WO2024036757A1 - 一种微纳复合纤维结构氮化硅基陶瓷分离膜的制备方法及其应用 - Google Patents

一种微纳复合纤维结构氮化硅基陶瓷分离膜的制备方法及其应用 Download PDF

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WO2024036757A1
WO2024036757A1 PCT/CN2022/128948 CN2022128948W WO2024036757A1 WO 2024036757 A1 WO2024036757 A1 WO 2024036757A1 CN 2022128948 W CN2022128948 W CN 2022128948W WO 2024036757 A1 WO2024036757 A1 WO 2024036757A1
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silicon nitride
membrane
micro
based ceramic
fiber structure
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PCT/CN2022/128948
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English (en)
French (fr)
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王俊伟
杨雄
尹良君
慕春红
杨成韬
简贤
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电子科技大学长三角研究院(湖州)
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/02—Inorganic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
    • B01D17/02—Separation of non-miscible liquids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D65/00—Accessories or auxiliary operations, in general, for separation processes or apparatus using semi-permeable membranes
    • B01D65/02—Membrane cleaning or sterilisation ; Membrane regeneration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0039—Inorganic membrane manufacture
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis

Definitions

  • the invention relates to the technical field of ceramic separation membrane preparation, and specifically relates to a preparation method and application of a micro-nano composite fiber structure silicon nitride-based ceramic separation membrane.
  • Membrane separation is a simple and efficient separation technology that separates, purifies, and concentrates target materials under the action of driving force. It is widely used in food processing, chemical production, environmental protection and other industries.
  • the key to membrane separation technology is the selection of membrane materials and membrane structures. Selecting appropriate membrane materials and membrane structures based on different material conditions to be separated is the key to improving membrane separation efficiency.
  • the existing ceramic separation membrane has a relatively large pore structure and low bending strength. It can only intercept micron-sized particles and is difficult to separate smaller particles. At the same time, the separation efficiency is low and the applicable industry range is small.
  • the purpose of the present invention is to solve the existing problems and provide a preparation method and application of a silicon nitride-based ceramic separation membrane with a micro-nano composite fiber structure.
  • a method for preparing a silicon nitride-based ceramic separation membrane with a micro-nano composite fiber structure including the following steps:
  • Step 1 Ultrasonic cleaning and drying of the porous ⁇ -phase silicon nitride-based ceramic membrane
  • Step two impregnate the ⁇ -phase silicon nitride-based ceramic membrane with the catalyst solution and then calcine it at low temperature to form a metal oxide catalyst on the surface of the ceramic grains;
  • Step 3 Place the ⁇ -phase silicon nitride-based ceramic membrane with the catalyst attached and the silicon powder in a high-temperature furnace, and the ceramic membrane is suspended above the silicon powder;
  • Step 4 Pour nitrogen-containing gas into the high-temperature furnace.
  • the nitrogen-containing gas flux is 0.01 to 3 m 3 /h. Heating is performed at a heating rate of 0.5 to 5°C/min.
  • the furnace temperature is heated to 1000 to 1500°C.
  • the silicon powder is Volatilized, the gas phase is transmitted to the surface of ⁇ -phase silicon nitride-based crystal grains. Under the catalysis of its own metal oxide, it reacts with nitrogen-containing gas and grows nano-scale silicon nitride fibers on the surface of the grains. After being kept warm for 0.1 to 4 hours, After natural cooling, a micro-nano composite fiber structure silicon nitride-based ceramic separation membrane was obtained.
  • the preparation material of the ⁇ -phase silicon nitride-based ceramic membrane in step one is any one of silicon nitride, silicon oxynitride, and ⁇ -Sialon ceramic membranes.
  • the catalyst described in step 2 is an inorganic salt containing cobalt or iron, including one or more of cobalt nitrate, iron nitrate, cobalt carbonate, iron carbonate, cobalt hydroxide, and iron hydroxide, and the solvent is water.
  • the concentration of the catalyst solution is 0.01% to saturation concentration.
  • the low-temperature calcination described in step 2 is 300-800°C under air conditions and maintained for 0.2-4 hours.
  • the nitrogen-containing gas passed into the high-temperature furnace in step 4 can be ammonia or a composite gas.
  • the composite gas is a composite gas of nitrogen and hydrogen, in which the hydrogen content is 5%.
  • a micro-nano composite fiber structure silicon nitride-based ceramic separation membrane is used as a membrane separation component in wastewater treatment, oil-water separation treatment, and as a catalyst carrier in the field of catalysis.
  • the prepared silicon nitride-based ceramic separation membrane is a micro-nano composite three-dimensional fiber structure composed of micron-scale fibrous crystal grains and nano-scale fibrous crystal grains. The pore size is reduced to the nanometer level, and the surface is rougher, improving Its separation efficiency in the membrane separation process.
