阅读说明：本技术 氧化锆纤维及其制备方法、氧化锆纤维过滤材料及其制备方法 (Zirconia fiber and preparation method thereof, zirconia fiber filter material and preparation method thereof ) 是由 傅超 郑维金 岳耀辉 刘焕英 史新友 鹿明 于 2021-08-17 设计创作，主要内容包括：本发明提供了一种氧化锆纤维的制备方法,包括：S1)将氧氯化锆与液体醋酸锆混合加热水解,然后加入相稳定剂、助纺剂与消泡剂,减压蒸馏,得到纺丝液；S2)将所述纺丝液经喷吹成纤、集棉与摆锤布棉后,得到氧化锆初生纤；S3)将所述氧化锆初生纤经热处理后,得到氧化锆纤维。与现有技术相比,本发明以氧氯化锆与液体醋酸锆为锆源提高了纺丝液的固含量,同时利用氧氯化锆中的氯离子在纺丝液中形成卤键,使纺丝液具有二维线性结构,具有较高的流变性和纺丝性,从而使得到的氧化锆纤维直径均匀,渣球含量较少,分散均匀,交织均匀,具有更高的回弹性和柔韧性,较高的使用温度与孔隙率。(The invention provides a preparation method of zirconia fiber, which comprises the following steps: s1) mixing zirconium oxychloride with liquid zirconium acetate, heating for hydrolysis, adding a phase stabilizer, a spinning aid and a defoaming agent, and distilling under reduced pressure to obtain a spinning solution; s2) performing fiber forming, cotton collecting and pendulum cloth cotton blowing on the spinning solution to obtain zirconia primary fibers; s3), carrying out heat treatment on the zirconia primary fiber to obtain the zirconia fiber. Compared with the prior art, the method takes zirconium oxychloride and liquid zirconium acetate as zirconium sources, so that the solid content of the spinning solution is improved, and chloride ions in the zirconium oxychloride form halogen bonds in the spinning solution, so that the spinning solution has a two-dimensional linear structure and higher rheological property and spinnability, and the obtained zirconium oxide fibers have uniform diameters, less slag ball content, uniform dispersion, uniform interweaving, higher rebound resilience and flexibility, and higher service temperature and porosity.)

1. A method for preparing zirconia fiber, comprising:

s1) mixing zirconium oxychloride with liquid zirconium acetate, heating for hydrolysis, then adding a phase stabilizer, a spinning aid and a defoaming agent, and carrying out reduced pressure distillation to obtain a spinning solution;

s2) performing fiber forming, cotton collecting and pendulum cloth cotton blowing on the spinning solution to obtain zirconia primary fibers;

s3), carrying out heat treatment on the zirconia primary fiber to obtain the zirconia fiber.

2. The method according to claim 1, wherein the mass ratio of the zirconium oxychloride to the liquid zirconium acetate is 1: (3-8.5).

3. The preparation method according to claim 1, wherein the temperature of the heating hydrolysis is 150-180 ℃; heating and hydrolyzing for 30-90 min; the heating hydrolysis is carried out under the condition of stirring; the stirring speed is 55-65 r/min.

4. The method according to claim 1, wherein the phase stabilizer is selected from yttrium nitrate and/or yttrium carbonate; the addition amount of the phase stabilizer enables the molar ratio of zirconium element to yttrium element in the spinning solution to be (97-95): (6-10).

5. The preparation method according to claim 1, wherein the spinning aid is selected from one or more of polyvinylpyrrolidone, polyvinyl alcohol, partially hydrolyzed polyvinyl acetate, polyacrylamide, partially hydrolyzed polyacrylamide, polyoxyethylene, hydroxyalkyl cellulose, carboxyalkyl cellulose and polyethylene glycol; the mass of the spinning aid is 3-15% of the mass of zirconia in the spinning solution by solid content;

the spinning aid is added in the form of an aqueous solution of the spinning aid; the mass concentration of the spinning aid aqueous solution is 4-9%;

the defoaming agent is an organic silicon defoaming agent; the mass of the defoaming agent is 0.1-0.5% of the mass of the spinning assistant aqueous solution.

6. The preparation method according to claim 1, wherein the vacuum degree of the reduced pressure distillation is 0.08-0.095 MPa; distilling under reduced pressure until the viscosity of the solution is more than or equal to 800mpa.s at 50 +/-2 ℃;

distilling under reduced pressure, and aging to obtain spinning solution; the viscosity of the spinning solution at room temperature is 3500-5500 mpa.s.

7. The preparation method according to claim 1, wherein the blowing fiberization wind pressure is 0.2-0.3 MPa; the curing distance is 3-8 m; the temperature is 40-50 ℃; the humidity is 10-20 RH%; the aperture of the spray needle is 0.1-0.3 mm; the distance between the transverse spray needles in one row is 1-2 mm;

the conveying speed of the cotton collection is 0.5-1 m/min; the air induction of cotton collection is 15 to 20 hz;

the conveying speed of the pendulum cloth cotton is 0.02-0.03 m/min; the pendulum speed of the pendulum cloth cotton is 0.52-1.1 m/min; the swing amplitude of the pendulum is 1.1-1.3 m.

8. The method according to claim 1, characterized in that the heat treatment is in particular: heating to 400-600 ℃ at a heating rate of 0.5-1 ℃/min for processing for 30-60 min, and then heating to 1100-1300 ℃ at a heating rate of 8-15 ℃/min for processing for 3-5 h.

9. The zirconia fiber prepared by the method of any one of claims 1 to 8.

10. A zirconia fiber filter material, characterized in that it is sewn from the zirconia fiber prepared by the preparation method of any one of claims 1 to 8.

