CN106087426B - 一种用于油水分离的亲水性高分子交联膜改性纺织品的制备方法 - Google Patents
一种用于油水分离的亲水性高分子交联膜改性纺织品的制备方法 Download PDFInfo
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Abstract
本发明涉及水处理领域,公开了一种用于油水分离的亲水性高分子交联膜改性纺织品的制备方法,包括:(1)聚乙烯醇溶液和交联剂溶液的配制:聚乙烯醇溶液的浓度为5‑40wt%,交联剂溶液由以下成分组成:戊二醛1‑20wt%,甲醇浓度1‑40wt%,醋酸浓度0.1‑10wt%,硫酸浓度0.1‑10wt%,水余量;(2)纺织品浸轧和烘干:将纺织品浸入聚乙烯醇溶液中搅动,接着取出进行浸轧;然后取出放入交联剂溶液中反应,用轧车轧掉多余交联剂溶液;最后放入烘箱。(3)取出纺织品,经冷水洗和烘干,制得成品。本发明制得的纺织品,亲水性高分子交联膜与纺织品结合牢度高,油水分离效果佳,且方法简单,成本低,可循环使用。
Description
技术领域
本发明涉及水处理技术领域,尤其涉及一种用于油水分离的亲水性高分子交联膜改性纺织品的制备方法。
背景技术
随着现代工业和社会的发展,海上漏油事件频发导致海水污染,以及由于纺织、食品、石油化工相关企业的含油污水大量排放,对生态环境和人类健康造成极大的威胁。浮油易在水面形成油膜,导致水体缺氧,对水生生物造成破坏。同时油类及其分解产物中含有大量有毒的苯并芘等多环芳烃,可通过食物链进入人体,危害人类健康。进入新世纪以来,油水分离技术已在原油回收、污水治理领域得到广泛应用。然而,常用的油水分离技术存在选择性差、分离效率低、成本高、分离工序复杂等问题。现有的专利所介绍的油水方法主要基于复杂的油水分离器和油水分离装置。
随着表面与界面科学的迅速发展,特别是具有特殊浸润性表面的发展,为制备高效、自动、智能的油水分离材料提供了一种全新的方法。最常用的方法是通过超疏水、超亲油材料对油的高浸润性,选择性地吸附(吸附型分离材料)或渗透(过滤型分离材料)油体,进而实现油与水的高效分离。但此类材料在应用过程中易被高粘度的油污染,微孔堵塞,降低其分离效率,反复利用率差,具有较高的维护成本。基于材料应用于水体环境,江雷院士提出超亲水和水下超疏油材料用于油水分离。通过光交联方法在不锈钢网覆盖聚丙烯酰胺(PAM)膜,在水中膜溶胀形成水凝胶排斥油的浸润和粘附,在实现油水分离的同时阻抗油污的粘附。也有文献报道通过在不锈钢网上自组装硅酸钠和二氧化钛微粒,也可得到水下超疏油材料用于油水分离,并且该材料可实现光催化的自清洁,利于循环使用。但是基于不锈钢网、电纺纳米纤维膜、碳纳米管或无机纳米粒子等材料制备的油水分离材料成本高,工艺复杂,更重要的是材料表面精细的物理结构很容易在储存和使用过程中丧失。
发明内容
为了解决上述技术问题,本发明提供了一种用于油水分离的亲水性高分子交联膜改性纺织品的制备方法。本发明方法制得的油水分离用纺织品,亲水性高分子交联膜与纺织品的结合牢度高,通量大,油水分离效果佳,柔韧性好,且制备方法简单,成本低,纺织品可循环使用。
本发明的具体技术方案为:一种用于油水分离的亲水性高分子交联膜改性纺织品的制备方法,包括如下步骤:
(1)聚乙烯醇溶液和交联剂溶液的配制:所述聚乙烯醇溶液的浓度为5wt%-20wt%,所述交联剂溶液由以下成分组成:戊二醛1wt%-20wt%,甲醇浓度1wt%-40wt%,醋酸浓度0.1wt%-10wt%,硫酸浓度0.1wt-10wt%,水余量。
(2)纺织品浸轧和烘干:按1:10-50的浴比将纺织品浸入聚乙烯醇溶液中搅动10-60min,接着将纺织品取出放在轧车上均匀浸轧,辊轮压力为0.1-0.5MPa;然后取出,按1:10-50的浴比将纺织品放入交联剂溶液中反应2-30min,用轧车轧掉多余交联剂溶液,辊轮压力为0.1-0.5MPa;最后放入烘箱,温度为40-90℃,保温时间为1-5h。
在制备过程中,需要严格控制浴比、辊轮压力、反应时间、温度等各项工艺参数,从而确保纺织品在拥有出色油水分离效果、较高水通量的基础上,同时具备较好的柔韧性,便于油水分离使用时满足各种形变要求。
(3)保温完毕后,取出纺织品,经过冷水洗和烘干,制得成品。