  • This micro-nano composite fiber structure silicon nitride-based ceramic separation membrane has ultra-high bending strength, controllable pore size distribution and surface roughness. As a separation membrane and support, it has high performance in wastewater treatment, oil-water separation and other separation fields. Application prospects.
  • Figure 1 is the SEM morphology of the ⁇ -phase silicon nitride ceramic membrane and the micro-nano composite fiber structure silicon nitride ceramic separation membrane in Example 1 of the present invention
  • Figure 2 is the XRD pattern of the ⁇ -phase silicon nitride ceramic membrane and the micro-nano composite fiber structure silicon nitride ceramic separation membrane in Example 1 of the present invention
  • Figure 3 is the SEM morphology of the micro-nano composite fiber structure silicon nitride ceramic separation membrane in Example 2 of the present invention.
  • Figure 4 is the SEM morphology of the micro-nano composite fiber structure silicon nitride ceramic separation membrane in Example 3 of the present invention.
  • Figure 5 is the SEM morphology of the micro-nano composite fiber structure silicon nitride ceramic separation membrane in Example 4 of the present invention.
  • Figure 6 is the SEM morphology of the micro-nano composite fiber structure silicon nitride ceramic separation membrane in Example 5 of the present invention.
  • Figure 7 is the SEM morphology of the micro-nano composite fiber structure silicon nitride ceramic separation membrane in Example 6 of the present invention.
  • Figure 8 shows the SEM morphology of the micro-nano composite fiber structure silicon nitride ceramic separation membrane in Example 7 of the present invention.
  • Figure 9 is an SEM morphology of the micro-nano composite fiber structure silicon nitride ceramic separation membrane in Example 8 of the present invention.
  • Figure 10 is an SEM morphology of the micro-nano composite fiber structure silicon nitride ceramic separation membrane in Example 9 of the present invention.
  • a method for preparing a silicon nitride-based ceramic separation membrane with a micro-nano composite fiber structure including the following steps: first, a diameter of 20 mm and a thickness of 0.8 mm porous ⁇ -phase silicon nitride ceramic membrane was ultrasonically cleaned in water and dried. Then, a 10 wt% cobalt nitrate aqueous solution was prepared. The cleaned ceramic membrane was immersed in the solution. Ultrasonic treatment allowed the solution to fully enter the membrane pores. The impregnated ceramic membrane is dried and calcined at 400°C1 h;
  • Figure 1 shows the scanning electron microscope image of the ⁇ -phase silicon nitride ceramic membrane and the micro-nano composite fiber structure silicon nitride-based ceramic separation membrane. From Figure 1 (left), it can be seen that the ceramic grains of the ⁇ -phase silicon nitride ceramic membrane are A spatial network structure composed of micron-sized fibers. After a catalytic growth process, nano-scale ceramic fibers grow on the surface of the ceramic grains of the ⁇ -phase silicon nitride ceramic film. Based on the micron-scale spatial network structure, a nano-scale fiber network structure is formed (right in Figure 1) .
  • Figure 2 shows the XRD patterns of the ⁇ -phase silicon nitride ceramic membrane and the micro-nano composite fiber structure silicon nitride-based ceramic separation membrane. From Figure 2, it can be seen that the ⁇ -phase silicon nitride ceramic membrane is pure ⁇ -phase silicon nitride.
  • the micro-nano composite fiber structure silicon nitride-based ceramic separation membrane is based on the ⁇ -silicon nitride phase and the ⁇ -phase silicon nitride nanofibers are grown.
  • a method for preparing a silicon nitride-based ceramic separation membrane with a micro-nano composite fiber structure including the following steps: first, a diameter of 20 mm and a thickness of 0.8 mm porous ⁇ -phase silicon nitride ceramic membrane is ultrasonically cleaned in water and dried; then prepare a 10% cobalt nitrate aqueous solution, immerse the cleaned ceramic membrane into the solution, and use ultrasonic treatment to allow the solution to fully enter the membrane pores, and then immerse the immersed ceramic membrane into the membrane pores. The ceramic membrane is then dried and calcined at 400°C for 1 h;
  • Figure 3 shows a scanning electron microscope image of a silicon nitride-based ceramic separation membrane with a micro-nano composite fiber structure. It can be seen from Figure 3 that after the catalytic growth process, granular particles grew on the surface of the ceramic grains of the ⁇ -phase silicon nitride ceramic membrane. Silicon nitride grains and ⁇ -phase silicon nitride nanofibers are not completely grown.
