CN111621921A - Attapulgite-reinforced alumina nanofiber membrane and preparation method thereof - Google Patents
Attapulgite-reinforced alumina nanofiber membrane and preparation method thereof Download PDFInfo
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Abstract
The invention relates to an attapulgite reinforced alumina nano-fiber membrane and a preparation method thereof, wherein the nano-fiber membrane comprises attapulgite and alumina in a mass ratio of (1-30): 100. The preparation method comprises the following steps: firstly, heating and refluxing inorganic aluminum salt, aluminum isopropoxide and aluminum powder under certain pH value and temperature conditions to prepare aluminum sol, and then adding the screened attapulgite and the spinning aid in a certain proportion into the aluminum sol to obtain a composite spinning solution; spinning by using high-voltage electrostatic spinning equipment to obtain an attapulgite reinforced alumina precursor nanofiber membrane; finally, the attapulgite reinforced alumina nano-fiber membrane is obtained through drying and high-temperature heat treatment. Compared with the existing alumina nanofiber membrane, the nanofiber membrane prepared by the method is lower in cost, higher in yield, and more excellent in flexibility and higher in strength.
Description
Technical Field
The invention relates to the field of preparation of alumina nanofiber membranes, in particular to an attapulgite reinforced alumina nanofiber membrane and a preparation method thereof.
Background
With the advancement of science and technology and the improvement of industrial level, the development of functional ceramic fibers becomes the development direction of the ceramic materials at present. The alumina fiber has the advantages of light weight, high temperature resistance, corrosion resistance, good thermal stability, low thermal conductivity, small specific heat and the like, and has wide application in various fields [ Jingxiang, Shenxiangqian, research status and development trend of alumina fiber [ J ] mineral engineering, 2004(24)69-71 ]. First, alumina has been widely used as a heat insulating material for heat insulation and refractories of industrial kilns, a heat insulating material for high-temperature and high-pressure steam pipes, a high-temperature sealing heat insulating material, and the like. And secondly, the alumina fiber has larger specific surface area, high catalytic efficiency as a catalyst carrier and great application potential in the aspect of engine exhaust gas treatment. In addition, compared with the traditional filter material, the alumina fiber has better filtering effect, higher precision and more excellent thermal stability, chemical stability and thermal shock resistance, so the alumina fiber also has great application prospect in the aspect of high-temperature filtration [ Cao Feng, Li Xiao Dong, Von Chun Xiang, and the like.
From the angle of microstructure design, the diameter of the ceramic fiber is reduced from the current 10-20 microns to the nanometer order of magnitude, the specific surface area of the ceramic fiber is greatly improved, meanwhile, the fiber cloth is lighter, the functionality of the ceramic fiber is expected to be exerted to a greater extent, and the application field of the ceramic fiber is expanded. The electrostatic spinning technology is a method for preparing continuous micro-nanofibers by using a high-voltage electrostatic field, and has the characteristics of high efficiency, rapidness, low cost, controllable process, environmental friendliness and no pollution compared with other methods for preparing nanofibers. The fiber membrane prepared by the electrostatic spinning technology has the advantages of higher specific surface area, larger porosity and the like, and has better performance and wider application prospect in the aspects of heat insulation, filtration, adsorption, catalysis and the like [ F.E. Ahmed, B.S. Lalia, R.Hashaaike.Farah Ejaz Ahmed, Boor Singh Lalia, Raed Hashaaike [ J ]. desalinization 356(2015) 15-30 ].
However, the nano ceramic fiber membranes prepared by the electrostatic spinning method generally have the defects of large brittleness and low strength of the fiber membranes. Although much work has been done by many researchers, the strength of the fiber membrane is mainly concentrated below 1MPa, and the strength requirement of the fiber membrane when the fiber membrane is used independently [ J.Jiang, N.Ni, X.ZHao, F.Guo, X.Fan, P.Xiao, Flexible and robust YAG-Al ] cannot be met2O3composite nanofibrous membranes enabledby a hybrid nanocrystalline-amorphous structure J.Eur.Ceram.Soc.40(2020)2463-2469.]。
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a preparation method of an attapulgite reinforced alumina nanofiber membrane, which solves the problem of low strength of the alumina nanofiber membrane prepared by electrostatic spinning in the prior art.
