A continuous macro-preparation device and method of a soft and elastic ceramic ultra-fine fiber material

Abstract

The application relates to a continuous macro-preparation device and method of a soft and elastic ceramic superfine fiber material, which sequentially comprises a feeding and liquid preparation system, a multi-jet uniform electrostatic spinning system, a low-temperature calcination system and a winding system. Raw materials are mixed, low-temperature dispersed and vacuum concentrated to obtain a sol; the sol and a polymer flow into a polymer mixing device to be mixed and bubble removed; the mixed sol flows into an inorganic component content control device to be pumped by negative pressure to obtain a spinning solution; the spinning solution flows into a multi-jet electrostatic spinning module to adjust and control the temperature, humidity and multi-directional differential speed during spinning to obtain a fiber membrane material or a fiber flake material; the fiber material is sequentially transmitted to a drying area, a microwave pretreatment area, a polymer removal area, an oxygen-poor atmosphere heat treatment area and a cooling area to be calcined in multiple temperature zones to obtain the soft and elastic ceramic superfine fiber material; and winding and packaging are realized to realize the continuous macro-manufacture of the soft and elastic ceramic superfine fiber material.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of ceramic fiber material preparation, in particular to a continuous macro-preparation device and method of soft and elastic ceramic ultra-fine fiber material. BACKGROUND

[0002] Ceramic fibers have the advantages of high temperature resistance, fire resistance, good chemical stability, etc., and are important materials in the fields of aerospace, energy and environment. The preparation methods of ceramic fibers mainly include centrifugal spinning, melt blowing and dry spinning, etc. The fibers prepared by these methods are usually thick and lack flexibility. Currently, electrospinning is the main method for preparing ceramic ultra-fine fibers, but this method has the following problems:

[0003] (1) The preparation method of the soft and elastic ceramic fiber material usually does not have continuity, and cannot realize the simultaneous preparation of liquid preparation, spinning and calcination, resulting in long production cycle and low production efficiency.

[0004] (2) In order to ensure the spinnability of the solution, high molecular weight polymers are often selected as spinning aids and added to the inorganic sol, resulting in low conversion rate of the hybrid fiber and low inorganic component content in the hybrid fiber.

[0005] (3) A single electrospinning nozzle can only form a single jet, and the electric field interference between multiple nozzles is large, which cannot stabilize the spinning.

[0006] (4) The existing electrospinning equipment cannot accurately control the structure and morphology of the fiber, and can only prepare fiber membrane materials, and cannot obtain bulk materials in one step.

[0007] (5) The existing calcination device has the problems of slow removal of polymer components and easy residue, and cannot control the grain size, resulting in the lack of soft and elastic properties of the obtained fiber material.

[0008] (6) The mechanical properties of the ceramic ultra-fine fiber material prepared by the existing technology still cannot meet the actual application requirements, and the fiber flake material cannot be obtained in one step, and it is difficult to realize continuous production.

[0009] Therefore, how to realize the continuous macro-production of various soft and elastic ceramic ultra-fine fiber materials has become a difficult problem to be solved.

[0010] In view of the above problems, some researchers have conducted relevant research in this field. Patent 202111376349.1 discloses a large-scale continuous manufacturing device for flexible ceramic nanofiber, which includes a linear inorganic polymer sol spinning solution prepared by a batch preparation device, a spinning solution is quickly electrospun into fibers by using an electrostatic spinning nozzle, the gel nanofiber is calcined at low temperature, and the flexible ceramic nanofiber is obtained. However, the electrospinning mechanism of the device is only a single nozzle, which limits the improvement of the production rate of fiber materials. Patent 201810442177.5 discloses an electrospinning device and method for batch preparation of uniform nanofiber, the spinning solution forms multiple Taylor cones on the auxiliary Taylor cone assembly, the generated Taylor cones are thinned into filaments under the action of the electrostatic field of the high-voltage static generator, and are received on the negative receiving mechanism to form nanofiber. However, this method does not accurately control the morphological structure of the fiber, and can only prepare fiber membrane materials stacked by straight fibers, and cannot realize one-step forming of fiber bulk materials. Patent CN202210756271.4 discloses a device and method for continuous production of flexible oxide nanofiber membrane, the spinning module electrospins the precursor liquid, continuously collects the spun fiber on the high-temperature ceramic fiber cloth, and then directly conveys the fiber to the heating device for rapid sintering, thereby continuously preparing flexible oxide nanofiber material. However, the sintering device in the device does not pretreat the polymer template in the oxide fiber, resulting in slow decomposition rate and long time consumption of the polymer template.

[0011] Therefore, it is of great significance to develop a continuous macro-preparation device and method for flexible and elastic ceramic ultrafine fiber material, which is expected to solve the above bottleneck problems. SUMMARY

[0012] The purpose of the present application is to provide a continuous macro-preparation device and method for flexible and elastic ceramic ultrafine fiber material to overcome the above problems existing in the prior art.

[0013] The purpose of the present application can be achieved by the following technical solutions:

[0014] One of the technical solutions of the present application is to provide a continuous macro-preparation device for flexible and elastic ceramic ultrafine fiber material, which includes a feeding and liquid preparation system, a multi-jet uniform electrospinning system, a low-temperature calcination system and a winding system in sequence.

[0015] The feeding and liquid preparation system includes a mixing device, a polymer mixing device and an inorganic component content control device connected in sequence through a liquid conveying pipeline.

[0016] The multi-jet uniform electrospinning system comprises a temperature and humidity control device, a multi-jet electrospinning module electrically connected to the temperature and humidity control device and in communication with the inorganic component content control device, and a solvent vapor removal device.

[0017] The low-temperature calcination system comprises a multi-temperature zone temperature control device, a drying zone, a microwave pretreatment zone, a polymer removal zone, an oxygen-poor atmosphere heat treatment zone, and a cooling zone connected to and independently separated from the multi-temperature zone temperature control device.

[0018] In some embodiments, the mixing device comprises a primary tank, an in-situ infrared analyzer, a viscosity detector, a primary feeding port, a vacuum concentration assembly arranged on the primary tank, a gelation inhibition assembly surrounding the primary tank and the bottom thereof, a primary layered stirring assembly arranged in the primary tank, and a primary flow control valve arranged on the liquid delivery pipeline at the outlet of the mixing device.

[0019] More preferably, the primary layered stirring assembly comprises stirring blades and a motor, the structure of the stirring blades is selected from any one of paddle type, turbine type, propeller type, anchor type, frame type, ribbon type, and screw type, the material of the stirring blades comprises stainless steel, carbon steel, carbon steel lined with rubber, and carbon steel lined with glass fiber reinforced plastic, the rotating speed of the stirring rollers is 50-5000 rpm, the number of stirring layers is 1-5, the number of stirring rollers is 1-5, the material of the stirring rollers comprises stainless steel, carbon steel, rubber, cast iron, and polyurethane, the distance between the stirring rollers is 5-20 cm, and the equivalent diameter is 3-10 cm.

[0020] In some embodiments, the vacuum concentration assembly comprises a vacuum concentrator, a heat exchanger, a condensate tank, and a vacuum pump.

[0021] More preferably, the outer diameter of the primary tank is 30-100 cm, the thickness is 2-35 cm, the height is 60-160 cm, and the material comprises stainless steel, titanium alloy, glass, quartz glass, polytetrafluoroethylene, and nickel-chromium-molybdenum alloy.

[0022] In some embodiments, the gelation inhibition assembly comprises a cold air assembly, a low-temperature pipe connected to the cold air assembly and surrounding the primary tank and the bottom thereof, and a temperature insulation layer arranged outside the low-temperature pipe, and a plurality of air outlets are formed in the low-temperature pipe and penetrate the bottom of the primary tank.

[0023] More preferably, the number of air outlets is 5-20, the diameter of the air outlets is 1-5 cm, and the material comprises stainless steel, galvanized steel, aluminum alloy, polyethylene, and polytetrafluoroethylene.

[0024] As more preferably, the low-temperature pipe has a thickness of 0.2-2 cm and an outer diameter of 2-10 cm, and the low-temperature material includes stainless steel, low-temperature carbon steel, and alloy steel.

[0025] As more preferably, the temperature insulation layer has a thickness of 2-5 cm, and the material of the temperature insulation layer 1053 includes glass fiber, polyurethane foam, rock wool, and aluminum silicate fiber.

[0026] In some embodiments, the polymer mixing device comprises a secondary tank body in communication with the primary tank body, a secondary feeding port, an ultrasonic assembly, a bubble removing assembly provided on the secondary tank body, a secondary layered stirring assembly provided in the secondary tank body, and a secondary flow control valve provided on the liquid delivery pipeline at the outlet of the secondary tank body.

[0027] As more preferably, the secondary layered stirring assembly comprises stirring blades and a motor, the structure of the stirring blades is selected from any one of paddle type, turbine type, propeller type, anchor type, frame type, ribbon type, and screw type, the material of the stirring blades includes stainless steel, carbon steel, carbon steel lined with rubber, and carbon steel lined with glass fiber reinforced plastic, the rotating speed of the stirring rollers is 50-5000 rpm, the number of stirring layers is 1-3, the number of stirring rollers is 1-3, the material of the stirring rollers includes stainless steel, carbon steel, rubber, cast iron, and polyurethane, the distance between the stirring rollers is 5-20 cm, and the equivalent diameter is 3-10 cm.

[0028] As more preferably, the secondary tank body has an outer diameter of 30-100 cm, a thickness of 2-35 cm, and a height of 30-120 cm, and the material includes stainless steel, titanium alloy, glass, quartz glass, polytetrafluoroethylene, polyvinyl chloride, and nickel-chromium-molybdenum alloy.