  • a method for preparing a silicon nitride-based ceramic separation membrane with a micro-nano composite fiber structure including the following steps: first, a diameter of 20 mm and a thickness of 0.8 mm porous ⁇ -phase silicon nitride ceramic membrane is ultrasonically cleaned in water and dried; then prepare a 10% cobalt nitrate aqueous solution, immerse the cleaned ceramic membrane into the solution, and use ultrasonic treatment to allow the solution to fully enter the membrane pores, and then immerse the immersed ceramic membrane into the membrane pores. The ceramic membrane is then dried and calcined at 400°C for 1 h;
  • Figure 4 shows the scanning electron microscope image of the micro-nano composite fiber structure silicon nitride-based ceramic separation membrane. From Figure 4, it can be seen that after the catalytic growth process, the ⁇ phase grew on the surface of the ceramic grains of the ⁇ phase silicon nitride ceramic membrane. Silicon nitride nanofibers have thicker fiber diameters.
  • ⁇ -phase silicon nitride can be grown on the ceramic grain surface of the ⁇ -phase silicon nitride ceramic film. As the temperature increases, ⁇ -phase nitrogen grows. Silicon changes from granular to fibrous, and as the temperature increases, the fibers become thicker.
  • a method for preparing a silicon nitride-based ceramic separation membrane with a micro-nano composite fiber structure including the following steps: first, a diameter of 20 mm and a thickness of 0.8 mm porous ⁇ -phase silicon nitride ceramic membrane is ultrasonically cleaned in water and dried; then prepare a 1% cobalt nitrate aqueous solution, immerse the cleaned ceramic membrane into the solution, and use ultrasonic treatment to allow the solution to fully enter the membrane pores. The ceramic membrane is then dried and calcined at 400°C for 1 h;
  • Figure 5 shows the scanning electron microscope image of the micro-nano composite fiber structure silicon nitride-based ceramic separation membrane. From Figure 5, it can be seen that after the catalytic growth process, the ⁇ phase grew on the surface of the ceramic grains of the ⁇ phase silicon nitride ceramic membrane. For silicon nitride nanofibers, the number of fibers is smaller due to the lower catalyst concentration.
  • a method for preparing a silicon nitride-based ceramic separation membrane with a micro-nano composite fiber structure including the following steps: first, a diameter of 20 mm and a thickness of 0.8 mm porous ⁇ -phase silicon nitride ceramic membrane is ultrasonically cleaned in water and dried; then prepare a 20% cobalt nitrate aqueous solution, immerse the cleaned ceramic membrane into the solution, and use ultrasonic treatment to allow the solution to fully enter the membrane pores. The ceramic membrane is then dried and calcined at 400°C for 1 h;
  • Figure 6 shows a scanning electron microscope image of a silicon nitride-based ceramic separation membrane with a micro-nano composite fiber structure. It can be seen from Figure 6 that after a catalytic growth process, the ⁇ phase grows on the surface of the ceramic grains of the ⁇ phase silicon nitride ceramic membrane. Silicon nitride nanofibers have a larger number of fibers due to the higher catalyst concentration.
  • ⁇ -phase silicon nitride can be grown on the ceramic grain surface of the ⁇ -phase silicon nitride ceramic film under different catalyst concentrations. As the catalyst concentration increases, ⁇ -phase silicon nitride grows. Fiber growth density increases.
  • a method for preparing a silicon nitride-based ceramic separation membrane with a micro-nano composite fiber structure including the following steps: first, a diameter of 20 mm and a thickness of 0.8 mm porous ⁇ -phase silicon nitride ceramic membrane is ultrasonically cleaned in water and dried; then prepare a 10% ferric nitrate aqueous solution, immerse the cleaned ceramic membrane into the solution, and use ultrasonic treatment to allow the solution to fully enter the membrane pores. The ceramic membrane is then dried and calcined at 400°C for 1 h;
  • Figure 7 shows a scanning electron microscope image of a silicon nitride-based ceramic separation membrane with a micro-nano composite fiber structure. From Figure 7, it can be seen that with iron nitrate as the catalyst solvent, iron oxide can also catalyze the formation of ⁇ -phase silicon nitride nanofibers. The growth of the ceramic grain surface of the ⁇ -phase silicon nitride ceramic film forms a micro-nano composite three-dimensional fiber structure composed of micron-scale fibrous grains and nano-scale fibrous grains.
  • both iron and cobalt salt precursors as catalysts can achieve the growth of ⁇ -phase silicon nitride on the surface of ceramic grains of the ⁇ -phase silicon nitride ceramic film.
  • a method for preparing a silicon nitride-based ceramic separation membrane with a micro-nano composite fiber structure including the following steps: first, a diameter of 20 mm and a thickness of 0.8 mm porous ⁇ -phase silicon nitride ceramic membrane is ultrasonically cleaned in water and dried; then prepare a 10% cobalt nitrate aqueous solution, immerse the cleaned ceramic membrane into the solution, and use ultrasonic treatment to allow the solution to fully enter the membrane pores, and then immerse the immersed ceramic membrane into the membrane pores. The ceramic membrane is then dried and calcined at 400°C for 1 h;
  • Figure 8 shows the scanning electron microscope image of the micro-nano composite fiber structure silicon nitride-based ceramic separation membrane. It can be seen from Figure 8 that when the holding time is 1 h, after a catalytic reaction, the ceramic in the ⁇ -phase silicon nitride ceramic membrane ⁇ -phase silicon nitride nanofibers grow on the surface of the crystal grains, forming a micro-nano composite three-dimensional fiber structure composed of micron-scale fibrous crystal grains and nano-scale fibrous crystal grains. In its structure, ⁇ -phase silicon nitride nanofibers are relatively small. short.