The purpose of the invention can be realized by the following technical scheme: the attapulgite reinforced alumina nanofiber membrane is characterized by comprising attapulgite and alumina in a mass ratio of (1-30): 100.
The porosity of the nanofiber membrane is 90-95%, and the diameter of the nanofiber is 200-300 nm.
The preparation method of the attapulgite reinforced alumina nanofiber membrane is characterized by comprising the following steps:
step 1: placing inorganic aluminum salt into deionized water, adding glacial acetic acid to adjust the pH value of the solution after the inorganic aluminum salt is dissolved, then adding aluminum isopropoxide or aluminum powder, heating the obtained solution to a set temperature, refluxing and stirring to obtain aluminum sol;
step 2: putting the attapulgite into deionized water for ultrasonic treatment to obtain dispersed suspension, removing lower-layer precipitates, putting the rest suspension into a drying oven for drying, and then adding the dried attapulgite into the aluminum sol obtained in the step 1 to obtain attapulgite-doped aluminum sol;
and step 3: adding a water-soluble spinning aid into the attapulgite-doped aluminum sol obtained in the step 2, uniformly stirring, and then, aging for a period of time to remove gas to obtain a spinning solution;
and 4, step 4: putting the spinning solution obtained in the step 3 into high-voltage electrostatic spinning equipment for spinning to obtain an attapulgite reinforced alumina precursor fiber membrane;
and 5: and (4) drying and carrying out high-temperature heat treatment on the attapulgite reinforced alumina precursor fiber membrane obtained in the step (4) to obtain the attapulgite reinforced alumina nano fiber membrane.
Further, the inorganic aluminum salt in step 1 is Al (NO)3)2.6H2O or AlCl3The molar ratio of the inorganic aluminum salt to the deionized water is 1 (10-30), and the molar ratio of the aluminum isopropoxide or the aluminum powder to the inorganic aluminum salt is (1-3): 5.
Further, in the preparation process of the alumina sol in the step 1, the pH value of the solution is kept between 3 and 5;
further, the reflux temperature is 60-100 ℃, and the reflux time is 4-24 h
Further, the mass ratio of the attapulgite to the water in the step 2 is 1 (20-200), and the ultrasonic dispersion is carried out for 0.5-4 h.
Further, in the step 3, the water-soluble spinning aid is polyvinyl alcohol, polyvinylpyrrolidone or polyethylene oxide, the mass ratio of the water-soluble spinning aid to the alumina in the aluminum sol is (5-30): 100, the mixture is stirred for 4-24 hours, and the mixture is aged for 24-48 hours.
Further, the parameters for preparing the nanofiber membrane by electrostatic spinning in the step 4 are as follows: voltage 15-25 kv, injection speed: 0.3-1 ml/h, the spinning distance is 10-30 cm, and the temperature is controlled at 20-40 ℃.
Furthermore, in the step 5, the drying temperature is 60-80 ℃, and the heat treatment time is 12-48 h.
Further, the heat treatment parameters in step 5 are as follows: the temperature rise speed is 0.5-2 ℃/min within the temperature range of room temperature to 600 ℃, and the heat preservation time at 600 ℃ is 60-240 min; the temperature rise speed in a high temperature region above 600 ℃ is 5-15 ℃/min, and the temperature is kept for 60-240 min at the maximum heat treatment temperature of 800-1000 ℃.
Compared with the prior art, the invention has the following beneficial effects:
1. the attapulgite is added into the alumina nano fiber membrane as a second phase and a reinforcement, and the attapulgite is a layer chain-shaped water-containing magnesium-rich aluminosilicate clay mineral and has the advantages of rich reserves, low cost and the like in nature. The basic structural unit of the attapulgite is needle-shaped rod crystal, the diameter is 10 nm-30 nm, the rod crystal is tightly and parallelly gathered into rod crystal bundles, various aggregates formed by mutual gathering of the rod crystal bundles have the particle size of 0.01-0.1 mm, and the attapulgite can be subjected to ultrasonic dispersion in deionized water to obtain the needle-shaped nanorod crystal which is used as a nano particle and is an effective way for improving the fiber strength. Meanwhile, the nanometer pore canal of the concave-convex rod crystal has a large amount of active centers and Si-OH groups, and can also be used as a catalyst. In addition, the attapulgite loses structural water at high temperature to generate water vapor, can block oxygen, can generate an oxide isolation layer with better thermal stability, and has better flame retardant effect. The extremely low thermal conductivity of the concave-convex rod material and the nanometer-sized pore channel in the concave-convex rod material also enable the concave-convex rod material to have good heat insulation performance. The attapulgite-reinforced alumina nano-fiber membrane can be obtained by an electrostatic spinning technology, and the ultra-light attapulgite-alumina complex phase nano-fiber cloth with flexibility and enough strength is prepared.