[0029] In some embodiments, the ultrasonic assembly comprises an ultrasonic signal generator, a transducer, and a variable amplitude device.

[0030] In some embodiments, the inorganic component content control device comprises a tertiary tank body in communication with the secondary tank body, a negative pressure suction assembly and an inorganic component content monitor provided on the tertiary tank body, a tertiary layered stirring assembly provided in the tertiary tank body, and a tertiary flow control valve provided on the liquid delivery pipeline at the outlet of the tertiary tank body.

[0031] As more preferably, the tertiary tank body has an outer diameter of 30-100 cm, a thickness of 2-35 cm, and a height of 30-120 cm, and the material includes stainless steel, titanium alloy, glass, quartz glass, polytetrafluoroethylene, polyvinyl chloride, and nickel-chromium-molybdenum alloy.

[0032] As more preferably, the three-layered stirring assembly comprises stirring blades and a motor, the structure of the stirring blades is selected from any one of paddle type, turbine type, propeller type, anchor type, frame type, ribbon type, screw type, the material of the stirring blades includes but is not limited to stainless steel, carbon steel, carbon steel lined with rubber, carbon steel lined with glass fiber reinforced plastic, the rotating speed of the stirring roller is 50-5000 rpm, the stirring layer is 1-3 layers, the number of the stirring rollers is 1-3, the material of the stirring rollers includes but is not limited to stainless steel, carbon steel, rubber, cast iron, polyurethane, the distance between the stirring rollers is 5-20 cm, and the equivalent diameter is 3-10 cm.

[0033] In some embodiments, the multi-jet electrospinning module comprises a conveying assembly, a plurality of spinnerets arranged above the conveying assembly and in communication with the liquid conveying pipeline, and a plurality of low-curvature liquid surface multi-jet nozzles arranged at the bottom of the spinnerets.

[0034] The conveying assembly comprises a conveying roller and a conveying belt arranged on the conveying roller.

[0035] The spinnerets comprise thickness-compensating spinnerets arranged along the conveying direction of the conveying roller, superfine fiber spinnerets vertically arranged between two adjacent thickness-compensating spinnerets, and the low-curvature liquid surface multi-jet nozzles are arranged at the bottom of the thickness-compensating spinnerets and the superfine fiber spinnerets.

[0036] As more preferably, the length of the superfine fiber spinneret is 80-320 cm, the width is 4-8 cm, the number is 4-16, and the height is 4-8 cm; the material includes stainless steel, titanium alloy, nickel-based alloy, copper alloy, ceramic, tungsten carbide, and platinum.

[0037] The length of the thickness-compensating spinneret is 20-120 cm, the width is 8-24 cm, the number is 4-16, the height of the spinneret is 4-8 cm, and the material includes stainless steel, titanium alloy, nickel-based alloy, copper alloy, ceramic, tungsten carbide, and platinum.

[0038] In some embodiments, the low-curvature liquid surface multi-jet nozzles are arranged in an array, the low-curvature liquid surface multi-jet nozzles comprise dumbbell-shaped liquid outlet channels with a wide upper and lower part and a narrow middle part, cantilever rods horizontally arranged inside the dumbbell-shaped liquid outlet channels, and conductive wires vertically arranged on the cantilever rods and used for electric field strengthening and uniformity.

[0039] As more preferably, the inner diameter of the upper and lower ends of the liquid outlet channel of the low-curvature liquid surface multi-jet nozzle is 1-4 mm, the inner diameter of the middle part of the channel is 0.1-0.9 mm, the included angle between the lower end of the channel and the extension line of the middle part of the channel is 45-90°, and the length of the nozzle is 20-50 mm; the included angle between the low-curvature liquid surface and the nozzle is 10-30°, and the number of single-nozzle jets is 2-30.

[0040] The number of the spinneret of the ultra-fine fiber spinneret is 40-80, the distance between the spinnerets is 20-40mm, and the number of the rows of the spinneret of the ultra-fine fiber spinneret is 1 row;

[0041] The number of the spinneret of the thickness compensation spinneret is 20-40, the distance between the spinnerets is 40-60mm, the number of the liquid outlet spinneret is 10-20, the number of the non-liquid outlet spinneret is 10-20, and the number of the rows of the spinneret of the thickness compensation spinneret is 2-4 rows;

[0042] The array arrangement of the low-radian liquid surface multi-jet spinneret is selected from any one of linear array, rectangular array, circular array, spiral array, triangular array, honeycomb array, random array, staggered array, spherical array and cubic array.

[0043] The height of the conductive wire is 15-45mm, the structure of the conductive wire is selected from any one of needle shape, plate shape, ring shape and column shape, and the material includes stainless steel, copper, aluminum or titanium.

[0044] In some embodiments, the temperature and humidity control device comprises a microprocessor, a temperature and humidity detector electrically connected to the microprocessor and connected to the liquid delivery pipeline, a two-way temperature control pipeline in communication with the ultra-fine fiber spinneret, a wetting device, and a temperature control hollow plate in communication with the two-way temperature control pipeline and located below the conveying belt.

[0045] More preferably, the air flow temperature range of the two-way temperature control pipeline is -20-90℃, the pipeline thickness is 0.3-3cm, the outer diameter is 2-10cm, the temperature range of the temperature control hollow plate is -10-80℃, the thickness is 3-5cm, the length is 5-10cm, the number is 3-10, the plate spacing is 2-10cm, and the material includes stainless steel, carbon steel, galvanized steel and aluminum alloy.

[0046] More preferably, the humidity adjustment range of the wetting device is 10-99%.

[0047] In some embodiments, the solvent vapor removal device comprises a housing in communication with the liquid delivery pipeline, a main air suction pipeline arranged in the inner cavity of the housing, a secondary air suction pipeline arranged on the outer wall of the housing, and a gradient distribution honeycomb partition plate arranged in the main air suction pipeline and the secondary air suction pipeline along the axial direction of the air suction pipeline.

[0048] More preferably, the thickness of the main air suction pipeline is 0.5-2cm, the diameter is 5-20cm, the number is 1-3, and the material includes galvanized steel plate, stainless steel, aluminum alloy and PVC plastic.

[0049] The thickness of the secondary air suction pipe is 0.5-2cm, the diameter is 2-10cm, the number is 2-6, and the material includes galvanized steel sheet, stainless steel, aluminum alloy, PVC plastic;

[0050] The diameter of the gradient distribution honeycomb type separator is 2-20cm.

[0051] In some embodiments, the static electricity elimination and insulation device includes a nozzle insulation base arranged between the spinneret and the low-curvature liquid surface multi-jet nozzle, an insulation plate arranged at both ends of the bottom of the spinneret, a static electricity elimination voltage roller arranged on the conveyor belt, an inner insulation layer arranged on the inner side of the low-curvature liquid surface multi-jet nozzle, and an outer insulation tube arranged on the outer side of the low-curvature liquid surface multi-jet nozzle.

[0052] More preferably, the static electricity elimination voltage roller is provided with 3-10.

[0053] The material of the nozzle insulation base, the inner insulation layer, the outer insulation tube, the insulation plate, and the static electricity elimination voltage roller includes polyformaldehyde, polypropylene, polyethylene, polycarbonate, poly-p-phenyleneterephthalamide, polyvinyl chloride, or polyether ether ketone.

[0054] In some embodiments, the multi-temperature zone temperature control device includes a central processing unit, a temperature sensor, an analog-to-digital converter, a heating element combination distributor electrically connected to the central processing unit, and a heating roller arranged below the drying zone, the microwave pretreatment zone, the polymer removal zone, and the oxygen-poor atmosphere heat treatment zone.

[0055] In some embodiments, the drying zone is provided with a first heating element electrically connected to the multi-temperature zone temperature control device, the microwave pretreatment zone is provided with a microwave generator, a microwave reflector, a second heating element electrically connected to the multi-temperature zone temperature control device, and a waveguide tube in communication with the microwave generator, the polymer removal zone is provided with a third heating element electrically connected to the multi-temperature zone temperature control device, the oxygen-poor atmosphere heat treatment zone is provided with an atmosphere concentration controller, a fourth heating element electrically connected to the multi-temperature zone temperature control device, and a double air cavity supply device electrically connected to the atmosphere concentration controller, and the cooling zone is provided with a fifth heating element electrically connected to the multi-temperature zone temperature control device.

[0056] In some embodiments, the winding system includes a winding support and a winding roller arranged on the winding support.

[0057] More preferably, the material of the winding roller includes aluminum alloy, stainless steel, polypropylene, polyethylene, and carbon fiber, and the diameter is 30-100cm.

[0058] The second technical solution of the present application provides a continuous macro-preparation method of the flexible and elastic ceramic ultra-fine fiber material, based on the continuous macro-preparation device of the flexible and elastic ceramic ultra-fine fiber material in the first technical solution, including the following steps:

[0059] S1, the raw materials are put into the mixing device for mixing, low-temperature dispersion, vacuum concentration, removal of solvent, and a sol is obtained;

[0060] S2, the sol obtained in the step S1 is flowed into the polymer mixing device, mixed, and bubble removal is performed;

[0061] S3, the mixed sol obtained in the step S2 is flowed into the inorganic component content control device, and a spinning solution is obtained through negative pressure suction;

[0062] S4, the spinning solution obtained in the step S3 is flowed into the multi-jet electrospinning module, the temperature, humidity, and multi-directional differential speed during spinning are adjusted and controlled, and a fiber membrane material or a fiber flake material is obtained;

[0063] S5, the fiber material obtained in the step S4 is sequentially conveyed to the drying area, the microwave pretreatment area, the polymer removal area, the oxygen-poor atmosphere heat treatment area, and the cooling area for multi-temperature zone calcination, and a flexible and elastic ceramic ultra-fine fiber material is obtained;

[0064] S6, the flexible and elastic ceramic ultra-fine fiber material obtained in the step S5 is rolled and packaged through the rolling system.

