CN112028608B - 一种利用赤泥制备的陶瓷过滤膜及其制备方法 - Google Patents

一种利用赤泥制备的陶瓷过滤膜及其制备方法 Download PDF

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CN112028608B
CN112028608B CN202010927929.4A CN202010927929A CN112028608B CN 112028608 B CN112028608 B CN 112028608B CN 202010927929 A CN202010927929 A CN 202010927929A CN 112028608 B CN112028608 B CN 112028608B
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乐红志
李洪达
朱建平
孙海滨
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Shandong University of Technology
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Abstract

本发明公开了一种利用赤泥制备的陶瓷过滤膜,所述陶瓷过滤膜包括基体和膜层,按重量份数计,所述基体制备原料包括:赤泥微球为60~80份,花岗岩粉为7~15份,塑性粘土为5~12份,增塑剂为4~7份,润滑剂为1~2份;所述膜层制备原料包括:赤泥微球为60~80份,花岗岩粉为7~15份,塑性粘土为5~12份,分散剂为0.1~0.5份;其中,所述基体制备原料中的赤泥微球球径为45~60um;所述膜层制备原料中的赤泥微球球径为10~20um。通过本发明能够生产一种陶瓷过滤膜,孔径为70~100nm,抗弯强度为20~30MPa,纯水通量为25~30m3/m2·d。

Description

一种利用赤泥制备的陶瓷过滤膜及其制备方法
技术领域
本发明涉及陶瓷过滤膜,尤其涉及一种利用赤泥制备的陶瓷过滤膜及其制备方法。
背景技术
目前制备陶瓷过滤膜的方法,原料为氧化铝或氢氧化铝。工艺为将氧化铝或氢氧化铝研磨,成型,烧制,得到陶瓷过滤膜。但是由于氧化铝或氢氧化铝本身性质,硬度大,抗弯强度低。这就导致制备的陶瓷过滤膜的时候出现以下问题:
1、氧化铝或氢氧化铝硬度大,经过研磨虽然得到了氧化铝或氢氧化铝的粉末,但是粉末粒度较大。氧化铝或氢氧化铝的粉末粒度较大在后续步骤中,会导致形成的氧化铝或氢氧化铝微球的圆度不好,进而烧制的陶瓷过滤膜孔径在30~50um,孔径较大影响陶瓷过滤膜的过滤性能。
2、氧化铝或氢氧化铝抗弯强度低,导致陶瓷过滤膜的强度难以提升。这也就导致以氧化铝或氢氧化铝为原料生产的陶瓷过滤膜在生产,运输,使用时常常发生损坏,造成成本增加。
3、使用氧化铝或氢氧化铝制备陶瓷过滤膜成本高。一方面是原料氧化铝或氢氧化铝本身价格高,导致成本高,另一方面是以氧化铝或氢氧化铝烧成陶瓷过滤膜需要的烧成温度高,导致烧成成本高。再就是氧化铝硬度较高,难以研磨,研磨浆料、喷雾造粒的成本高。
正是由于现有陶瓷过滤膜有以上不足,所以迫切需要人们解决。