Technical Field

The invention belongs to the technical field of ceramic fibers, and particularly relates to a zirconia fiber and a preparation method thereof, and a zirconia fiber filtering material and a preparation method thereof.

Background

The ceramic fiber is a fibrous high-performance inorganic material, has the advantages of high temperature resistance, corrosion resistance, good heat insulation, light weight, small heat capacity, good thermal stability, mechanical shock resistance and the like, and is widely applied to the fields of aerospace, machinery, metallurgy, chemical industry and the like. In recent years, with the continuous development of the aerospace industry and the high-temperature heat insulation field, higher requirements are put on the high-temperature service performance of fiber materials.

At present, the highest temperature resistance of the filter material reaches 1600 ℃, for example, Chinese patent with publication number CN111362712A discloses a preparation method of an alumina fiber filter material, the highest temperature resistance reaches 1600 ℃, but the filter material is prepared by a filament throwing process, the dispersibility and uniformity of fibers are good, but the bending and winding phenomena of the fibers are serious, the diameter is thick, and alumina aerogel needs to be added, so that the uniformity of the filter material is not ideal.

The existing refractory fiber material cannot meet the long-term use requirement of a high-temperature environment with the temperature of more than 1700 ℃, and a new high-temperature refractory fiber is urgently needed to solve the bottleneck of lack of heat insulating materials in the current high-temperature field.

Current research indicates that polycrystalline ZrO₂The fiber is the only high-grade light refractory fiber material which can meet the long-term use in the high-temperature environment of more than 1700 ℃. ZrO (ZrO)₂The application of the fiber has two main aspects: the material can be applied to the fields of refractory heat-insulating lining materials of various high-temperature special industrial furnaces, ultra-high-temperature industrial kilns at 1500-2200 ℃, ultra-high-temperature experimental electric furnaces, other ultra-high-temperature heating devices and the like, can also be applied to the fields of ceramic sintering, metal smelting, pyrolysis, semiconductor manufacturing, quartz melting, crystal growth, experimental research and other industries and scientific researches, and particularly can be applied to the environment where high-temperature filter materials are used for filtering and removing impurities of liquid or gas at high temperature.

Therefore, the production of zirconia fiber products from zirconia sol prepared from inexpensive inorganic zirconium salt is one of the main trends in future development.

Disclosure of Invention

In view of this, the technical problem to be solved by the present invention is to provide a zirconia fiber with high use temperature and good flexibility, a preparation method thereof, a zirconia fiber filter material, and a preparation method thereof.

The invention provides a preparation method of zirconia fiber, which comprises the following steps:

s1) mixing zirconium oxychloride with liquid zirconium acetate, heating for hydrolysis, then adding a phase stabilizer, a spinning aid and a defoaming agent, and carrying out reduced pressure distillation to obtain a spinning solution;

s2) performing fiber forming, cotton collecting and pendulum cloth cotton blowing on the spinning solution to obtain zirconia primary fibers;

s3), carrying out heat treatment on the zirconia primary fiber to obtain the zirconia fiber.

Preferably, the mass ratio of the zirconium oxychloride to the liquid zirconium acetate is 1: (3-8.5);

preferably, the temperature of the heating hydrolysis is 150-180 ℃; heating and hydrolyzing for 30-90 min; the heating hydrolysis is carried out under the condition of stirring; the stirring speed is 55-65 r/min.

Preferably, the phase stabilizer is selected from yttrium nitrate and/or yttrium carbonate; the addition amount of the phase stabilizer enables the molar ratio of zirconium element to yttrium element in the spinning solution to be (97-95): (6-10).

Preferably, the spinning aid is selected from one or more of polyvinylpyrrolidone, polyvinyl alcohol, partially hydrolyzed polyvinyl acetate, polyacrylamide, partially hydrolyzed polyacrylamide, polyoxyethylene, hydroxyalkyl cellulose, carboxyalkyl cellulose and polyethylene glycol; the mass of the spinning aid is 3-15% of the mass of zirconia in the spinning solution by solid content;

the spinning aid is added in the form of an aqueous solution of the spinning aid; the mass concentration of the spinning aid aqueous solution is 4-9%;

the defoaming agent is an organic silicon defoaming agent; the mass of the defoaming agent is 0.1-0.5% of the mass of the spinning assistant aqueous solution.

Preferably, the vacuum degree of the reduced pressure distillation is 0.08-0.095 MPa; distilling under reduced pressure until the viscosity of the solution is more than or equal to 800mpa.s at 50 +/-2 ℃;

distilling under reduced pressure, and aging to obtain spinning solution; the viscosity of the spinning solution at room temperature is 3500-5500 mpa.s.

Preferably, the wind pressure of the blowing fiber forming is 0.2-0.3 MPa; the curing distance is 3-8 m; the temperature is 40-50 ℃; the humidity is 10-20 RH%; the aperture of the spray needle is 0.1-0.3 mm; the distance between the transverse spray needles in one row is 1-2 mm;

the conveying speed of the cotton collection is 0.5-1 m/min; the air induction of cotton collection is 15 to 20 hz;

the conveying speed of the pendulum cloth cotton is 0.02-0.03 m/min; the pendulum speed of the pendulum cloth cotton is 0.52-1.1 m/min; the swing amplitude of the pendulum is 1.1-1.3 m.

Preferably, the heat treatment specifically comprises: heating to 400-600 ℃ at a heating rate of 0.5-1 ℃/min for processing for 30-60 min, and then heating to 1100-1300 ℃ at a heating rate of 8-15 ℃/min for processing for 3-5 h.

The invention also provides the zirconia fiber prepared by the preparation method.

