WO2023050481A1 - 一种抗污染碳化硅陶瓷膜的制备方法及其应用 - Google Patents

一种抗污染碳化硅陶瓷膜的制备方法及其应用 Download PDF

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WO2023050481A1
WO2023050481A1 PCT/CN2021/123547 CN2021123547W WO2023050481A1 WO 2023050481 A1 WO2023050481 A1 WO 2023050481A1 CN 2021123547 W CN2021123547 W CN 2021123547W WO 2023050481 A1 WO2023050481 A1 WO 2023050481A1
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silicon carbide
carbide ceramic
carrier
pollution
membrane
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PCT/CN2021/123547
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French (fr)
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徐慢
朱丽
汪炜
王树林
王颖
王恒
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武汉工程大学
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    • 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
    • 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
    • B01D67/0072—Inorganic membrane manufacture by deposition from the gaseous phase, e.g. sputtering, CVD, PVD
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
    • 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
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/20—Carbon compounds
    • B01J27/22—Carbides
    • B01J27/224—Silicon carbide
    • 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

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  • the invention relates to the field of inorganic membranes, in particular to a preparation method and application of an anti-pollution silicon carbide ceramic membrane.
  • TiO 2 powder is a traditional and commonly used heterogeneous catalytic material, but TiO 2 is an amphoteric oxide, which is easily corroded and unstable in strong acid and strong alkali systems. At present, there is no mature TiO 2 photocatalytic functional membrane separation technology applied in engineering practice in China. The development of high-performance membrane materials has been highly valued worldwide. It has been included in my country's "Strategic Emerging Industries for Accelerated Cultivation and Development” and "Key Fields of High-tech Industrialization for Priority Development”.
  • the purpose of the present invention is to provide an anti-pollution silicon carbide ceramic membrane which not only has the function of membrane separation, but also has catalytic activity, which is expected to solve the membrane fouling behavior in the membrane separation process.
  • a method for preparing an anti-pollution silicon carbide ceramic film comprising the following steps:
  • Carrier pretreatment select silicon carbide ceramic sheet or silicon carbide ceramic tube as the carrier, after the carrier is subjected to anhydrous ethanol ultrasonic vibration treatment, it is washed with deionized water until neutral, and dried;
  • Ventilation reaction place the silicon carbide ceramic sheet or silicon carbide ceramic tube obtained in S2 in a quartz reaction tube, pass nitrogen and hydrogen into the quartz reaction tube for a period of time, and then pass trichloroform under carrier gas conditions
  • the base silane liquid is used for deposition reaction, and after the reaction is completed, an anti-pollution silicon carbide ceramic film can be obtained.
  • the treatment time of anhydrous ethanol ultrasonic shock in S1 is 1 h
  • the drying temperature is 100° C.
  • the drying time is 2 h.
  • Ni(NO 3 ) 2 solution in S2 is a solution with a mass concentration of 10-30%.
  • the temperature condition of the drying treatment is 80°C, and the time condition is 1h, and the temperature condition of the roasting treatment is 300-400°C, and the time condition is 2h.
  • aeration in S3 is as follows: feed N 2 and H 2 into the quartz reaction tube, react at 400-600°C for 1 hour, then raise the temperature to 550-750°C, use H 2 as the carrier gas, Pass trichloromethylsilane liquid into the quartz reaction tube for deposition reaction.
  • the flow rates of N 2 and H 2 in S3 are both 10-30ml/min, the flow rate of trichloromethylsilane liquid is 0.1-3g/min, the temperature conditions of the deposition reaction are 850-1350°C, and the pressure conditions are 10 ⁇ 1000Pa, the deposition time is 0.5 ⁇ 6h.
  • the anti-pollution silicon carbide ceramic membrane obtained by the above-mentioned preparation method of the anti-pollution silicon carbide ceramic membrane.
  • the anti-pollution silicon carbide ceramic membrane has a film thickness of 2-8 ⁇ m and a membrane pore diameter of 10-100 nm.
  • the invention utilizes a chemical vapor deposition (CVD) method to directly synthesize a silicon carbide nanowire film in situ, thereby effectively improving the bonding strength between the silicon carbide nanowire and a carrier.
  • the anti-pollution silicon carbide ceramic film uses silicon carbide nanowires as the functional layer material to form a network structure with staggered pores.