  • a method for preparing a silicon nitride-based ceramic separation membrane with a micro-nano composite fiber structure including the following steps: first, a diameter of 20 mm and a thickness of 0.8 mm porous ⁇ -phase silicon nitride ceramic membrane is ultrasonically cleaned in water and dried; then prepare a 10% cobalt nitrate aqueous solution, immerse the cleaned ceramic membrane into the solution, and use ultrasonic treatment to allow the solution to fully enter the membrane pores, and then immerse the immersed ceramic membrane into the membrane pores. The ceramic membrane is then dried and calcined at 400°C for 1 h;
  • Figure 9 shows the scanning electron microscope image of the micro-nano composite fiber structure silicon nitride-based ceramic separation membrane. From Figure 9, it can be seen that when the holding time is 4 h, after a catalytic reaction, the ceramic in the ⁇ -phase silicon nitride ceramic membrane ⁇ -phase silicon nitride nanofibers grow on the surface of the crystal grains. Due to the long heat preservation time, the ⁇ -phase silicon nitride nanofibers completely cover the surface of the ceramic film.
  • ⁇ -phase silicon nitride can be grown on the surface of ceramic grains of ⁇ -phase silicon nitride ceramic films under different heat preservation conditions. As the heat preservation time increases, ⁇ -phase silicon nitride grows. The length of the fiber increases.
  • a method for preparing a silicon nitride-based ceramic separation membrane with a micro-nano composite fiber structure including the following steps: first, a diameter of 20 mm and a thickness of 0.8 mm porous ⁇ -phase silicon nitride ceramic membrane is ultrasonically cleaned in water and dried; then prepare a 10% cobalt nitrate aqueous solution, immerse the cleaned ceramic membrane into the solution, and use ultrasonic treatment to allow the solution to fully enter the membrane pores, and then immerse the immersed ceramic membrane into the membrane pores. The ceramic membrane is then dried and calcined at 400°C for 1 h;