2. Polyvinyl alcohol, polyvinylpyrrolidone or polyethylene oxide are used as water-soluble spinning aids, and a proper amount of the spinning aids are introduced into the sol, so that the rheological property of the sol can be improved, and the smooth spinning is facilitated; meanwhile, the spinning aid, the aluminum sol and the attapulgite generate cohesive force, so that the sol can endow molecules with certain arrangement and orientation during spinning, and the spinning aid plays a role of a template.
3. Adopting electrostatic spinning: in the electrostatic spinning process, the spinnable sol is stretched under the action of an electric field force, the attapulgite and the colloidal particles are wrapped by the water-soluble spinning aid and are stretched into fibers, the solvent is continuously volatilized to form the attapulgite-reinforced alumina gel fiber, the spinning environment and conditions are strictly controlled, the environmental temperature is kept at 20-40 ℃ in the spinning process, and most of the solvent can be evaporated when the gel fiber falls into a receiving tray, so that the gel fiber is solidified into fibers; meanwhile, the fiber is not dried too much, so that the problems of poor uniformity and strength reduction of the fiber are avoided.
4. The gel fiber is calcined in two stages, the first stage is the pyrolysis process of the gel fiber, the mass loss and the volume shrinkage are basically completed in the stage, the temperature rise speed is usually kept to be slower, the defects of holes, layering and the like caused by the excessively fast temperature rise speed are avoided, the process is carried out at the speed of 0.5-2 ℃/min from the room temperature to 600 ℃, and the heat is preserved for 60-240 min at the temperature of 600 ℃, so that the organic matters are completely decomposed. The second stage is a ceramic sintering process, mainly an amorphous ceramic crystallization process, and a high temperature rise speed is selected to avoid grain growth, so that the temperature is raised to 800-1000 ℃ at a speed of 5-15 ℃/min, and the temperature is kept for 60-240 min to convert amorphous alumina into gamma-Al2O3。
5. The nanofiber in the fiber membrane obtained by the invention has smooth surface, uniform thickness and diameter of 200-300nm, and the prepared attapulgite nanofiber membrane has extremely high porosity (90-95%) and extremely low density, lower cost, higher yield, more excellent flexibility and higher strength. The method has wide application prospect in various fields such as filtration and adsorption membranes, catalyst carriers, high-efficiency catalysts with self-supporting structures, heat-insulating flame-retardant fabrics and the like.
Drawings
FIG. 1 is a photograph of a product obtained in example 1;
FIG. 2 is a photograph of the product prepared in example 2.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
A preparation method of an attapulgite reinforced alumina nanofiber membrane comprises the following steps:
step 1: weighing a certain amount of inorganic aluminum salt (Al (NO)3)2.6H2O and AlCl3One or two of the aluminum salts and the deionized water) are placed into deionized water, the molar ratio of the aluminum salt to the deionized water is 1 (10-30), glacial acetic acid is added after the aluminum salt and the deionized water are dissolved to adjust the pH value to 3-5, then aluminum isopropoxide or aluminum powder is weighed and added into the solution, the molar ratio of the aluminum isopropoxide or aluminum powder to the inorganic aluminum salt is (1-3): 5, and the solution is heated to 60-100 ℃ and stirred under reflux for 4-24 hours to prepare alumina sol;
step 2: putting the attapulgite into deionized water for ultrasonic treatment for 0.5-4 h, wherein the mass ratio of the attapulgite to the water is 1 (20-200), obtaining dispersed suspension, removing lower-layer precipitates, putting the suspension into a drying oven for drying, and adding the attapulgite according to the mass ratio of the attapulgite to alumina in the alumina sol (1-30): 100 to obtain attapulgite-doped alumina sol;
and step 3: adding polyvinyl alcohol, polyvinyl pyrrolidone or polyethylene oxide into the attapulgite-doped aluminum sol obtained in the step 2 according to the mass ratio (5-30) of the spinning aid to aluminum oxide in the aluminum sol to be 100, magnetically stirring for 4-24 h, ageing for 24-48 h after uniform stirring, and removing gas to obtain spinning solution;
and 4, step 4: and (3) putting the spinning solution obtained in the step (3) into high-voltage electrostatic spinning equipment for spinning, wherein the spinning parameters are as follows: voltage 15-25 kv, injection speed: 0.3-1 ml/h, the spinning distance is 10-30 cm, and the temperature is controlled at 20-40 ℃. Obtaining an attapulgite reinforced alumina precursor nanofiber membrane;
and 5: putting the attapulgite-reinforced alumina precursor nanofiber membrane obtained in the step (4) into an oven to be dried for 12-48 h at the temperature of 60-80 ℃, then putting the membrane into a muffle furnace to be subjected to high-temperature heat treatment, wherein the heating rate is 0.5-2 ℃/min within the temperature range of room temperature-600 ℃, and keeping the temperature at 600 ℃ for 60-240 min; the temperature rise speed in a high-temperature region above 600 ℃ is 5-15 ℃/min, and the temperature is kept at the highest heat treatment temperature for 60-240 min.