The invention also provides a zirconia fiber filtering material which is sewn from the zirconia fiber prepared by the preparation method.

The invention provides a preparation method of zirconia fiber, which comprises the following steps: s1) mixing zirconium oxychloride with liquid zirconium acetate, heating for hydrolysis, adding a phase stabilizer, a spinning aid and a defoaming agent, and distilling under reduced pressure to obtain a spinning solution; s2) performing fiber forming, cotton collecting and pendulum cloth cotton blowing on the spinning solution to obtain zirconia primary fibers; s3), carrying out heat treatment on the zirconia primary fiber to obtain the zirconia fiber. Compared with the prior art, the method takes zirconium oxychloride and liquid zirconium acetate as zirconium sources, so that the solid content of the spinning solution is improved, and chloride ions in the zirconium oxychloride form halogen bonds in the spinning solution, so that the spinning solution has a two-dimensional linear structure and higher rheological property and spinnability, and the obtained zirconium oxide fibers have uniform diameters, less slag ball content, uniform dispersion, uniform interweaving, higher rebound resilience and flexibility, and higher service temperature and porosity.

Experiments show that the zirconia fiber and the zirconia fiber filtering material prepared by the invention have less slag ball content (the slag ball content of more than 212 mu m is 0.1-0.5%) than the zirconia fiber produced by a wire throwing process; the fiber diameter is 2-3.5 mu m, the concentration ratio is high (55-65%), the dispersion is uniform (the winding adhesion among fibers is less), and the interweaving is uniform, so that the fiber has higher resilience and softness; the use temperature is higher, the long-term use temperature is 1500-1800 ℃, and the maximum use temperature is 2200 ℃; the powder is not dropped, the porosity is high (more than 92 percent, the porous material is suitable for being used as a filter material), the breaking angle is more than 80 degrees (the larger the breaking angle is, the stronger the breaking resistance of the product is, the better the flexibility is, the more suitable the product is for being wrapped when being used for wrapping), and the tensile strength is more than 0.055 MPa.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

The invention provides a preparation method of zirconia fiber, which comprises the following steps: s1) mixing zirconium oxychloride with liquid zirconium acetate, heating for hydrolysis, then adding a phase stabilizer, a spinning aid and a defoaming agent, and carrying out reduced pressure distillation to obtain a spinning solution; s2) performing fiber forming, cotton collecting and pendulum cloth cotton blowing on the spinning solution to obtain zirconia primary fibers; s3), carrying out heat treatment on the zirconia primary fiber to obtain the zirconia fiber.

In the present invention, the sources of all raw materials are not particularly limited, and they may be commercially available.

Mixing zirconium oxychloride with liquid zirconium acetate, and heating for hydrolysis; wherein, calculated by zirconia, the content of zirconia in the zirconium oxychloride is 35.76wt percent, and the content of zirconia in the liquid zirconium acetate is 22.5wt percent; the zirconium oxychloride can be well dissolved in the liquid zirconium acetate, so that the solid content in the initial mixed zirconium solution can be obviously improved, the concentration time and the concentration energy consumption are reduced, and the existence of chloride ions in the zirconium oxychloride can easily form halogen bonds in sol, so that the formation and the stability of a linear structure are easy. In the present invention, the mass ratio of the zirconium oxychloride to the liquid zirconium acetate is preferably 1: (3-8.5); the zirconium sol formed by the proportion has a two-dimensional linear structure, and has good rheological property and spinning property, so that spun fibers are longer, uniform in diameter and less in slag balls; in the present invention, the mass ratio of the zirconium oxychloride to the liquid zirconium acetate is more preferably 1: (4-7), and more preferably 1: (5-6); in the embodiment provided by the invention, the mass ratio of the zirconium oxychloride to the liquid zirconium acetate is specifically 1: 5; the temperature of the heating hydrolysis is preferably 150-180 ℃, more preferably 160-180 ℃, and further preferably 170-180 ℃; in the embodiment provided by the invention, the temperature of the heating hydrolysis is 175 ℃; the heating hydrolysis time is preferably 30-90 min, more preferably 50-70 min, and further preferably 60 min; the heating hydrolysis is preferably carried out under stirring; the stirring speed is preferably 55-65 r/min; in the examples provided by the present invention, the stirring rate is specifically 60 r/min.

Then adding a phase stabilizer, a spinning aid and a defoaming agent; the phase stabilizer is preferably an yttrium salt, more preferably yttrium nitrate and/or yttrium carbonate; the addition amount of the phase stabilizer is preferably such that the molar ratio of zirconium element to yttrium element in the spinning solution is (97-95): (6-10), namely the molar ratio of the zirconium oxide to the yttrium oxide is (97-95): (3-5) so that tetragonal zirconia is formed after the heat treatment; in the examples provided by the present invention, the molar ratio of zirconia to yttria, calculated as oxides, was specifically 97: 3; the spinning aid is preferably a water-soluble polymer, and more preferably is one or more of polyvinylpyrrolidone, polyvinyl alcohol, partially hydrolyzed polyvinyl acetate, polyacrylamide, partially hydrolyzed polyacrylamide, polyoxyethylene, hydroxyalkyl cellulose, carboxyalkyl cellulose and polyethylene glycol; average of the water-soluble polymerThe molecular weight is preferably 5X 10⁴～5×10⁵(ii) a The mass of the spinning aid is preferably 3-15%, more preferably 5-12%, and even more preferably 8-10% of the mass of zirconia in the spinning solution calculated by oxide; in the embodiment provided by the invention, the mass of the spinning aid is specifically 10% of the mass of zirconia in the spinning solution calculated by oxide; in the invention, the spinning aid is preferably added in the form of an aqueous solution thereof, and the mass concentration of the aqueous solution of the spinning aid is preferably 4-9%, more preferably 6-9%, and still more preferably 7-8%; the defoaming agent is preferably a silicone defoaming agent; in the examples provided herein, the defoamer is specifically Hill material XE-058; the mass of the defoaming agent is preferably 0.1 to 0.5 percent, and more preferably 0.1 to 0.3 percent of the mass of the spinning aid aqueous solution.