[0065] In some specific embodiments, in the step S1, the inorganic salt, the solvent, and the catalyst are put into the primary tank body, the primary layered stirring assembly is started to stir, the in-situ infrared analyzer and the viscosity detector are started to monitor, the gelation inhibition assembly is started to make the low-temperature inert atmosphere flow around the outer wall of the primary tank body and flow into the primary tank body, and the vacuum concentration assembly is started to perform vacuum concentration, wherein the inert atmosphere is selected from any one or more of nitrogen, helium, neon, argon, krypton, or xenon, the temperature of the inert atmosphere is 5-25℃, and the vacuum degree ranges from -0.01 to -0.1 MPa.

[0066] More preferably, the inorganic salt is selected from any one or more of a silicon salt, a titanium salt, a zirconium salt, or an aluminum salt, wherein:

[0067] The silicon salt is selected from any one or more of tetraethyl orthosilicate, tetra-n-propoxy silane, tetraethoxysilane, or methyl triethoxysilane;

[0068] The titanium salt is selected from any one or more of isopropyl titanate, butyl titanate, titanium propoxide, titanium isopropoxide, titanium n-butoxide, titanium isobutoxide, or titanium n-octoxide;

[0069] The zirconium salt is selected from any one or more of zirconium n-propoxide, zirconium iso-propoxide, zirconium n-butoxide, zirconium iso-butoxide or zirconium n-octoxide;

[0070] The aluminum salt is selected from any one or more of aluminum iso-propoxide, aluminum n-butoxide, aluminum iso-butoxide, aluminum n-propoxide or aluminum ethoxide;

[0071] The inorganic salt component is 20-70wt% of the spinning solution.

[0072] As more preferably, the solvent is selected from any one or more of deionized water, an alcoholic solvent or a non-polar solvent, wherein:

[0073] The alcoholic solvent is selected from any one or more of methanol, ethanol, iso-propanol, butanol, pentanol, hexanol, ethylene glycol, propylene glycol, benzyl alcohol, allyl alcohol or octanol;

[0074] The non-polar solvent is selected from any one or more of carbon tetrachloride, benzene, toluene, dichloromethane, chloroform, diethyl ether, diphenyl ether, ethyl acetate, acetone, tetrahydrofuran, N-methyl pyrrolidone or N,N-dimethylformamide.

[0075] As more preferably, the catalyst is selected from any one or more of oxalic acid, acetic acid, phosphoric acid, hydrofluoric acid or trifluoroacetic acid.

[0076] As more preferably, the spinning solution can be maintained in a non-gel state for 200-400h.

[0077] In some embodiments, at S2, the sol and the polymer obtained from S1 are flowed into a secondary tank, a secondary layered stirring assembly is turned on to stir, an ultrasonic assembly is turned on to mix the sol and the polymer, and a bubble removal assembly is turned on to remove bubbles during mixing, and the ultrasonic assembly has an ultrasonic output frequency range of 20-130kHz.

[0078] As more preferably, the polymer has a molecular weight range of 1-50W, and the polymer is selected from any one or more of polyvinyl alcohol, hydroxypropyl methyl cellulose, polyethylene oxide, polyvinylpyrrolidone, polyacrylonitrile, polylactic acid or polymethyl methacrylate.

[0079] In some embodiments, at S3, the mixed sol obtained from S2 is flowed into a tertiary tank, a tertiary layered stirring assembly is turned on to mix, a negative pressure suction assembly is turned on to make the interior of the tertiary tank a low pressure or negative pressure state to remove the solvent, and an inorganic component content monitor is turned on to monitor.

[0080] As more preferably, the negative pressure suction assembly has a suction pressure range of 0-5MPa.

[0081] More preferably, the viscosity of the spinning solution is 0.1-1000 mPa·s.

[0082] In some embodiments, in the S4 step, the spinning solution obtained in the S3 step is sprayed through a low-curvature liquid surface multi-jet nozzle of a spinneret to a conveying belt for deposition molding, the solvent vapor removal device and the electrostatic elimination and insulation device are turned on, the temperature control device is turned on to control the temperature at the low-curvature liquid surface multi-jet nozzle to be 10-30℃, the temperature at the conveying belt to be 20-50℃, the humidity of the spinning environment to be 10-99%, the movement speed of the ultra-fine fiber spinneret to be 0.4-0.6 m / min, the movement speed of the thickness compensation spinneret to be 0.4-0.6 m / min, and the conveying speed of the conveying roller to be 0.2-0.5 m / min.

[0083] In some embodiments, in the S5 step, the temperature of the drying zone is 180-220℃, the temperature of the microwave pretreatment zone is 350-450℃, the frequency is 300-300000 MHz, the temperature of the polymer removal zone is 550-600℃, the temperature of the oxygen-poor atmosphere heat treatment zone is 700-1200℃, the oxygen concentration is less than 20%, the temperature of the cooling zone is 160-200℃, and the heating temperature of the heating rod is 20-1300℃.

[0084] The preparation method provided by the application is a high-efficiency and stable forming method for ceramic fiber materials, which greatly improves the mechanical properties of ceramic fiber materials and realizes the continuous and large-scale manufacturing of the flexible and elastic ceramic ultra-fine fiber material, wherein:

[0085] (1) In the process of configuring the spinning solution: the in-situ infrared analysis equipment is used to monitor and analyze the hydrolysis-polycondensation reaction rate of the inorganic alkoxide in the large-capacity reaction device online, the viscosity online monitoring equipment is used to detect the sol state in real time, and the online real-time configuration of the sol is realized; the vacuum concentration assembly is used to remove the solvent and promote the forward reaction; the cold gas equipment is used to generate low-temperature inert gas, the cold gas flows around the outer wall of the primary tank, an insulation layer is configured on the outer layer to reduce temperature changes, and the cold gas enters the primary tank to increase the sol flow rate, accelerate the diffusion of components, inhibit sol gelation, and ensure the long-term stability and controllable preparation of the polymer / sol spinning solution.

[0086] (2) In the multi-jet electrospinning process of the spinning solution: the temperature and humidity control device is used to control the spinning environment in the nozzle area and the receiving area, realizing the precise control of the fiber morphology structure; the solvent vapor rapid removal device is set, and the honeycomb type partition is set in the main suction pipeline, reducing the influence of airflow on the jet, realizing the environmental protection and efficient treatment of the solvent; the fiber is subjected to multi-directional differential motion in the jet deposition, the spinneret motion direction and the conveying mechanism motion direction, the entanglement degree of the fiber is controlled, and the controllable formation of the fiber membrane material and the fiber flake material is ensured.

[0087] (3) In the low-temperature calcination process of the ceramic ultra-fine fiber material, the microwave pretreatment area is used, under the dual action of electromagnetic field and heat flow field, the polymer macromolecular long chain is cracked into small molecular short chain, which is helpful for the rapid and sufficient removal of the polymer template; the oxygen-poor atmosphere heat treatment area is used, the oxygen concentration at the grain boundary is reduced, the grain growth is slow, the pore defects in the fiber are reduced, and the densification of the fiber is promoted, so that the ceramic ultra-fine fiber material with soft / poly characteristics is obtained.

[0088] In summary, the preparation method has the following progress:

[0089] (1) Stable storage of inorganic sol: the low-temperature inert atmosphere flows around the outer wall of the primary tank and enters the inside of the primary tank, accelerating the diffusion of the components, thereby inhibiting the instability gelation of the sol.

[0090] (2) Control of the content of inorganic components in the spinning solution: the prepared spinning solution is subjected to negative pressure suction, the overlapping concentration of the polymer concentration is controlled, the solution is monitored in real time by using the inorganic component content monitor, and the polymer / inorganic colloidal particle spinning solution with controllable inorganic component content is obtained.

[0091] (3) Uniform and stable spinning of the multi-jet electrospinning module: by setting the low-arc liquid surface multi-jet nozzle, the number of jet nozzles is increased, the ultra-fine fiber spinneret with multiple low-arc liquid surface multi-jet nozzles and thickness compensation spinneret are configured, and the fibers are uniformly deposited on the conveying belt.

[0092] (4) Control of the morphology of single fiber: by controlling the temperature and humidity of the nozzle area and the receiving area respectively, fibers with different curling degrees are obtained.

[0093] (5) Preparation of various kinds of fiber materials: by the multi-jet electrospinning module, straight fibers or curled fibers are subjected to differential motion in the jet deposition, the spinneret motion direction and the conveying belt motion direction, so as to control the entanglement degree between the fibers, and the fiber membrane material or the fiber flake material can be obtained.

[0094] (6) The rapid removal of polymer template: through setting microwave pretreatment area in low temperature calcination system, under the double action of electromagnetic field and heat flow field, the long chain of polymer macromolecule is cracked into small molecule short chain which is easy to remove, which promotes the rapid and sufficient removal of polymer template.

[0095] (7) The preparation of soft and elastic ceramic ultrafine fiber material; the fiber is calcined under the oxygen-poor atmosphere in the oxygen-poor atmosphere heat treatment area, which reduces the oxygen concentration at the grain boundary, thereby inhibiting the growth of the grain, and promotes the densification of the fiber, the fiber has small grain, many grain boundaries and few pore defects, which is beneficial to the transmission and dissipation of the internal stress of the fiber, and the ceramic ultrafine fiber material exhibits good soft and elastic property. BRIEF DESCRIPTION OF DRAWINGS

[0096] Figure 1 It is a structural schematic view of the application.