The following are more detailed embodiments, and the technical solutions and the technical effects obtained by the present invention will be further described by the following embodiments.
Example 1:
a preparation method of an attapulgite reinforced alumina nanofiber membrane comprises the following steps:
step 1: 0.05mol of Al (NO) is weighed out3)2.9H2Placing O in 1mol of deionized water, adding glacial acetic acid after the O is dissolved to adjust the pH value to 4, then weighing 0.02mol of aluminum isopropoxide, adding the solution into the solution, heating the solution to 80 ℃, and stirring the solution under reflux for 4 hours to obtain aluminum sol;
step 2: putting the attapulgite into deionized water for ultrasonic treatment for 1h, wherein the mass ratio of the attapulgite to the water is 1:100, obtaining dispersed suspension, removing lower-layer precipitates, putting the suspension into a drying oven for drying, and adding the attapulgite according to the mass ratio of the attapulgite to alumina in the alumina sol of 1:100 to obtain attapulgite-doped alumina sol;
and step 3: adding polyvinylpyrrolidone (K90) into the attapulgite-doped aluminum sol obtained in the step 2 according to the mass ratio of the spinning aid to the aluminum oxide in the aluminum sol of 10:100, magnetically stirring for 8 hours, standing for 24 hours after uniform stirring to remove gas, and obtaining spinning solution;
and 4, step 4: and (3) putting the spinning solution obtained in the step (3) into high-voltage electrostatic spinning equipment for spinning, wherein the spinning parameters are as follows: voltage 18kv, bolus rate: 0.5ml/h, spinning distance 15cm, temperature control at 35 ℃. Obtaining an attapulgite reinforced alumina precursor nanofiber membrane;
and 5: putting the attapulgite-reinforced alumina precursor nanofiber membrane obtained in the step 4 into an oven to be dried for 24 hours at the temperature of 80 ℃, and then putting the membrane into a muffle furnace to be subjected to high-temperature heat treatment, wherein the heating rate is 1 ℃/min within the temperature range of room temperature to 600 ℃, and the membrane is kept at the temperature of 600 ℃ for 120 min; the temperature rise speed in a high temperature zone above 600 ℃ is 5 ℃/min, and the temperature is preserved for 120min at 800 ℃.
FIG. 1 is an SEM image of the attapulgite-reinforced alumina nanofiber membrane prepared in this example, and it can be seen that the fiber membrane is composed of randomly arranged single nanofibers with a fiber diameter of 200-300 nm. The porosity of the fiber membrane can reach 95%, but the interior of a single fiber is compact without obvious defects, and the strength of the fiber membrane is 1.36 MPa.