Then carrying out reduced pressure distillation; the vacuum degree of the reduced pressure distillation is preferably 0.08-0.095 MPa, more preferably 0.08-0.09 MPa, and still more preferably 0.085 MPa; the reduced pressure distillation is preferably carried out until the viscosity (50 ℃ +/-2) of the solution discharged from the kettle is more than or equal to 800 mpa.s; in the examples provided by the present invention, the reduced pressure distillation was carried out until the solution out-of-kettle viscosity (50 ℃. + -. 2) was 900 mpa.s.

After reduced pressure distillation, preferably aging to obtain a spinning solution; the aging is preferably constant temperature aging; the temperature of the aging is preferably 25-30 ℃, and more preferably 28 ℃; the aging is preferably carried out to ensure that the viscosity of the spinning solution at room temperature is 3500-5500 mpa.s, more preferably 4000-5500 mpa.s, and even more preferably 4000-5000 mpa.s; in the examples provided herein, the aging was carried out specifically to a dope viscosity of 4500mpa.s at room temperature. Certain viscosity corresponds to certain solid content, on the premise that the fiber forming process is the same, the larger the viscosity is, the larger the fiber diameter is, but the viscosity is too large, which is unfavorable for long-term storage, and the fiber forming of colloid with too large viscosity has higher requirements on the process and equipment for preparing proper fiber, otherwise, the fiber quality can be reduced, such as too coarse diameter and too many slag balls.

Blowing the spinning solution into fibers; the blowing fiber forming wind pressure is preferably 0.2-0.3 MPa, and more preferably 0.25 MPa; the curing distance is preferably 3-8 m, more preferably 4-7 m, and further preferably 5-6 m; the temperature is preferably 40 ℃ to 50 ℃, and more preferably 45 ℃; the humidity is preferably 10-20 RH%, more preferably 13-17 RH%, and further preferably 15 RH%; the aperture of the spray needle is preferably 0.1-0.3 mm, and more preferably 0.2 m; the distance between the transverse spray needles in the row is preferably 1-2 mm, and more preferably 1.5 mm. Wind pressure generates wind speed in the fiber forming process, and the wind speed mainly influences the fiber diameter; meanwhile, the aperture of the spray needle determines the size of colloid drops formed by extrusion, thus determining the area of wind power, and influencing the diameter and length of the fiber.

Then, cotton collection is carried out, namely precursor fibers obtained by blowing fall on a cotton collection mesh belt to form a thin net; the conveying speed of the cotton collection is preferably 0.5-1 m/min, more preferably 0.6-0.9 m/min, and still more preferably 0.7-0.8 m/min; in the embodiment provided by the invention, the conveying speed of the cotton collection is specifically 0.75 m/min; the preferable selection of cotton collection and air induction is 15-20 hz; in the embodiment provided by the invention, the cotton collection induced air is specifically 15 hz. The cotton collecting and air inducing effect does not affect the diameter of the fiber, and only collects the fiber into a layer which is then conveyed to the next mesh belt by the cotton collecting mesh belt.

Then, pendulum cloth cotton is carried out to obtain zirconia primary fiber; the conveying speed of the pendulum cloth cotton is preferably 0.02-0.03 m/min; the pendulum speed of the pendulum cloth cotton is preferably 0.52-1.1 m/min, more preferably 0.6-1 m/min, still more preferably 0.6-0.9 m/min, still more preferably 0.7-0.8 m/min; in the embodiment provided by the invention, the pendulum speed of the pendulum cloth cotton is specifically 0.77 m/min; the preferred swing amplitude of the pendulum is 1.1-1.3 m; in the embodiment provided by the invention, the pendulum swing is 1.2m in particular. The cotton is spread layer by layer into thick cotton blanks with uniform thickness through the cloth cotton of the pendulum bob.

Carrying out heat treatment on the zirconia primary fiber to obtain zirconia fiber; the heat treatment is preferably carried out by heating to 400-600 ℃ at a heating rate of 0.5-1 ℃/min for 30-60 min, and then heating to 1100-1300 ℃ at a heating rate of 8-15 ℃/min for 3-5 h; more preferably, the temperature is raised to 450-550 ℃ at the heating rate of 0.5-1 ℃/min for treatment for 30-60 min, and then the temperature is raised to 1200-1300 ℃ at the heating rate of 8-12 ℃/min for treatment for 4 h; then preferably heating to 500 ℃ at the heating rate of 0.5-1 ℃/min for processing for 40-60 min, and then heating to 1250 ℃ at the heating rate of 10 ℃/min for processing for 4 h; in the embodiment provided by the invention, the heating treatment is specifically to heat up to 500 ℃ at the heating rate of 0.5 ℃/min for 50min, and then heat up to 1250 ℃ at the heating rate of 10 ℃/min for 4 h.

The zirconium oxychloride fiber spinning solution disclosed by the invention takes the zirconium oxychloride and the liquid zirconium acetate as zirconium sources, so that the solid content of the spinning solution is improved, and chloride ions in the zirconium oxychloride form halogen bonds in the spinning solution, so that the spinning solution has a two-dimensional linear structure and has higher rheological property and spinning property, and the obtained zirconium oxide fiber has the advantages of uniform diameter, less slag ball content, uniform dispersion, uniform interweaving, higher resilience and flexibility, and higher use temperature and porosity.