公开于该背景技术部分的信息仅仅旨在增加对本发明的总体背景的理解,而不应当被视为承认或以任何形式暗示该信息构成已为本领域一般技术人员所公知的现有技术。
发明内容
为了解决上述技术问题,本发明提供了一种利用赤泥制备的陶瓷过滤膜及其制备方法。
根据本发明的一个方面,提供了一种利用赤泥制备的陶瓷过滤膜,所述陶瓷过滤膜包括基体和膜层,按重量份数计,
所述基体制备原料包括:赤泥微球为60~80份,花岗岩粉为7~15 份,塑性粘土为5~12份,增塑剂为4~7份,润滑剂为1~2份;
所述膜层制备原料包括:赤泥微球为60~80份,花岗岩粉为7~15 份,塑性粘土为5~12份,分散剂0.1~0.5份;
其中,
所述基体制备原料中的赤泥微球球径为45~60um;
所述膜层制备原料中的赤泥微球球径为10~20um。
相比于现有技术,本发明具有的优点和有益效果,本发明将传统工艺中的原料氧化铝或氢氧化铝替换为赤泥。一方面赤泥替换氧化铝或氢氧化铝,生产出来的陶瓷过滤膜性能与传统工艺生产出来的陶瓷过滤膜性能相比,本发明以赤泥为原料生产出来的陶瓷过滤膜性能更优越。同时以赤泥为主要原料,赤泥相比氧化铝或氢氧化铝,赤泥有价格优势,而且赤泥本身是工业废物,同时花岗岩也可以采用花岗岩石材的锯泥,能进一步降低成本。本发明利用赤泥,石材的锯泥等无机非金属工业固废,制备出能替代传统陶瓷过滤膜的陶瓷过滤膜,陶瓷过滤膜可以用来过滤污水,本发明实现了以污治污,具有极大的发展前景。
进一步的,所述基体制备原料中的赤泥微球和所述膜层制备原料中的赤泥微球都经过热处理固化,所述热处理温度为950~1000℃,热处理时间45~60min。
采用上述进一步技术方案的优点和有益效果在于,本发明中,基体赤泥微球和膜层赤泥微球需要具有一定的强度,陶瓷过滤膜的过滤效果会更好,并且可以增加陶瓷过滤膜的整体强度。当温度低于950℃时,赤泥微球热处理难以形成玻璃化外壳,导致微球强度不足;当温度高于1000℃时,赤泥微球之间发生黏连,破坏赤泥微球的圆度,影响形成的陶瓷过滤膜的孔隙,进而影响过滤效果。
进一步的,所述陶瓷过滤膜孔径为70~100nm,抗弯强度为20~ 30MPa,纯水通量为25~30m3/m2·d。
采用上述进一步技术方案的优点和有益效果在于,氧化铝或氢氧化铝硬度大,经过研磨得到的氧化铝或氢氧化铝的粉末,但是粉末粒度较大。氧化铝或氢氧化铝的粉末粒度较大在后续步骤中,会导致形成的氧化铝或氢氧化铝微球的圆度不好,形成的微球表面坑坑洼洼,微球与微球间距不均匀,进而烧制的陶瓷过滤膜孔径在30~50um,孔径较大影响陶瓷过滤膜的过滤性能。本发明利用赤泥的粒度小的优点,将陶瓷过滤膜的孔径从原先的um级降为70~100nm。陶瓷过滤膜孔径的减小,孔隙减小,可以过滤更细的悬浮物,过滤效果提高。其中,本发明所制备的所述陶瓷过滤膜过滤压为0.1~0.7MPa,反冲压力≤ 0.4MPa。
根据本发明的另一个方面,提供了一种利用赤泥制备的陶瓷过滤膜的制备方法,包括以下步骤:
制备赤泥料浆,所述赤泥料浆的固含量为50-60wt%;
将所述赤泥料浆喷雾造粒制成赤泥微球,经热处理使所述赤泥微球表面固化,所述赤泥微球球径45~60um;
按重量份,将表面固化后的赤泥微球,花岗岩粉末,塑性粘土,增塑剂和润滑剂混合得塑性泥料;
将所述塑性泥料可塑成型为基体,经镀膜处理使膜层泥浆覆盖所述基体;
将膜层覆盖的所述基体烧结处理,得到陶瓷过滤膜。