Example 2:
a preparation method of an attapulgite reinforced alumina nanofiber membrane comprises the following steps:
step 1: 0.05mol of Al (NO) is weighed out3)2.9H2Placing O in 1mol of deionized water, adding glacial acetic acid after the O is dissolved to adjust the pH value to 4, then weighing 0.03mol of aluminum isopropoxide, adding the solution into the solution, heating the solution to 80 ℃, and stirring the solution under reflux for 6 hours to obtain aluminum sol;
step 2: putting the attapulgite into deionized water for ultrasonic treatment for 1h, wherein the mass ratio of the attapulgite to the water is 1:80, obtaining dispersed suspension, removing lower-layer precipitates, putting the suspension into a drying oven for drying, and adding the attapulgite according to the mass ratio of the attapulgite to alumina in the alumina sol of 5:100 to obtain attapulgite-doped alumina sol;
and step 3: adding polyvinylpyrrolidone (K90) into the attapulgite-doped aluminum sol obtained in the step 2 according to the mass ratio of the spinning aid to the aluminum oxide in the aluminum sol of 10:100, magnetically stirring for 8 hours, standing for 24 hours after uniform stirring to remove gas, and obtaining spinning solution;
and 4, step 4: and (3) putting the spinning solution obtained in the step (3) into high-voltage electrostatic spinning equipment for spinning, wherein the spinning parameters are as follows: voltage 18kv, bolus rate: 0.5ml/h, spinning distance 15cm, temperature control at 35 ℃. Obtaining an attapulgite reinforced alumina precursor nanofiber membrane;
and 5: putting the attapulgite-reinforced alumina precursor nanofiber membrane obtained in the step 4 into an oven to be dried for 24 hours at the temperature of 80 ℃, and then putting the membrane into a muffle furnace to be subjected to high-temperature heat treatment, wherein the heating rate is 1 ℃/min within the temperature range of room temperature to 600 ℃, and the membrane is kept at the temperature of 600 ℃ for 120 min; the temperature rise speed in a high temperature zone above 600 ℃ is 5 ℃/min, and the temperature is preserved for 120min at 800 ℃.
FIG. 2 is an SEM image of the attapulgite-reinforced alumina nanofiber membrane prepared in this example, and it can be seen that the fiber membrane is composed of randomly arranged single nanofibers with a fiber diameter of 200-300 nm. Because more attapulgite is added, the fiber is bent, but the inside of a single fiber is compact without obvious defects. The porosity of the fibrous membrane was 94% and the strength of the membrane was 1.72 MPa.
Example 3:
a preparation method of an attapulgite reinforced alumina nanofiber membrane comprises the following steps:
step 1: weighing 0.05mol of AlCl3Putting the aluminum powder into 1mol of deionized water, adding glacial acetic acid to adjust the pH value to 4 after the aluminum powder is dissolved, then weighing 0.03mol of aluminum powder, adding the aluminum powder into the solution, heating the solution to 100 ℃, and stirring the solution under reflux for 6 hours to obtain aluminum sol;
step 2: putting the attapulgite into deionized water for ultrasonic treatment for 1h, wherein the mass ratio of the attapulgite to the water is 1:100, obtaining dispersed suspension, removing lower-layer precipitates, putting the suspension into a drying oven for drying, and adding the attapulgite according to the mass ratio of the attapulgite to alumina in the alumina sol of 10:100 to obtain attapulgite-doped alumina sol;
and step 3: adding polyvinylpyrrolidone (K90) into the attapulgite-doped aluminum sol obtained in the step 2 according to the mass ratio of the spinning aid to the aluminum oxide in the aluminum sol of 10:100, magnetically stirring for 8 hours, standing for 24 hours after uniform stirring to remove gas, and obtaining spinning solution;
and 4, step 4: and (3) putting the spinning solution obtained in the step (3) into high-voltage electrostatic spinning equipment for spinning, wherein the spinning parameters are as follows: voltage 18kv, bolus rate: 0.5ml/h, spinning distance 15cm, temperature control at 35 ℃. Obtaining an attapulgite reinforced alumina precursor nanofiber membrane;
and 5: putting the attapulgite-reinforced alumina precursor nanofiber membrane obtained in the step 4 into an oven to be dried for 24 hours at the temperature of 80 ℃, and then putting the membrane into a muffle furnace to be subjected to high-temperature heat treatment, wherein the heating rate is 1 ℃/min within the temperature range of room temperature to 600 ℃, and the membrane is kept at the temperature of 600 ℃ for 120 min; the temperature rise speed in a high temperature zone above 600 ℃ is 5 ℃/min, and the temperature is preserved for 120min at 800 ℃.