The invention also provides the zirconia fiber prepared by the method; the slag ball content of the zirconia fiber with the diameter of 212 mu m is preferably 0.1 to 0.5 percent; the fiber diameter is 55-65% concentrated in 2-3.5 μm; the long-term use temperature of the zirconia fiber is preferably 1500-1800 ℃; the maximum service temperature of the zirconia fiber is preferably 2200 ℃.

The invention also provides a zirconia fiber filtering material which is sewn from the zirconia fibers; the sewing thread is preferably an alumina fiber rope; the sewing density is preferably 12-20 needles/cm²(ii) a In the embodiment provided by the invention, the sewing density is preferably 15 needles/cm²。

The porosity of the zirconia fiber filter material provided by the invention is preferably 92%, and the porosity is high, so that the zirconia fiber filter material is suitable for being used as a filter material; the folding angle is larger than 80 degrees (the larger the folding angle is, the stronger the folding resistance of the product is, the better the flexibility is, and the more suitable the product is for wrapping when being used for wrapping); the tensile strength of the zirconia fiber filtering material is more than 0.055 MPa. And the needle pattern obtained by needling is easy to break, and the filter material is not easy to break by compounding by adopting a sewing method, so that the breaking strength of the filter material is high.

In order to further illustrate the present invention, the following describes the zirconia fiber and the preparation method thereof, the zirconia fiber filter material and the preparation method thereof provided by the present invention in detail with reference to the examples.

The reagents used in the following examples are all commercially available.

The detection of the slag ball content, the diameter and the tensile strength in the examples and the comparative examples is determined according to GB/T17911 test method for refractory ceramic fiber products.

The detection method of the flexural strength comprises the following steps:

(1) the sample was cut and had a width of 5cm and a length of at least 15 cm.

(2) The sample was laid flat on the top surface of the 90 ° device with a portion of the sample 2/3 in the length direction extending beyond the edge of the 90 ° device.

(3) The sample is kept flat and placed on the upper surface of the device, the bottom end of the sample extending out of the edge part of the device is grasped, and the sample is slowly bent downwards by 90 degrees along the profile of the side surface of the device by 90 degrees. The sample is not allowed to be pulled hard during the bending process.

(4) The angle at which the sample bends to develop cracks was examined.

The porosity was measured by a Gemini VII 2390 series specific surface area Analyzer from Mike instruments.

Example 1

(1) Weighing zirconium oxychloride (ZrO)₂35.76 wt.%), dissolved in 100kg of liquid zirconium acetate (ZrO)₂22.05 wt.%), hydrolyzing at 175 deg.C for 60min with stirring at a frequency of 60r/min, and then ZrO based₂：Y₂O₃In a molar ratio of 97: 3 ratio of Yttrium carbonate 3.76kg (Y) was added₂(CO₃)₃Middle Y₂O₃44% of solid content), 33.4kg (7% by mass) of polyvinyl alcohol (average molecular weight 75000) solution and 0.034kg of silicone antifoaming agent (Hill material XE-058) were added at 8% of the zirconia solid content, the vacuum degree was controlled at 0.085MPa, and the distillation was concentrated until the solution viscosity was 900mpa.s (50 ℃. + -. 2), to form a transparent solution.

(2) The solution was aged at a constant temperature of 28 ℃ to a viscosity of 4500mpa.s (room temperature) and blown to form fibers.

(3) The blowing fiber forming parameters are as follows: the wind pressure is 0.25MPa, the curing distance is 5m, the constant temperature is 45 ℃, the humidity is controlled at 15RH percent, and the aperture of the spray needle is 0.2 mm; the distance between the transverse spray needles in one row is 1.5 mm. The conveying speed of the cotton collecting net belt is controlled to be 0.75m/min, and the cotton collecting and air inducing speed is 15 hz.

(4) And after cotton collection, carrying out pendulum cotton distribution, wherein the speed of a pendulum is 0.77m/min, the swing amplitude is 1.2m, and the transmission rate is 0.07m/min, so as to obtain the zirconium oxide nascent fiber.

(5) Heating the zirconia primary fiber to 500 ℃ at a speed of 0.5 ℃/min, preserving heat for 50min, heating to 1250 ℃ at a speed of 10 ℃/min, and keeping the temperature for 4h to obtain 96kg/m³And zirconia fiber with thickness of 10 mm.

(6) Sewing the zirconia fiber by using an alumina fiber rope (the fiber diameter is 7-15 microns) to obtain the zirconia fiber filtering material, wherein the sewing density is 15 needles/cm²。

The performance of the zirconia fiber filtering material obtained in the example 1 is detected, and the obtained slag ball with the tensile strength of 0.067MPa, the diameter of 2-3.5 mu m and the diameter of more than or equal to 212 mu m is 0.2 percent; the folding angle resistance is 87 degrees; the porosity was 92%. The temperature resistance is 2200 ℃.

Example 2

(1) Weighing zirconium oxychloride (ZrO)₂35.76 wt.%), dissolved in 100kg of liquid zirconium acetate (ZrO)₂22.05 wt.%), hydrolyzing at 175 deg.C for 60min with stirring at a frequency of 60r/min, and then ZrO based₂：Y₂O₃In a molar ratio of 97: 3 ratio of Yttrium carbonate 3.76kg (Y) was added₂(CO₃)₃Middle Y₂O₃44% of solid content), 33.4kg (7% by mass) of polyvinyl alcohol (average molecular weight 75000) solution and 0.034kg of silicone antifoaming agent (Hill material XE-058) were added at 8% of the zirconia solid content, the vacuum degree was controlled at 0.085MPa, and the distillation was concentrated until the solution viscosity was 900mpa.s (50 ℃. + -. 2), to form a transparent solution.

