Glass fiber carrier as well as preparation method and application thereof

A glass fiber carrier and its preparation method and application technical field

[0001] The present invention relates to the field of hollow fiber membranes, and in particular to a glass fiber carrier and a preparation method and application thereof.

Background Art

Glass fiber membrane is a common carrier in the field of photocatalysis, and has always been favored. Glass hollow fiber membrane is a kind of inorganic separation membrane material. As a hollow fiber membrane, compared with roll membrane and flat membrane, it has the advantages of high specific surface area, large self-supporting structure packing density. It is widely used in dye wastewater treatment and gas separation. As an inorganic hollow fiber membrane, compared with organic hollow fiber membrane, it is not resistant to high temperature, poor acid and alkali corrosion resistance, easy to age, short service life and other shortcomings, inorganic hollow fiber membrane has unique performances such as wear resistance, high temperature resistance, corrosion resistance, high mechanical strength. Among various inorganic hollow fiber membranes, glass hollow fiber membrane has outstanding advantages such as good formability, controllable pore size distribution and narrow pore size distribution.

[0003] By loading photocatalysts on glass fiber membranes, the contact area between the catalyst and pollutants can be increased, thereby improving the photocatalytic efficiency. Hollow fiber membranes can be designed to have special structures, such as porous or super hydrophilic structures, to enhance the light absorption capacity of photocatalysts, thereby improving photocatalytic performance. However, hollow fiber membranes currently still have certain disadvantages. For example, for some photocatalysts with smaller particle sizes, there will be problems of uneven loading and distribution. It may be challenging to evenly load photocatalysts on hollow fiber membranes. Uneven distribution may affect the photocatalytic efficiency. In some reactions, the light transmission effect of hollow fiber membranes is also uneven.

Summary of the invention

[0004] Based on this, the present invention proposes a glass fiber carrier and a preparation method and application thereof, which solves the current problem of uneven loading of small-particle catalysts on hollow fiber membranes and improves the light transmission effect of hollow fiber membrane carriers.

[0005] According to a first aspect of the present invention, there is provided a glass fiber carrier, which is formed by loading hollow glass balls inside a hollow glass fiber membrane;

[0006] Wherein, the pore size of the hollow glass fiber membrane is not greater than 0.5nm, the particle size of the hollow glass ball is 10-250μη, and the wall thickness is 1-2μη.

[0007] According to a second aspect of the present invention, there is provided a method for preparing the above-mentioned glass fiber carrier, comprising the following steps:

Prepare hollow glass fiber membrane;

Prepare hollow glass ball impregnation solution;

[0010] The hollow glass fiber membrane is immersed in the hollow glass ball impregnation solution, dried, and repeatedly immersed twice or more to obtain the hollow glass fiber membrane loaded with the hollow glass ball;

[0011] Forging the hollow glass fiber membrane of the hollow glass ball loaded to obtain the glass fiber carrier.

[0012] According to an embodiment of the present invention, the preparation of the hollow glass fiber membrane comprises:

Preparation of film casting solution;

[0014] Under a nitrogen pressure of 100-120KPa, the casting solution is allowed to enter a coagulation bath through a spinneret, and a glass hollow fiber membrane green body is obtained by double diffusion between an organic solvent and the coagulation bath;

[0015] The dried glass hollow fiber membrane green body is forged at high temperature to decompose the carbonate pore-forming agent to produce carbon dioxide gas at high temperature, forming a pore structure in the hollow fiber membrane, and then cooled to obtain the hollow glass fiber membrane.

According to an embodiment of the present invention, the casting solution comprises:

[0017] A polymer, glass powder and a carbonate pore-forming agent dispersed in a solvent;

[0018] Wherein, the polymer accounts for 8-30% of the mass fraction of the casting solution; the mass percentage of the glass powder is 40-60%, and the mass fraction of the carbonate pore-forming agent is 5-15%.

[0019] According to an embodiment of the present invention, the polymer is any one or two of polyvinylidene fluoride, polyvinyl chloride, and polyacrylonitrile;

[0020] The carbonate pore-forming agent is one or both of calcium carbonate and magnesium carbonate.

[0021] According to an embodiment of the present invention, the high temperature forging includes: heating to 400-600°C at a heating rate of 1-5°C/min, keeping warm for 1-2h, and then heating to 800-1000°C at a rate of 6-10°C/min and keeping warm for 1-2h.

[0022] According to an embodiment of the present invention, the preparation of the hollow glass ball impregnation liquid comprises:

Dispersing the hollow glass ball powder into an organic resin impregnating agent by ultrasonic physical dispersion;

[0024] Wherein, the main component of the hollow glass microsphere is a borate raw material, the particle size of the hollow glass sphere is 10-250 μ lh, and the wall thickness is 1-2 μ m;

[0025] The organic resin selected in the organic resin impregnating agent is two kinds of epoxy resin, phenolic resin and urea-formaldehyde resin.