相比于现有技术,本发明具有的优点和有益效果,本发明首先制备赤泥料浆,其中赤泥料浆的固含量为50~60wt%,因为本发明赤泥料浆的固含量与赤泥微球的球径有关,固含量越低,喷雾造粒时得到的赤泥微球球径越小,球径越小,过滤效率就越不好,所以需要将赤泥料浆的固含量确定在50~60wt%,保证陶瓷过滤膜具有较好的过滤效率。同时按重量份计,添加1~2份的润滑剂,可以减少塑性泥料的开裂。
进一步的,所述膜层泥浆的制备方法包括以下步骤:
制备赤泥料浆,所述赤泥料浆的固含量为30-40wt%;
将所述赤泥料浆喷雾造粒制成赤泥微球,经热处理使所述赤泥微球表面固化,所述赤泥微球球径10~20um;
按重量份,将表面固化后的赤泥微球,花岗岩粉末,塑性粘土和分散剂混合得膜层泥浆。
采用上述进一步技术方案的优点和有益效果在于,通过改变赤泥料浆的固含量,制备出球径较小的赤泥微球。膜层泥浆覆盖在基体,使陶瓷过滤膜具有了双层结构。双层结构的陶瓷过滤膜具有了梯度孔,膜层是工作层,基体为支撑体。如果基体也做成膜层那样的细孔,会导致总体过滤阻力大,通量、反冲洗都受影响,过滤效率太低。而如果膜层也做成基体那样的粗孔,虽然过滤效率提升了,但是过滤效果不好,所以双层结构的陶瓷过滤膜才符合生产要求。
进一步的,所述塑性粘土包括膨润土、苏州土、高岭土中一种或多种。
采用上述进一步技术方案的优点和有益效果在于,塑性黏土使用包括膨润土、苏州土、高岭土中一种或多种,能够更好的将赤泥微球和花岗岩粉等其他物质黏合在一起,提高陶瓷过滤膜的过滤性能和陶瓷过滤膜的强度。
进一步的,所述增塑剂包括纤维素、PVA、PVB中一种或多种。
采用上述进一步的技术方案的优点和有益效果在于,增塑剂采用包括纤维素、PVA、PVB中一种或多种,能够提高塑性泥料的可塑性,使塑性泥料不易在后续步骤中变形。
进一步的,其特征在于,所述镀膜处理为将所述膜层浆料喷涂至所述基体表面;或将所述基体浸渍至所述膜层浆料,所述浸渍时间为1~5 分钟。
采用上述进一步的技术方案的优点和有益效果在于,本技术方案能够将膜层浆料均匀快速的覆盖在基体表面,使生产的陶瓷过滤膜结构稳定并能达到预期的过滤效果。
进一步的,所述分散剂包括聚丙烯酸钠或聚丙烯酸铵中一种或多种。
采用上述进一步的技术方案的优点和有益效果在于,分散剂采用包括聚丙烯酸钠或聚丙烯酸铵中一种或多种,能够将物料分散的更为均匀,有利于膜层均匀覆盖在基体表面。
进一步的,所述烧结处理,烧结温度为1050~1100℃,烧结时间为 2~12h。
采用上述进一步的技术方案的优点和有益效果在于,通过将氧化铝或氢氧化铝替换为赤泥,降低了烧结温度和烧结时间,降低了成本。同时陶瓷过滤膜由于使用花岗岩粉,有效组份是Na2O、K2O、SiO2、Al2O3,花岗岩粉为粘结剂,其作用是高温下助熔,产生少量液相,将赤泥微球粘结,提升陶瓷过滤膜的强度,作用和长石类似。使用花岗岩粉,是因为这也是一种量大的固废,可以降低成本。同时现有技术中,陶瓷过滤膜由于膜层和基体的烧结温度不同,需要不同温度烧结两次,而本发明由于基体和膜层原料基本相同,只需一次烧结,节省时间和成本。
附图说明
图1为陶瓷过滤膜局部放大图。
图2为陶瓷过滤膜。
图3为陶瓷过滤膜使用状态图。
附图中所示标记:1、陶瓷过滤膜基体;2、陶瓷过滤膜膜层;3、污水;4、清水。
具体实施方式
为了更好的了解本发明的技术方案,下面结合具体实施例、说明书、附图对本发明作进一步说明。