[0097] Figure 2 It is a schematic view of low arc liquid surface multi-jet single nozzle.

[0098] The symbols in the figure are as follows:

[0099] 1-mixing device, 101-in-situ infrared analyzer, 102-viscosity detector, 1031-first-stage feeding port, 1032-first-stage tank body, 104-vacuum concentration assembly, 1041-vacuum concentrator, 1042-heat exchanger, 1043-condensate tank, 1044-vacuum pump, 105-gelation inhibition assembly, 1051-cooling gas assembly, 1052-low-temperature pipe, 1053-temperature insulation layer, 1054-jet port, 106-first-stage layered stirring assembly, 107-first-stage flow control valve, 2-polymer mixing device, 2011-second-stage feeding port, 2012-second-stage tank body, 202-ultrasonic assembly, 2021-ultrasonic signal generator, 2022-transducer, 2023-amplifier, 203-bubble removal assembly, 204-second-stage layered stirring assembly, 205-second-stage flow control valve, 3-inorganic component content control device, 301-third-stage layered stirring assembly, 302-negative pressure suction assembly, 303-inorganic component content monitor, 304-third-stage flow control valve, 4-multi-jet electrospinning module, 401-low-arc liquid surface multi-jet nozzle, 4011-dumbbell-shaped flow channel, 4012-conductive wire, 4013-cantilever rod, 4021-spinning plate for ultrafine fibers, 4022-thickness compensation spinning plate, 4023-conveying assembly, 5-temperature and humidity control device, 501-temperature and humidity detector, 502-microprocessor, 503-bidirectional temperature control pipeline, 504-temperature control hollow plate, 505-wetting device, 6-solvent vapor rapid removal device, 601-main air suction pipeline, 602-secondary air suction pipeline, 603-gradient distribution honeycomb partition, 7-static electricity elimination and insulation device, 701-nozzle insulation base, 702-insulation plate, 703-static electricity elimination voltage roller, 704-inner insulation layer, 705-outer insulation pipe, 8-multi-temperature zone temperature control device, 801-heating element combination distributor, 802-temperature sensor, 803-analog-to-digital converter, 804-central processing unit, 805-heating rod, 9-drying zone, 10-microwave pretreatment zone, 1001-microwave generator, 1002-waveguide tube, 1003-microwave reflector, 11-polymer removal zone, 12-oxygen-poor atmosphere heat treatment zone, 1201-double-gas-cavity supply device, 1202-atmosphere concentration controller, 13-cooling zone, 1401-winding roller, 1402-winding support, 15-liquid conveying pipeline. DETAILED DESCRIPTION

[0100] The application will be described in greater detail below with reference to the drawings and specific embodiments. The embodiments are implemented on the premise of the technical solutions of the application, and detailed implementation modes and specific operation processes are given, but the protection scope of the application is not limited to the following embodiments.

[0101] It should be noted that similar labels and letters in the following figures indicate similar items. Therefore, once an item is defined in one figure, it does not need to be further defined and explained in subsequent figures.

[0102] The following detailed description of some embodiments of the present invention is provided in conjunction with the accompanying drawings. Unless otherwise specified, the following embodiments and features can be combined with each other.

[0103] In the following embodiments, unless otherwise specified, the functional components or structures are conventional components or structures used in the art to achieve the corresponding functions. Unless otherwise specified, the raw materials or processing technologies are conventional commercially available raw material products or conventional processing technologies used in the art.

[0104] Example 1:

[0105] like Figure 1 The diagram shows a continuous mass production apparatus for flexible ceramic ultrafine fiber materials, comprising, in sequence, a feeding and dispensing system, a multi-jet uniform electrospinning system, a low-temperature calcination system, and a winding system.

[0106] The feeding and liquid preparation system includes a mixing device 1, a polymer mixing device 2, and an inorganic component content control device 3 connected in series through a liquid delivery pipe 15.

[0107] The multi-jet uniform electrospinning system includes a temperature and humidity control device 5, a multi-jet electrospinning module 4 electrically connected to the temperature and humidity control device 5 and connected to the inorganic component content control device 3, a solvent vapor removal device 6, and an electrostatic elimination and insulation device 7 connected to the multi-jet electrospinning module 4.

[0108] The low-temperature calcination system includes a multi-temperature zone temperature control device 8, a drying zone 9 connected to the multi-temperature zone temperature control device 8 and independently separated from it, a microwave pretreatment zone 10, a polymer removal zone 11, an oxygen-deficient atmosphere heat treatment zone 12, and a cooling zone 13.

[0109] in:

[0110] In the feeding and solution preparation system part, the mixing device 1 comprises a primary tank 1032, an in-situ infrared analyzer 101, a viscosity detector 102, a primary feeding port 1031, a vacuum concentration assembly 104, a gelation inhibition assembly 105 wrapping the primary tank 1032, a primary layered stirring assembly 106 arranged in the primary tank 1032, and a primary flow control valve 107 arranged on the liquid conveying pipeline at the outlet of the mixing device 1. The vacuum concentration assembly 104 comprises a vacuum concentrator 1041, a heat exchanger 1042, a condensate tank 1043, and a vacuum pump 1044. The gelation inhibition assembly 105 comprises a cold gas assembly 1051, a low-temperature pipe 1052 connected to the cold gas assembly 1051 and wrapping the primary tank 1032, a temperature insulation layer 1053 arranged outside the low-temperature pipe 1052, and a plurality of air injection ports 1054 arranged on the low-temperature pipe 1052 and penetrating the bottom of the primary tank 1032. The in-situ infrared analyzer 101 is used to monitor and analyze the hydrolysis-polycondensation reaction rate of inorganic alkoxide in the primary tank 1032 online, and the viscosity detector 102 is used to detect the sol state in real time, so as to realize online and real-time preparation of sol. The vacuum concentration assembly 104 is used to remove solvent and promote the forward reaction. The cold gas assembly 1051 is used to generate low-temperature inert gas, so that the cold gas flows around the outer wall of the primary tank, and the temperature insulation layer is arranged outside to reduce temperature change. Meanwhile, the cold gas enters the primary tank 1032 to increase the flow rate of sol, accelerate the diffusion of components, inhibit the gelation of sol, and ensure the long-term stability and controllable preparation of polymer / sol spinning solution.

[0111] As a preferred technical scheme, the primary layered stirring assembly 106 comprises stirring blades and a motor, the structure of the stirring blades is selected from any one of paddle type, turbine type, propeller type, anchor type, frame type, ribbon type and screw type, the material of the stirring blades comprises stainless steel, carbon steel, carbon steel lined with rubber, and carbon steel lined with glass fiber reinforced plastic, the rotating speed of the stirring rollers is 50-5000 rpm, the number of stirring layers is 1-5, the number of stirring rollers is 1-5, the material of the stirring rollers comprises stainless steel, carbon steel, rubber, cast iron and polyurethane, the distance between the stirring rollers is 5-20 cm, and the equivalent diameter is 3-10 cm. The outer diameter of the primary can 1032 is 30-100 cm, the thickness is 2-35 cm, the height is 60-160 cm, and the material comprises stainless steel, titanium alloy, glass, quartz glass, polytetrafluoroethylene and nickel-chromium-molybdenum alloy. The number of the air injection ports 1054 is 5-20, the diameter of the air injection ports 1054 is 1-5 cm, and the material comprises stainless steel, galvanized steel, aluminum alloy, polyethylene and polytetrafluoroethylene. The thickness of the low-temperature pipe 1052 is 0.2-2 cm, the outer diameter is 2-10 cm, and the material of the low-temperature pipe 1052 comprises stainless steel, low-temperature carbon steel and alloy steel. The thickness of the temperature insulation layer 1053 is 2-5 cm, and the material of the temperature insulation layer 1053 comprises glass fiber, polyurethane foam, rock wool and aluminum silicate fiber.

[0112] The polymer mixing device 2 comprises a secondary can body 2012 in communication with the primary can body 1032, a secondary feeding port 2011, an ultrasonic assembly 202 and a bubble removing assembly 203 arranged on the secondary can body 2012, a secondary layered stirring assembly 204 arranged in the secondary can body 2012, and a secondary flow control valve 205 arranged on the liquid conveying pipeline 15 at the outlet of the secondary can body 2012. The ultrasonic assembly 202 comprises an ultrasonic signal generator 2021, a transducer 2022 and a variable amplitude device 2023.

[0113] As a preferred technical scheme, the secondary layered stirring assembly 204 comprises stirring blades and a motor, the structure of the stirring blades is selected from any one of paddle type, turbine type, propeller type, anchor type, frame type, ribbon type and screw type, the material of the stirring blades comprises stainless steel, carbon steel, carbon steel lined with rubber, and carbon steel lined with glass fiber reinforced plastic, the rotating speed of the stirring rollers is 50-5000 rpm, the number of stirring layers is 1-3, the number of stirring rollers is 1-3, the material of the stirring rollers comprises stainless steel, carbon steel, rubber, cast iron and polyurethane, the distance between the stirring rollers is 5-20 cm, and the equivalent diameter is 3-10 cm. The outer diameter of the secondary can body 2012 is 30-100 cm, the thickness is 2-35 cm, the height is 30-120 cm, and the material comprises stainless steel, titanium alloy, glass, quartz glass, polytetrafluoroethylene, polyvinyl chloride and nickel-chromium-molybdenum alloy.

[0114] The inorganic component content control device 3 comprises a third tank 305 in communication with the secondary tank 2012, a negative pressure suction assembly 302 and an inorganic component content monitor 303 arranged on the third tank 305, a third layered stirring assembly 301 arranged in the third tank 305, and a third flow control valve 304 arranged on the liquid delivery pipeline 15 at the outlet of the third tank 305. The prepared spinning solution is subjected to negative pressure suction, the overlapping concentration of the polymer concentration is controlled, the solution is monitored in real time by the inorganic component content monitor 303, and the polymer / inorganic colloidal particle spinning solution with controllable inorganic component content is obtained.

