CN113800942A - 一种碳化硅分子筛膜支撑体及其在分子筛膜上的应用 - Google Patents

一种碳化硅分子筛膜支撑体及其在分子筛膜上的应用 Download PDF

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CN113800942A
CN113800942A CN202111229905.2A CN202111229905A CN113800942A CN 113800942 A CN113800942 A CN 113800942A CN 202111229905 A CN202111229905 A CN 202111229905A CN 113800942 A CN113800942 A CN 113800942A
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silicon carbide
molecular sieve
sieve membrane
membrane support
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CN113800942B (zh
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陈纲领
彭文博
张建英
马田林
冯建华
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Chuzhou University
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Abstract

本发明提供的一种碳化硅分子筛膜支撑体及其在分子筛膜上的应用，属于膜材料制备领域，具体是以碳化硅为起始原料，外加剂分别为铝溶胶、AlF3、La2O3和有机添加剂聚乙烯醇、糊精；按一定比列将称量好的粉料置于三维混料机中进行机械混和，混合时间为3h；将混合好的粉料分别在捏合机、练泥机和真空挤出机、烘箱中进行捏合、练泥、成型、干燥等工艺处理，最后烘干后的生坯在1450℃下程序控温炉中以3℃/min的升温速率煅烧制得；本发明使多孔碳化硅陶瓷支撑体的制备工艺简化，烧结温度降低，成本降低，此外制备出的多孔碳化硅支撑体适合NaA分子筛膜的合成和工业应用，具有广阔的应用前景。

