CN113461998A - 一种填料的改性方法及其组分以及应用 - Google Patents

一种填料的改性方法及其组分以及应用 Download PDF

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CN113461998A
CN113461998A CN202110633260.2A CN202110633260A CN113461998A CN 113461998 A CN113461998 A CN 113461998A CN 202110633260 A CN202110633260 A CN 202110633260A CN 113461998 A CN113461998 A CN 113461998A
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polyelectrolyte
modifying
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linking agent
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李申
何新
李冬冬
路怡涵
卢凯
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Anhui Jiuwu Tianhong Environmental Protection Technology Co ltd
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Abstract

本发明涉及一种填料的改性方法及其组分以及应用，所述的一种填料的改性方法，包括如下步骤：(1)将填料浸泡于聚电解质和亲水整理剂的混合液中；(2)对步骤(1)得到的产物均匀喷涂聚电解质和交联剂的共混液；(3)将步骤(2)得到的填料，烘箱进行干燥，得到改性填料；步骤(1)所述的浸泡的时间为10‑120分钟，步骤(3)所述的烘箱的干燥温度为110℃‑200℃、干燥时间为10分钟‑120分钟；所述步骤(1)中的聚电解质包括聚乙烯胺、聚乙烯亚胺、壳聚糖、聚二烯丙基二甲基氯化铵、聚乙烯酰胺中一种或多种；形成聚阳离子单元；所述步骤(2)中的聚电解质包括羧甲基纤维素钠、羧甲基纤维素淀粉、纤维素、海藻酸钠、海藻酸钙、聚丙烯酸、聚苯乙烯磺酸中的一种或多种；形成聚阴离子单元。