(2) The solution was aged at a constant temperature of 28 ℃ to a viscosity of 5000mpa.s (room temperature) and blown into fibers.

(3) The blowing fiber forming parameters are as follows: the wind pressure is 0.25MPa, the curing distance is 5m, the constant temperature is 45 ℃, the humidity is controlled at 15RH percent, and the aperture of the spray needle is 0.2 mm; the distance between the transverse spray needles in one row is 1.5 mm. The conveying speed of the cotton collecting net belt is controlled to be 0.75m/min, and the cotton collecting and air inducing speed is 15 hz.

(4) And after cotton collection, carrying out pendulum cotton distribution, wherein the speed of a pendulum is 0.77m/min, the swing amplitude is 1.2m, and the transmission rate is 0.07m/min, so as to obtain the zirconium oxide nascent fiber.

(5) Heating the zirconia primary fiber to 500 ℃ at the speed of 0.5 ℃/min, preserving the heat for 50min, then heating to 1250 ℃ at the speed of 10 ℃/min, and keeping the temperature for 4h to obtain the zirconia fiber with the thickness of 10mm and the density of 96kg/m 3.

(6) Sewing the zirconia fiber by using an alumina fiber rope (the fiber diameter is 7-15 microns) to obtain the zirconia fiber filtering material, wherein the sewing density is 15 needles/cm²。

The performance of the zirconia fiber filtering material obtained in the example 2 is detected, and the obtained slag ball with the tensile strength of 0.065MPa, the diameter of 2.5-3.5 mu m and the diameter of more than or equal to 212 mu m is 0.25 percent; the folding angle is 85 degrees; the porosity was 93%. The temperature resistance is 2200 ℃.

Example 3

(1) Weighing zirconium oxychloride (ZrO)₂35.76 wt.%), dissolved in 100kg of liquid zirconium acetate (ZrO)₂22.05 wt.%), hydrolyzing at 175 deg.C for 60min with stirring at a frequency of 60r/min, and then ZrO based₂：Y₂O₃In a molar ratio of 97: 3 ratio of Yttrium carbonate 3.76kg (Y) was added₂(CO₃)₃Middle Y₂O₃44% of solid content), 33.4kg (7% by mass) of a polyvinyl alcohol (average molecular weight 75000) solution and 0.034kg of a silicone antifoaming agent (Hill material XE-058) were added in an amount of 8% of the solid content of zirconia, the vacuum degree was controlled at 0.085MPa, and concentration and distillation were carried out until the solution viscosity became 1100mpa.s (50 ℃. + -. 2) to form a transparent solution.

(2) The solution was aged at a constant temperature of 28 ℃ to a viscosity of 5000mpa.s (room temperature) and blown into fibers.

(3) The blowing fiber forming parameters are as follows: the wind pressure is 0.25MPa, the curing distance is 5m, the constant temperature is 45 ℃, the humidity is controlled at 15RH percent, and the aperture of the spray needle is 0.2 mm; the distance between the transverse spray needles in one row is 1.5 mm. The conveying speed of the cotton collecting net belt is controlled to be 0.75m/min, and the cotton collecting and air inducing speed is 15 hz.

(4) And after cotton collection, carrying out pendulum cotton distribution, wherein the speed of a pendulum is 0.77m/min, the swing amplitude is 1.2m, and the transmission rate is 0.07m/min, so as to obtain the zirconium oxide nascent fiber.

(5) Heating the zirconia primary fiber to 500 ℃ at a speed of 0.5 ℃/min, preserving heat for 50min, heating to 1250 ℃ at a speed of 10 ℃/min, and keeping the temperature for 4h to obtain 96kg/m³And zirconia fiber with thickness of 10 mm.

(6) Sewing the zirconia fiber by using an alumina fiber rope (the fiber diameter is 7-15 microns) to obtain the zirconia fiber filtering material, wherein the sewing density is 15 needles/cm²。

The performance of the zirconia fiber filtering material obtained in the embodiment 3 is detected, and the obtained slag ball with the tensile strength of 0.07MPa, the diameter of 2.5-4 mu m and the diameter of more than or equal to 212 mu m is 0.22 percent; the folding angle is 86 degrees; the porosity was 93.8%. The temperature resistance is 2200 ℃.

Comparative example 1: (by needling process)

(1) Weighing zirconium oxychloride (ZrO)₂35.76 wt.%), dissolved in 100kg of liquid zirconium acetate (ZrO)₂22.05 wt.%), hydrolyzing at 175 deg.C for 60min with stirring at a frequency of 60r/min, and then ZrO based₂：Y₂O₃In a molar ratio of 97: 3 ratio of Yttrium carbonate 3.76kg (Y) was added₂(CO₃)₃Middle Y₂O₃44% of solid content), adding 33.4kg (mass fraction 7%) of polyvinyl alcohol solution and 0.034kg of silicone defoamer (Hill material XE-058) according to 8% of the solid content of zirconium oxide, controlling the vacuum degree at 0.085MPa, and concentrating and distilling until the solution viscosity is 900mpa.s (50 ℃ +/-2) to form a transparent solution.

(2) The solution was aged at a constant temperature of 28 ℃ to a viscosity of 4500mpa.s (room temperature) and blown to form fibers.