Description

一种碳化硅分子筛膜支撑体及其在分子筛膜上的应用
技术领域
本发明涉及膜材料制备领域，特别涉及一种碳化硅分子筛膜支撑体及其在分子筛膜上的应用。
背景技术
膜技术是一种新型分离技术，具有高效节能，过程易控制，操作方便等特点。目前，一些新型的膜技术已经或正在实现工业化，渗透气化技术就是其中发展较快的一种。由于NaA分子筛膜在有机物脱水、共沸物的分离、污染物的去除及气体分离方面具有独特优势和良好的应用前景而成为近期无机膜材料研究的热点之一。
虽然NaA分子筛膜的研究取得了很多成果,但要真正实现工业应用还存在诸多困难,如支撑体孔结构及微观形貌的控制问题，支撑体和分子筛层之间由于热应力的不同而存在粘附强度差的问题,对合成条件的控制和合成的重复性问题等。其中，分子筛膜支撑体的研究和发展水平制约着分子筛膜的研究及其工业化应用。分子筛膜常用的支撑体材料有氧化铝(Al2O3)、莫来石(3Al2O3·2SiO2)、多孔玻璃、不锈钢等。其中，碳化硅陶瓷材料除具有氧化物陶瓷材料的共性外，还具有耐强酸强碱、高抗热震和与水润湿角近乎为零等优异性能，如果采用碳化硅材料来制备符合分子筛膜合成要求的支撑体膜材料，这种亲水性能的碳化硅分子筛膜支撑体膜材料在分子筛膜工业溶剂脱水过程中由于其独特的亲水性，将会大大提高膜的分离效率。李宝伟（CN 104402446 B）发明了一种以碳化硅陶瓷粉为主要原料通过添加碱性硅溶胶作为硅源与酚醛溶液、蔗糖溶液、碳素墨水等充当碳源在高温氩气气氛保护烧结炉中1600--2200℃进行高温烧结制备传统的碳化硅多孔陶瓷的方法。虽然该方法提供了一种制备碳化硅多孔陶瓷的方法，但由于其制备工艺复杂、烧结温度高（1600-2200℃烧成），烧结气氛要求高（高温氩气气氛保护），且制备出的多孔陶瓷孔结构参数未给出限制了其作为分子筛膜支撑体的应用。然而，纯的多孔 SiC 陶瓷采用重结晶的方法来制备，此方法生产工艺复杂，烧结温度高，生产成本高，限制了其工业应用。200610119233.9发明了一种凝胶包覆-冷冻干燥工艺制备高孔隙率定向孔结构的多孔碳化硅陶瓷方法，但采用该方法难以制备出适合工业应用和NaA分子筛膜合成的管式支撑体，且该制备工艺相对复杂。CN 104761274 A提供了一种采用 300 目和 400 目筛的两种规格的片状碳化硅颗粒碳制备抗氧化性能好、膨胀系数低，碳化硅晶体表面覆盖层和粘结相导热性能好的工业多孔碳化硅陶瓷，该工艺制备出的多孔碳化硅陶瓷由于其孔径过大，且其表面物理和化学性能不适合NaA分子筛膜的合成同样无法作为NaA分子筛膜支撑体的制备工艺。CN 110935237A利用泡沫浸渍法采用埋炭气氛或氮气保护气氛下制备一种大孔径高温烟气过滤用多级孔碳化硅多孔陶瓷。上述多孔碳化硅陶瓷的制备均应用与其他不同的工业领域，由于NaA分子筛膜的合成不仅对支撑体的微观结构、孔结构参数具有严格的要求，且对支撑体表面物理化学性质匹配性具有较高的要求，并且作为工业应用分子筛膜支撑体须具有一定的构型（通常为单管或4通道），且具有较高的机械强度，容易生产。碳化硅陶瓷材料除具有氧化物陶瓷材料的共性外，还具有耐强酸强碱、高抗热震和与水润湿角近乎为零等优异性能，如果采用碳化硅材料来制备符合分子筛膜合成要求的支撑体膜材料，这种亲水性能的碳化硅分子筛膜支撑体膜材料在分子筛膜工业溶剂脱水过程中由于其独特的亲水性，将会大大提高膜的分离效率。同时由于莫来石元素组成与NaA分子筛组成接近，在NaA分子筛膜的合成中不会引入外界离子影响膜的性能，同时莫来石与碳化硅具有良好的化学兼容性和相近的热膨胀系数。基于上述技术现状，本发明开发了一种既解决碳化硅多孔陶瓷的低温空气气氛烧结问题又能批量制备出适合NaA分子筛膜合成要求的管式支撑体且生产工艺简单，可有效降低生产成本，可大规模应用。
发明内容
本发明提供一种NaA分子筛膜支撑体制备方法,其具体制备步骤如下：
①向碳化硅微粉中分别加入AlF3、La2O3和有机添加剂羟甲基纤维素，机械混合；
②将混合好的粉料添加质量浓度为20~30%的铝溶胶，其中，所述铝溶胶的质量为碳化硅粉料的15~25%，捏合处理，形成块状泥料；
③将步骤②得到的块状泥料练泥处理，在真空度为-0.1~-0.05Mpa的压力下挤出成型的湿坯；
④将步骤③挤出的湿坯烘干处理，形成生坯；
⑤将步骤④烘干的生坯在1350-1550℃的环境中以1-10℃/min的升温速率在空气气氛下1350-1550℃保温1~3h，得到碳化硅分子筛膜支撑体。
其中，所述碳化硅微粉具体为D50为3~10微米的碳化硅微粉。
其中，所述AlF3、La2O3和羟甲基纤维素的添加量分别为碳化硅原料的1~3%、0.05~0.2%和1~4%。
其中，所述机械混合的时间为1~6h。
其中，所述捏合处理的时间为30~180min。
其中，所述烘干处理的条件为在100~120℃的条件下烘干处理8~12h。
同时，本发明还提供了所述碳化硅分子筛膜支撑体在NaA分子筛膜的合成的应用，所述碳化硅分子筛膜支撑体用于NaA分子筛膜的合成。
有益效果
本发明开发了一种新的制备多孔碳化硅分子筛膜支撑体的制备方法，采用该方法生产出的多孔碳化硅支撑体的孔径在0.2－1µm，孔隙率在25％－50％内可调。由于碳化硅耐强酸强碱、高抗热震和与水润湿角近乎为零等优异性能，这种亲水性能使得碳化硅多孔陶瓷作为NaA分子筛膜支撑体在工业溶剂脱水过程中与水很好的润湿，大大提高了分离效率，有效地降低了成本。本发明制备的碳化硅支撑体具有好的表面物理化学性质，同时具有高的机械强度，并且其平均孔径和孔隙率可以达到分子筛膜对支撑体的要求，因此本发明制备出的多孔碳化硅支撑体可以用来作为分子筛膜支撑体，尤其适合作为NaA分子筛膜支撑体。
由于碳化硅在空气气氛中高温烧结过程表面会发生碳化碳化硅会分解成氧化硅和CO2，由于氧化硅的存在会大大影响碳化硅陶瓷支撑体的机械强度和耐碱性能，本发明中通过铝溶胶的添加，不仅在支撑体成型阶段替代PVA等有机粘结剂的添加减少因烧结产生的环境污染，而且在高温阶段包覆在碳化硅上的铝溶胶分解生成的氧化铝与在碳化硅颗粒高温氧化的氧化硅发生反应形成化学稳定性优良的莫来石相，大大提高了碳化硅陶瓷的机械性能和化学稳定性。采用该方法制备的多孔碳化硅由于其具有良好的孔结构和结合相，使其具备高的孔隙率的同时还具备高的强度和韧性，同时由于铝溶胶的添加不仅消耗掉了碳化硅高温氧化分解产生的氧化硅，而且生成了莫来石相，使其表面物理化学性质大大改善，这样都有助于提高支撑体的性能。此外，通过制备过程参数的控制还可以获得不同孔径和孔隙率的多孔碳化硅陶瓷分子筛膜支撑体。
