CN114085082B - 一种碳化硅/黑滑石复合陶瓷膜支撑体及其制备方法 - Google Patents

一种碳化硅/黑滑石复合陶瓷膜支撑体及其制备方法 Download PDF

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CN114085082B
CN114085082B CN202111399713.6A CN202111399713A CN114085082B CN 114085082 B CN114085082 B CN 114085082B CN 202111399713 A CN202111399713 A CN 202111399713A CN 114085082 B CN114085082 B CN 114085082B
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silicon carbide
ceramic membrane
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membrane support
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CN114085082A (zh
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张国亮
尹敏
孟琴
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Zhejiang University of Technology ZJUT
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Abstract

本发明公开了一种碳化硅/黑滑石复合陶瓷膜支撑体及其制备方法，该支撑体原料按以下重量份数组成：碳化硅粉5‑20质量份、黑滑石粉5‑10质量份、烧结助剂2‑5质量份、造孔剂1‑5质量份、粘结剂0.01‑0.3质量份、分散剂0.01‑0.1质量份。本发明中使用的黑滑石，其主要化学成分为氧化镁、氧化硅、氧化铝等可起到烧结助剂的作用，能够降低支撑体的烧结温度。本发明可以克服碳化硅陶瓷膜支撑体制备过程中存在烧结温度过高的问题；制备的碳化硅/黑滑石复合陶瓷膜支撑体产品的通量大，机械强度高，同时能够显著降低其生产成本，应用前景广阔。

Description

一种碳化硅/黑滑石复合陶瓷膜支撑体及其制备方法
技术领域
本发明属于陶瓷膜技术领域，具体涉及一种碳化硅/黑滑石复合陶瓷膜支撑体及其制备方法。
背景技术
随着各国政府对废水排放及原油采收率的要求日渐严格，碳化硅陶瓷膜由于具有膜通量大、可清洗性强、使用寿命长、耐高温高压、耐化学腐蚀、化学稳定性高、机械强度高、孔隙率高等优点，在水处理应用方面凸显出较大优势。在最近几年，以丹麦Liqtech为代表的商用碳化硅陶瓷膜开始在高温气固分离，工业废水处理等方面崭露头角，碳化硅陶瓷膜有着巨大的潜在应用前景。
制备碳化硅陶瓷膜常用的碳化硅属于强共价键结合，烧结时质点扩散速率很低，其晶界能、和表面能之比很高，不易获得足够的能量形成晶界，其表面的氧化膜也起到扩散势垒作用。因此碳化硅陶瓷膜坯体需要在很高的温度下才能烧结，通常达到1700-2200℃。这就使得碳化硅陶瓷膜的生产成本提高，限制了它们的应用。一些研究在制备过程中添加烧结助剂(如氧化钙、二氧化锆、碳化硼和氧化镁等)，来降低高烧结温度，从而降低生产成本。近年来，一些天然矿物材料也被应用于制备碳化硅复合陶瓷膜，如高岭土、滑石和凹凸棒土等，它们富含Al2O3和SiO2等氧化物，通常能够将碳化硅陶瓷膜的烧结温度降低至1500℃以下。