(3) The blowing fiber forming parameters are as follows: the wind pressure is 0.25MPa, the curing distance is 5m, the constant temperature is 45 ℃, the humidity is controlled at 15RH percent, and the aperture of the spray needle is 0.2 mm; the distance between the transverse spray needles in one row is 1.5 mm. The conveying speed of the cotton collecting net belt is controlled to be 0.75m/min, and the cotton collecting and air inducing speed is 15 hz.

(4) And after cotton collection, carrying out pendulum cotton distribution, wherein the speed of a pendulum is 0.77m/min, the swing amplitude is 1.2m, and thus obtaining the zirconia nascent fiber.

(5) Carrying out needling on the zirconia primary fiber to obtain a zirconia fiber blanket green body, wherein the needling density is as follows: 15 needles/cm²。

(6) Heating the zirconia fiber blanket green body to 500 ℃ at a speed of 0.5 ℃/min, preserving heat for 50min, heating to 1250 ℃ at a speed of 10 ℃/min, and keeping the temperature for 4h to obtain 96kg/m³10mm zirconia fiber filter material.

Detecting the performance of the zirconia fiber filtering material obtained in the comparative example 1 to obtain a slag ball with the tensile strength of 0.034MPa, the diameter of 2-3.5 mu m and the diameter of more than or equal to 212 mu m of 0.2 percent; the folding angle resistance was 60 degrees, the surface cracking (strength decreased after needling) and the porosity was 92.1%. The temperature resistance is 2200 ℃.

Comparative example 2 (induced air and wind pressure low)

(1) Weighing zirconium oxychloride (ZrO)₂35.76 wt.%), dissolved in 100kg of liquid zirconium acetate (ZrO)₂22.05 wt.%), hydrolyzing at 175 deg.C for 60min with stirring at a frequency of 60r/min, and then ZrO based₂：Y₂O₃In a molar ratio of 97: 3 ratio of Yttrium carbonate 3.76kg (Y) was added₂(CO₃)₃Middle Y₂O₃44% of solid content), adding 33.4kg (mass fraction 7%) of polyvinyl alcohol solution and 0.034kg of silicone defoamer (Hill material EX-107) according to 8% of the solid content of zirconium oxide, controlling the vacuum degree at 0.085MPa, and concentrating and distilling until the solution viscosity is 900mpa.s (50 ℃ +/-2) to form a transparent solution.

(2) The solution was aged at a constant temperature of 28 ℃ to a viscosity of 4500mpa.s (room temperature) and blown to form fibers.

(3) The blowing fiber forming parameters are as follows: the wind pressure is 0.15MPa, the curing distance is 5m, the constant temperature is 45 ℃, the humidity is controlled at 15RH percent, and the aperture of the spray needle is 0.2 mm; the distance between the transverse spray needles in one row is 1.5 mm. The conveying speed of the cotton collecting net belt is controlled to be 0.75m/min, and the cotton collecting and air inducing speed is 10 hz.

(4) And after cotton collection, carrying out pendulum cotton distribution, wherein the speed of a pendulum is 0.77m/min, the swing amplitude is 1.2m, and thus obtaining the zirconia nascent fiber.

(5) Heating the zirconia primary fiber to 500 ℃ at the speed of 0.5 ℃/min, preserving the heat for 50min, then heating to 1250 ℃ at the speed of 10 ℃/min,keeping the temperature for 4 hours to obtain 96kg/m³10mm zirconia fiber.

(6) Sewing the zirconia fiber by using an alumina fiber rope (the fiber diameter is 7-15 microns), wherein the sewing density is as follows: 15 needles/cm²。

The performance of the zirconia fiber obtained in the comparative example 2 is detected, and the obtained zirconia fiber has the tensile strength of 0.032MPa, the diameter of 2-5 mu m (the diameter distribution is not concentrated and the distribution range is wide) and the slag ball size of more than or equal to 212 mu m is 1.1 percent; the folding resistance angle was 73 degrees. The porosity was 85%. The temperature resistance is 2200 ℃.

Comparative example 3 (by throwing technique)

(1) Weighing zirconium oxychloride (ZrO)₂35.76 wt.%), dissolved in 100kg of liquid zirconium acetate (ZrO)₂22.05 wt.%), hydrolyzing at 175 deg.C for 60min with stirring at a frequency of 60r/min, and then ZrO based₂：Y₂O₃In a molar ratio of 97: 3 ratio of Yttrium carbonate 3.76kg (Y) was added₂(CO₃)₃Middle Y₂O₃44% of solid content), adding 33.4kg (mass fraction 7%) of polyvinyl alcohol solution and 0.034kg of silicone defoamer (Hill material EX-107) according to 8% of the solid content of zirconium oxide, controlling the vacuum degree at 0.085MPa, and concentrating and distilling until the solution viscosity is 900mpa.s (50 ℃ +/-2) to form a transparent solution.

(2) The solution was aged at a constant temperature of 28 ℃ until the viscosity reached 4500mpa.s (room temperature) and then spun into fibers.

(3) The spinning parameters are as follows: wind pressure is 0.25MPa, curing distance is 5m, constant temperature is 45 ℃, humidity is controlled at 15 RH%, spinning disc rotating speed is 3000r/min, and cotton collecting net belt conveying speed is controlled at 0.2 m/min; the cotton is collected to induce 15 hz.

(4) And after cotton collection, carrying out pendulum cotton distribution, wherein the speed of a pendulum is 0.77m/min, the swing amplitude is 1.2m, and the transmission rate is 0.07m/min, so as to obtain the zirconium oxide nascent fiber.

(5) Heating the zirconia primary fiber to 500 ℃ at a speed of 0.5 ℃/min, preserving heat for 50min, heating to 1250 ℃ at a speed of 10 ℃/min, and keeping the temperature for 4h to obtain 96kg/m³And zirconia fiber with thickness of 10 mm.