[0026] According to an embodiment of the present invention, the step of immersing the hollow glass fiber membrane in the hollow glass ball impregnation liquid, drying, and repeatedly immersing twice or more comprises:

[0027] The hollow glass fiber membrane is immersed in the hollow glass ball impregnation solution and taken out after 1-10min;

The hollow glass fiber membrane after impregnation is dried;

[0029] Repeat the above dipping and drying process twice or more to obtain the hollow glass fiber membrane loaded with the hollow glass balls.

[0030] According to an embodiment of the present invention, the forging of the hollow glass fiber membrane loaded with the hollow glass ball to obtain the glass fiber carrier comprises:

[0031] The hollow glass fiber membrane loaded with the hollow glass balls is placed in a high temperature furnace at a heating rate of 1-5°C/min, kept at 450-600°C for 1-2h, and cooled to obtain the glass fiber carrier.

[0032] According to the third aspect of the present invention, there is provided an application of the above-mentioned glass fiber carrier in a photocatalytic carrier.

[0033] It can be seen from the above technical solution that the glass fiber carrier provided by the present invention and its preparation method and application have the following beneficial effects:

[0034] The present invention provides a novel method for preparing and applying a glass fiber carrier, which has the advantages of high efficiency and environmental protection. The carrier has excellent photocatalytic performance and stable structural characteristics. By loading hollow glass balls inside the hollow glass fiber membrane, the utilization efficiency and stability of the photocatalyst can be effectively improved, and the uniformity of the carrier can be improved, which is conducive to the uniform loading of the catalyst and helps the uniform transmission of light in the carrier, thereby achieving better photocatalytic efficiency. In addition, the preparation method and process flow of the present invention are also relatively simple, with high production efficiency and operability.

[0035] The present invention provides a novel glass fiber carrier for use in the field of photocatalysis. Since it has good photocatalytic performance, it is very suitable as a user of a photocatalyst. For example, it can be used as a core component of a device for preparing efficient photocatalytic degradation of organic pollutants.

[0036] The present invention provides a novel glass fiber carrier with good flexibility and compressive strength. The hollow glass ball plays a role in supporting and protecting the photocatalyst, and can also increase the contact area between the photocatalyst and light, thereby improving the photocatalytic performance of the photocatalyst. Finally, the hollow glass fiber membrane itself is responsible for adsorbing and fixing the photocatalyst to ensure its stability and durability during use.

[0037] The glass fiber carrier of the present invention not only has good structure and performance, but also has good application prospects. It can be widely used in the field of photocatalysis, such as water treatment, air purification and other environmental protection fields.

DETAILED DESCRIPTION

[0038] In order to make the objects, technical solutions and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with specific embodiments.

[0039] The technical solution of the present invention is described in detail below through preferred embodiments. It should be noted that the specific embodiments below are only used for illustration and are not intended to limit the present invention.

[0040] A method for preparing the above-mentioned glass fiber carrier is provided, comprising the following steps:

Prepare film casting solution;

[0042] Under a nitrogen pressure of 100-120 KPa, the casting solution is allowed to enter a coagulation bath through a spinneret, and a glass hollow fiber membrane green body is obtained through double diffusion between an organic solvent and the coagulation bath;

[0043] The dried glass hollow fiber membrane green body is subjected to high-temperature forging to decompose the carbonate pore-forming agent at high temperature to produce carbon dioxide gas, thereby forming a pore structure in the hollow fiber membrane. After cooling, the hollow glass fiber membrane is obtained. The high-temperature forging is performed at a heating rate of 1-5°C/min to 400-600°C, and the temperature is kept at this temperature for 1-2h. The temperature is then raised to 800-1000°C at a rate of 6-10°C/min and the temperature is kept at this temperature for 1-2h.

Dispersing the hollow glass ball powder into an organic resin impregnating agent by ultrasonic physical dispersion;

[0045] The hollow glass fiber membrane is immersed in the hollow glass ball impregnation solution and taken out after 1-10 minutes; the hollow glass fiber membrane after impregnation is dried; and the above impregnation and drying process is repeated more than twice to obtain the hollow glass fiber membrane loaded with the hollow glass ball.

[0046] The hollow glass fiber membrane loaded with the hollow glass balls is placed in a high temperature furnace at a heating rate of 1-5°C/min, kept at 450-600°C for 1-2h, and cooled to obtain the glass fiber carrier.

Embodiment 1:

A glass fiber carrier, according to weight fraction, comprises the following material components:

The casting solution comprises: a polymer, glass powder and a carbonate pore-forming agent dispersed in a solvent;

[0050] Wherein, the polyvinylidene fluoride accounts for 25% of the mass fraction of the casting solution; the mass percentage of the glass powder is 50%, the mass fraction of calcium carbonate is 10%, and the rest is dimethyl sulfoxide.

[0051] Wherein, the main component of the hollow glass microsphere is a borate raw material, the particle size of the hollow glass microsphere is 100 μ 1d, and the wall thickness is 2 μ n;

[0052] The organic resin selected in the organic resin impregnating agent is phenolic resin and urea-formaldehyde resin.