本发明采用添加铝溶胶的方法原位反应烧结制备多孔碳化硅陶瓷支撑体，不仅使碳化硅支撑体具有好的表面物理化学性质，同时具有高的机械强度，并且其平均孔径和孔隙率可以达到分子筛膜对支撑体的要求，尤其适合作为NaA分子筛膜支撑体，同时使碳化硅多孔陶瓷烧结温度大大降低，而且可以碳化硅的烧结在空气气氛中进行，使多孔碳化硅陶瓷支撑体的制备工艺大大简化，成本大大降低，该制备工艺具有广阔的应用前景。
附图说明
图1为制备出的颗粒结合良好的多孔碳化硅陶瓷支撑体。
图2为根据本发明所制备的多孔碳化硅支撑体的XRD。
图3为在制备出的多孔碳化硅陶瓷支撑体合成的NaA分子筛膜。
具体实施方式
下面对本发明的一个具体实施方式进行详细描述，但应当理解本发明的保护范围并不受具体实施方式的限制。
实施例1
本实施例提供一种碳化硅分子筛膜支撑体的制备方法，具体步骤如下：
①称取D50为3微米的碳化硅微粉；向称量好的碳化硅微粉中分别加入AlF3、La2O3和有机添加剂羟甲基纤维素;所述AlF3、La2O3和HPMC的添加量分别为碳化硅原料的2%、0.1%和2%;
②将配好的粉料置于三维混料机中进行机械混和，混合时间为3h;
③混合好的粉料添加质量浓度为20%的铝溶胶,所述铝溶胶的质量为碳化硅粉料的25%;之后放入捏合机中,在室温下捏合60min形成块状的泥料;
④将③得到的块状泥料放入练泥机中练泥2h，之后将练好的泥料放入真空挤出机的装料桶中,在保持真空度-0.1Mpa的压力下进行挤出成型的湿坯;
⑤将步骤④挤出的湿坯放入100℃烘箱中烘干10h,形成生坯;
⑥将步骤⑤烘干的生坯放入1450℃的程序控温炉中以3℃/min的升温速率在空气气氛下1450℃保温2h制得出孔径在0.2µm，孔隙率在50％碳化硅分子筛膜支撑体。
实施例2
本实施例提供一种碳化硅分子筛膜支撑体的制备方法，具体步骤如下：
①称取D50为5微米的碳化硅微粉；向称量好的碳化硅微粉中分别加入AlF3、La2O3和有机添加剂羟甲基纤维素;所述AlF3、La2O3和HPMC的添加量分别为碳化硅原料的1%、0.05%和1%;
②将配好的粉料置于三维混料机中进行机械混和，混合时间为6h;
③混合好的粉料添加质量浓度为25%的铝溶胶,所述铝溶胶的质量为碳化硅粉料的20%;之后放入捏合机中,在室温下捏合30min形成块状的泥料;
④将③得到的块状泥料放入练泥机中练泥2h，之后将练好的泥料放入真空挤出机的装料桶中,在保持真空度-0.05Mpa的压力下进行挤出成型的湿坯;
⑤将步骤④挤出的湿坯放入100℃烘箱中烘干12h,形成生坯;
⑥将步骤⑤烘干的生坯放入1350℃的程序控温炉中以1℃/min的升温速率在空气气氛下1350℃保温1h制得出孔径在0.6µm，孔隙率在40％碳化硅分子筛膜支撑体。
实施例3
本实施例提供一种碳化硅分子筛膜支撑体的制备方法，具体步骤如下：
①称取D50为10微米的碳化硅微粉；向称量好的碳化硅微粉中分别加入AlF3、La2O3和有机添加剂羟甲基纤维素;所述AlF3、La2O3和HPMC的添加量分别为碳化硅原料的3%、0.2%和4%;
②将配好的粉料置于三维混料机中进行机械混和，混合时间为1h;
③混合好的粉料添加质量浓度为30%的铝溶胶,所述铝溶胶的质量为碳化硅粉料的15%;之后放入捏合机中,在室温下捏合180min形成块状的泥料;
④将③得到的块状泥料放入练泥机中练泥2h，之后将练好的泥料放入真空挤出机的装料桶中,在保持真空度-0.08Mpa的压力下进行挤出成型的湿坯;
⑤将步骤④挤出的湿坯放入105℃烘箱中烘干8h,形成生坯;
⑥将步骤⑤烘干的生坯放入1550℃的程序控温炉中以10℃/min的升温速率在空气气氛下1550℃保温3h制得出孔径在1µm，孔隙率在30％碳化硅分子筛膜支撑体。
实施例4
本发明实施例提供的一种多孔碳化硅分子筛膜支撑体制备NaA分子筛膜的方法，其具体制备步骤如下：
①向碳化硅混粉料中加入AlF3、La2O3和有机添加剂羟甲基纤维素;所述AlF3、La2O3和HPMC的添加量分别为碳化硅原料的2%、0.1%和2%。
②将配好的粉料置于三维混料机中进行机械混和，混合时间为3h。
③混合好的粉料添加质量浓度为20-30%的铝溶胶,所述铝溶胶的质量为碳化硅粉料的15-25%;之后放入捏合机中,在室温下捏合60min形成块状的泥料。
④将③得到的块状泥料放入练泥机中练泥2h，之后将练好的泥料放入真空挤出机的装料桶中,在保持真空度-0.1Mpa的压力下进行挤出成型的湿坯。
⑤将步骤④挤出的湿坯放入100℃烘箱中烘干10h,形成生坯。
⑥将步骤⑤烘干的生坯放入1400℃的程序控温炉中以5℃/min的升温速率在空气气氛下1400℃保温2h制得出碳化硅分子筛膜支撑体。
根据《GBT1966-1996多孔陶瓷显气孔率、容重试验方法》对所制备的样品进行孔隙率测定，其孔隙率在孔隙率在25％－50％，依据气体泡压法对其进行平均孔径测定，其平均孔径为0.2－1µm，该样品的孔隙率和孔径结构非常适合分子筛膜的合成。以该制备的碳化硅支撑体作为分子筛膜支撑体在其表面采用水热合成的方法在反应釜中进行NaA分子筛膜合成，合成液各组分摩尔比例为Al2O3：SiO2：Na2O：H2O=1：2：2：120，所合成的NaA分子筛膜用于渗透汽化性能测定，在温度为75℃、质量90%的乙醇水体系中时，该分子筛膜的分离系数超过10000，表明该发明方法制备出的碳化硅分子筛膜支撑体适合NaA分子筛膜的合成。
本发明采用添加铝溶胶的方法原位反应烧结制备多孔碳化硅陶瓷支撑体，不仅使碳化硅多孔陶瓷烧结温度大大降低，而且可以碳化硅的烧结在空气气氛中进行，使多孔碳化硅陶瓷支撑体的制备工艺大大简化，成本大大降低，该制备工艺具有广阔的应用前景。

