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CN-121972193-A - Preparation method of photo-cured 3D printed FCC structure high-flux SiC catalytic membrane

CN121972193ACN 121972193 ACN121972193 ACN 121972193ACN-121972193-A

Abstract

The invention discloses a preparation method of a photo-cured 3D printed FCC structure high-flux SiC catalytic membrane. SiC powder, a catalytic active component, photosensitive resin and the like are used as raw materials to prepare SiC slurry, a photo-curing 3D printing process is adopted to obtain a ceramic membrane green body with an FCC structure, and the high flux SiC catalytic membrane is prepared through a glue discharging, sintering and etching process. The method can successfully prepare the FCC structural ceramic membrane green body by regulating and controlling the components in the slurry to ensure that the slurry shows higher solidification depth and lower solidification width. Meanwhile, the introduced catalytic active component has the catalytic function and the sintering aid function, so that the subsequent sintering temperature is effectively reduced. Finally, the excellent acid and alkali corrosion resistance of the SiC framework material is utilized, and the acid and alkali solution only selectively etches the SiC catalytic film, so that the structure is optimized and the catalytic performance is improved. The prepared SiC catalytic membrane can retain dust and degrade nitrogen oxides, has extremely high gas permeability, and is suitable for being applied to the field of atmospheric pollution treatment.

Inventors

  • ZHONG ZHAOXIANG
  • JIANG RONGKUN
  • ZENG YIQING
  • XING WEIHONG

Assignees

  • 南京工业大学
  • 南京工业大学苏州未来膜技术创新中心

Dates

Publication Date
20260505
Application Date
20260320

Claims (8)

  1. 1. The preparation method of the photo-cured 3D printed FCC structure high-flux SiC catalytic membrane is characterized by comprising the following steps of: A. weighing SiC powder with a certain particle size and a catalytic active component according to a certain proportion, adding photosensitive resin, an auxiliary additive and a photoinitiator, ball-milling for a certain time at a certain rotating speed, uniformly mixing, and then rotating and defoaming to obtain homogeneous SiC slurry; B. Pouring the prepared SiC slurry into a trough of a 3D printer, constructing a digital model of a traditional structure and an FCC structure SiC film through three-dimensional modeling software, setting the thickness of a printed slice and the exposure intensity, and forming a SiC film green body; C. Placing the SiC film green compact in a high-temperature sintering furnace, setting the heating rate and the heat preservation time in the glue discharging and sintering process, and cooling along with the furnace after the sintering is completed to obtain a SiC film material; D. Preparing an acid solution and an alkali solution according to a certain molar ratio, respectively soaking the prepared SiC membrane material in the acid solution and the alkali solution for a certain time, and drying the SiC membrane material subjected to acid treatment at a certain temperature to obtain the SiC catalytic membrane material with enhanced catalytic performance, wherein the SiC membrane material subjected to alkali treatment needs to be washed clean by deionized water and then is dried.
  2. 2. The preparation method of the photo-curing 3D printing FCC structure high-flux SiC catalytic membrane is characterized in that in the step A, the particle size of SiC powder is 10-50 microns, the content of SiC powder is 40-55 wt% of SiC slurry, the catalytic active component is tricobalt tetraoxide, the particle size is 0.5-20 microns, the content of the photo-active component is 1-10 wt% of the SiC slurry, the photosensitive resin is trimethylolpropane triacrylate, hexafunctional polyurethane acrylate and bisphenol A epoxy acrylate, the content of the photosensitive resin is 37-57 wt%, 0-10 wt% and 0-10 wt% of the SiC slurry respectively, the auxiliary additives are BYK-P104S dispersing agent and BYK-045 defoaming agent, the content of the auxiliary additives is 0.5-2 wt% of the SiC slurry, the photo-initiator is 814 photo-initiator and 789 photo-initiator, and the content of the photo-initiator is 0.5-2 wt% of the SiC slurry.
  3. 3. The preparation method of the photo-cured 3D printed FCC structure high-flux SiC catalytic membrane is characterized in that the ball milling mixing rotating speed in the step A is 300-500 rpm, the mixing time is 2-6 h, the SiC slurry defoaming rotating speed is 1000-2000 rpm, and the defoaming time is 0.5-1 h.
  4. 4. The preparation method of the photo-cured 3D printed FCC structure high-flux SiC catalytic membrane is characterized in that a traditional structure constructed by three-dimensional modeling software in the photo-cured 3D printing process in the step B is a uniform microporous structure and has no macroscopic three-dimensional structure, the size of a structural unit in the size of an FCC structural unit is 1.0-5.0 mm, the wall thickness of the structural unit is 0.1-0.5 mm, and the thickness of a separation layer is 50-200 mu m.
  5. 5. The method for preparing the photo-cured 3D printed FCC structure high-flux SiC catalytic film according to claim 1, wherein the slice thickness in the photo-cured 3D printing process in the step B is 10-50 μm, and the exposure intensity is 150-450 mJ/cm 2 .
  6. 6. The preparation method of the photo-curing 3D-printed FCC structure high-flux SiC catalytic film is characterized in that the cleaning agent used in the step B is 1, 6-hexanediol diacrylate, the drying temperature is 60-100 ℃, the drying time is 4-8 h, and the secondary ultraviolet curing time is 15-60 min.
  7. 7. The preparation method of the photo-curing 3D-printed FCC structure high-flux SiC catalytic film is characterized in that the temperature of the glue discharging process in the step C is 600-1000 ℃, the temperature rising rate is 0.5-2 ℃ per minute, the heat preservation time is 2-6 hours, the sintering process temperature is 1100-1400 ℃, the temperature rising rate is 2-3 ℃ per minute, and the heat preservation time is 2-4 hours.
  8. 8. The preparation method of the photo-curing 3D-printed FCC structure high-flux SiC catalytic membrane is characterized in that in the step D, an impregnating acid solution is nitric acid solution, the concentration of the acid solution is 0.5-3 mol/L, the impregnating time is 1-4 h, the drying temperature is 80-140 ℃, the drying time is 12-16 h, an impregnating alkali solution is sodium hydroxide solution, the concentration of the alkali solution is 0.5-3 mol/L, the impregnating time is 1-4 h, the drying temperature is 80-140 ℃, and the drying time is 12-16 h.