中国发明专利CN201810075180.8公开了液相烧结多通道碳化硅陶瓷膜支撑体及其制备方法，将平均粒径范围在20-60μm碳化硅粉、高岭土、滑石、造孔剂和结合剂，与水配置成泥料并成型，经过1500℃以下的温度烧结得到液相烧结多通道碳化硅陶瓷膜支撑体，由于所述支撑体的原料中含有高岭土和滑石，利用液相烧结有效地降低了烧结温度，同时，高岭土、滑石与碳化硅液相烧结得到的多通道碳化硅陶瓷膜支撑体具有很高的强度。
黑滑石也是一种片层状的富镁硅酸盐矿物粘土，由滑石层(两个硅氧四面体层和一个镁氧八面体层)和类石墨烯碳层结合而成的矿物材料。首先，黑滑石的主要化学成分为氧化镁、氧化硅、氧化铝等，并且黑滑石中的矿物成分白云石在750℃开始分解，生成MgO、CaO，至850℃分解完全，由于这些金属氧化物的存在，能够显著降低碳化硅陶瓷膜的烧结温度。另外，黑滑石矿产资源储量丰富，价格便宜，可以降低碳化硅陶瓷膜的生产成本，提高产品竞争力，具有较好的经济效益和社会效益，应用前景广阔。
发明内容
为解决现有技术中碳化硅陶瓷膜制备过程中存在烧结温度过高的问题，本发明提供了一种碳化硅/黑滑石复合陶瓷膜支撑体及其制备方法。首先，黑滑石具有润滑性，与碳化硅互相穿插，可以有效抑制它们自身的聚集，从而得到分散均匀的纳米复合材料。其次，黑滑石在N2气氛中高温煅烧时，其中的类石墨烯有机碳层会保留下来，煅烧产物顽火辉石颗粒均匀分散在多层类石墨烯表面，将其紧密包覆，减少了内部缺陷，并阻碍了裂纹的扩散，从而在制备碳化硅/黑滑石复合陶瓷膜的支撑体时，其机械稳定性和分离性能得到改善。
为实现上述目的，本发明采用如下技术方案：
第一方面，本发明提供一种碳化硅/黑滑石复合陶瓷膜支撑体，所述碳化硅/黑滑石复合陶瓷膜支撑体的制备原料包括如下质量份的各组分：碳化硅粉5-20质量份、黑滑石粉5-10质量份、烧结助剂2-5质量份、造孔剂1-5质量份、粘结剂0.01-0.3质量份、分散剂0.01-0.1质量份；
所述烧结助剂为氧化铝、氧化钇、氧化镁、氧化锌、氧化钙、氧化锆、氧化钛中的一种或者两种以上的混合物(优选氧化铝、氧化钇、氧化镁或氧化锌中的一种或者两种以上的混合物，特别优选为质量比为3:2的氧化铝和氧化镁的混合物)；所述粘结剂为聚乙烯醇、聚乙二醇、羧甲基纤维素钠、羧乙基纤维素钠、甲基纤维素、聚丙烯酸中的一种或两种以上的混合物(优选聚乙烯醇或羧甲基纤维素钠)；所述造孔剂为活性炭粉、淀粉、聚乙烯醇缩丁醛、聚乙烯、聚甲基丙烯酸甲酯、石墨粉中的一种或者两种以上的混合物(优选活性炭粉或石墨粉)；所述分散剂为四甲基氢氧化铵、聚丙烯酸铵、聚丙烯酸钠、聚乙烯亚胺、聚碳酸酯、聚乙烯吡咯烷酮、海藻酸钠、木质磺酸钠、磷酸酯、聚甲基丙烯酸铵中的一种或两种以上的混合物(优选四甲基氢氧化铵或聚丙烯酸铵)。
优选地，所述碳化硅粉的细度为60-100μm。
优选地，所述黑滑石粉的细度为20-80μm；具体地，所述黑滑石粉按如下方法制备：将黑滑石原矿(江西省上饶市广丰区)清洗泥垢、晾干、破碎后，将所得破碎后的黑滑石加入体积比为1:1的乙醇与水的混合溶液中，用行星球磨机在500r/min的转速下湿法球磨6h，离心，用水离心洗涤3次后，烘干，再在行星球磨机中500r/min的转速下干磨10min，依次过200目筛和625目筛后，得到细度为20-80μm的黑滑石粉。
进一步，所述乙醇与水的混合溶液的体积以破碎后的黑滑石的质量计为1-5mL/g(优选2mL/g)。
优选地，所述烧结助剂的平均粒径为0.1-2μm。
优选地，所述造孔剂的平均粒径为2-10μm。