实施例1:
将60g赤泥砂磨后得到赤泥浆料120g,赤泥浆料固含量为50wt%。对赤泥浆料进行喷雾造粒,使用离心式喷雾造粒机,得到45um的赤泥微球,得到的赤泥微球通过950℃加热炉热处理45min。将轻烧后的赤泥微球,7g花岗岩石材锯泥,5g高岭土,4g PVA,1g甘油混练成塑性泥料。
将60g赤泥砂磨后得到赤泥浆料180g,赤泥浆料固含量为30wt%。对赤泥浆料进行喷雾造粒,使用离心式喷雾造粒机,得到10um的赤泥微球,得到的赤泥微球通过950℃加热炉热处理45min。将轻烧后的赤泥微球,7g花岗岩石材锯泥,5g高岭土,0.1g聚丙烯酸钠混合成膜层泥浆。
将塑性泥料固定成型为赤泥陶瓷膜基体,基体尺寸为 1000*250*6mm,中间均匀分布孔洞,孔洞直径5mm。将基体浸入膜层泥浆5min,拿出基体并干燥;将表面膜层和基体放入高温炉1050℃高温烧结2h,得到孔径为70nm,抗弯强度为20MPa,纯水通量为25m3/m2·d,过滤压为0.1,反冲压力为0.4MPa的陶瓷过滤膜。
实施例2:
将60g赤泥砂磨后得到赤泥浆料100g,赤泥浆料固含量为60wt%。对赤泥浆料进行喷雾造粒,使用离心式喷雾造粒机,得到60um的赤泥微球,得到的赤泥微球通过1000℃加热炉热处理60min。将轻烧后的赤泥微球,15g花岗岩石材锯泥,12g高岭土,7g PVB,2g甘油混练成塑性泥料。
将60g赤泥砂磨后得到赤泥浆料150g,赤泥浆料固含量为40wt%。对赤泥浆料进行喷雾造粒,使用离心式喷雾造粒机,得到20um的赤泥微球,得到的赤泥微球通过1000℃加热炉热处理60min。将轻烧后的赤泥微球,15g花岗岩石材锯泥,12g高岭土,0.5g聚丙烯酸钠混合成膜层泥浆。
将塑性泥料固定成型为赤泥陶瓷膜基体,基体尺寸为 1000*200*8mm,中间均匀分布孔洞,孔洞直径5mm。将基体浸入膜层泥浆1min,拿出基体并干燥;将表面膜层和基体放入高温炉1100℃高温烧结12h,得到孔径为100nm,抗弯强度为30MPa,纯水通量为 30m3/m2·d,过滤压为0.7,反冲压力为0.1MPa的陶瓷过滤膜。
实施例3:
将55g赤泥砂磨后得到赤泥浆料100g,赤泥浆料固含量为55wt%。对赤泥浆料进行喷雾造粒,使用离心式喷雾造粒机,得到50um的赤泥微球,得到的赤泥微球通过980℃加热炉热处理50min。将轻烧后的赤泥微球,10g花岗岩石材锯泥,10g苏州土,5g PVA,1.5g甘油混练成塑性泥料。
将70g赤泥砂磨后得到赤泥浆料200g,赤泥浆料固含量为35wt%。对赤泥浆料进行喷雾造粒,使用离心式喷雾造粒机,得到15um的赤泥微球,得到的赤泥微球通过980℃加热炉热处理50min。将轻烧后的赤泥微球,10g花岗岩石材锯泥,10g高岭土,0.3g聚丙烯酸钠混合成膜层泥浆。
将塑性泥料固定成型为赤泥陶瓷膜基体,基体尺寸为 1000*250*8mm,中间均匀分布孔洞,孔洞直径5mm。将基体浸入膜层泥浆3min,拿出基体并干燥;将表面膜层和基体放入高温炉1070℃高温烧结8h,得到孔径为85nm,抗弯强度为25MPa,纯水通量为25m3/m2·d,过滤压为0.4,反冲压力为0.2MPa的陶瓷过滤膜。