(6) Alumina for zirconia fiberSewing a fiber rope (the fiber diameter is 7-15 microns) to obtain the zirconia fiber filtering material, wherein the sewing density is as follows: 15 needles/cm²。

Detecting the performance of the zirconia fiber filtering material obtained in the comparative example 3 to obtain a slag ball with the tensile strength of 0.06MPa, the diameter of 3-5 mu m and the diameter of more than or equal to 212 mu m of 0.8 percent; the folding angle is 82 degrees; the porosity was 94%. The temperature resistance is 2200 ℃.

Comparative example 4: comparative example of a single zirconium source.

(1) 100kg of liquid zirconium acetate solution (ZrO) were weighed₂22.05 wt.%), hydrolyzing at 175 deg.C for 60min with stirring at 60r/min, and then ZrO based₂：Y₂O₃In a molar ratio of 97: 3 ratio of 2.84kg (Y) of yttrium carbonate₂(CO₃)₃Middle Y₂O₃44% of solid content), adding 25.2kg (mass fraction 7%) of polyvinyl alcohol solution and 0.025kg of silicone defoamer (Hill material EX-107) according to 8% of the solid content of zirconium oxide, controlling the vacuum degree at 0.085MPa, and concentrating and distilling until the solution viscosity is 900mpa.s (50 ℃ +/-2) to form a transparent solution.

(2) The solution was aged at a constant temperature of 28 ℃ to a viscosity of 4500mpa.s (room temperature) and blown to form fibers.

(3) The blowing fiber forming parameters are as follows: the wind pressure is 0.25MPa, the curing distance is 5m, the constant temperature is 45 ℃, the humidity is controlled at 15RH percent, and the aperture of the spray needle is 0.2 mm; the distance between the transverse spray needles in one row is 1.5 mm. The conveying speed of the cotton collecting net belt is controlled to be 0.75m/min, and the cotton collecting and air inducing speed is 15 hz.

(4) And after cotton collection, carrying out pendulum cotton distribution, wherein the speed of a pendulum is 0.77m/min, the swing amplitude is 1.2m, and the transmission rate is 0.07m/min, so as to obtain the zirconium oxide nascent fiber.

(5) Heating the zirconia primary fiber to 500 ℃ at a speed of 0.5 ℃/min, preserving heat for 50min, heating to 1250 ℃ at a speed of 10 ℃/min, and keeping the temperature for 4h to obtain 96kg/m³And zirconia fiber with thickness of 10 mm.

6) Sewing the zirconia fiber by using an alumina fiber rope (the fiber diameter is 7-15 microns) to obtain the zirconia fiber filtering material, wherein the sewing density is as follows: 15 needles/cm²。

Detecting the performance of the zirconia fiber obtained in the comparative example 4 to obtain a slag ball with the tensile strength of 0.02MPa, the diameter of 3-5 microns (the diameter is too thick) and the diameter of not less than 212 microns of 1.2 percent; the folding angle is 55 degrees; the porosity was 92.5%. The temperature resistance is 2200 ℃.

Comparative example 5: comparative examples with viscosities after aging of not 3500mPa.s to 5500mPa.s (room temperature).

(1) Weighing zirconium oxychloride (ZrO)₂35.76 wt.%), dissolved in 100kg of liquid zirconium acetate (ZrO)₂22.05 wt.%), hydrolyzing at 175 deg.C for 60min with stirring at a frequency of 60r/min, and then ZrO based₂：Y₂O₃In a molar ratio of 97: 3 ratio of Yttrium carbonate 3.76kg (Y) was added₂(CO₃)₃Middle Y₂O₃44% of solid content), adding 33.4kg (mass fraction 7%) of polyvinyl alcohol solution and 0.034kg of silicone defoamer (Hill material EX-107) according to 8% of the solid content of zirconium oxide, controlling the vacuum degree at 0.085MPa, and concentrating and distilling until the solution viscosity is 900mpa.s (50 ℃ +/-2) to form a transparent solution.

(2) The solution was aged at a constant temperature of 28 ℃ to a viscosity of 6500mpa.s (room temperature) and blown to form fibers.

(3) The blowing fiber forming parameters are as follows: the wind pressure is 0.25MPa, the curing distance is 5m, the constant temperature is 45 ℃, the humidity is controlled at 15RH percent, and the aperture of the spray needle is 0.2 mm; the distance between the transverse spray needles in one row is 1.5 mm. The conveying speed of the cotton collecting net belt is controlled to be 0.75m/min, and the cotton collecting and air inducing speed is 15 hz.

(4) And after cotton collection, carrying out pendulum cotton distribution, wherein the speed of a pendulum is 0.77m/min, the swing amplitude is 1.2m, and the transmission rate is 0.07m/min, so as to obtain the zirconium oxide nascent fiber.

(5) Heating the zirconia primary fiber to 500 ℃ at a speed of 0.5 ℃/min, preserving heat for 50min, heating to 1250 ℃ at a speed of 10 ℃/min, and keeping the temperature for 4h to obtain 96kg/m³And zirconia fiber with thickness of 10 mm.

(6) Sewing the zirconia fiber by using an alumina fiber rope (the fiber diameter is 7-15 microns) to obtain the zirconia fiber filtering material, wherein the sewing density is as follows: 15 needles/cm²。

Detecting the performance of the zirconia fiber obtained in the comparative example 5 to obtain a slag ball with the tensile strength of 0.056MPa, the diameter of 3-6 mu m and the diameter of more than or equal to 212 mu m of 1.32 percent; the folding angle is 88 degrees; the porosity was 93.2%. The temperature resistance is 2200 ℃.