本发明尤其推荐所述碳化硅/黑滑石复合陶瓷膜支撑体的制备原料包括如下质量份的各组分：碳化硅粉20质量份、黑滑石粉6质量份、烧结助剂5质量份、造孔剂4质量份、粘结剂0.2质量份、分散剂0.032质量份；
所述烧结助剂为质量比为3:2的氧化铝和氧化镁的混合物；所述粘结剂为聚乙烯醇；所述造孔剂为石墨粉；所述分散剂为聚丙烯酸铵。
第二方面，本发明还提供一种上述碳化硅/黑滑石复合陶瓷膜支撑体的制备方法，所述方法为：
将组方量的碳化硅粉、黑滑石粉、烧结助剂、造孔剂混合后研磨均匀，再放入组方量的粘结剂与分散剂，继续研磨均匀；将所得混合物料于8-15MPa(优选10-12MPa，特别优选10MPa)下干压成型，所得成型坯体在室温下干燥12-24h后(优选12h)，在60℃-80℃下干燥12-24h(优选60℃下干燥12h)进一步成型；然后于保护氛围(如惰性气体氛围或氮气氛围，优选N2氛围)下在管式炉中烧结，烧结程序为：以2-3℃/min的升温速率升至550-700℃(优选600℃)后保温1-2h，再以3-5℃/min的升温速率升至950-1100℃(优选1000℃)后保温2-4h(优选3h)，自然冷却，得到所述碳化硅/黑滑石复合陶瓷膜支撑体。
碳化硅粉、黑滑石粉、烧结助剂、造孔剂、粘结剂与分散剂的定义同上。
优选地，所述粘结剂以粘结剂的水溶液形式加入，粘结剂的浓度为2-8wt％，优选5wt％。
优选地，所述分散剂以分散剂的水溶液形式加入，分散剂的浓度为5-10wt％，优选8wt％。
优选地，所述碳化硅粉的细度为60-100μm。
优选地，所述黑滑石粉的细度为20-80μm；具体地，所述黑滑石粉按如下方法制备：将黑滑石原矿(江西省上饶市广丰区)清洗泥垢、晾干、破碎后，将所得破碎后的黑滑石加入体积比为1:1的乙醇与水的混合溶液中，用行星球磨机在500r/min的转速下湿法球磨6h，离心，用水离心洗涤3次后，烘干，再在行星球磨机中500r/min的转速下干磨10min，依次过200目筛和625目筛后，得到细度为20-80μm的黑滑石粉。
进一步，所述乙醇与水的混合溶液的体积以破碎后的黑滑石的质量计为1-5mL/g(优选每2mL/g)。
优选地，所述烧结助剂的平均粒径为0.1-2μm。
优选地，所述造孔剂的平均粒径为2-10μm。
优选地，所述烧结程序为：以2℃/min的升温速率升至600℃后保温2h，再以3℃/min的升温速率升至1100℃后保温3h。
与现有技术相比，本发明的有益效果在于：
(1)黑滑石具有润滑性，与碳化硅互相穿插，可以有效抑制它们自身的聚集，从而得到分散均匀的碳化硅/黑滑石复合物料，制得高质量的碳化硅复合陶瓷膜支撑体生坯。
(2)黑滑石不仅可替代部分碳化硅原材料，还可起到烧结助剂的作用，由于黑滑石的主要化学成分为氧化镁、氧化硅、氧化铝等，能够形成低粘度液相，促进原子在较低温度下的传质传递，从而降低膜的烧结温度，减少碳化硅复合陶瓷膜支撑体生产成本。
(3)综上所述，本发明制备的碳化硅/黑滑石复合陶瓷膜支撑体产品的水通量大，机械强度高，同时能够显著降低其生产成本，应用前景广阔。
附图说明
图1为本发明中使用的黑滑石SEM电镜图。
具体实施方式
下面结合具体实施例，对本发明进行进一步描述，但本发明并不限于下述实施例，在不脱离本发明内容和范围内，变化实施都应包含在本发明的技术范围内。
以下实施例中细度为20-80μm的黑滑石粉按如下方法制备：将500g黑滑石原矿(江西省上饶市广丰区)清洗泥垢、晾干、破碎后，将452g所得破碎后的黑滑石加入904mL体积比为1:1的乙醇与水的混合溶液中，用行星球磨机在500r/min的转速下湿法球磨6h，离心，用水离心洗涤3次后，烘干，再在行星球磨机中500r/min的转速下干磨10min，依次过200目筛和625目筛后，得到338g细度为20-80μm的黑滑石粉。
实施例1