  • Figure 10 shows a scanning electron microscope image of a silicon nitride-based ceramic separation membrane with a micro-nano composite fiber structure. It can be seen from Figure 10 that under high temperature ammonia gas, ⁇ -phase silicon nitride nanofibers can also catalyze the formation of ⁇ -phase silicon nitride nanofibers. The growth of the ceramic grain surface of the ceramic film forms a micro-nano composite three-dimensional fiber structure composed of micron-sized fibrous grains and nano-sized fibrous grains.
  • ⁇ -phase silicon nitride can be grown on the surface of ceramic grains of the ⁇ -phase silicon nitride ceramic film under different nitrogen-containing atmospheres.

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Abstract

一种微纳复合纤维结构氮化硅基陶瓷分离膜的制备方法，包括以下步骤：步骤一，对多孔β相氮化硅基陶瓷膜进行超声清洗和干燥；步骤二，将β相氮化硅基陶瓷膜浸渍催化剂溶液，然后低温煅烧，在陶瓷晶粒表面形成金属氧化物催化剂；步骤三，将附着催化剂的β相氮化硅基陶瓷膜和硅粉置于高温炉中，陶瓷膜悬于硅粉的上方；步骤四，高温炉中通入含氮气体，该含氮气体通量为0.01～3m 3/h，按照0.5～5℃/min的升温速率加热，将炉温加热到1000～1500℃，硅粉挥发，气相传输到β相氮化硅基晶粒表面，在其自身金属氧化物催化作用下，与含氮气体发生反应，在晶粒表面生长纳米级氮化硅纤维，保温0.1～4h后，自然降温，制得微纳复合纤维结构氮化硅基陶瓷分离膜，其作为膜分离组件在废水处理、油水分离处理中的应用，以及作为催化剂载体应用于催化领域。

Description

一种微纳复合纤维结构氮化硅基陶瓷分离膜的制备方法及其应用 技术领域
本发明涉及陶瓷分离膜制备技术领域，具体涉及一种微纳复合纤维结构氮化硅基陶瓷分离膜的制备方法及其应用。
 背景技术
膜分离是一项简单高效的分离技术，在驱动力的作用下对目标物料就行分离、提纯、浓缩，广泛应用于食品加工、化工生产、环境保护等行业。膜分离技术的关键是膜材料和膜结构的选择，根据不同的待分离物料条件，选择合适的膜材料和膜结构，是提高膜分离效率的关键。
 技术问题
现有的陶瓷分离膜其孔结构相对较大，弯曲强度低，只能截留微米级颗粒物，难以分离更小的颗粒物，同时分离效率低，适用的行业范围小。
 技术解决方案
本发明的目的就是为了解决现有问题，而提供一种微纳复合纤维结构氮化硅基陶瓷分离膜的制备方法及其应用。
本发明的技术解决措施如下：
一种微纳复合纤维结构氮化硅基陶瓷分离膜的制备方法，包括以下步骤：
步骤一，对多孔β相氮化硅基陶瓷膜进行超声清洗和干燥；
步骤二，将β相氮化硅基陶瓷膜浸渍催化剂溶液，然后低温煅烧，在陶瓷晶粒表面形成金属氧化物催化剂；
步骤三，将附着催化剂的β相氮化硅基陶瓷膜和硅粉置于高温炉中，陶瓷膜悬于硅粉的上方；
步骤四，高温炉中通入含氮气体，该含氮气体通量为0.01～3m 3/h，按照0.5～5℃/min的升温速率加热，将炉温加热到1000～1500℃，硅粉挥发，气相传输到β相氮化硅基晶粒表面，在其自身金属氧化物催化作用下，与含氮气体发生反应，在晶粒表面生长纳米级氮化硅纤维，保温0.1～4h后，自然降温，制得微纳复合纤维结构氮化硅基陶瓷分离膜。
作为优选，步骤一中β相氮化硅基陶瓷膜的制备材质为氮化硅、氧氮化硅、β-Sialon陶瓷膜中的任一一种。