[0115] As a preferred technical solution, the outer diameter of the third tank 305 is 30-100 cm, the thickness is 2-35 cm, the height is 30-120 cm, and the material includes stainless steel, titanium alloy, glass, quartz glass, polytetrafluoroethylene, polyvinyl chloride, and nickel-chromium-molybdenum alloy. The third layered stirring assembly 301 comprises stirring paddles and a motor. The structure of the stirring paddles is selected from any one of paddle type, turbine type, propeller type, anchor type, frame type, ribbon type, and screw type. The material of the stirring paddles includes but is not limited to stainless steel, carbon steel, carbon steel lined with rubber, and carbon steel lined with glass fiber reinforced plastic. The stirring roller speed is 50-5000 rpm, the stirring layer is 1-3 layers, the number of stirring rollers is 1-3, and the material of the stirring rollers includes but is not limited to stainless steel, carbon steel, rubber, cast iron, and polyurethane. The spacing between the stirring rollers is 5-20 cm, and the equivalent diameter is 3-10 cm.

[0116] In the multi-jet uniform electrospinning system part, the multi-jet electrospinning module 4 comprises a conveying assembly 4023, a plurality of spinnerets located above the conveying assembly 4023 and in communication with the liquid delivery pipeline 15, and a plurality of low-curvature liquid surface multi-jet nozzles 401 arranged at the bottom of the spinnerets.

[0117] The conveying assembly 4023 comprises a conveying roller and a conveying belt arranged on the conveying roller.

[0118] The spinneret comprises a thickness compensation spinneret 4022 arranged along the conveying roller conveying direction, a superfine fiber spinneret 4021 vertically arranged between two adjacent thickness compensation spinnerets 4022, and a low-arc liquid surface multi-jet nozzle 401 arranged at the bottom of the thickness compensation spinneret 4022 and the superfine fiber spinneret 4021. The low-arc liquid surface multi-jet nozzle 401 is arranged in an array, and comprises a dumbbell-shaped liquid outlet channel 4011 which is wide at the top and bottom and narrow in the middle, a cantilever rod 4013 horizontally arranged inside the dumbbell-shaped liquid outlet channel 4011, and a conductive wire 4012 vertically arranged on the cantilever rod 4013 and used for electric field strengthening and uniformity. By arranging the low-arc liquid surface multi-jet nozzle 401, the number of jets of the nozzle is increased, so that the fibers are uniformly deposited on the conveying belt.

[0119] The temperature and humidity control device 5 comprises a microprocessor 502, a temperature and humidity detector 501 electrically connected to the microprocessor 502 and connected to the liquid conveying pipeline 15, a two-way temperature control pipeline 503 in communication with the superfine fiber spinneret 4021, a wet sprayer 505, and a temperature control hollow plate 504 located below the conveying belt and in communication with the two-way temperature control pipeline 503. The temperature and humidity of the nozzle area and the receiving area are controlled by the two-way temperature control pipeline 503 and the wet sprayer 505 respectively, so as to obtain fibers with different degrees of curling.

[0120] The solvent vapor removal device 6 comprises a housing in communication with the liquid conveying pipeline 15, a main air suction pipeline 601 arranged in the inner cavity of the housing, a secondary air suction pipeline 602 arranged on the outer wall of the housing, and a gradient distribution honeycomb type partition plate 603 arranged in the main air suction pipeline 601 and the secondary air suction pipeline 602 along the axial direction of the air suction pipeline.

[0121] The static electricity elimination and insulation device 7 comprises a nozzle insulation base 701 arranged between the spinneret and the low-arc liquid surface multi-jet nozzle 401, an insulation plate 702 arranged at both ends of the bottom of the spinneret, a static electricity elimination roller 703 arranged on the conveying belt, an inner insulation layer 704 and an outer insulation tube 705 arranged on the inner and outer sides of the low-arc liquid surface multi-jet nozzle 401.

[0122] The temperature and humidity control device 5 is used to control the spinning environment in the nozzle area and the receiving area, so as to realize precise control of the fiber morphology structure. The solvent vapor fast removal device 6 is arranged, and the honeycomb type partition plate 603 is arranged in the main air suction pipeline 601 and the secondary air suction pipeline 602, so as to reduce the influence of airflow on the jet, and realize the environmental protection and efficient treatment of the solvent. The fiber performs multi-directional differential motion in the jet deposition direction, the spinneret motion direction, and the conveying mechanism motion direction, so as to control the entanglement degree of the fiber, and ensure the controllable forming of the fiber membrane material and the fiber flake material.

[0123] As a preferred technical scheme, the low-radian liquid surface multi-jet nozzle 401 has an inner diameter of 1-4 mm at the upper and lower ends of the liquid outlet channel, an inner diameter of 0.1-0.9 mm at the middle of the channel, an included angle of 45-90° between the lower end channel and the extension line of the middle of the channel, and a length of 20-50 mm; the included angle between the low-radian liquid surface and the nozzle is 10-30°, and the number of single-nozzle jets is 2-30; the length of the ultra-fine fiber spinneret 4021 is 80-320 cm, the width is 4-8 cm, the number is 4-16, the height is 4-8 cm, and the material includes stainless steel, titanium alloy, nickel-based alloy, copper alloy, ceramic, tungsten carbide, and platinum; the number of nozzles of the ultra-fine fiber spinneret 4021 is 40-80, the nozzle spacing is 20-40 mm, and the number of nozzle arrangement columns on the ultra-fine fiber spinneret 4021 is 1. The length of the thickness compensation spinneret 4022 is 20-120 cm, the width is 8-24 cm, the number is 4-16, the height is 4-8 cm, and the material includes stainless steel, titanium alloy, nickel-based alloy, copper alloy, ceramic, tungsten carbide, and platinum; the number of nozzles of the thickness compensation spinneret 4022 is 20-40, the nozzle spacing is 40-60 mm, the number of liquid outlet nozzles is 10-20, the number of non-liquid outlet nozzles is 10-20, and the number of nozzle arrangement columns on the thickness compensation spinneret 4022 is 2-4. The array arrangement of the low-radian liquid surface multi-jet nozzle 401 is selected from any one of linear array, rectangular array, circular array, spiral array, triangular array, honeycomb array, random array, staggered array, spherical array, and cubic array. The height of the conductive wire 4012 is 15-45 mm, the structure of the conductive wire 4012 is selected from any one of needle-shaped, plate-shaped, ring-shaped, and column-shaped, and the material includes stainless steel, copper, aluminum, or titanium. The air flow temperature range of the two-way temperature control pipeline 503 is -20-90℃, the pipeline thickness is 0.3-3 cm, the outer diameter is 2-10 cm, the temperature range of the temperature control hollow plate is -10-80℃, the thickness is 3-5 cm, the length is 5-10 cm, the number is 3-10, the plate spacing is 2-10 cm, and the material includes stainless steel, carbon steel, galvanized steel, aluminum alloy. The humidity adjustment range of the wet sprayer 505 is 10-99%. The thickness of the main air suction pipeline 601 is 0.5-2 cm, the diameter is 5-20 cm, the number is 1-3, and the material includes galvanized steel plate, stainless steel, aluminum alloy, and PVC plastic. The thickness of the secondary air suction pipeline 602 is 0.5-2 cm, the diameter is 2-10 cm, the number is 2-6, and the material includes galvanized steel plate, stainless steel, aluminum alloy, and PVC plastic. The diameter of the gradient distribution honeycomb type partition plate 603 is 2-20 cm. The number of the static electricity removal voltage rollers 703 is 3-10. The materials of the nozzle insulation base 701, the inner insulation layer 704, the outer insulation tube 705, the insulation plate 702, and the static electricity removal voltage rollers 703 include polyformaldehyde, polypropylene, polyethylene, polycarbonate, poly-p-phenylene terephthalamide, polyvinyl chloride, or polyether ether ketone.

[0124] In the low-temperature calcination system part, the multi-temperature zone temperature control device 8 comprises a heating element combination distributor 801, a temperature sensor 802, an analog-to-digital converter 803, a central processing unit 804, and a heating rod 805 arranged below the drying zone 9, the microwave pretreatment zone 10, the polymer removal zone 11, and the oxygen-poor atmosphere heat treatment zone 12. The drying zone 9 is provided with a first heating element electrically connected to the heating element combination distributor 801, the microwave pretreatment zone 10 is provided with a microwave generator 1001 electrically connected to the central processing unit 804, a microwave reflector 1003, a second heating element electrically connected to the heating element combination distributor 801, and a waveguide 1002 in communication with the microwave generator 1001, the polymer removal zone 11 is provided with a third heating element electrically connected to the heating element combination distributor 801, and the oxygen-poor atmosphere heat treatment zone 12 is provided with an atmosphere concentration controller 1202 electrically connected to the central processing unit 804, a fourth heating element electrically connected to the heating element combination distributor 801, and a double-gas-cavity supply device 1201 electrically connected to the atmosphere concentration controller 1202. The cooling zone 13 is provided with a fifth heating element electrically connected to the heating element combination distributor 801.

[0125] The microwave pretreatment zone 10 is used to crack the long polymer macromolecular chains into small molecular short chains under the dual action of electromagnetic fields and thermal flow fields, which helps to quickly and fully remove the polymer template. The oxygen-poor atmosphere heat treatment zone 12 is used to reduce the oxygen concentration at the grain boundaries, slow down the growth of the crystal grains, reduce the pore defects in the fibers, and promote the densification of the fibers, thereby obtaining ceramic ultra-fine fiber materials with soft and elastic properties.