  • the anti-fouling silicon carbide ceramic membrane prepared by this method not only has the function of membrane separation, but also has catalytic activity, which is expected to solve the membrane fouling behavior that occurs during the membrane separation process, and at the same time enhance the removal efficiency of pollutants.
  • Fig. 1 is the XRD pattern that the embodiment 1 of the present invention makes anti-pollution silicon carbide ceramic film
  • Fig. 2 is the actual figure and scanning electron microscope photo of the silicon carbide ceramic sheet (a) and the contaminated silicon carbide ceramic film (b) obtained in Example 1 of the present invention;
  • Fig. 3 is the mass loss rate curve of ⁇ -SiCNWs on the surface of the membrane under different transmembrane pressure differences obtained in Example 1 of the present invention
  • Fig. 4 is the photocatalytic performance evaluation of the anti-pollution silicon carbide ceramic film prepared in Example 1 of the present invention.
  • a method for preparing an anti-pollution silicon carbide ceramic film comprising the following steps:
  • Carrier pretreatment select silicon carbide ceramic sheet or silicon carbide ceramic tube as the carrier, after the carrier is subjected to anhydrous ethanol ultrasonic vibration treatment, it is cleaned with deionized water until neutral, and dried; cleaning with anhydrous ethanol can increase The hydrophilicity of the carrier surface is conducive to the coating of the catalyst in the S2 step.
  • Ventilation reaction place the silicon carbide ceramic sheet or silicon carbide ceramic tube obtained in S2 in a quartz reaction tube, pass nitrogen and hydrogen into the quartz reaction tube for a period of time, and then pass trichloroform under carrier gas conditions
  • the base silane liquid is used for deposition reaction, and after the reaction is completed, an anti-pollution silicon carbide ceramic film can be obtained.
  • the ultrasonic shock treatment time of anhydrous ethanol in S1 is 1 h
  • the drying temperature is 100° C.
  • the drying time is 2 h.
  • the Ni(NO 3 ) 2 solution in S2 is a solution with a mass concentration of 10-30%.
  • the temperature condition of the drying treatment is 80°C and the time condition is 1h
  • the temperature condition of the roasting treatment is 300-400°C and the time condition is 2h.
  • the specific operation of aeration in S3 is as follows: feed N 2 and H 2 into the quartz reaction tube, react at 400-600°C for 1 hour, then raise the temperature to 550-750°C, and use H 2 as the load Gas, and trichloromethylsilane liquid was passed into the quartz reaction tube for deposition reaction.
  • the flow rates of N 2 and H 2 in S3 are both 10-30ml/min, the flow rate of trichloromethylsilane liquid is 0.1-3g/min, the temperature conditions of the deposition reaction are 850-1350°C, and the pressure conditions 10 ⁇ 1000Pa, and the deposition time is 0.5 ⁇ 6h.
  • the anti-pollution silicon carbide ceramic membrane obtained by the above-mentioned preparation method of the anti-pollution silicon carbide ceramic membrane.
  • the anti-pollution silicon carbide ceramic membrane has a film thickness of 2-8 ⁇ m and a membrane pore diameter of 10-100 nm.
  • the anti-pollution silicon carbide ceramic membrane in the present invention, utilizes CVD technology to grow nanowires, and the separation layer is composed of silicon carbide nanowires interlaced to form a porous network structure, with a pore size of 10-100nm and an average pore size of about 40nm, belonging to ultrafiltration membranes scope.
  • a silicon carbide ceramic sheet with an average pore diameter of 3.0 ⁇ m is used as a carrier to prepare an anti-pollution silicon carbide ceramic membrane with a pore diameter ⁇ 100 nm, which includes the following steps:
  • a silicon carbide ceramic sheet with a pore size of 3.0 ⁇ m used as a carrier was ultrasonically oscillated with absolute ethanol for 1 hour, then washed with deionized water until neutral, and dried at 100°C for 2 hours to obtain a processed carrier;
  • Ni(NO 3 ) 2 is formulated into a solution with a mass concentration of 20%, and the Ni(NO 3 ) 2 solution is coated on the pretreated carrier by dip-coating (dipping coating), and the After drying at °C for 1 hour, place it in a muffle furnace and bake at 400 °C for 2 hours.
  • XRD X-ray diffractometer
  • the material was analyzed by Raman spectroscopy (Raman spectrum) and transmission electron microscopy (TEM) to analyze that the black material was silicon carbide nanowires, indicating that an anti-pollution silicon carbide ceramic film ( ⁇ -SiCNWs film) was obtained.