作为优选，步骤二中所述的催化剂为含有钴或者铁的无机盐，包括硝酸钴、硝酸铁、碳酸钴、碳酸铁、氢氧化钴、氢氧化铁中的一种或几种，溶剂为水，催化剂溶液的浓度为0.01%到饱和浓度。
作为优选，步骤二中所述的低温煅烧为空气条件下300-800℃，保温0.2-4h。
作为优选，所述步骤四中通入高温炉的含氮气体可以为氨气或复合气体，所述复合气体为氮气和氢气的复合气体，其中氢气含量为5%。
一种微纳复合纤维结构氮化硅基陶瓷分离膜作为膜分离组件在废水处理、油水分离处理中的应用，以及作为催化剂载体应用于催化领域。
 有益效果
1、在微米级纤维状晶粒组成的β相氮化硅基陶瓷膜的基础上，通过气相传输和催化反应在陶瓷晶粒表面生长纳米氮化硅纤维，形成微纳复合纤维结构氮化硅基陶瓷分离膜，制备的氮化硅基陶瓷分离膜是由微米级纤维状晶粒和纳米级纤维状晶粒共同组成的微纳复合三维纤维结构，孔径降低到纳米级，表面更加粗糙，提高其在膜分离过程中的分离效率。
2、该微纳复合纤维结构氮化硅基陶瓷分离膜具有超高弯曲强度、可控的孔径分布和表面粗糙度，作为分离膜和支撑体在废水处理、油水分离等分离领域具有较高的应用前景。
 附图说明
图1为本发明实施例1中β相氮化硅陶瓷膜和微纳复合纤维结构氮化硅陶瓷分离膜SEM形貌；
图2为本发明实施例1中β相氮化硅陶瓷膜和微纳复合纤维结构氮化硅陶瓷分离膜XRD图；
图3为本发明实施例2中微纳复合纤维结构氮化硅陶瓷分离膜SEM形貌；
图4为本发明实施例3中微纳复合纤维结构氮化硅陶瓷分离膜SEM形貌；
图5为本发明实施例4中微纳复合纤维结构氮化硅陶瓷分离膜SEM形貌；
图6为本发明实施例5中微纳复合纤维结构氮化硅陶瓷分离膜SEM形貌；
图7为本发明实施例6中微纳复合纤维结构氮化硅陶瓷分离膜SEM形貌；
图8为本发明实施例7中微纳复合纤维结构氮化硅陶瓷分离膜SEM形貌。
图9为本发明实施例8中微纳复合纤维结构氮化硅陶瓷分离膜SEM形貌。
图10为本发明实施例9中微纳复合纤维结构氮化硅陶瓷分离膜SEM形貌。
 本发明的实施方式
下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
除非另有定义，本文所使用的所有的技术和科学术语与属于本发明的技术领域的技术人员通常理解的含义相同。本文中在本发明的说明书中所使用的术语只是为了描述具体的实施例的目的，不是旨在于限制本发明。本文所使用的术语“或/及”包括一个或多个相关的所列项目的任意的和所有的组合。
实施例1
一种微纳复合纤维结构氮化硅基陶瓷分离膜的制备方法，包括以下步骤：首先对直径20 mm厚度0.8 mm的多孔β相氮化硅陶瓷膜在水中进行超声清洗后干燥，然后配置10 wt%的硝酸钴水溶液，将清洗好的陶瓷膜浸渍到溶液中，超声处理让溶液充分进入膜孔道内，将浸渍后的陶瓷膜烘干，并且在400 ℃煅烧1 h；
在高温炉中放置5g硅粉，并将陶瓷膜悬挂在硅粉上方1 cm处，在炉中通入氮气，通量为0.05 m 3/h，以3℃/min的升温速率将炉温加热到1250℃，保温2 h后自然降温，制得微纳复合纤维结构氮化硅基陶瓷分离膜。
如图1所示为β相氮化硅陶瓷膜和微纳复合纤维结构氮化硅基陶瓷分离膜扫描电镜图，由图1（左）可知，β相氮化硅陶瓷膜的陶瓷晶粒为微米级纤维状组成的空间网状结构。经过催化生长过程，在β相氮化硅陶瓷膜的陶瓷晶粒表面生长了纳米级陶瓷纤维，在微米级空间网状结构的基础上，又形成了纳米级纤维网状结构（图1右）。
如图2所示为β相氮化硅陶瓷膜和微纳复合纤维结构氮化硅基陶瓷分离膜的XRD图，由图2可知，β相氮化硅陶瓷膜是纯β相氮化硅，微纳复合纤维结构氮化硅基陶瓷分离膜是在β氮化硅相的基础上生长了α相氮化硅纳米纤维。
实施例2
一种微纳复合纤维结构氮化硅基陶瓷分离膜的制备方法，包括以下步骤：首先对直径20 mm厚度0.8 mm的多孔β相氮化硅陶瓷膜在水中进行超声清洗后干燥；然后配置10%的硝酸钴水溶液，将清洗好的陶瓷膜浸渍到溶液中，超声处理让溶液充分进入膜孔道内，将浸渍后的陶瓷膜烘干，并且在400 ℃煅烧1 h；
在高温炉中放置5g硅粉，并将陶瓷膜悬挂在硅粉上方1 cm处，在炉中通入氮气，通量为0.05 m 3/h，以3℃/min的升温速率将炉温加热到1100℃，保温2 h后自然降温，制得微纳复合纤维结构氮化硅基陶瓷分离膜。
如图3所示为微纳复合纤维结构氮化硅基陶瓷分离膜的扫描电镜图，由图3可知，经过催化生长过程，在β相氮化硅陶瓷膜的陶瓷晶粒表面生长了颗粒状氮化硅晶粒，α相氮化硅纳米纤维未完全生长。
实施例3