Description

Preparation method of photo-cured 3D printed FCC structure high-flux SiC catalytic membrane Technical Field The invention belongs to the field of air pollution control, and particularly relates to a preparation method of a photo-curing 3D-printed FCC structure high-flux SiC catalytic membrane. Background The silicon carbide (SiC) ceramic membrane has important application value in the field of high-temperature flue gas dust removal due to excellent chemical stability, mechanical strength and high-temperature resistance. By introducing the catalytic function into the SiC membrane, dust filtration and catalytic degradation of gas phase pollutants such as nitrogen oxides (NOx), volatile Organic Compounds (VOCs) and the like can be synchronously realized in a single device, so that the industrial tail gas treatment process is greatly simplified. The membrane layer prepared by the traditional extrusion molding technology is a random stacking pore canal, the pore canal has high tortuosity, the intrinsic gas flux is lower, and when the catalytic component is filled in the pore canal, the mass transfer resistance is further increased, so that the high flux application requirement is difficult to meet. In order to break through the above structural limitations, photo-curing 3D printing technology is introduced into the field of ceramic film preparation. The technology can accurately manufacture the SiC ceramic membrane with a regular pore canal structure (such as a three-period minimum curved surface structure), and remarkably reduces the tortuosity of the pore canal, thereby greatly improving the air permeability. The SiC porous ceramic membrane with the characteristics of high precision and high porosity is successfully prepared by the methods disclosed in CN119161204A and CN 119219425A. However, these advanced molding techniques focus mainly on structural optimization of SiC films and do not involve integration of catalytic functions. In the prior art, the co-sintering method can form the catalytic component and the SiC powder at one time, and is an effective way for integrating the filtering and catalytic functions. For example, CN111167491a discloses a method for preparing SiC catalytic films by co-sintering, using in situ generated perovskite phases as binders and catalytically active sources. On the other hand, for SiC films in which the catalytic component has been introduced by the co-sintering method, acid/base etching has proven to be a key and effective performance enhancement measure in order to enhance their catalytic activity. As shown in CN115448726B, more active sites can be exposed by selectively etching the catalytic components in the membrane with an acid solution, forming a nano-scale catalyst, thereby significantly enhancing the degradation efficiency of NOx and VOCs. In view of the foregoing, there is a great need in the art for an innovative method that can systematically integrate the co-sintering of the support framework and the catalytic components, the design of the three-dimensional fine structure, and the enhancement of the etching activity, so as to prepare a new generation of SiC catalytic membrane having both high gas flux and high catalytic activity. Disclosure of Invention The invention aims to provide a preparation method of a photo-cured 3D printed FCC structure high-flux SiC catalytic membrane, which is used for preparing a complex structure green body by introducing catalytic active components into photo-cured slurry and combining a 3D printing technology, and then carrying out co-sintering and acid-base etching treatment, so that the technical problems that the conventional SiC catalytic membrane is low in gas flux and difficult to take into account the catalytic activity and high-flux structure are successfully solved, and the integrated preparation of the complex structure, high in air permeability and high in catalytic activity SiC catalytic membrane is realized. The technical scheme of the invention is as follows: The preparation method of the photo-cured 3D printed FCC structure high-flux SiC catalytic membrane is characterized by comprising the following steps of: A. weighing SiC powder with a certain particle size and a catalytic active component according to a certain proportion, adding photosensitive resin, an auxiliary additive and a photoinitiator, ball-milling for a certain time at a certain rotating speed, uniformly mixing, and then rotating and defoaming to obtain homogeneous SiC slurry; B. Pouring the prepared SiC slurry into a trough of a 3D printer, constructing a digital model of a traditional structure and an FCC structure SiC film through three-dimensional modeling software, setting the thickness of a printed slice and the exposure intensity, and forming a SiC film green body; C. Placing the SiC film green compact in a high-temperature sintering furnace, setting the heating rate and the heat preservation time in the glue discharging and sintering process, a