CN115959926B - 一种相转化造孔剂及粉煤灰陶瓷平板膜支撑体的造孔方法 - Google Patents
一种相转化造孔剂及粉煤灰陶瓷平板膜支撑体的造孔方法 Download PDFInfo
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Abstract
本发明公开了一种相转化造孔剂及粉煤灰陶瓷平板膜支撑体的造孔方法,相转化造孔剂包括聚苯醚砜和N‑甲基吡咯烷酮,将其用于粉煤灰基陶瓷平板膜支撑体制备过程,可以通过相转化的方式进行造孔,在陶瓷平板膜支撑体内部形成具有梯度分布的直通孔,能够解决现有粉煤灰陶瓷平板膜支撑体孔隙率低,水通量低,成孔不均匀等问题。
Description
技术领域
本发明涉及一种相转化造孔剂,特别涉及一种用于粉煤灰基陶瓷平板膜支撑体造孔的相转化造孔剂,还涉及粉煤灰陶瓷平板膜支撑体的造孔方法,属于陶瓷膜制备技术领域。
背景技术
粉煤灰是燃料(主要是煤)燃烧过程中排出的微小灰粒,其粒径一般在1~100μm之间。又称粉煤灰或烟灰。由燃料燃烧所产生烟气灰分中的细微固体颗粒物。如燃煤电厂从烟道气体中收集的细灰。据我国用煤情况,燃用1t煤约产生250~300kg粉煤灰。大量粉煤灰如不加控制或处理,会造成大气污染,进入水体会淤塞河道,其中某些化学物质对生物和人体造成危害。
粉煤灰主要含二氧化硅(SiO2)、氧化铝(Al2O3)和氧化铁(Fe2O3)等,已广泛用于制水泥及制各种轻质建材。粉煤灰基陶瓷平板膜可用于水处理行业,从而对粉煤灰固废进行有效利用。
作为水处理用陶瓷平板膜需要高孔隙率以及高水通量,目前采用的造孔剂一般为淀粉、石墨等成分,通过混料机进行干粉混合,由于粉煤灰的密度比重与上述造孔剂的相差较大,难以在混合过程中做到均一稳定,容易在烧结过程中,造孔剂内部发生团聚形成不均匀空洞,并且不连通孔较多,对水通量提升有限。
发明内容
针对现有技术中粉煤灰基陶瓷平板膜的制备存在孔隙率低、成孔不均匀,水通量低等技术问题,本发明的第一个目的是在于提供一种相转化造孔剂,其可以通过相转化方式进行造孔,可以形成具有梯度分布的直通孔,有利于改善陶瓷平板膜的孔隙率和过滤效率。
本发明的第二个目的是在于提供一种粉煤灰陶瓷平板膜支撑体的造孔方法,该方法在粉煤灰原料中混入特殊的相转化造孔剂,其利用造孔剂相转化过程达到造孔和稳定孔结构的目的,从而在陶瓷平板膜支撑体内部形成具有梯度分布的直通孔,有利于改善陶瓷平板膜支撑体的孔隙率和过滤效率。
为了实现上述技术目的,本发明提供了一种用于陶瓷材料的相转化造孔剂,其包括聚苯醚砜和N-甲基吡咯烷酮。
本发明的相转化造孔剂包括聚苯醚砜和N-甲基吡咯烷酮两种成分,聚苯醚溶解在N-甲基吡咯烷酮形成溶液,其以溶液形式与陶瓷材料原料混合,相比固体造孔剂具有更加明显的优势,与原料混合更加均匀,而待原料成型后可以利用水将N-甲基吡咯烷酮溶解和置换脱除,从而形成孔隙,同时N-甲基吡咯烷酮的脱除使得聚苯醚砜由液态转变为固态,对N-甲基吡咯烷酮溶解遗留的孔隙起到支撑作用,而最终在烧结过程中,随着聚苯醚砜的脱除,可以在陶瓷材料内部形成直通孔道。
作为一个优选的方案,所述相转化造孔剂由聚苯醚砜和N-甲基吡咯烷酮按照质量比1:(3.5~5)组成。所述聚苯醚砜的数据分子量一般为4100~4800。如果聚苯醚砜相对N-甲基吡咯烷酮的比例过高,会导致聚苯醚砜难以充分溶解到N-甲基吡咯烷酮中,如果聚苯醚砜相对N-甲基吡咯烷酮的比例过低,会导致相转化过程中无法形成直通孔道。
本发明的相转化造孔剂通过以下方法制备得到:将聚苯醚砜和N-甲基吡咯烷酮按比例配制,使用搅拌器,于50~75℃下加热搅拌5~7h至完全相溶。