一种微纳复合纤维结构氮化硅基陶瓷分离膜的制备方法，包括以下步骤：首先对直径20 mm厚度0.8 mm的多孔β相氮化硅陶瓷膜在水中进行超声清洗后干燥；然后配置10%的硝酸钴水溶液，将清洗好的陶瓷膜浸渍到溶液中，超声处理让溶液充分进入膜孔道内，将浸渍后的陶瓷膜烘干，并且在400 ℃煅烧1 h；
在高温炉中放置5g硅粉，并将陶瓷膜悬挂在硅粉上方1 cm处，在炉中通入氮气，通量为0.05 m 3/h，以3℃/min的升温速率将炉温加热到1400℃，保温2 h后自然降温，制得微纳复合纤维结构氮化硅基陶瓷分离膜。
如图4所示为微纳复合纤维结构氮化硅基陶瓷分离膜的扫描电镜图，由图4可知，经过催化生长过程，在β相氮化硅陶瓷膜的陶瓷晶粒表面生长了α相氮化硅纳米纤维，纤维的直径较粗。
由实施例1，2，3可以发现，在1100-1400 ℃范围内，都能实现在β相氮化硅陶瓷膜的陶瓷晶粒表面生长α相氮化硅，随着温度的增加α相氮化硅由颗粒状转变为纤维状，且温度增加，纤维变粗。
实施例4
一种微纳复合纤维结构氮化硅基陶瓷分离膜的制备方法，包括以下步骤：首先对直径20 mm厚度0.8 mm的多孔β相氮化硅陶瓷膜在水中进行超声清洗后干燥；然后配置1%的硝酸钴水溶液，将清洗好的陶瓷膜浸渍到溶液中，超声处理让溶液充分进入膜孔道内，将浸渍后的陶瓷膜烘干，并且在400 ℃煅烧1 h；
在高温炉中放置5g硅粉，并将陶瓷膜悬挂在硅粉上方1 cm处，在炉中通入氮气，通量为0.05 m 3/h，以3℃/min的升温速率将炉温加热到1250℃，保温2 h后自然降温，制得微纳复合纤维结构氮化硅基陶瓷分离膜。
如图5所示为微纳复合纤维结构氮化硅基陶瓷分离膜的扫描电镜图，由图5可知，经过催化生长过程，在β相氮化硅陶瓷膜的陶瓷晶粒表面生长了α相氮化硅纳米纤维，由于催化剂浓度较低，所以纤维的数量较少。
实施例5
一种微纳复合纤维结构氮化硅基陶瓷分离膜的制备方法，包括以下步骤：首先对直径20 mm厚度0.8 mm的多孔β相氮化硅陶瓷膜在水中进行超声清洗后干燥；然后配置20%的硝酸钴水溶液，将清洗好的陶瓷膜浸渍到溶液中，超声处理让溶液充分进入膜孔道内，将浸渍后的陶瓷膜烘干，并且在400 ℃煅烧1 h；
在高温炉中放置5g硅粉，并将陶瓷膜悬挂在硅粉上方1 cm处，在炉中通入氮气，通量为0.05 m 3/h，以3℃/min的升温速率将炉温加热到1250℃，保温2 h后自然降温，制得微纳复合纤维结构氮化硅基陶瓷分离膜。
如图6所示为微纳复合纤维结构氮化硅基陶瓷分离膜的扫描电镜图，由图6可知，经过催化生长过程，在β相氮化硅陶瓷膜的陶瓷晶粒表面生长了α相氮化硅纳米纤维，由于催化剂浓度较高，所以纤维的数量较多。
由实施例1，4，5可知，不同催化剂浓度条件下都能实现在β相氮化硅陶瓷膜的陶瓷晶粒表面生长α相氮化硅，随着催化剂浓度的增加，α相氮化硅纤维的生长密度增加。
实施例6
一种微纳复合纤维结构氮化硅基陶瓷分离膜的制备方法，包括以下步骤：首先对直径20 mm厚度0.8 mm的多孔β相氮化硅陶瓷膜在水中进行超声清洗后干燥；然后配置10%的硝酸铁水溶液，将清洗好的陶瓷膜浸渍到溶液中，超声处理让溶液充分进入膜孔道内，将浸渍后的陶瓷膜烘干，并且在400 ℃煅烧1 h；
在高温炉中放置5g硅粉，并将陶瓷膜悬挂在硅粉上方1 cm处，在炉中通入氮气，通量为0.05 m 3/h，以3℃/min的升温速率将炉温加热到1250℃，保温2 h后自然降温，制得微纳复合纤维结构氮化硅基陶瓷分离膜。
如图7所示为微纳复合纤维结构氮化硅基陶瓷分离膜的扫描电镜图，由图7可知，在硝酸铁作为催化剂溶剂条件下，氧化铁也能催化α相氮化硅纳米纤维在β相氮化硅陶瓷膜的陶瓷晶粒表面的生长，形成由微米级纤维状晶粒和纳米级纤维状晶粒共同组成的微纳复合三维纤维结构。
由实施例1，6可知，铁和钴盐前驱体作为催化剂，都能实现在β相氮化硅陶瓷膜的陶瓷晶粒表面生长α相氮化硅。
实施例7
一种微纳复合纤维结构氮化硅基陶瓷分离膜的制备方法，包括以下步骤：首先对直径20 mm厚度0.8 mm的多孔β相氮化硅陶瓷膜在水中进行超声清洗后干燥；然后配置10%的硝酸钴水溶液，将清洗好的陶瓷膜浸渍到溶液中，超声处理让溶液充分进入膜孔道内，将浸渍后的陶瓷膜烘干，并且在400 ℃煅烧1 h；
在高温炉中放置5g硅粉，并将陶瓷膜悬挂在硅粉上方1 cm处，在炉中通入氮气，通量为0.05 m 3/h，以3℃/min的升温速率将炉温加热到1250℃，保温1 h后自然降温，制得微纳复合纤维结构氮化硅基陶瓷分离膜。