[0126] The winding system comprises a winding support and a winding roller 1401 arranged on the winding support 1402.

[0127] As a preferred technical solution, the material of the winding roller 1401 comprises aluminum alloy, stainless steel, polypropylene, polyethylene, and carbon fiber, and the diameter is 30-100 cm.

[0128] Embodiment 2

[0129] Based on the continuous macro-preparation device for soft and elastic ceramic ultra-fine fiber materials in Embodiment 1, the present embodiment provides a continuous macro-preparation method for soft and elastic ceramic ultra-fine fiber membrane materials, which comprises the following steps:

[0130] First step: open the first hierarchical stirring assembly 106, set the speed of the first hierarchical stirring roller to 5000 rpm, feed 12 kg of tetraethoxysilane, 2 kg of deionized water, 3.5 kg of ethanol, and 15 g of hydrochloric acid into the first tank 1032 at one time from the first feeding port 1031, open the in-situ infrared analyzer 101 to detect the hydrolysis-polycondensation reaction rate of the alkoxide, open the viscosity detector 102 to detect the sol state in real time, open the vacuum concentration assembly 104 and set the vacuum degree to-0.098 MPa, open the gelation inhibition assembly 105 to regulate the cold air temperature, and make the 20℃ low-temperature helium gas flow around the outer wall of the first tank 1032 and flow into the first tank 1032 from the air outlet 1054 to accelerate the diffusion of each component. The prepared silica sol can be stably stored for 400 hours without gelation.

[0131] Open the second hierarchical stirring assembly 204 and set the speed of the second hierarchical stirring roller to 4900 rpm, open the first flow control valve 107 to make the prepared silica sol flow into the second tank 2012, feed 100,000 molecular weight polyvinyl alcohol into the second tank 2012 through the second feeding port 2011, and open the ultrasonic assembly 22 and the bubble removal assembly 203 to make the output frequency 80 kHz, so that the polymer is fully dissolved in the sol.

[0132] Open the second flow control valve 205 to make the mixed liquid flow into the third tank 305, open the third hierarchical stirring assembly 301 and set the speed of the third hierarchical stirring roller to 4500 rpm, open the negative pressure suction assembly 302, and set the pressure of the suction pump to 3 MPa to remove a large amount of solvent and discharge, and open the inorganic component content monitor 303.

[0133] Second step: make the spinning solution flow into the ultrafine fiber spinneret 4021, the thickness compensation spinneret 4022, and the low-arc liquid surface multi-jet nozzle 401 in sequence through the liquid conveying pipeline 15. The inner diameter of the upper and lower ends of the flow channel in the nozzle is 2 mm, the inner diameter of the middle part of the flow channel is 0.5 mm, the included angle between the lower end of the flow channel and the extension line of the middle part of the flow channel is in the range of 45°, and the length of the nozzle is 45 mm. The height of the conductive wire 4012 is 35 mm, the included angle between the low-arc liquid surface and the nozzle is 30°, the number of single-nozzle jets is 20, the length of the ultrafine fiber spinneret 4021 is 200 cm, the length of the thickness compensation spinneret 4022 is 120 cm, the height of the spinnerets is 6 cm, the number of nozzles on the ultrafine fiber spinneret 4021 is 65, and the nozzle spacing is 26 mm. The number of nozzles on the thickness compensation spinneret 4022 is 40, the nozzle spacing is 25 mm, the number of liquid outlet nozzles is 20, and the number of non-liquid outlet nozzles is 20.

[0134] The transfer roller, the microfiber spinneret 4021 and the thickness compensation spinneret 4022 move along their axial direction, i.e. different directions, at a speed of 0.55 m / min, the transfer roller moves at a speed of 0.45 m / min, the temperature and humidity control device 5 is turned on, the relative humidity of the spinning area is adjusted to 38%, the temperature of the nozzle area is 18℃, and the temperature of the receiving area is 23℃.

[0135] The solvent vapor rapid removal device 6 is turned on to remove the solvent in the spinning area, so that the jet is uniformly and stably deposited, and the number of electrostatic voltage rollers 703 is 5.

[0136] Step 3: The hybrid fiber film is sent into the low-temperature calcination system, the multi-temperature zone temperature control device 8 is turned on, the temperature of the drying zone 9 is set to 180℃, the temperature of the microwave pretreatment zone 10 is set to 400℃, the temperature of the polymer removal zone 11 is set to 600℃, the temperature of the oxygen-poor atmosphere heat treatment zone 12 is 800℃, the oxygen concentration is less than 20%, the temperature of the cooling zone 13 is 200℃, and the frequency of the microwave generator 1001 is set to 300000MHz. The hybrid fiber film after cooling is wound and packaged, and finally a flexible silica fiber film is obtained, with a production capacity of 54m 2 / h.

[0137] Example 3:

[0138] Based on the continuous macro-preparation device for flexible and elastic ceramic microfiber material in Example 1, the present embodiment provides a continuous macro-preparation method for flexible and elastic ceramic microfiber film material, comprising the following steps:

[0139] Step 1: Turn on the first layered stirring assembly 106, set the rotating speed of the first layered stirring roller to 5000 rpm, feed 4 kg of zirconium n-propyl alcohol, 0.3 kg of deionized water, 15 kg of ethanol, and 2.5 kg of acetic acid into the first tank 1032 from the first feeding port 1031 at one time, turn on the in-situ infrared analyzer 101 to detect the hydrolysis-polycondensation reaction rate of the alkoxide, turn on the viscosity detector 102 to detect the sol state in real time, turn on the vacuum concentration assembly 104 and set the vacuum degree to -0.099 MPa, turn on the gelation inhibition assembly 105 to regulate the cold air temperature, so that the 25℃ low-temperature nitrogen gas flows around the outer wall of the first tank 1032 and flows into the first tank 1032 from the air outlet 1054 to accelerate the diffusion of each component. The prepared zirconium sol can be stably stored for 350 hours without gelation.

[0140] Open the secondary layered stirring assembly 204 and set the rotation speed of the secondary layered stirring roller to 4700 rpm, open the primary flow control valve 107 to make the prepared zirconium sol flow into the secondary tank body 2012, feed 150,000 molecular weight polyvinyl alcohol into the secondary tank body 2012 through the secondary feeding port 2011, open the ultrasonic assembly 22 and the bubble removal assembly 203 to make the output frequency 130 kHz, so that the polymer is fully dissolved in the sol.

[0141] Open the secondary flow control valve 205 to make the mixed solution flow into the tertiary tank body 305, open the tertiary layered stirring assembly 301 and set the rotation speed of the tertiary layered stirring roller to 4500 rpm, open the negative pressure suction assembly 302, and set the pressure of the suction pump to 5 MPa to remove a large amount of solvent and discharge, and open the inorganic component content monitor 303.

[0142] Second step: The spinning solution flows into the ultra-fine fiber spinneret 4021, the thickness compensation spinneret 4022 and the low-arc liquid surface multi-jet nozzle 401 in sequence through the liquid conveying pipeline 15. The inner diameter of the upper and lower ends of the flow channel in the nozzle is 3 mm, the inner diameter of the middle part of the flow channel is 0.8 mm, the included angle between the lower end of the flow channel and the extension line of the middle part of the flow channel is 55°, and the length of the nozzle is 40 mm. The height of the conductive wire 4012 is 45 mm, the included angle between the low-arc liquid surface and the nozzle is 15°, and the number of single-nozzle jets is 30. The length of the ultra-fine fiber spinneret 4021 is 320 cm, the length of the thickness compensation spinneret 4022 is 100 cm, and the height of the spinneret is 8 cm. The number of nozzles on the ultra-fine fiber spinneret 4021 is 80, and the nozzle spacing is 35 mm. The number of nozzles on the thickness compensation spinneret 4022 is 20, and the nozzle spacing is 45 mm. Among them, the number of liquid outlet nozzles is 10, and the number of non-liquid outlet nozzles is 10.

[0143] The conveying roller, the ultra-fine fiber spinneret 4021 and the thickness compensation spinneret 4022 move in different directions along their axial directions, the movement speed of the spinneret is 0.45 m / min, and the movement speed of the conveying roller is 0.3 m / min. Open the temperature and humidity control device 5 to adjust the relative humidity of the spinning area to 40%, the temperature of the nozzle area is 20℃, and the temperature of the receiving area is 26℃.

[0144] Open the solvent vapor rapid removal device 6 to remove the solvent in the spinning area, so that the jet flow is uniform and stable deposition. The number of electrostatic voltage rollers 703 is 6.

[0145] Third step: send the hybrid fiber membrane into the low-temperature calcination system, open the multi-temperature zone temperature control device 8, the temperature of the drying zone 9 is set to 200℃, the temperature of the microwave pretreatment zone 10 is set to 450℃, the temperature of the polymer removal zone 11 is set to 550℃, the temperature of the oxygen-poor atmosphere heat treatment zone 12 is 800℃, the oxygen concentration is less than 20%, the temperature of the cooling zone 13 is 200℃, the frequency of the microwave generator 1001 is set to 250000MHz, and the hybrid fiber membrane after cooling is wound and packaged, finally obtaining a flexible zirconium dioxide fiber membrane with a production capacity of 36m 2 / h.