Example 4:
a preparation method of an attapulgite reinforced alumina nanofiber membrane comprises the following steps:
step 1: weighing 0.05mol of AlCl3Putting the aluminum powder into 1mol of deionized water, adding glacial acetic acid to adjust the pH value to 4 after the aluminum powder is dissolved, then weighing 0.02mol of aluminum powder, adding the aluminum powder into the solution, heating the solution to 100 ℃, and stirring the solution under reflux for 6 hours to obtain aluminum sol;
step 2: putting the attapulgite into deionized water for ultrasonic treatment for 1h, wherein the mass ratio of the attapulgite to the water is 1:100, obtaining dispersed suspension, removing lower-layer precipitates, putting the suspension into a drying oven for drying, and adding the attapulgite according to the mass ratio of the attapulgite to alumina in the alumina sol of 15:100 to obtain attapulgite-doped alumina sol;
and step 3: adding polyoxyethylene into the attapulgite-doped aluminum sol obtained in the step 2 according to the mass ratio of the spinning aid to the aluminum oxide in the aluminum sol of 10:100, magnetically stirring for 12 hours, standing for 24 hours after uniform stirring to remove gas, and obtaining spinning solution;
and 4, step 4: and (3) putting the spinning solution obtained in the step (3) into high-voltage electrostatic spinning equipment for spinning, wherein the spinning parameters are as follows: voltage 18kv, bolus rate: 0.5ml/h, spinning distance 15cm, temperature control at 35 ℃. Obtaining an attapulgite reinforced alumina precursor nanofiber membrane;
and 5: putting the attapulgite-reinforced alumina precursor nanofiber membrane obtained in the step 4 into an oven to be dried for 24 hours at the temperature of 80 ℃, and then putting the membrane into a muffle furnace to be subjected to high-temperature heat treatment, wherein the heating rate is 1 ℃/min within the temperature range of room temperature to 600 ℃, and the membrane is kept at the temperature of 600 ℃ for 120 min; the temperature rise speed in a high temperature zone above 600 ℃ is 5 ℃/min, and the temperature is preserved for 120min at 800 ℃.
Example 5:
a preparation method of an attapulgite reinforced alumina nanofiber membrane comprises the following steps:
step 1: weighing 0.02mol of AlCl3And 0.03mol of Al (NO)3)2.9H2O, putting the mixture into 1mol of deionized water, adding glacial acetic acid to adjust the pH value to 4 after the mixture is dissolved, then weighing 0.02mol of aluminum powder to add into the solution, heating the solution to 100 ℃, and stirring the solution under reflux for 6 hours to prepare aluminum sol;
step 2: putting the attapulgite into deionized water for ultrasonic treatment for 1h, wherein the mass ratio of the attapulgite to the water is 1:100, obtaining dispersed suspension, removing lower-layer precipitates, putting the suspension into a drying oven for drying, and adding the attapulgite according to the mass ratio of the attapulgite to alumina in the alumina sol of 10:100 to obtain attapulgite-doped alumina sol;
and step 3: adding polyoxyethylene into the attapulgite-doped aluminum sol obtained in the step 2 according to the mass ratio of the spinning aid to the aluminum oxide in the aluminum sol of 20:100, magnetically stirring for 12 hours, standing for 24 hours after uniform stirring to remove gas, and obtaining spinning solution;
and 4, step 4: and (3) putting the spinning solution obtained in the step (3) into high-voltage electrostatic spinning equipment for spinning, wherein the spinning parameters are as follows: voltage 18kv, bolus rate: 0.5ml/h, spinning distance 15cm, temperature control at 35 ℃. Obtaining an attapulgite reinforced alumina precursor nanofiber membrane;
and 5: putting the attapulgite-reinforced alumina precursor nanofiber membrane obtained in the step 4 into an oven to be dried for 24 hours at the temperature of 80 ℃, and then putting the membrane into a muffle furnace to be subjected to high-temperature heat treatment, wherein the heating rate is 1 ℃/min within the temperature range of room temperature to 600 ℃, and the membrane is kept at the temperature of 600 ℃ for 120 min; the temperature rise speed in a high temperature zone above 600 ℃ is 5 ℃/min, and the temperature is preserved for 120min at 800 ℃.