将10g碳化硅粉、6g黑滑石粉、2g氧化铝、1g氧化钇、2g活性炭粉放入研钵中研磨均匀，再放入2g浓度为8wt％的聚乙烯醇水溶液与0.2g浓度为5wt％的四甲基氢氧化铵水溶液，继续研磨至物料均匀；将上述物料在10MPa下干压成型：取10g上述混合物料压制出直径50mm，厚度3mm的圆片状碳化硅陶瓷膜支撑体生坯，取1.5g上述混合物料压制出30mm×5mm×6mm的条状碳化硅陶瓷膜支撑体生坯；成型坯体在室温下干燥24h，之后在60℃下干燥24h进一步成型；然后将坯体放入N2氛围下的管式炉中烧结，烧结程序为：以2℃/min的升温速率升至600℃后保温2h，再以3℃/min的升温速率升至1100℃后保温3h，待自然冷却后，得到碳化硅/黑滑石复合陶瓷膜支撑体。
实施例2
将10g碳化硅粉、3g黑滑石粉、1.5g氧化铝、1g氧化镁、2g石墨粉放入研钵中研磨均匀，再放入2g浓度为5wt％的聚乙烯醇水溶液与0.2g浓度为8wt％的聚丙烯酸铵水溶液，继续研磨至物料均匀；将上述物料在10MPa下干压成型：取10g上述混合物料压制出直径50mm，厚度3mm的圆片状碳化硅陶瓷膜支撑体生坯，取1.5g上述混合物料压制出30mm×5mm×6mm的条状碳化硅陶瓷膜支撑体生坯，成型坯体在室温下干燥12h，之后在60℃下干燥12h进一步成型；然后将坯体放入N2氛围下的管式炉中烧结，烧结程序为：以2℃/min的升温速率升至600℃后保温1h，再以3℃/min的升温速率升至1000℃后保温3h，待自然冷却后，得到碳化硅/黑滑石复合陶瓷膜支撑体。
实施例3
将12g碳化硅粉、3g黑滑石粉、1.8g氧化铝、1.2g氧化锌、3g活性炭粉放入研钵中研磨均匀，再放入2g浓度为2wt％的羧甲基纤维素钠水溶液与0.2g浓度为8wt％的聚丙烯酸铵水溶液，继续研磨至物料均匀；将上述物料在10MPa下干压成型：取10g上述混合物料压制出直径50mm，厚度3mm的圆片状碳化硅陶瓷膜支撑体生坯，取1.5g上述混合物料压制出30mm×5mm×6mm的条状碳化硅陶瓷膜支撑体生坯，成型坯体在室温下干燥24h，之后在60℃下干燥24h进一步成型；然后将坯体放入N2氛围下的管式炉中烧结，烧结程序为：以2℃/min的升温速率升至600℃后保温2h，再以3℃/min的升温速率升至1100℃后保温3h，待自然冷却后，得到碳化硅/黑滑石复合陶瓷膜支撑体。
实施例4
将8g碳化硅粉、4g黑滑石粉、1.5g氧化铝、0.5g氧化钇、2g活性炭粉放入研钵中研磨均匀，再放入2g浓度为2wt％的羧甲基纤维素钠水溶液与0.2g浓度为5wt％的四甲基氢氧化铵水溶液，继续研磨至物料均匀；将上述物料在10MPa下干压成型：取10g上述混合物料压制出直径50mm，厚度3mm的圆片状碳化硅陶瓷膜支撑体生坯，取1.5g上述混合物料压制出30mm×5mm×6mm的条状碳化硅陶瓷膜支撑体生坯，成型坯体在室温下干燥24h，之后在80℃下干燥24h进一步成型；然后将坯体放入N2氛围下的管式炉中烧结，烧结程序为：以2℃/min的升温速率升至600℃后保温2h，再以3℃/min的升温速率升至1100℃后保温3h，待自然冷却后，得到碳化硅/黑滑石复合陶瓷膜支撑体。
实施例5
其他操作同实施例1，区别仅在于干压成型的压力为15MPa。
实施例6
其他操作同实施例1，区别仅在于烧结程序为：以2℃/min的升温速率升至600℃后保温2h，再以3℃/min的升温速率升至950℃后保温3h。
对比例1