Claims (7)

1.一种碳化硅分子筛膜支撑体的制备方法，其特征在于，具体步骤如下：
①向碳化硅微粉中分别加入AlF3、La2O3和有机添加剂羟甲基纤维素，机械混合；
②将混合好的粉料添加质量浓度为20~30%的铝溶胶，其中，所述铝溶胶的质量为碳化硅粉料的15~25%，捏合处理，形成块状泥料；
③将步骤②得到的块状泥料练泥处理，在真空度为-0.1~-0.05Mpa的压力下挤出成型的湿坯；
④将步骤③挤出的湿坯烘干处理，形成生坯；
⑤将步骤④烘干的生坯在1350-1550℃的环境中以1-10℃/min的升温速率在空气气氛下1350-1550℃保温1~3h，得到得到碳化硅分子筛膜支撑体。
2.根据权利要求1所述的碳化硅分子筛膜支撑体的制备方法，其特征在于，所述碳化硅微粉具体为D50为3~10微米的碳化硅微粉。
3.根据权利要求1所述的碳化硅分子筛膜支撑体的制备方法，其特征在于，所述AlF3、La2O3和羟甲基纤维素的添加量分别为碳化硅原料的1~3%、0.05~0.2%和1~4%。
4.根据权利要求1所述的碳化硅分子筛膜支撑体的制备方法，其特征在于，所述机械混合的时间为1~6h。
5.根据权利要求1所述的碳化硅分子筛膜支撑体的制备方法，其特征在于，所述捏合处理的时间为30~180min。
6.根据权利要求1所述的碳化硅分子筛膜支撑体的制备方法，其特征在于，所述烘干处理的条件为在100~120℃的条件下烘干处理8~12h。
7.一种权利要求1~6所述的碳化硅分子筛膜支撑体的应用，其特征在于：所述碳化硅分子筛膜支撑体NaA分子筛膜的合成。
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