Description

一种填料的改性方法及其组分以及应用
技术领域
本发明涉及材料改性技术领域，具体涉及一种填料的改性方法及其组分以及应用，应用于水处理行业，特别适用水处理行业微生物膜反应器。
背景技术
填料作为微生物吸附生长的载体和吸附并截留水中的污染物及脱落生物膜介质，其表面的介电特性和官能团结构对其吸附特性有很重要的影响。通过物理、化学手段可以改变填料表面的介电特性和官能团结构，从而实现填料的表面改性，强化其吸附效能，进而提高整个(微生物膜)反应器的处理能力。目前，填料的改性按照改性的作用范围可以分为本体改性和表面改性。本体改性是指在填料生产过程中人为的加入改性材料，使填料本身的性质发生改变，提高了填料的性能，使其更适应废水的处理工艺；或直接将几种性质不同的材料相互混合，发挥各自优点，使改性填料具有更广泛的应用价值。本体改性的填料一般不会改变原来材料的物理性质，因此人们目前用的改性填料多来源于本体改性。对于本体改性过程而言，具有操作简单，改性材料容易获得等诸多优点。表面改性指改变载体表面的分子或原子性能，或直接导入载体表面一些新物质，使其具有特殊功能或增强填料的特性，如亲水性，韧性等。常见的表面改性方法是涂覆改性、离子覆盖法等。
接着上述，常用的(表面)改性方法主要有亲水改性、表面带电改性、生物亲和改性以及磁化改性。表面改性主要是用化学或物理方法在填料表面接枝一些极性官能团，从而提高填料的亲水性、荷电性以及生物亲和性。
但应用改性方法时，现有的填料具有如下缺点：填料表面呈疏水性、使其在MBBR工艺中挂膜周期长、影响微生物在膜表面的生长状态和附着量、生物菌群的生长结构以及微生物膜对废水的处理效果不佳，虽然有一些改善填料表面亲水性的研究，但是对其亲水性的改善程度有限。可以同时提高填料亲水性、荷电性以及生物亲和性的改性方法甚少。
中国专利《一种无机填料改性聚氨酯泡沫材料及其制备方法》(申请公布号CN107722230A；申请公布日2018.02.23)公开的方案主要针对聚氨酯填料进行改性，对象要求较高，应用范围窄，效用能力不高；中国专利《一种塑料填料改性方法》(申请公布号CN107188305A；申请公布日2017.09.22)同样主要是针对塑料填料进行改性，且需要强氧化剂(浓硫酸、浓硝酸等)，对安全性要求极高，效用能力也不高。
发明内容
为了克服现有填料改性的局限性和操作复杂性，本发明要解决的技术问题是提供一种填料的改性方法及其组分以及应用，其不仅能对聚氨酯填料进行改性，还可以对各种纤维类填料(聚酯纤维、维纶醛化纤维、聚丙烯、聚乙烯等)进行改性；不仅可以对各种纤维填料、聚氨酯填料进行改性，同时不需要强的氧化剂，操作简单，改性效果好。简单有效，以提高填料的亲水性、荷电性以及生物亲和性。
为了实现上述功能，本发明采用如下技术方案：
一种填料的改性方法，包括如下步骤：
(1)将填料浸泡于聚电解质和亲水整理剂的混合液中；
(2)对步骤(1)得到的产物均匀喷涂聚电解质和交联剂的共混液；
(3)将步骤(2)得到的填料，烘箱进行干燥，得到改性填料；
步骤(1)所述的浸泡的时间为10-120分钟，步骤(3)所述的烘箱的干燥温度为110℃-200℃、干燥时间为10分钟-120分钟；
所述步骤(1)中的聚电解质包括聚乙烯胺、聚乙烯亚胺、壳聚糖、聚二烯丙基二甲基氯化铵、聚乙烯酰胺中一种或多种；形成聚阳离子单元；
所述步骤(2)中的聚电解质包括羧甲基纤维素钠、羧甲基纤维素淀粉、纤维素、海藻酸钠、海藻酸钙、聚丙烯酸、聚苯乙烯磺酸中的一种或多种；形成聚阴离子单元。
进一步的，步骤(1)所述的浸泡的时间为30分钟；步骤(3)所述的烘箱的干燥温度为150℃、干燥时间为30分钟。
再进一步的，步骤(1)中填料为聚氨酯、维纶醛化纤维、聚酯纤维、聚丙烯纤维、聚乙烯纤维中的一种。
再进一步的，步骤(1)中聚电解质为壳聚糖、聚乙烯亚胺；聚阳离子浓度为0.01％-2％；步骤(1)中亲水整理剂浓度为0.1％-5％。
再进一步的，聚阳离子浓度为0.1％。
再进一步的，亲水整理剂浓度为1％。
进一步的，步骤(2)中的聚电解质为羧甲基纤维素钠、海藻酸钠；聚阴离子浓度为0.01％-2％；步骤(2)中所述的纤维素为木质或竹质；步骤(2)中的交联剂包括氨基树脂交联剂、异氰酸酯交联剂、硅氧烷偶联剂、硼砂、戊二醛中的一种或多种；
再进一步的，聚阴离子浓度为0.05％；步骤(2)中的交联剂为氨基树脂交联剂、异氰酸酯交联剂，交联剂的浓度为0.001％-1％；
再进一步的，交联剂的浓度为0.005％。
一种所述的填料的改性方法及其组分的应用，该改性的填料在河、湖泊、生活污水、工业废水处理以及其他废水处理中应用。
本发明的技术效果：填料采用表面改性法，将亲水整理剂(本发明的有机硅系列整理剂)、聚电解质(正电荷)复合作为改性液1，聚电解质(负电荷)和交联剂复合作为改性液2。先用改性液1浸泡填料(优选地30分钟)，再用改性液2均匀喷涂到填料表面，(优选地130℃)烘干。通过本发明方案提高填料的亲水性、荷电性以及生物亲和性，以此使微生物更易附着生长，提高填料的挂膜量。改性(的)填料可广泛应用于河道湖泊、生活废水以及工业废水领域。
附图说明
图1为本发明优选实施例中聚氨酯填料的未改性填料挂膜量与改性填料挂膜量对比图；
图2为本发明优选实施例中聚酯纤维球填料的未改性填料挂膜量与改性填料挂膜量对比图；
图3为本发明优选实施例中醛化纤维组合填料的未改性填料挂膜量与改性填料挂膜量对比图。
具体实施方式
下面结合实施例对本发明的方案作进一步详述。
本发明提供一种填料的改性方法及其组分以及应用，通过本发明方案提高填料的亲水性、荷电性以及生物亲和性，以此使微生物更易附着生长，提高填料的挂膜量。改性(的)填料可广泛应用于河道湖泊、生活废水以及工业废水领域。填料采用表面改性法，将亲水整理剂(本发明的有机硅系列整理剂)、聚电解质(正电荷)复合作为改性液1，聚电解质(负电荷)和交联剂复合作为改性液2。先用改性液1浸泡填料(优选地30分钟)，再用改性液2均匀喷涂到填料表面，(优选地130℃)烘干。
具体的，一种填料的改性方法，包括如下步骤：
(1)将填料浸泡于聚电解质和亲水整理剂的混合液中；
(2)对步骤(1)得到的产物均匀喷涂聚电解质和交联剂的共混液(得到填料)；
(3)将步骤(2)得到的填料，烘箱进行干燥，得到改性(塑料)填料。
进一步的，步骤(1)的聚电解质包括聚乙烯胺、聚乙烯亚胺、壳聚糖、聚二烯丙基二甲基氯化铵、聚乙烯酰胺中一种或多种(形成混合物)；(形成聚阳离子单元)。优选地，该聚电解质为壳聚糖、聚乙烯亚胺；聚阳离子浓度为0.01％-2％，进一步优选地为0.1％。
进一步的，步骤(1)中的亲水整理剂浓度为0.1％-5％。进一步优选地，亲水整理剂浓度为1％。
进一步的，步骤(2)中聚电解质包括羧甲基纤维素钠、羧甲基纤维素淀粉、纤维素(木质或竹质)、海藻酸钠、海藻酸钙、聚丙烯酸、聚苯乙烯磺酸中的一种或多种(形成混合物)；(形成聚阴离子单元)。优选地，该聚电解质为羧甲基纤维素钠、海藻酸钠；聚阴离子浓度为0.01％-2％，进一步优选地，为0.05％。
进一步的，步骤(2)中的交联剂包括氨基树脂交联剂、异氰酸酯交联剂、硅氧烷偶联剂、硼砂、戊二醛中的一种或多种(形成混合物)。优选地，该交联剂为氨基树脂交联剂、异氰酸酯交联剂；该交联剂的浓度为0.001％-1％，进一步优选地，为0.005％。
进一步的，步骤(1)的浸泡的时间为10-120分钟，优选地，浸泡的时间为30分钟。
进一步的，步骤(3)的烘箱的干燥温度为110℃-200℃，优选地，为150℃；干燥时间为10分钟-120分钟，优选地，为30分钟。
进一步的，步骤(1)中填料为聚氨酯、维纶醛化纤维、聚酯纤维、聚丙烯纤维、聚乙烯纤维中的一种。
上述组分及方法制备得到的改性(的)填料在河、湖泊、生活污水、工业废水处理以及其他废水处理中应用。
上述方案优选的实施例：
以下百分比为浓度百分比：
a.配制1％亲水整理剂+0.05％聚乙烯亚胺共混液，浸泡聚氨酯填料、醛化纤维组合填料、聚酯纤维球填料，浸泡时间30分钟。
b.将浸泡过的填料取出，用0.005％异氰酸酯交联剂+0.1％海藻酸钠混合液均匀喷涂。
c.喷涂完毕后，将填料放入150℃烘箱加热30分钟，取出备用。
d.将改性后的填料和未改性的填料，逐个称重。放入河道进行挂膜实验。
e.经过10天的挂膜，取出填料烘干称重。