  • the flow rates of N 2 and H 2 are both 20ml/min
  • the flow rate of trichloromethylsilane liquid is 1g/min
  • the deposition temperature is 1050°C
  • the deposition pressure is 500Pa
  • the deposition time is 4h.
  • the silicon carbide nanowires are evenly covered on the ceramic substrate without defects such as cracks and pinholes, and the nanowires are interlaced to form a network structure (wherein, Fig. Contaminated ⁇ -SiCNWs film scanning electron microscope), so the SiC nanowire film has better toughness.
  • the ⁇ -SiCNWs membrane was prepared in situ on the ceramic membrane carrier by CVD method. The mechanical stability of the composite membrane is very important in environmental applications.
  • the photocatalytic performance of the ⁇ -SiCNWs membrane can effectively degrade MO, slow down the membrane fouling caused by MO in situ, and gradually restore the membrane flux to about 110LMH, and due to the synergistic effect of photocatalysis and membrane separation
  • the ⁇ -SiCNWs membrane can achieve 100% removal rate of MO molecules.
  • the surface porosity of the anti-pollution silicon carbide ceramic membrane reaches 50-80%.
  • the average pore diameter of the anti-pollution silicon carbide ceramic membrane measured by the liquid-liquid displacement method is about 40nm, and the thickness of the membrane layer is about 6 ⁇ m.
  • the nanowire and the ceramic substrate are hollow.
  • the combination of the fiber membrane is relatively firm, which can effectively improve the mechanical strength of the composite membrane.
  • a silicon carbide ceramic tube with an average pore diameter of 3.0 ⁇ m is used as a carrier to prepare an anti-pollution silicon carbide ceramic membrane with a pore diameter ⁇ 100 nm, which includes the following steps:
  • the first step the pretreatment of the carrier
  • a silicon carbide ceramic tube with a pore size of 3.0 ⁇ m used as a carrier was ultrasonically oscillated with absolute ethanol for 1 hour, then washed with deionized water until neutral, and dried at 100°C for 2 hours to obtain a processed carrier;