本发明还提供了一种粉煤灰陶瓷平板膜支撑体的造孔方法,该方法是将粉煤灰与所述相转化造孔剂以及油类添加剂进行混合,再依次进行陈腐和挤出成型,得到生坯;所述生坯先置于恒温恒湿环境中静置养护,再置于水中进行相转化反应,最后进行干燥和烧结。
作为一个优选的方案,所述相转化造孔剂与粉煤灰的质量比为(1~2):4。相转化造孔剂的添加比例过低则达不到改善陶瓷平板膜的孔隙率和过滤效率的目的,而造孔剂的添加比例过高,则会影响陶瓷平板膜的力学性能。
作为一个优选的方案,所述油类添加剂包括甘油、油酸和桐油。油类添加剂的作用主要是润滑、保湿等作用,能够保证在挤出过程中脱模顺利,而将甘油、油酸和桐油三者组合使用,可提高挤出支撑体的合格率,并且能防止在干燥过程中出现支撑体开裂。
作为一个优选的方案,所述油类添加剂由甘油、油酸和桐油按照质量比(1.2~2):1:(1.5~2.5)组成。甘油主要作为保水剂,其添加过高比例会导致支撑体塌陷,但是如果添加比例过低,会导致干燥过程开裂;而油酸作为减水剂,其添加过高比例会导致支撑体含水率低无法挤出,添加比例过低比例会导致支撑体含水率高,干燥过程易变形;而桐油作为润滑剂,其添加过高比例会影响支撑体的成型效果,其添加过低比例会增加挤出阻力,降低合格率。
作为一个优选的方案,所述油类添加剂与粉煤灰质量比为(0.8~1.5):10。油类添加剂比例过高,会导致支撑体韧性变大,干燥后容易出现弯曲,油类添加剂比例过低会导致支撑体塑性变小,无法挤出成型。
作为一个优选的方案,所述静置养护的条件为:湿度90~95%rh,温度为35±3℃,反应时间为4~6h。本发明的相转化造孔剂以混合溶液形式直接引入陶瓷膜支撑体坯体中,坯体置于高湿度恒温恒湿环境中并保持表面水润,造孔剂与水相溶进而成孔。
作为一个优选的方案,所述相转化反应的条件为:温度为25~35℃,时间为5~8h。
相对现有技术,本发明技术方案带来的有益技术效果:
本发明的相转化造孔剂是由聚苯醚砜溶于N-甲基吡咯烷酮形成的混合液,其以液态的方式与粉煤灰原料进行混合,提高了造孔剂在泥料中的均一程度;并且混合液中的N-甲基吡咯烷酮可与水进行互溶,在其与水互溶过程中,聚苯醚砜经过相转化过程有液态转变为固态,对N-甲基吡咯烷酮溶解遗留的孔隙起到支撑作用,在粉煤灰平板膜内部形成直通孔道,提高粉煤灰平板膜的孔隙率以及过滤效率。
附图说明
图1为对比例2淀粉作为造孔剂时获得的孔隙结构微观照片;
图2为实施例1使用相转化造孔剂获得的孔隙结构微观照片;从图1和图2中对比可以看出,利用相转化造孔剂的制备的支撑体孔隙率要高于淀粉造孔剂,并且相转化造孔后,孔道笔直,物质传输阻力小。
具体实施方式
以下具体实施例旨在进一步详细说明本发明内容,而不是限制权利要求的保护范围。
以下实施例中涉及的化学试剂如果没有特殊说明均为常规的市售商品原料。
实施例1
1.称取260g聚苯醚砜(分子量4200),称取1040g N-甲基吡咯烷酮,在50℃下搅拌6h,直至完全溶解,形成混合液;
2.称取150g桐油、150g甘油、100g油酸,在室温下搅拌10min;
3.称取4kg粉煤灰,加入上述混合液,通过混料机搅拌10min,然后加入步骤2混好的油类混合物继续搅拌5min;
4.通过练泥机对泥料进一步混合,使其具备一定的塑性,练泥结束后,置于陈腐室中陈腐,在25℃下陈腐24h;
5.通过挤出机对泥料进行挤出成型,然后将挤出的生坯放置于95%rh,35℃的环境中静置4h,然后将生坯置于纯净水中,室温下与水进行相转化5h,生坯中的N-甲基吡咯烷酮通过毛细作用溶解到水中,在生坯中形成具有梯度的孔道;
6.对步骤5的生坯进行常规的烘干和烧结,形成具有梯度孔结构的粉煤灰基陶瓷平板膜支撑体。
