.

[0063] A preparation method of a glass fiber carrier with high specific surface area, comprising the following steps:

[0064] S1. The SiO2, Al2O3, B2O3, CaO, and Na2O are mixed according to the ratio, ammonium carbonate and a mineralizer are added, and ball milling is performed for 4 hours to obtain a mixture;

[0065] S2. The mixture obtained in S1 is melted at 1400°C for 6 hours, and is formed into a glass fiber with a diameter of 20 μm by using a roller drawing method at a roller speed of 800 rpm and a drawing speed of 50 m / min;

[0066] S3. The surface activation stabilizer prepared in Example 1 is prepared into an ethanol solution with a concentration of 2 wt%, and is used for surface treatment of the glass fiber;

[0067] S4. The surface-treated glass fiber is immersed in an ethanol solution of tetrabutyl titanate containing 3% of TiO2 based on the total mass of the glass fiber carrier, and is calcined at 500°C for 2 hours to obtain a glass fiber carrier with metal oxide nanoparticles loaded on the surface.

[0068] Application Examples 2-10

[0069] A glass fiber carrier with high specific surface area is prepared according to the preparation method of Application Example 1, and the surface activation stabilizer prepared in Example 1 is replaced by the surface activation stabilizers prepared in Examples 2-10, respectively, and the rest remains unchanged.

[0070] Comparative Example 1

[0071] A glass fiber carrier is prepared according to the preparation method of Application Example 1, and the surface activation stabilizer prepared in Example 1 is not added, and the rest remains unchanged.

[0072] Comparative Example 2

[0073] A glass fiber carrier was prepared according to the preparation method of Application Example 1, without adding 3% TiO2tetrabutyl titanate ethanol solution, and the rest remained unchanged.

[0074] Performance test:

[0075] Nitrogen adsorption and desorption isotherms were measured using an AutosorbiQ automatic gas adsorption analyzer, and specific surface area and pore size distribution were calculated by Brunauer-Emmett-Teller (BET) method and Barret-Joyner-Halenda (BJH) analysis. The specific surface area data are shown in Table 2.

[0076] Sample No. Specific surface area (m 2 / g)]]> Pore volume (cm 3 / g) Application Example 1 220 0.63 Application Example 2 235 0.67 Application Example 3 205 0.56 Application Example 4 248 0.74 Application Example 5 228 0.66 Application Example 6 185 0.47 Application Example 7 252 0.76 Application Example 8 215 0.61 Application Example 9 241 0.7 Application Example 10 170 0.43 Comparative Example 1 120 0.2 Comparative Example 2 155 0.34

[0077] The specific surface areas of the application examples 1-10 were significantly higher than those of the comparative examples 1 and 2. Among them, the specific surface areas of the application examples 4 and 7 reached 248 m 2 / g and 252 m 2 / g, respectively, showing the best performance. The specific surface area of the comparative example 1 was only 120 m 2 / g due to the absence of the surface activation stabilizer; and the specific surface area of the comparative example 2 was 155 m 2 / g due to the absence of the impregnation of the metal oxide precursor solution. This indicates that the surface activation stabilizer and the loading of the metal oxide nanoparticles play an important role in improving the specific surface area of the glass fiber carrier.

[0078] Although embodiments of the present application have been shown and described, it is to be understood that various modifications, substitutions, replacements and changes can be made to these embodiments without departing from the principles and spirit of the present application, and the scope of the present application is defined by the appended claims and their equivalents.

Claims

1. A high surface area glass fiber support characterized by, The components include the following quality parts: 50-70 parts of SiO2, 10-20 parts of Al2O3, 5-10 parts of B2O3, 5-15 parts of CaO and / or MgO, 1-5 parts of Na2O and / or K2O, 10-20 parts of pore-forming agent, 1-3 parts of surface-activated stabilizer, 1-2 parts of mineralizer; The diameter of the glass fiber carrier glass fiber is 5-20 μm, and the surface is loaded with metal oxide nanoparticles, and the metal oxide is selected from TiO2 or ZrO2; The structure of the surface-activated stabilizer is the structure shown in formula 1: Formula 1; The D represents deuterium; The R1 is selected from: H, D, alkyl with carbon atom number of 1-5, aryl with carbon atom number of 6-15, alkoxy with carbon atom number of 1-5, deuterated alkyl with carbon atom number of 1-5, deuterated aryl with carbon atom number of 6-15; Or the R1 is selected from: aryl with carbon atom number of 6-15 substituted with alkoxy with carbon atom number of 1-5, deuterated alkyl with carbon atom number of 1-5, alkyl with carbon atom number of 1-5, deuterated aryl with carbon atom number of 6-15; The R2 is selected from: H or D; The n is selected from: 1, 2, 3, 4; The m is selected from:

2.

2. A high surface area glass fiber support according to claim 1, wherein, The alkyl with carbon atom number of 1-5 is selected from: methyl, ethyl, propyl, tert-butyl; the deuterated alkyl with carbon atom number of 1-5 is selected from: deuterated methyl, deuterated ethyl, deuterated propyl, deuterated tert-butyl.

3. The high surface area glass fiber support of claim 1, wherein, The alkoxy with carbon atom number of 1-5 is selected from: methoxy, ethoxy.

4. The high surface area glass fiber support of claim 1, wherein, The aryl with carbon atom number of 6-15 is selected from: phenyl, biphenyl, naphthyl, anthracene; The deuterated aryl with carbon atom number of 6-15 is selected from: deuterated phenyl, deuterated biphenyl, deuterated naphthyl, deuterated anthracene.

5. The high surface area glass fiber support of claim 1, wherein, The structure of the surface-activated stabilizer is selected from any one of the following compounds: ； ； ； ； ； ； ； 。 6. The high surface area glass fiber support of claim 1, wherein, The pore-forming agent is selected from polymethyl methacrylate or ammonium carbonate; and the mineralizer is sodium fluoride.

7. A method of making a high surface area glass fiber support according to any one of claims 1-6, characterized in that, The method comprises the following steps: S1. The SiO2, Al2O3, B2O3, CaO and / or MgO, Na2O and / or K2O are mixed according to the ratio, the pore-forming agent and the mineralizer are added, and ball milling is carried out for 2-4 hours to obtain a mixture; S2. The mixture in S1 is melted at 1400-1600 ℃ for 4-6 hours, and is formed into glass fiber with a diameter of 5-20 μm by drawing; S3. The surface-activated stabilizer is prepared into an ethanol solution with a concentration of 0.5-2 wt%, and the glass fiber is surface-treated; S4. The surface-treated glass fiber is immersed in a precursor solution of the metal oxide, and is calcined at 500-600 ℃ for 2-4 hours to obtain a glass fiber carrier loaded with metal oxide nanoparticles on the surface.

8. The method of claim 7, wherein the glass fiber support has a specific surface area of at least 100 m2 / g. In S2, the drawing is carried out by roller drawing, the roller speed is 800-1200 rpm, and the drawing speed is 50-80 m / min.

9. The method of claim 7, wherein the glass fiber support has a specific surface area of at least 100 m2 / g. In S4, the precursor solution of the metal oxide is a tetrabutyl titanate ethanol solution or a zirconium oxychloride aqueous solution, and the loading amount of the metal oxide is 3-8% of the total mass of the glass fiber carrier.

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