[0146] Example 4

[0147] Based on the continuous macro-preparation device of the flexible and elastic ceramic ultra-fine fiber material of example 1, the present embodiment provides a continuous macro-preparation method of the flexible and elastic ceramic ultra-fine fiber sheet material, which comprises the following steps:

[0148] First step: open the first layered stirring assembly 106, set the rotating speed of the first layered stirring roller to 5000rpm, feed 5kg of aluminum isopropoxide, 2kg of aluminum oxide, 2.5kg of tetraethoxysilane, 3kg of deionized water, 10kg of ethanol and 30g of oxalic acid into the first tank body 1032 from the first feeding port 1031 at one time, open the in-situ infrared analyzer 101 to detect the hydrolysis-polycondensation reaction rate of the alkoxide, open the viscosity detector 102 to detect the sol state in real time, open the vacuum concentration assembly 104 and set the vacuum degree to-0.075MPa, open the gelation inhibition assembly 105 and adjust the cold air temperature to make 16℃ low-temperature neon gas flow around the outer wall of the first tank body 1032 and flow into the first tank body 1032 from the air outlet 1054 to accelerate the diffusion of each component. The prepared mullite sol can be stably stored for 450 hours without gelation.

[0149] Open the second layered stirring assembly 204 and set the rotating speed of the second layered stirring roller to 4500rpm, open the first flow control valve 107 to make the prepared mullite sol flow into the second tank body 2012, feed 40,000 molecular weight polyethylene oxide alcohol into the second tank body 2012 through the second feeding port 2011, open the ultrasonic assembly 22 and the bubble removal assembly 203 to make the output frequency 100kHz, so that the polymer is fully dissolved in the sol.

[0150] Open the second flow control valve 205 to make the mixed solution flow into the third tank body 305, open the third layered stirring assembly 301 and set the rotating speed of the third layered stirring roller to 4000rpm, open the negative pressure suction assembly 302 and set the pressure of the suction pump to 5MPa to remove a large amount of solvent and discharge.

[0151] Second step: the spinning solution flows into the ultra-fine fiber spinneret 4021, the thickness compensation spinneret 4022 and the low-arc liquid surface multi-jet nozzle 401 in sequence through the liquid conveying pipeline 15. The inner diameter of the upper and lower ends of the inner channel of the nozzle is 2.8 mm, the inner diameter of the middle part of the channel is 0.6 mm, the included angle between the lower end of the channel and the extension line of the middle part of the channel is 90°, the length of the nozzle is 47 mm, the height of the conductive wire 4012 is 40 mm, the included angle between the low-arc liquid surface and the nozzle is 20°, and the number of single-nozzle jets is 27. The length of the ultra-fine fiber spinneret 4021 is 240 cm, the length of the thickness compensation spinneret 4022 is 85 cm, and the height of the spinneret is 7 cm. The number of nozzles on the ultra-fine fiber spinneret 4021 is 80, and the nozzle spacing is 25 mm. The number of nozzles on the thickness compensation spinneret 4022 is 20, and the nozzle spacing is 40 mm. Among them, the number of liquid outlet nozzles is 10, and the number of non-liquid outlet nozzles is 10.

[0152] The conveying roller, the ultra-fine fiber spinneret 4021 and the thickness compensation spinneret 4022 move in different directions along their axial directions. The movement speed of the spinneret is 0.45 m / min, and the movement speed of the conveying roller is 0.35 m / min. The temperature and humidity precision control device 5 is turned on to adjust the relative humidity of the spinning area to 42%, the temperature of the nozzle area is 19℃, and the temperature of the receiving area is 40℃.

[0153] The solvent vapor rapid removal device 6 is turned on to remove the solvent in the spinning area to make the jet flow uniform and stable. The number of electrostatic voltage rollers 703 is 5.

[0154] Third step: the hybrid fiber sheet is sent into the low-temperature calcination system. The multi-temperature zone temperature control device 8 is turned on. The temperature of the drying zone 9 is set to 200℃, the temperature of the microwave pretreatment zone 10 is set to 450℃, the temperature of the polymer removal zone 11 is set to 600℃, the temperature of the oxygen-poor atmosphere heat treatment zone 12 is 1200℃, the oxygen concentration is less than 20%, the temperature of the cooling zone 13 is 180℃, and the frequency of the microwave generator 1001 is set to 200000 MHz. The hybrid fiber sheet after cooling is wound and packaged to obtain a flexible mullite fiber sheet with a production capacity of 42m 2 / h.

[0155] Example 5

[0156] Based on the continuous macro-preparation device of the flexible and elastic ceramic ultra-fine fiber material of Example 1, the present embodiment provides a continuous macro-preparation method of a flexible and elastic ceramic ultra-fine fiber sheet material, which comprises the following steps:

[0157] First step: start the first-stage layered stirring assembly 106, set the rotating speed of the first-stage layered stirring roller to 4900 rpm, feed 9 kg of isopropyl titanate, 0.45 kg of deionized water, 1 kg of ethanol and 7.5 kg of acetic acid into the first-stage tank 1032 from the first-stage feeding port 1031 at one time, open the in-situ infrared analyzer 101 to detect the hydrolysis-polycondensation reaction rate of the alkoxide, open the viscosity detector 102 to detect the sol state in real time, open the vacuum concentration assembly 104 and set the vacuum degree to -0.08 MPa, open the gelation inhibition assembly 105 to make 22℃ low-temperature argon flow around the outer wall of the first-stage tank 1032 and flow into the first-stage tank 1032 from the air outlet 1054 to accelerate the diffusion of the components, and the prepared titanium sol can be stably stored for 400 hours without gelation.

[0158] Open the second-stage layered stirring assembly 204 and set the rotating speed of the second-stage layered stirring roller to 5000 rpm, open the first-stage flow control valve 107 to make the prepared titanium sol flow into the second-stage tank 2012, feed 9 kg of polyvinylpyrrolidone with a molecular weight of 90000 into the second-stage tank 2012 through the second-stage feeding port 2011, open the ultrasonic assembly 22 and the bubble removal assembly 203 to make the output frequency 110 kHz, so that the polymer is sufficiently dissolved in the sol.

[0159] Open the second-stage flow control valve 205 to make the mixed solution flow into the third-stage tank 305, open the third-stage layered stirring assembly 301 and set the rotating speed of the third-stage layered stirring roller to 5000 rpm, open the negative pressure suction assembly 302 and set the pressure of the suction pump to 4 MPa to remove a large amount of solvent and discharge.

[0160] Second step: make the spinning solution flow into the superfine fiber spinneret 4021, the thickness compensation spinneret 4022 and the low-arc liquid surface multi-jet nozzle 401 in sequence through the liquid conveying pipeline 15, the inner diameter of the upper and lower ends of the flow channel in the nozzle is 4 mm, the inner diameter of the middle part of the flow channel is 0.9 mm, the included angle between the lower end of the flow channel and the extension line of the middle part of the flow channel is in the range of 80°, and the length of the nozzle is 50 mm. The height of the conductive wire 4012 is 43 mm, the included angle between the low-arc liquid surface and the nozzle is 25°, the number of single-nozzle jets is 23, the length of the superfine fiber spinneret 4021 is 300 cm, the length of the thickness compensation spinneret 4022 is 115 cm, the height of the spinnerets is 6 cm, the number of nozzles on the superfine fiber spinneret 4021 is 70, the nozzle spacing is 40 mm, the number of nozzles on the thickness compensation spinneret 4022 is 25, the nozzle spacing is 45 mm, wherein the number of liquid outlet nozzles is 15, and the number of non-liquid outlet nozzles is 10.

[0161] The transfer roller, the microfiber spinneret 4021 and the thickness compensation spinneret 4022 move along their axial direction, i.e. different directions, at a speed of 0.55 m / min, the transfer roller moves at a speed of 0.4 m / min, the temperature and humidity precision control device 5 is opened, the relative humidity of the spinning area is adjusted to 40%, the temperature of the nozzle area is 23℃, and the temperature of the receiving area is 39℃.

[0162] The solvent vapor rapid removal device 6 is opened to remove the solvent in the spinning area, so that the jet is uniformly and stably deposited, and the number of electrostatic voltage rollers 703 is 7.

[0163] Step 3: Put the hybrid fiber sheet into the low-temperature calcination system, open the multi-temperature zone temperature control device 8, set the temperature of the drying zone 9 to 200℃, the temperature of the microwave pretreatment zone 10 to 400℃, the temperature of the polymer removal zone 11 to 570℃, the temperature of the oxygen-poor atmosphere heat treatment zone 12 to 1000℃, the oxygen concentration to less than 20%, the temperature of the cooling zone 13 to 160℃, and the frequency of the microwave generator 1001 to 300000 MHz. Roll and package the hybrid fiber sheet after cooling, and finally obtain a flexible titanium dioxide fiber sheet with a production capacity of 48 m 2 / h.

[0164] The above description of the embodiments is to facilitate the understanding and use of the invention by those skilled in the art. Those skilled in the art can easily make various modifications to these embodiments and apply the general principles described herein to other embodiments without creative labor. Therefore, the present application is not limited to the above embodiments, and improvements and modifications made by those skilled in the art based on the disclosure of the present application without departing from the scope of the present application should be within the scope of the present application.