Example 6:
a preparation method of an attapulgite reinforced alumina nanofiber membrane comprises the following steps:
step 1: weighing a certain amount of inorganic aluminum salt (Al (NO)3)2.6H2O), placing the aluminum salt and the deionized water in a molar ratio of 1:10, adding glacial acetic acid to adjust the pH value to 3 after the aluminum salt and the deionized water are dissolved, then weighing aluminum isopropoxide or aluminum powder and adding the aluminum isopropoxide or aluminum powder into the solution in a molar ratio of 1:3, heating the solution to 60 ℃, refluxing and stirring for 24 hours to obtain aluminum sol;
step 2: putting the attapulgite into deionized water for ultrasonic treatment for 0.5h, wherein the mass ratio of the attapulgite to the water is 1:20, obtaining dispersed suspension, removing lower-layer precipitates, putting the suspension into a drying oven for drying, and adding the attapulgite according to the mass ratio of the attapulgite to alumina in the alumina sol of 25:100 to obtain attapulgite-doped alumina sol;
and step 3: adding polyvinyl alcohol, polyvinylpyrrolidone or polyethylene oxide into the attapulgite-doped aluminum sol obtained in the step 2 according to the mass ratio of the spinning aid to the aluminum oxide in the aluminum sol of 5:100, magnetically stirring for 4-24 h, standing for 24-48 h after uniform stirring to remove gas, and obtaining spinning solution;
and 4, step 4: and (3) putting the spinning solution obtained in the step (3) into high-voltage electrostatic spinning equipment for spinning, wherein the spinning parameters are as follows: voltage 15kv, bolus rate: 0.3ml/h, spinning distance 10cm, temperature control at 20 ℃. Obtaining an attapulgite reinforced alumina precursor nanofiber membrane;
and 5: putting the attapulgite-reinforced alumina precursor nanofiber membrane obtained in the step 4 into an oven to be dried for 48 hours at the temperature of 60 ℃, and then putting the membrane into a muffle furnace to be subjected to high-temperature heat treatment, wherein the heating rate is 0.5 ℃/min within the temperature range of room temperature to 600 ℃, and the temperature is kept for 60 minutes at the temperature of 600 ℃; the temperature rise speed in a high temperature zone above 600 ℃ is 5 ℃/min, and the temperature is kept at 800 ℃ for 60 min.
Example 7:
a preparation method of an attapulgite reinforced alumina nanofiber membrane comprises the following steps:
step 1: weighing a certain amount of inorganic aluminum salt (AlCl)3) Placing the aluminum salt and the deionized water in a molar ratio of 1:30, adding glacial acetic acid to adjust the pH value to 5 after the aluminum salt and the deionized water are dissolved, then weighing aluminum isopropoxide or aluminum powder and adding the aluminum isopropoxide or aluminum powder into the solution in a molar ratio of 1:5, heating the solution to 100 ℃, and stirring the solution under reflux for 4 hours to obtain aluminum sol;
step 2: putting the attapulgite into deionized water for ultrasonic treatment for 4 hours, wherein the mass ratio of the attapulgite to the water is 1:200, obtaining dispersed suspension, removing lower-layer precipitates, putting the suspension into a drying oven for drying, and adding the attapulgite according to the mass ratio of the attapulgite to alumina in the alumina sol of 30:100 to obtain attapulgite-doped alumina sol;
and step 3: adding polyvinyl alcohol, polyvinylpyrrolidone or polyethylene oxide into the attapulgite-doped aluminum sol obtained in the step 2 according to the mass ratio of 30:100 of the spinning aid to the aluminum oxide in the aluminum sol, magnetically stirring for 24 hours, standing for 48 hours after uniform stirring to remove gas, and obtaining spinning solution;
and 4, step 4: and (3) putting the spinning solution obtained in the step (3) into high-voltage electrostatic spinning equipment for spinning, wherein the spinning parameters are as follows: voltage 25kv, bolus rate: 1ml/h, a spinning distance of 30cm and a temperature of 40 ℃. Obtaining an attapulgite reinforced alumina precursor nanofiber membrane;
and 5: putting the attapulgite-reinforced alumina precursor nanofiber membrane obtained in the step 4 into an oven to be dried for 12 hours at the temperature of 80 ℃, and then putting the membrane into a muffle furnace to be subjected to high-temperature heat treatment, wherein the heating rate is 2 ℃/min within the temperature range of room temperature to 600 ℃, and the membrane is kept warm for 240min at the temperature of 600 ℃; the temperature rise speed in a high temperature zone above 600 ℃ is 15 ℃/min, and the temperature is preserved for 240min at 800 ℃.