将10g碳化硅粉、2g氧化铝、1g氧化钇、2g活性炭粉放入研钵中研磨均匀，再放入2g浓度为8wt％的聚乙烯醇水溶液与0.2g浓度为5wt％的四甲基氢氧化铵水溶液，继续研磨至物料均匀；将上述物料通过干压成型，将上述物料在10MPa下干压成型：取10g上述混合物料压制出直径50mm，厚度3mm的圆片状碳化硅陶瓷膜支撑体生坯，取1.5g上述混合物料压制出30mm×5mm×6mm的条状碳化硅陶瓷膜支撑体生坯，成型坯体在室温下干燥24h，之后在60℃下干燥24h进一步成型；然后将坯体放入N2氛围下的管式炉中烧结，烧结程序为：以2℃/min的升温速率升至600℃后保温2h，再以3℃/min的升温速率升至1100℃后保温3h，待自然冷却后，得到碳化硅陶瓷膜支撑体。
对比例2
将10g黑滑石粉、2g氧化铝、1g氧化钇、2g活性炭粉放入研钵中研磨均匀，再放入2g浓度为8wt％的聚乙烯醇水溶液与0.2g浓度为5wt％的四甲基氢氧化铵水溶液，继续研磨至物料均匀；将上述物料通过干压成型，将上述物料在10MPa下干压成型：取10g上述混合物料压制出直径50mm，厚度3mm的圆片状碳化硅陶瓷膜支撑体生坯，取1.5g上述混合物料压制出30mm×5mm×6mm的条状碳化硅陶瓷膜支撑体生坯，成型坯体在室温下干燥24h，之后在60℃下干燥24h进一步成型；然后将坯体放入N2氛围下的管式炉中烧结，烧结程序为：以2℃/min的升温速率升至600℃后保温2h，再以3℃/min的升温速率升至1100℃后保温3h，待自然冷却后，得到黑滑石陶瓷膜支撑体。
对实施例1-6和对比例1-2中制备的碳化硅/黑滑石复合陶瓷膜支撑体的孔隙率、抗压强度、水通量进行了测定。用直径50mm，厚度3mm的圆片状碳化硅陶瓷膜支撑体生坯测试其孔隙率与水通量，用30mm×5mm×6mm的条状碳化硅陶瓷膜支撑体生坯测试其抗压强度。按照上述配方及工艺制备的碳化硅/黑滑石复合陶瓷膜支撑体的性能见表1。
表1：碳化硅/黑滑石复合陶瓷膜支撑体的性能
由表1可知，添加黑滑石制备的复合陶瓷膜支撑体的绝大多数抗压强度与水通量性能明显均优于纯碳化硅陶瓷膜，说明制备的碳化硅/黑滑石复合陶瓷膜支撑体具有优异的机械性能和渗透性能，对后续制备碳化硅/黑滑石复合陶瓷过滤膜应用于水处理工艺中发挥着重要作用。

Claims (4)

1.一种碳化硅/黑滑石复合陶瓷膜支撑体的制备方法，其特征在于所述碳化硅/黑滑石复合陶瓷膜支撑体的制备原料包括如下质量份的各组分：
碳化硅粉20质量份、黑滑石粉6质量份、烧结助剂5质量份、造孔剂4质量份、粘结剂0.2质量份、分散剂0.032质量份；
所述烧结助剂为质量比为3:2的氧化铝和氧化镁的混合物；所述粘结剂为聚乙烯醇；所述造孔剂为石墨粉；所述分散剂为聚丙烯酸铵；
所述的碳化硅/黑滑石复合陶瓷膜支撑体按如下方法制备：
将组方量的碳化硅粉、黑滑石粉、烧结助剂、造孔剂混合后研磨均匀，再放入组方量的粘结剂与分散剂，继续研磨均匀；将所得混合物料于8-15MPa下干压成型，所得成型坯体在室温下干燥12-24h后，在60℃-80℃下干燥12-24h进一步成型；然后于保护氛围下在管式炉中烧结，烧结程序为：以2-3℃/min的升温速率升至550-700℃后保温1-2h，再以3-5℃/min的升温速率升至950-1100℃后保温2-4h，自然冷却，得到所述碳化硅/黑滑石复合陶瓷膜支撑体；所述粘结剂以粘结剂的水溶液形式加入，所述分散剂以分散剂的水溶液形式加入。
2.如权利要求1所述的碳化硅/黑滑石复合陶瓷膜支撑体的制备方法，其特征在于：所述粘结剂的水溶液中粘结剂的浓度为2-8wt％。
3.如权利要求1所述的碳化硅/黑滑石复合陶瓷膜支撑体的制备方法，其特征在于：所述分散剂的水溶液中分散剂的浓度为5-10wt％。
4.如权利要求1所述的碳化硅/黑滑石复合陶瓷膜支撑体的制备方法，其特征在于：所述保护氛围为惰性气体氛围或氮气氛围。
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