Embodiment 2:

A glass fiber carrier, according to weight fraction, comprises the following material components:

The casting solution comprises: a polymer, glass powder and a carbonate pore-forming agent dispersed in a solvent;

[0056] Wherein, the polyvinyl chloride accounts for 8% of the mass fraction of the casting solution; the mass percentage of the glass powder is 60%, the mass fraction of magnesium carbonate is 15%, and the rest is dimethyl sulfoxide.

[0057] Wherein, the main component of the hollow glass microsphere is a borate raw material, the particle size of the hollow glass sphere is 250 μ lh, and the wall thickness is 2 μ n;

[0058] The organic resin selected in the organic resin impregnating agent is epoxy resin and urea-formaldehyde resin.

Embodiment 3:

A glass fiber carrier, according to weight fraction, comprises the following material components:

The casting solution comprises: a polymer, glass powder and a carbonate pore-forming agent dispersed in a solvent;

[0062] Wherein, polyvinyl chloride accounts for 15% of the mass fraction of the casting solution and polyacrylonitrile accounts for 15% of the mass fraction of the casting solution; the mass percentage of glass powder is 40%, the mass fraction of a mixture of calcium carbonate and magnesium carbonate in a mass ratio of 1:1 is 5%, and the rest is dimethyl sulfoxide.

[0063] Wherein, the main component of the hollow glass microsphere is a borate raw material, the particle size of the hollow glass sphere is 10 μl d, and the wall thickness is 1 μH;

[0064] The organic resin selected in the organic resin impregnating agent is epoxy resin and phenolic resin.

Experimental example 1:

[0066] The glass fiber carrier prepared in Examples 1-3 was loaded with a titanium dioxide photocatalyst with a mass ratio of 4% as experimental groups 1-3, a pure hollow glass fiber membrane without hollow glass balls was used as a carrier with a mass ratio of 4% titanium dioxide photocatalyst as a control group, and a pure titanium dioxide membrane of the same mass was used as a blank control group.

[0067] 6001 nl of 5 mg/L nitrobenzene solution was taken as the target degradation solution, and HCl was used to adjust the pH to 3.5. The photocatalytic properties of Examples 1-3, the control group and the blank control group were measured under a three-primary light intensity of 140 W. After the materials of Examples 1-3, the control group and the blank control group were placed in the solution to be degraded, the stirring device was turned on, and the samples were kept away from light for 20 min to reach adsorption equilibrium. Then, the light source was turned on to perform a degradation experiment for 12 hours. The degradation rate varied with time. The degradation rate of the composite film in Examples 1-3 reached more than 90% in 12 h, the degradation rate of the material film in the control group reached 83% in 12 h, and the degradation rate of the pure titanium dioxide film in 12 h was 55%, which was much lower than the degradation rate of the composite film.

Experimental example 2:

At the end of 12 hours of degradation, the film of titanium dioxide photocatalyst with a mass ratio of 4% on the glass fiber carrier prepared by Examples 1-3 in Experimental Example 1 was recovered, and the recovered composite film was calcined at 500° C. in a muffle furnace for 2 h to remove surface pollutants and residues. The test of Experimental Example 1 was then repeated and reused 4 times. There was no significant change in quality before and after use, indicating that the prepared composite film had good reusability.

[0070] The present invention provides a novel method for preparing and applying a glass fiber carrier, which has the advantages of high efficiency and environmental protection. The carrier has excellent photocatalytic performance and stable structural characteristics. By loading hollow glass balls inside the hollow glass fiber membrane, the utilization efficiency and stability of the photocatalyst can be effectively improved, and the uniformity of the carrier can be improved, which is conducive to the uniform loading of the catalyst and helps the uniform transmission of light in the carrier, thereby achieving better photocatalytic efficiency. In addition, the preparation method and process flow of the present invention are also relatively simple, with high production efficiency and operability.

[0071] The present invention provides a novel glass fiber carrier for use in the field of photocatalysis. Since it has good photocatalytic performance, it is very suitable as a user of a photocatalyst. For example, it can be used as a core component of a device for preparing efficient photocatalytic degradation of organic pollutants.

[0072] The present invention provides a novel glass fiber carrier with good flexibility and compressive strength. The hollow glass ball plays a role in supporting and protecting the photocatalyst, and can also increase the contact area between the photocatalyst and light, thereby improving the photocatalytic performance of the photocatalyst. Finally, the hollow glass fiber membrane itself is responsible for adsorbing and fixing the photocatalyst to ensure its stability and durability during use.

[0073] The glass fiber carrier of the present invention not only has good structure and performance, but also has good application prospects. It can be widely used in the field of photocatalysis, such as water treatment, air purification and other environmental protection fields.

The specific embodiments described above further illustrate the purpose, technical solutions and beneficial effects of the present invention. It should be understood that the above are only specific embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention shall be included in the protection scope of the present invention.