Claims (10)

1.一种填料的改性方法，其特征在于，包括如下步骤：
(1)将填料浸泡于聚电解质和亲水整理剂的混合液中；
(2)对步骤(1)得到的产物均匀喷涂聚电解质和交联剂的共混液；
(3)将步骤(2)得到的填料，烘箱进行干燥，得到改性填料；
步骤(1)所述的浸泡的时间为10-120分钟，步骤(3)所述的烘箱的干燥温度为110℃-200℃、干燥时间为10分钟-120分钟；
所述步骤(1)中的聚电解质包括聚乙烯胺、聚乙烯亚胺、壳聚糖、聚二烯丙基二甲基氯化铵、聚乙烯酰胺中一种或多种；形成聚阳离子单元；
所述步骤(2)中的聚电解质包括羧甲基纤维素钠、羧甲基纤维素淀粉、纤维素、海藻酸钠、海藻酸钙、聚丙烯酸、聚苯乙烯磺酸中的一种或多种；形成聚阴离子单元。
2.根据权利要求1所述的一种填料的改性方法，其特征在于，步骤(1)所述的浸泡的时间为30分钟；步骤(3)所述的烘箱的干燥温度为150℃、干燥时间为30分钟。
3.根据权利要求1或2所述的一种填料的改性方法的组分，其特征在于：步骤(1)中填料为聚氨酯、维纶醛化纤维、聚酯纤维、聚丙烯纤维、聚乙烯纤维中的一种。
4.根据权利要求1或2所述的一种填料的改性方法的组分，其特征在于：步骤(1)中聚电解质为壳聚糖、聚乙烯亚胺；聚阳离子浓度为0.01％-2％；步骤(1)中亲水整理剂浓度为0.1％-5％。
5.根据权利要求4所述的一种填料的改性方法的组分，其特征在于：聚阳离子浓度为0.1％。
6.根据权利要求4所述的一种填料的改性方法的组分，其特征在于：亲水整理剂浓度为1％。
7.根据权利要求1所述的一种填料的改性方法的组分，其特征在于：步骤(2)中的聚电解质为羧甲基纤维素钠、海藻酸钠；聚阴离子浓度为0.01％-2％；步骤(2)中所述的纤维素为木质或竹质；步骤(2)中的交联剂包括氨基树脂交联剂、异氰酸酯交联剂、硅氧烷偶联剂、硼砂、戊二醛中的一种或多种。
8.根据权利要求7所述的一种填料的改性方法的组分，其特征在于：聚阴离子浓度为0.05％；步骤(2)中的交联剂为氨基树脂交联剂、异氰酸酯交联剂，交联剂的浓度为0.001％-1％。
9.根据权利要求8所述的一种填料的改性方法的组分，其特征在于：交联剂的浓度为0.005％。
10.一种权利要求1-9任意一项所述的填料的改性方法及其组分的应用，其特征在于：该改性的填料在河、湖泊、生活污水、工业废水处理以及其他废水处理中应用。
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