  • Ni(NO 3 ) 2 is formulated into a solution with a mass concentration of 10%, and the Ni(NO 3 ) 2 solution is coated on the pretreated carrier by dip-coating (dipping coating), and the After drying at °C for 1 hour, place it in a muffle furnace and bake at 400 °C for 2 hours. According to X-ray diffractometer (XRD) analysis, it can be seen that this step obtains a silicon carbide ceramic tube loaded with NiO catalyst;
  • the flow rates of N 2 and H 2 are both 100ml/min, the flow rate of trichloromethylsilane liquid is 0.5g/min, the deposition temperature is 1000°C, the deposition pressure is 500Pa, and the deposition time is 2h.
  • the surface porosity of the anti-pollution silicon carbide ceramic membrane reaches 50-80%.
  • the average pore diameter of the membrane measured by the liquid-liquid displacement method is about 40nm, and the pore diameter can be effectively regulated by the CVD reaction time to achieve different targets. for effective removal.

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  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
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Abstract

一种抗污染碳化硅陶瓷膜的制备方法及其应用，涉及无机膜领域。制备方法包括以下步骤：S1、载体的预处理：选取将碳化硅陶瓷片或者碳化硅陶瓷管作为载体，将载体经过无水乙醇超声震荡处理后，用去离子水清洗至中性，烘干；S2、制备负载催化剂的碳化硅陶瓷片或者碳化硅陶瓷管：用浸渍涂覆方法将Ni(NO 3) 2溶液涂覆在经过预处理后的载体上，干燥后焙烧，得到负载氧化镍催化剂的碳化硅陶瓷片或者碳化硅陶瓷管；S3、通气反应：将S2得到的碳化硅陶瓷片或者碳化硅陶瓷管置于石英反应管中，通入氮气和氢气后，在载气条件下通入三氯甲基硅烷液体进行沉积反应，待反应完毕后，即可得到抗污染碳化硅陶瓷膜。

Description

一种抗污染碳化硅陶瓷膜的制备方法及其应用 技术领域
本发明涉及无机膜领域，尤其涉及一种抗污染碳化硅陶瓷膜的制备方法及其应用。
背景技术
随着水污染问题的日趋严峻，膜分离技术在废水处理中的应用已被证明是一种有效的方法。膜分离技术的共同优点是能耗低、分离效率高、操作方便、过程简单、无污染，因而该工艺的研究与应用得到了广泛关注。然而膜分离过程中发生的膜污染现象是制约该工艺发展的瓶颈。具有催化降解有机物及分离功能的催化分离膜的开发备受关注，依靠催化膜与光催化耦合可同时实现水中污染的去除及减缓膜污染的目的。催化分离膜不但具有膜分离功能，同时兼备催化活性，有望解决膜分离过程中发生的膜污染行为，同时强化污染物的去除效率。
TiO 2粉体作为传统且常用的异相催化材料，但TiO 2是两性氧化物，在强酸强碱体系中容易被腐蚀、性能不稳定。目前我国，还没有成熟的TiO 2光催化功能膜分离技术应用于工程实践中。高性能膜材料的开发受到了全球范围的高度重视。已被我国列入“加快培育和发展的战略性新兴产业”与“优先发展的高技术产业化重点领域”。