Claims

1. A continuous macro-scale production apparatus of a soft-elastic ceramic ultrafine fibrous material, characterized by, It comprises feeding and liquid preparation system, multi-jet uniform electrospinning system, low-temperature calcination system and winding system in sequence. The feeding and liquid preparation system comprises mixing device (1), polymer mixing device (2) and inorganic component content control device (3) connected in sequence through liquid feeding pipeline (15); The multi-jet uniform electrospinning system comprises temperature and humidity control device (5), multi-jet electrospinning module (4) electrically connected with the temperature and humidity control device (5) and communicated with the inorganic component content control device (3), and solvent vapor rapid removal device (6); and static electricity elimination and insulation device (7) connected with the multi-jet electrospinning module (4); The low-temperature calcination system comprises multi-temperature zone temperature control device (8), drying zone (9), microwave pretreatment zone (10), polymer removal zone (11), oxygen-poor atmosphere heat treatment zone (12) and cooling zone (13) connected with the multi-temperature zone temperature control device (8) in sequence and independently separated; The mixing device (1) comprises primary tank body (1032), in-situ infrared analyzer (101), viscosity detector (102), primary feeding port (1031), vacuum concentration assembly (104) arranged on the primary tank body (1032), gelation inhibition assembly (105) wrapping the periphery and bottom of the primary tank body (1032), primary layered stirring assembly (106) arranged in the primary tank body (1032), and primary flow control valve (107) arranged on the liquid feeding pipeline (15) at the outlet of the mixing device (1); The gelation inhibition assembly (105) comprises cold air assembly (1051), low-temperature pipe (1052) connected with the cold air assembly (1051) and surrounding the periphery and bottom of the primary tank body (1032), and temperature insulation layer (1053) arranged outside the low-temperature pipe (1052); a plurality of air injection ports (1054) are formed in the low-temperature pipe (1052) and penetrate the bottom of the primary tank body (1032); The multi-jet electrospinning module (4) comprises conveying assembly (4023), a plurality of spinnerets arranged above the conveying assembly (4023) and communicated with the liquid feeding pipeline (15), and a plurality of low-arc liquid surface multi-jet nozzles (401) arranged at the bottom of the spinnerets; The conveying assembly (4023) comprises conveying roller and conveying belt arranged on the conveying roller; The spinneret comprises thickness compensation spinneret (4022) arranged along the conveying direction of the conveying roller, and ultra-fine fiber spinneret (4021) arranged perpendicularly between adjacent two thickness compensation spinnerets (4022); and the low-arc liquid surface multi-jet nozzle (401) is arranged at the bottom of the thickness compensation spinneret (4022) and the ultra-fine fiber spinneret (4021). The multi-temperature zone temperature control device (8) comprises a central processing unit (804), a temperature sensor (802), an analog-to-digital converter (803), a heating element combined distributor (801) and a heating rod (805) arranged below the drying zone (9), the microwave pretreatment zone (10), the polymer removal zone (11) and the oxygen-poor atmosphere heat treatment zone (12) and electrically connected to the central processing unit (804). The drying zone (9) is provided with a first heating element electrically connected to the multi-temperature zone temperature control device (8), the microwave pretreatment zone (10) is provided with a microwave generator (1001), a microwave reflector (1003), a second heating element electrically connected to the multi-temperature zone temperature control device (8), a waveguide (1002) in communication with the microwave generator (1001), the polymer removal zone (11) is provided with a third heating element electrically connected to the multi-temperature zone temperature control device (8), and the oxygen-poor atmosphere heat treatment zone (12) is provided with an atmosphere concentration controller (1202), a fourth heating element electrically connected to the multi-temperature zone temperature control device (8) and a double-gas-cavity supply device (1201) electrically connected to the atmosphere concentration controller (1202).

2. The apparatus according to claim 1, wherein The polymer mixing device (2) comprises a secondary tank body (2012) in communication with the primary tank body (1032), a secondary feeding port (2011), an ultrasonic assembly (202) and a bubble removing assembly (203) arranged on the secondary tank body (2012), a secondary layered stirring assembly (204) arranged in the secondary tank body (2012), and a secondary flow control valve (205) arranged on the liquid conveying pipeline (15) at the outlet of the secondary tank body (2012).

3. The apparatus according to claim 2, wherein the apparatus is characterized by: The inorganic component content control device (3) comprises a tertiary tank body (305) in communication with the secondary tank body (2012), a negative pressure suction assembly (302) and an inorganic component content monitor (303) arranged on the tertiary tank body (305), a tertiary layered stirring assembly (301) arranged in the tertiary tank body (305), and a tertiary flow control valve (304) arranged on the liquid conveying pipeline (15) at the outlet of the tertiary tank body (305).

4. The apparatus according to claim 1, wherein The low-curvature liquid surface multi-jet nozzle (401) is arranged in an array, and comprises a dumbbell-shaped liquid outlet flow channel (4011) which is wide at the top and bottom and narrow in the middle, a cantilever rod (4013) arranged horizontally in the dumbbell-shaped liquid outlet flow channel (4011), and a conductive wire (4012) arranged vertically on the cantilever rod (4013) and used for electric field strengthening and uniformity. The temperature and humidity control device (5) comprises a microprocessor (502), a temperature and humidity detector (501) electrically connected to the microprocessor (502) and connected to the liquid conveying pipeline (15), a two-way temperature control pipeline (503) in communication with the ultrafine fiber spinneret (4021), a wet sprayer (505), and a temperature control hollow plate (504) in communication with the two-way temperature control pipeline (503) and located below the conveying belt. The solvent vapor rapid removal device (6) comprises a shell in communication with the liquid conveying pipeline (15), a main air suction pipeline (601) arranged in the inner cavity of the shell, a secondary air suction pipeline (602) arranged on the outer wall of the shell, and a gradient distribution honeycomb type partition plate (603) arranged in the main air suction pipeline (601) and the secondary air suction pipeline (602) along the axial direction of the air suction pipeline. The static electricity elimination and insulation device (7) comprises a nozzle insulation base (701) arranged between the spinneret and the low-curvature liquid surface multi-jet nozzle (401), an insulation plate (702) arranged at both ends of the bottom of the spinneret, a static electricity elimination voltage roller (703) arranged on the conveying belt, an inner insulation layer (704) and an outer insulation tube (705) arranged on the inner and outer sides of the low-curvature liquid surface multi-jet nozzle (401).

5. The apparatus according to claim 1, wherein The winding system comprises a winding support (1402) and a winding roller (1401) arranged on the winding support (1402).

6. A continuous macro-scale production method of a soft-elastic ceramic ultrafine fibrous material, characterized by, The continuous macro-preparation device of the flexible and elastic ceramic ultrafine fiber material based on any one of claims 1-5 comprises the following steps: S1, the raw materials are put into the mixing device (1) for mixing, low-temperature dispersion, vacuum concentration, and removal of solvents to obtain a sol; S2, the sol obtained in S1 is flowed into the polymer mixing device (2) for mixing and bubble removal; S3, the mixed sol obtained in S2 is flowed into the inorganic component content control device (3) for negative pressure suction to obtain a spinning solution; S4, the spinning solution obtained in S3 is flowed into the multi-jet electrospinning module (4) to adjust the temperature, humidity, and multi-directional differential speed during spinning to obtain a fiber membrane material or a fiber flake material; S5, the fiber material obtained in S4 is sequentially conveyed to the drying area (9), the microwave pretreatment area (10), the polymer removal area (11), the poor-oxygen atmosphere heat treatment area (12), and the cooling area (13) for multi-temperature zone calcination to obtain a flexible and elastic ceramic ultrafine fiber material; S6, the flexible and elastic ceramic ultrafine fiber material obtained in S5 is wound and packaged by the winding system.

7. The continuous macro-scale production process of a flexible ceramic ultrafine fibrous material according to claim 6, characterized in that, In the S1 step, the inorganic salt, solvent, and catalyst are put into the primary tank body (1032), the primary layered stirring assembly (106) is started to stir, the in-situ infrared analyzer (101) and the viscosity detector (102) are started to monitor, the gelation inhibition assembly (105) is started to make the low-temperature inert atmosphere flow around the outer wall of the primary tank body (1032) and into the primary tank body (1032), and the vacuum concentration assembly (104) is started to concentrate under vacuum. The inert atmosphere is selected from any one or more of nitrogen, helium, neon, argon, krypton, or xenon, and the temperature of the inert atmosphere is 5-25°C. The vacuum degree is in the range of -0.01 to -0.1 MPa. In the S2 step, the sol and polymer obtained in the S1 step are flowed into the secondary tank body (2012), the secondary layered stirring assembly (204) is started to stir, the ultrasonic assembly (202) is started to mix the sol and polymer, and the bubble removal assembly (203) is started to remove bubbles generated during mixing. The ultrasonic output frequency of the ultrasonic assembly (202) is in the range of 20-130 kHz. In the S3 step, the mixed sol obtained in the S2 step is flowed into the tertiary tank body (305), the tertiary layered stirring assembly (301) is started to mix, the negative pressure suction assembly (302) is started to make the inside of the tertiary tank body (305) in a low-pressure or negative-pressure state to remove the solvent, and the inorganic component content monitor (303) is started to monitor. In the S4 step, the spinning solution obtained in the S3 step is sprayed through the low-curvature liquid surface multi-jet nozzle (401) of the spinneret to the conveying belt for deposition molding. The solvent vapor rapid removal device (6) and the static electricity elimination and insulation device (7) are started, and the temperature and humidity control device (5) is started to control the temperature at the low-curvature liquid surface multi-jet nozzle (401) to be 10-30°C, the temperature at the conveying belt to be 20-50°C, the humidity of the spinning environment to be 10-99%, the movement speed of the ultrafine fiber spinneret (4021) to be 0.4-0.6 m / min, the movement speed of the thickness compensation spinneret (4022) to be 0.4-0.6 m / min, and the conveying speed of the conveying roller to be 0.2-0.5 m / min. In the S5 step, the temperature of the drying zone (9) is 180-220°C, the temperature of the microwave pretreatment zone (10) is 350-450°C, the frequency is 300-300000 MHz, the temperature of the polymer removal zone (11) is 550-600°C, the temperature of the oxygen-poor atmosphere heat treatment zone (12) is 700-1200°C, the oxygen concentration is less than 20%, the temperature of the cooling zone (13) is 160-200°C, and the heating temperature of the heating rod (805) is 20-1300°C.

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