Comparative example
The addition of the uneven bar in step 2 was not involved, and the procedure was otherwise the same as in example 1.
The properties of the nanofiber membranes obtained in the above examples are shown in the following table:
in the description herein, references to the description of "one embodiment," "an example," "a specific example," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The embodiments described above are intended to facilitate the understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (10)
1. The attapulgite reinforced alumina nanofiber membrane is characterized by comprising attapulgite and alumina in a mass ratio of (1-30): 100.
2. The attapulgite-reinforced alumina nanofiber membrane according to claim 1, wherein the porosity of the nanofiber membrane is 90-95%, and the diameter of the nanofiber is 200-300 nm.
3. The method for preparing the attapulgite reinforced alumina nano-fiber membrane according to claim 1 or 2, which is characterized by comprising the following steps:
step 1: placing inorganic aluminum salt into deionized water, adding glacial acetic acid to adjust the pH value of the solution after the inorganic aluminum salt is dissolved, then adding aluminum isopropoxide or aluminum powder, heating the obtained solution to a set temperature, refluxing and stirring to obtain aluminum sol;
step 2: putting the attapulgite into deionized water for ultrasonic treatment to obtain dispersed suspension, removing lower-layer precipitates, putting the rest suspension into a drying oven for drying, and then adding the dried attapulgite into the aluminum sol obtained in the step 1 to obtain attapulgite-doped aluminum sol;
and step 3: adding a water-soluble spinning aid into the attapulgite-doped aluminum sol obtained in the step 2, uniformly stirring, and then, aging for a period of time to remove gas to obtain a spinning solution;
and 4, step 4: putting the spinning solution obtained in the step 3 into high-voltage electrostatic spinning equipment for spinning to obtain an attapulgite reinforced alumina precursor fiber membrane;
and 5: and (4) drying and carrying out high-temperature heat treatment on the attapulgite reinforced alumina precursor fiber membrane obtained in the step (4) to obtain the attapulgite reinforced alumina nano fiber membrane.
4. According to claim 3The preparation method of the attapulgite reinforced alumina nanofiber membrane is characterized in that the inorganic aluminum salt in the step 1 is Al (NO)3)2.6H2O or AlCl3The molar ratio of the inorganic aluminum salt to the deionized water is 1 (10-30), and the molar ratio of the aluminum isopropoxide or the aluminum powder to the inorganic aluminum salt is (1-3): 5.
5. The preparation method of the attapulgite reinforced alumina nanofiber membrane according to claim 3, wherein in the preparation process of the alumina sol in the step 1, the pH of the solution is kept between 3 and 5; the reflux temperature is 60-100 ℃, and the reflux time is 4-24 h.
6. The preparation method of the attapulgite-reinforced alumina nanofiber membrane according to claim 3, wherein the mass ratio of the attapulgite to water in the step 2 is 1 (20-200), and the ultrasonic dispersion is carried out for 0.5-4 h.
7. The preparation method of the attapulgite-reinforced alumina nanofiber membrane according to claim 3, wherein the water-soluble spinning aid in the step 3 is polyvinyl alcohol, polyvinylpyrrolidone or polyethylene oxide, the mass ratio of the water-soluble spinning aid to alumina in the aluminum sol is (5-30): 100, the stirring is carried out for 4-24 h, and the aging is carried out for 24-48 h.
8. The method for preparing the attapulgite reinforced alumina nano-fiber membrane according to claim 3, wherein the parameters for preparing the nano-fiber membrane by electrostatic spinning in the step 4 are as follows: voltage 15-25 kv, injection speed: 0.3-1 ml/h, the spinning distance is 10-30 cm, and the temperature is controlled at 20-40 ℃.
9. The preparation method of the attapulgite-reinforced alumina nanofiber membrane according to claim 6, wherein the drying temperature in step 5 is 60-80 ℃ and the heat treatment time is 12-48 h.
10. The method for preparing the attapulgite reinforced alumina nano-fiber membrane according to claim 1, wherein the heat treatment parameters in the step 5 are as follows: the temperature rise speed is 0.5-2 ℃/min within the temperature range of room temperature to 600 ℃, and the heat preservation time at 600 ℃ is 60-240 min; the temperature rise speed in a high temperature region above 600 ℃ is 5-15 ℃/min, and the temperature is kept for 60-240 min at the maximum heat treatment temperature of 800-1000 ℃.
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