碳化硅(SiC)在pH0-14范围内表现为化学惰性，与氧化物陶瓷膜，如TiO 2膜相比，SiC陶瓷膜具有明显的耐强酸强碱优势，且SiC作为第三代宽禁带半导体，是一种重要的半导体催化剂材料。由于量子限阈效应，相比于块体β-SiC材 料的带隙2.24ev，β-SiC纳米线具有更为理想的带隙(Eg＝2.5eV)，且具有更强的紫外吸收能力。但碳化硅陶瓷膜由载体、过渡层和活性分离层构成，其传统的制备方法如溶胶凝胶法，大多以粒径递减的粉体、采用重复多次的“成型-烧结”循环工艺，以形成孔径渐小、逐层递变的微结构，制备过程复杂、工序繁琐和条件苛刻导致能耗和成本较高，难以实现可控性规模制备，且制备的膜层与基体的结合力较弱，在使用的过程中膜层容易脱落。
发明内容
本发明的目的在于提供一种不但具有膜分离功能，同时兼备催化活性，有望解决膜分离过程中发生的膜污染行为的抗污染碳化硅陶瓷膜。
一种抗污染碳化硅陶瓷膜的制备方法，包括以下步骤：
S1、载体的预处理：选取碳化硅陶瓷片或者碳化硅陶瓷管作为载体，将载体经过无水乙醇超声震荡处理后，用去离子水清洗至中性，烘干；
S2、制备负载催化剂的碳化硅陶瓷片或者碳化硅陶瓷管：用浸渍涂覆方法将Ni(NO 3) 2溶液涂覆在经过预处理后的载体上，干燥后焙烧，得到负载氧化镍催化剂的碳化硅陶瓷片或者碳化硅陶瓷管；
S3、通气反应：将S2得到的碳化硅陶瓷片或者碳化硅陶瓷管置于石英反应管中，向石英反应管中依次通入氮气和氢气一段时间后，在载气条件下通入三氯甲基硅烷液体进行沉积反应，待反应完毕后，即可得到抗污染碳化硅陶瓷膜。
进一步地，S1中无水乙醇超声震荡处理时间为1h，烘干温度为100℃，烘干时间为2h。
进一步地，S2中Ni(NO 3) 2溶液为质量浓度为10～30％的溶液。
进一步地，S2中，干燥处理的温度条件为80℃，时间条件为1h，焙烧处理 的温度条件为300-400℃，时间条件为2h。
进一步地，S3中通气的具体操作为：向石英反应管中通入N 2和H 2，在400～600℃温度条件下反应1h后，升温至550～750℃，以H 2为载气，向石英反应管中通入三氯甲基硅烷液体进行沉积反应。
进一步地，S3中N 2、H 2的流量均为10～30ml/min，三氯甲基硅烷液体流量为0.1～3g/min，沉积反应的温度条件为为850～1350℃，压力条件为10～1000Pa，沉积时间为0.5～6h。
如上述抗污染碳化硅陶瓷膜的制备方法得到的抗污染碳化硅陶瓷膜。
进一步地，所述抗污染碳化硅陶瓷膜的膜厚2～8μm，膜孔径为10～100nm。
上述抗污染碳化硅陶瓷膜在工业废水处理中的应用。
本发明提供的技术方案带来的有益效果是：
本发明利用化学气相沉积(CVD)方法直接原位合成一层碳化硅纳米线膜，有效提高碳化硅纳米线与载体间的结合强度。抗污染碳化硅陶瓷膜利用碳化硅纳米线作为功能层材料所形成的网状结构具有交错的孔隙。该方法制备的抗污染碳化硅陶瓷膜不但具有膜分离功能，同时兼备催化活性，有望解决膜分离过程中发生的膜污染行为，同时强化污染物的去除效率。
附图说明
图1为本发明实施例1制得抗污染碳化硅陶瓷膜的XRD图；
图2为本发明实施例1制得碳化硅陶瓷片(a)和污染碳化硅陶瓷膜(b)实物图及扫描电镜照片；
图3为本发明实施例1制得抗污染碳化硅陶瓷膜在不同跨膜压差下膜表面β-SiCNWs的质量损失率曲线；
图4为本发明实施例1制得抗污染碳化硅陶瓷膜光催化性能评价。
具体实施方式
为使本发明的目的、技术方案和优点更加清楚，下面将结合附图对本发明实施方式作进一步地描述。
一种抗污染碳化硅陶瓷膜的制备方法，包括以下步骤：
S1、载体的预处理：选取碳化硅陶瓷片或者碳化硅陶瓷管作为载体，将载体经过无水乙醇超声震荡处理后，用去离子水清洗至中性，烘干；利用无水乙醇清洗可以增加载体表面的亲水性，有利于S2步骤中催化剂的涂覆。
S2、制备负载催化剂的碳化硅陶瓷片或者碳化硅陶瓷管：用浸渍涂覆方法将Ni(NO 3) 2溶液涂覆在经过预处理后的载体上，干燥后焙烧，得到负载氧化镍催化剂的碳化硅陶瓷片或者碳化硅陶瓷管，NiO催化剂在载体上分布均匀，且颗粒较小；
S3、通气反应：将S2得到的碳化硅陶瓷片或者碳化硅陶瓷管置于石英反应管中，向石英反应管中依次通入氮气和氢气一段时间后，在载气条件下通入三氯甲基硅烷液体进行沉积反应，待反应完毕后，即可得到抗污染碳化硅陶瓷膜。
在本发明中，S1中无水乙醇超声震荡处理时间为1h，烘干温度为100℃，烘干时间为2h。
在本发明中，S2中Ni(NO 3) 2溶液为质量浓度为10-30％的溶液。
在本发明中，S2中，干燥处理的温度条件为80℃，时间条件为1h，焙烧处理的温度条件为300-400℃，时间条件为2h。