实施例2
1.称取200g聚苯醚砜(分子量4200),称取1000g N-甲基吡咯烷酮,在50℃下搅拌6h,直至完全溶解,形成混合液;
2.称取250g桐油、200g甘油、100g油酸,在室温下搅拌10min;
3.称取4kg粉煤灰,加入上述混合液,通过混料机搅拌10min,然后加入步骤2混好的油类混合物继续搅拌5min;
4.通过练泥机对泥料进一步混合,使其具备一定的塑性,练泥结束后,置于陈腐室中陈腐,在25℃下陈腐24h;
5.通过挤出机对泥料进行挤出成型,然后将挤出的生坯放置于95%rh,35℃的环境中静置4h,然后将生坯置于纯净水中,室温下与水进行相转化5h,生坯中的N-甲基吡咯烷酮通过毛细作用溶解到水中,在生坯中形成具有梯度的孔道;
6.对步骤5的生坯进行常规的烘干和烧结,形成具有梯度孔结构的粉煤灰基陶瓷平板膜支撑体。
实施例3
1.称取200g聚苯醚砜(分子量4600),称取900g N-甲基吡咯烷酮,在50℃下搅拌6h,直至完全溶解,形成混合液;
2.称取150g桐油、120g甘油、100g油酸,在室温下搅拌10min;
3.称取4kg粉煤灰,加入上述混合液,通过混料机搅拌10min,然后加入步骤2混好的油类混合物继续搅拌5min;
4.通过练泥机对泥料进一步混合,使其具备一定的塑性,练泥结束后,置于陈腐室中陈腐,在25℃下陈腐24h;
5.通过挤出机对泥料进行挤出成型,然后将挤出的生坯放置于95%rh,35℃的环境中静置4h,然后将生坯置于纯净水中,室温下与水进行相转化5h,生坯中的N-甲基吡咯烷酮通过毛细作用溶解到水中,在生坯中形成具有梯度的孔道;
6.对步骤5的生坯进行常规的烘干和烧结,形成具有梯度孔结构的粉煤灰基陶瓷平板膜支撑体。
对比例1
1.称取150g桐油、150g甘油、100g油酸,在室温下搅拌10min;
2.称取4kg粉煤灰通过混料机搅拌10min,然后加入步骤1混好的油类混合物继续搅拌5min;
3.通过练泥机对泥料进一步混合,使其具备一定的塑性,练泥结束后,置于陈腐室中陈腐,在25℃下陈腐24h;
4.通过挤出机对泥料进行挤出成型,然后将挤出的生坯放置于95%rh,35℃的环境中静置4h;
5.对步骤4的生坯进行常规的烘干和烧结,制备粉煤灰基陶瓷平板膜支撑体。
对比例2
操作步骤与实施例1相同,只是采用等量的淀粉替代聚苯醚砜和N-甲基吡咯烷酮混合溶液,具体如图1所示。
表1实施例1~3与对比实施例1~2制备的陶瓷平板膜的性能对比
Claims (4)
1.一种粉煤灰陶瓷平板膜支撑体的造孔方法,其特征在于:将粉煤灰与相转化造孔剂以及油类添加剂进行混合,再依次进行陈腐和挤出成型,得到生坯;所述生坯先置于恒温恒湿环境中静置养护,再置于水中进行相转化反应,最后进行干燥和烧结;
所述相转化造孔剂由聚苯醚砜和N-甲基吡咯烷酮按照质量比1:(3.5~5)组成;
所述油类添加剂由甘油、油酸和桐油按照质量比(1.2~2):1:(1.5~2.5)组成;
所述相转化造孔剂与粉煤灰的质量比为(1~2):4。
2.根据权利要求1所述的一种粉煤灰陶瓷平板膜支撑体的造孔方法,其特征在于:所述油类添加剂与粉煤灰质量比为(0.8~1.5):10。
3.根据权利要求2所述的一种粉煤灰陶瓷平板膜支撑体的造孔方法,其特征在于:所述静置养护的条件为:湿度90~95%rh,温度为35±3℃,反应时间为4~6h。
4.根据权利要求3所述的一种粉煤灰陶瓷平板膜支撑体的造孔方法,其特征在于:所述相转化反应的条件为:温度为25~35℃,时间为5~8h。
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