以上描述仅为本申请的较佳实施例以及对所运用技术原理的说明。本领域技术人员应当理解,本申请中所涉及的发明范围,并不限于上述技术特征的特定组合而成的技术方案,同时也应涵盖在不脱离所述发明构思的情况下,由上述技术特征或其等同特征进行任意组合而形成的其它技术方案。例如上述特征与本申请中公开的(但不限于)具有类似功能。

Claims (8)

1.一种利用赤泥制备的陶瓷过滤膜,其特征在于,所述陶瓷过滤膜由基体和膜层组成,按重量份数计,
所述基体制备原料包括:赤泥微球60~80份,花岗岩粉7~15份,塑性粘土为5~12份,增塑剂为4~7份,润滑剂1~2份;
所述膜层制备原料包括:赤泥微球60~80份,花岗岩粉7~15份,塑性粘土为5~12份,分散剂0.1~0.5份;
其中,
所述基体中的赤泥微球球径为45~60um;
所述膜层中的赤泥微球球径为10~20um;
所述基体赤泥微球和膜层赤泥微球经过热处理固化,所述热处理温度为950~1000℃,热处理时间45~60min;
所述利用赤泥制备的陶瓷过滤膜的制备方法,包括以下步骤:
制备赤泥料浆,所述赤泥料浆的固含量为50-60wt%;
将所述赤泥料浆喷雾造粒制成赤泥微球,经热处理使所述赤泥微球表面固化,所述赤泥微球球径45~60um;
按重量份,将表面固化后的赤泥微球,花岗岩粉,塑性粘土,增塑剂和润滑剂混合得塑性泥料;
将所述塑性泥料可塑成型为基体,经镀膜处理使膜层泥浆覆盖所述基体;
将膜层覆盖的所述基体烧结处理,得到陶瓷过滤膜;所述烧结处理的烧结温度为1050~1100℃,烧结时间为2~12h。
2.根据权利要求1所述一种利用赤泥制备的陶瓷过滤膜,其特征在于,所述陶瓷过滤膜孔径为70~100nm,抗弯强度为20~30MPa,纯水通量为25~30m3/m2·d。
3.一种权利要求1-2任一所述的利用赤泥制备的陶瓷过滤膜的制备方法,其特征在于,包括以下步骤:
制备赤泥料浆,所述赤泥料浆的固含量为50-60wt%;
将所述赤泥料浆喷雾造粒制成赤泥微球,经热处理使所述赤泥微球表面固化,所述赤泥微球球径45~60um;
按重量份,将表面固化后的赤泥微球,花岗岩粉,塑性粘土,增塑剂和润滑剂混合得塑性泥料;
将所述塑性泥料可塑成型为基体,经镀膜处理使膜层泥浆覆盖所述基体;
将膜层覆盖的所述基体烧结处理,得到陶瓷过滤膜。
4.根据权利要求3所述一种利用赤泥制备的陶瓷过滤膜的制备方法,其特征在于,所述膜层泥浆的制备方法包括以下步骤:
制备赤泥料浆,所述赤泥料浆的固含量为30-40wt%;
将所述赤泥料浆喷雾造粒制成赤泥微球,经热处理使所述赤泥微球表面固化,所述赤泥微球球径10~20um;
按重量份,将表面固化后的赤泥微球,花岗岩粉,塑性粘土和分散剂混合得膜层泥浆。
5.根据权利要求3所述一种利用赤泥制备的陶瓷过滤膜的制备方法,其特征在于,所述塑性粘土包括膨润土、苏州土、高岭土中一种或多种。
6.根据权利要求3所述一种利用赤泥制备的陶瓷过滤膜的制备方法,其特征在于,所述增塑剂包括纤维素、PVA、PVB中一种或多种。
7.根据权利要求3所述一种利用赤泥制备的陶瓷过滤膜的制备方法,其特征在于,所述镀膜处理为将所述膜层浆料喷涂至所述基体表面;
或将所述基体浸渍至所述膜层浆料,所述浸渍时间为1~5分钟。
8.根据权利要求4所述一种利用赤泥制备的陶瓷过滤膜的制备方法,其特征在于,所述分散剂包括聚丙烯酸钠或聚丙烯酸铵中一种或多种。
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