在本发明中，S3中通气的具体操作为：向石英反应管中通入N 2和H 2，在400-600℃温度条件下反应1h后，升温至550-750℃，以H 2为载气，向石英反应管中通入三氯甲基硅烷液体进行沉积反应。
在本发明中，S3中N 2、H 2的流量均为10～30ml/min，三氯甲基硅烷液体流量为0.1～3g/min，沉积反应的温度条件为为850～1350℃，压力条件为10～1000Pa，沉积时间为0.5～6h。
如上述抗污染碳化硅陶瓷膜的制备方法得到的抗污染碳化硅陶瓷膜。
在本发明中，所述抗污染碳化硅陶瓷膜的膜厚2-8μm，膜孔径为10-100nm。
上述抗污染碳化硅陶瓷膜在工业废水处理中的应用。
所述抗污染碳化硅陶瓷膜，本发明是利用CVD技术生长纳米线，分离层由碳化硅纳米线互相交错形成多孔的网络结构，孔径为10-100nm，平均孔径约为40nm，属于超滤膜范围。
<实施例1>
用平均孔径为3.0μm的碳化硅陶瓷片作为载体，制备孔径<100nm的抗污染碳化硅陶瓷膜，其包括以下步骤：
S1、载体的预处理
将作为载体的孔径为3.0μm的碳化硅陶瓷片，用无水乙醇超声震荡1h，然后用去离子水清洗至中性，于100℃条件下烘干处理2h，得到处理好的载体；
S2、将Ni(NO 3) 2配制成质量浓度为20％的溶液，用dip-coating(浸渍涂覆)方法将Ni(NO 3) 2溶液涂覆在经过预处理后的载体上，于80℃条件下干燥1h后，置于马弗炉中于400℃条件下焙烧2h，通过x-射线衍射仪(XRD)分析可知，此步骤得到负载NiO催化剂的碳化硅陶瓷片；
S3、将S2得到的碳化硅陶瓷片置于石英反应管中，向石英反应管中通入N 2和H 2，于500℃条件下对碳化硅陶瓷片进行还原反应1h，以还原碳化硅陶瓷片上负载的催化剂，升温至550-750℃，然后以H 2为载气，向石英反应管中通入三氯甲基硅烷液体，进行沉积反应后，碳化硅陶瓷片载体上沉积了一层黑色 物质，经拉曼光谱分析(Raman spectra)和透射电镜分析(TEM)分析该黑色物质为碳化硅纳米线，表明得到了抗污染碳化硅陶瓷膜(β-SiCNWs膜)。其中，N 2、H 2的流量都为20ml/min，三氯甲基硅烷液体流量为1g/min，沉积温度为1050℃，沉积压力为500Pa，沉积时间为4h，进行沉积反应后，碳化硅陶瓷片载体上沉积了一层黑色物质，经XRD(图1)分析该黑色物质为碳化硅纳米线，在35.8°、41.3°、60.0°、72.0°和75.41°处有五个衍射峰，经过标定发现这些峰位和强度与β-SiC的标准图谱(JCPDS卡No 0029-1129)一致，分别对应于β-SiCNWs的(111)，(200)，(220)，(311)和(222)晶面，并且这几个峰的信号强度都比较强，说明本实施例制得的β-SiCNWs的结晶性非常好。在35.7°、41.5°、60.1°、71.8°和75.5°处存在5个衍射峰，这分别对应α-SiC陶瓷膜载体的(111)，(200)，(220)，(311)和(222)晶面(JCPDS卡号73-1665)。碳化硅纳米线均匀覆盖于陶瓷基底上，无开裂与针孔等缺陷，纳米线之间相互交错形成网络结构(其中，图2a为S1中处理后的碳化硅载体电镜扫描图，图2b为抗污染β-SiCNWs膜的电镜扫描图)，因此该碳化硅纳米线膜具有更好的韧性。采用CVD法在陶瓷膜载体上原位制备β-SiCNWs膜，复合膜的机械稳定性在环境应用中至关重要，β-SiCNWs膜与载体之间应具有较强的结合力，防止在实际应用过程中β-SiCNWs膜从载体上脱落造成二次污染，降低复合膜的分离效率。对于β-SiCNWs膜在不同跨膜压差下的机械稳定性，考察了不同跨膜压差下β-SiCNWs的质量损失情况。从图3可以看出，跨膜压差为0、100MPa、200MPa、300MPa和400MPa时，β-SiCNWs的损失率分别为0、0.65wt.％、0.87wt.％、0.95wt.％和0.97wt.％，且该损失发生在前30min内，之后并未出现β-SiCNWs的继续损失，其原因可能是由于少量β-SiCNWs因结合不牢而被冲刷脱落，纳米线与陶瓷基底结合较牢固，可以有效提高复合膜的机械强度。该膜层具有发达 的空隙结构，使该种陶瓷基纳米线复合分离膜具有高孔隙率，高通量。
通过在模拟太阳光的条件下，光催化过滤降解模拟工业废水甲基橙(MO)溶液评价β-SiCNWs膜的抗污染性能。图4为本实施例制得的β-SiCNWs膜光催化性能评价，结果表明，在实验前60分钟，无光照单一膜过滤阶段，β-SiCNWs膜通量由120LMH下降到92LMH，膜污染严重。开启光照后发现，β-SiCNWs膜的光催化性能可实现对MO的有效降解，原位减缓MO造成的膜污染，使膜通量逐渐恢复到约110LMH，且由于光催化和膜分离的协同作用β-SiCNWs膜可实现对MO分子100％的去除率。