如图8所示为微纳复合纤维结构氮化硅基陶瓷分离膜的扫描电镜图，由图8可知，在保温时间为1 h时，经过催化反应，在β相氮化硅陶瓷膜的陶瓷晶粒表面的生长了α相氮化硅纳米纤维，形成由微米级纤维状晶粒和纳米级纤维状晶粒共同组成的微纳复合三维纤维结构，其结构中α相氮化硅纳米纤维较短。
实施例8
一种微纳复合纤维结构氮化硅基陶瓷分离膜的制备方法，包括以下步骤：首先对直径20 mm厚度0.8 mm的多孔β相氮化硅陶瓷膜在水中进行超声清洗后干燥；然后配置10%的硝酸钴水溶液，将清洗好的陶瓷膜浸渍到溶液中，超声处理让溶液充分进入膜孔道内，将浸渍后的陶瓷膜烘干，并且在400 ℃煅烧1 h；
在高温炉中放置5g硅粉，并将陶瓷膜悬挂在硅粉上方1 cm处，在炉中通入氮气，通量为0.05 m 3/h，以3℃/min的升温速率将炉温加热到1250℃，保温4 h后自然降温，制得微纳复合纤维结构氮化硅基陶瓷分离膜。
如图9所示为微纳复合纤维结构氮化硅基陶瓷分离膜的扫描电镜图，由图9可知，在保温时间为4 h时，经过催化反应，在β相氮化硅陶瓷膜的陶瓷晶粒表面的生长了α相氮化硅纳米纤维，由于保温时间较长，α相氮化硅纳米纤维完全覆盖了陶瓷膜表面。
由实施例1，7，8可知，不同的保温条件下都能实现在β相氮化硅陶瓷膜的陶瓷晶粒表面生长α相氮化硅，随着保温时间的增加，α相氮化硅纤维的长度增加。
实施例9
一种微纳复合纤维结构氮化硅基陶瓷分离膜的制备方法，包括以下步骤：首先对直径20 mm厚度0.8 mm的多孔β相氮化硅陶瓷膜在水中进行超声清洗后干燥；然后配置10%的硝酸钴水溶液，将清洗好的陶瓷膜浸渍到溶液中，超声处理让溶液充分进入膜孔道内，将浸渍后的陶瓷膜烘干，并且在400 ℃煅烧1 h；
在高温炉中放置5g硅粉，并将陶瓷膜悬挂在硅粉上方1 cm处，在炉中通入氨气，通量为0.05 m 3/h，以3℃/min的升温速率将炉温加热到1250℃，保温2 h后自然降温，制得微纳复合纤维结构氮化硅基陶瓷分离膜。
如图10所示为微纳复合纤维结构氮化硅基陶瓷分离膜的扫描电镜图，由图10可知，在氨气高温下，也能催化α相氮化硅纳米纤维在β相氮化硅陶瓷膜的陶瓷晶粒表面的生长，形成由微米级纤维状晶粒和纳米级纤维状晶粒共同组成的微纳复合三维纤维结构。
由实施例1，9可知，不同含氮气氛下，都能实现在β相氮化硅陶瓷膜的陶瓷晶粒表面生长α相氮化硅。
以上所述只是用于理解本发明的方法和核心思想，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，可以对本发明进行若干改进和修饰，这些改进和修饰也落入本发明权利的保护范围。

Claims (6)

  1. 一种微纳复合纤维结构氮化硅基陶瓷分离膜的制备方法，其特征在于，包括以下步骤：
    步骤一，对多孔β相氮化硅基陶瓷膜进行超声清洗和干燥；
    步骤二，将β相氮化硅基陶瓷膜浸渍催化剂溶液，然后低温煅烧，在陶瓷晶粒表面形成金属氧化物催化剂；
    步骤三，将附着催化剂的β相氮化硅基陶瓷膜和硅粉置于高温炉中，陶瓷膜悬于硅粉的上方；
    步骤四，高温炉中通入含氮气体，该含氮气体通量为0.01～3m 3/h，按照0.5～5℃/min的升温速率加热，将炉温加热到1000～1500℃，硅粉挥发，气相传输到β相氮化硅基晶粒表面，在其自身金属氧化物催化作用下，与含氮气体发生反应，在晶粒表面生长纳米级氮化硅纤维，保温0.1～4h后，自然降温，制得微纳复合纤维结构氮化硅基陶瓷分离膜。
  2. 根据权利要求1所述的微纳复合纤维结构氮化硅基陶瓷分离膜的制备方法，其特征在于：步骤一中β相氮化硅基陶瓷膜的制备材质为氮化硅、氧氮化硅、β-Sialon陶瓷膜中的任一一种。
  3. 根据权利要求1所述的微纳复合纤维结构氮化硅基陶瓷分离膜的制备方法，其特征在于：步骤二中所述的催化剂为含有钴或者铁的无机盐，包括硝酸钴、硝酸铁、碳酸钴、碳酸铁、氢氧化钴、氢氧化铁中的一种或几种，溶剂为水，催化剂溶液的浓度为0.01%到饱和浓度。
  4. 根据权利要求1所述的微纳复合纤维结构氮化硅基陶瓷分离膜的制备方法，其特征在于：步骤二中所述的低温煅烧为空气条件下300-800℃，保温0.2-4h。
  5. 根据权利要求1所述的微纳复合纤维结构氮化硅基陶瓷分离膜的制备方法，其特征在于：所述步骤四中通入高温炉的含氮气体可以为氨气或复合气体，所述复合气体为氮气和氢气的复合气体，其中氢气含量为5%。
  6. 一种根据权利要求1-5任一项所述制备方法制备的微纳复合纤维结构氮化硅基陶瓷分离膜作为膜分离组件在废水处理、油水分离处理中的应用，以及作为催化剂载体应用于催化领域。
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