经测量，抗污染碳化硅陶瓷膜的表面孔隙率达到50～80％，利用液液置换法测得抗污染碳化硅陶瓷膜平均孔径为40nm左右，膜层厚度约6μm，纳米线与陶瓷基底中空纤维膜结合较牢固，可以有效提高复合膜的机械强度。
<实施例2>
用平均孔径为3.0μm的碳化硅陶瓷管作为载体，制备孔径<100nm的抗污染碳化硅陶瓷膜，其包括以下步骤：
第一步，载体的预处理
S1、载体的预处理
将作为载体的孔径为3.0μm的碳化硅陶瓷管，用无水乙醇超声震荡1h，然后用去离子水清洗至中性，于100℃条件下烘干处理2h，得到处理好的载体；
S2、将Ni(NO 3) 2配制成质量浓度为10％的溶液，用dip-coating(浸渍涂覆)方法将Ni(NO 3) 2溶液涂覆在经过预处理后的载体上，于80℃条件下干燥1h后，置于马弗炉中于400℃条件下焙烧2h，通过x-射线衍射仪(XRD)分析可知，此步骤得到负载NiO催化剂的碳化硅陶瓷管；
S3、将S2得到的碳化硅陶瓷片置于石英反应管中，向石英反应管中通入N 2和H 2，于400℃条件下对碳化硅陶瓷片进行还原反应1h后，升温至所需的反应温度550℃，以H 2为载气，向石英反应管中通入三氯甲基硅烷液体进行沉积反应，并升温至所需的沉积温度1000℃，沉积反应后，碳化硅陶瓷管载体上沉积了一层黑色物质，将分析，该黑色物质为抗污染碳化硅陶瓷膜。其中，N 2、H 2的流量都为100ml/min，三氯甲基硅烷液体流量为0.5g/min，沉积温度为1000℃，沉积压力为500Pa，沉积时间为2h。
经测量，抗污染碳化硅陶瓷膜的表面孔隙率达到50～80％，利用液液置换法测得膜平均孔径为40nm左右，且该孔径可以通过CVD反应时间进行有效调控，实现对不同目标物进行有效去除。
在本文中，所涉及的前、后、上、下等方位词是以附图中零部件位于图中以及零部件相互之间的位置来定义的，只是为了表达技术方案的清楚及方便。应当理解，所述方位词的使用不应限制本申请请求保护的范围。
在不冲突的情况下，本文中上述实施例及实施例中的特征可以相互结合。
以上所述仅为本发明的较佳实施例，并不用以限制本发明，凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (9)

  1. 一种抗污染碳化硅陶瓷膜的制备方法，其特征在于，包括以下步骤：
    S1、载体的预处理：选取碳化硅陶瓷片或者碳化硅陶瓷管作为载体，将载体经过无水乙醇超声震荡处理后，用去离子水清洗至中性，烘干；
    S2、制备负载催化剂的碳化硅陶瓷片或者碳化硅陶瓷管：用浸渍涂覆方法将Ni(NO 3) 2溶液涂覆在经过预处理后的载体上，干燥后焙烧，得到负载氧化镍催化剂的碳化硅陶瓷片或者碳化硅陶瓷管；
    S3、通气反应：将S2得到的碳化硅陶瓷片或者碳化硅陶瓷管置于石英反应管中，向石英反应管中依次通入氮气和氢气一段时间后，在载气条件下通入三氯甲基硅烷液体进行沉积反应，待反应完毕后，即可得到抗污染碳化硅陶瓷膜。
  2. 根据权利要求1所述一种抗污染碳化硅陶瓷膜的制备方法，其特征在于，S1中无水乙醇超声震荡处理时间为1h，烘干温度为100℃，烘干时间为2h。
  3. 根据权利要求1所述一种抗污染碳化硅陶瓷膜的制备方法，其特征在于，S2中Ni(NO 3) 2溶液为质量浓度为10～30％的溶液。
  4. 根据权利要求1所述一种抗污染碳化硅陶瓷膜的制备方法及其应用，其特征在于，S2中干燥处理的温度条件为80℃，时间条件为1h，焙烧处理的温度条件为300～400℃，时间条件为2h。
  5. 根据权利要求1所述一种抗污染碳化硅陶瓷膜的制备方法及其应用，其特征在于，S3中通气的具体操作为：向石英反应管中通入N 2和H 2，在400～600℃温度条件下反应1h后，升温至550～750℃，以H 2为载气，向石英反应管中通入三氯甲基硅烷液体进行沉积反应。
  6. 根据权利要求5所述一种抗污染碳化硅陶瓷膜的制备方法，其特征在于，S3中N 2、H 2的流量均为10～30ml/min，三氯甲基硅烷液体流量为0.1～3g/min，沉积反应的温度条件为850～1350℃，压力条件为10～1000Pa，沉积时间为0.5～6h。
  7. 如权利要求1-6任一项所述抗污染碳化硅陶瓷膜的制备方法得到的抗污染碳化硅陶瓷膜。
  8. 根据权利要求7所述抗污染碳化硅陶瓷膜，其特征在于，所述抗污染碳化硅陶瓷膜的膜厚2～8μm，膜孔径为10～100nm。
  9. 根据权利要求7或8所述抗污染碳化硅陶瓷膜在工业废水处理中的应用。
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