纺织品是一种价格低廉的多孔材料,以其为基材制备的超亲水、水下超疏油分离纺织材料具有分离效率高、通量高、清洁容易、循环使用时间长、价格低廉、柔性易运输、可剪裁成任意形状等优点,可用于大范围打捞浮油,具有很好的应用前景。
本发明制得的用于油水分离的纺织品为PVA交联膜改性的织物,在水体环境中具有超疏油性质,可选择性的过滤水而截留油,实现油水混合物的分离。将其作为油水分离材料具有分离效果好、水通量高、成本低、制备简单等优点。其中,纺织品上PVA接枝率在4%~18%范围内,具有相似的分离效果,且接枝率越低,改性后织物柔性越好。
采用本发明的纺织品进行油水分离的方法为:将用水润湿的织物放置在分离设备上(如漏斗、滤器等),倒入油水混合物,下方容器收集的滤液为水,织物上残留的液体即为油。通量大于10000L/m2/h,收集方便,分离产物可回收,无污染。
其中,可分离的油水混合物中油的种类包括:玉米油、泵油、机油、正己烷、柴油等。油水混合物中油的含量为1%~90%,分离后收集得到的水中含油量低于1%。
作为优选,所述聚乙烯醇溶液的浓度为10wt%,所述交联剂溶液由以下成分组成:戊二醛3wt%,甲醇浓度12wt%,醋酸浓度1wt%,硫酸浓度0.5wt%,水余量。
作为优选,所述聚乙烯醇的分子量为30000-100000。
作为优选,所述聚乙烯醇的分子量为60000。
作为优选,所述纺织品为涤纶、尼龙、丙纶中的一种,且纺织品结构为针织或网孔。
作为优选,所述纺织品为涤纶针织布。
作为优选,所述纺织品的平均孔径为200-500微米。
作为优选,所述纺织品的平均孔径为300-400微米。
作为优选,步骤(2)中,辊轮压力均为0.2-0.3MPa;烘箱温度为50-60℃。
作为优选,步骤(2)中,所述纺织品与聚乙烯醇的浴比为1:20,纺织品在聚乙烯醇溶液中搅动时间为30min;纺织品与交联剂溶液的浴比为1:20,交联反应时间为5min。
与现有技术对比,本发明具有如下特点:
1、本发明采用的油水分离材料制备简单、价格低廉、安全无害、柔韧性好、可重复使用、易于生产。
2、本发明制得的纺织品制备方法简单易行,且用于油水分离时水通量大,分离后的油或水可收集,无污染,可满足不同环境、目的以及处理效果的需求,是一种具有良好前景的油水分离技术。
综上所述,本发明通过浸轧工艺和化学交联方法结合起来,制备出具有高效油水分离效率的纺织品,不同于油污染水体处理常用的吸油毡吸附、分散剂乳化、生物降解等方法,通过对水中油污进行打捞收集,可分离油水、回收油品、高效便捷且不会造成二次污染。
附图说明
图1为实施例1所得的PVA改性布样的用于不同类型油水分离中循环使用分离效率维持率图。
具体实施方式
下面结合实施例对本发明作进一步的描述。
实施例1
一种用于油水分离的亲水性高分子交联膜改性纺织品的制备方法,包括如下步骤:
(1)聚乙烯醇溶液和交联剂溶液的配制:所述聚乙烯醇溶液的浓度为5wt%,聚乙烯醇的分子量为67000。所述交联剂溶液由以下成分组成:戊二醛1.5wt%,甲醇浓度20wt%,醋酸浓度2wt%,硫酸浓度0.5wt%,水余量。
(2)纺织品浸轧和烘干:按1:20的浴比将平均孔径为310微米的涤纶针织布浸入聚乙烯醇溶液中搅动30min,接着将涤纶针织布取出放在轧车上均匀浸轧,辊轮压力为0.2MPa;然后取出,按1:20的浴比将涤纶针织布放入交联剂溶液中反应10min,用轧车轧掉多余交联剂溶液,辊轮压力为0.2MPa;最后放入烘箱,温度为60℃,保温时间为2h。
(3)保温完毕后,取出涤纶针织布,经过冷水洗和烘干,制得成品。
实施例2-8的配方及工艺如表1所示:
表1
在上述实施例1-8中,PVA在织物上交联成膜后,用冷水浸泡过夜,除去未交联PVA,烘干后称重,即获得增重率。实施例1~实施例8所得PVA改性织物的增重率具体如表2所示。
对比例1:选用不经PVA改性的涤纶针织布为对比例。
将实施例1~实施例8所得PVA改性织物和对比例1的涤纶针织布用于玉米油与水混合物的分离实验,实施例1-8均获得很高的分离效率(即水中含油量降低的比例),而对比例1不具备油水分离功能。具体数值如表2所示:
表2:
实施例1所得PVA改性布样可用于多种油水混合物的分离,对于玉米油、泵油、机油、正己烷和柴油与水的混合物的分离效率如表3所示:
表3
油的种类 | 玉米油 | 泵油 | 机油 | 正己烷 | 柴油 |
油水分离效率% | 99.6 | 99.9 | 100 | 99.5 | 99.1 |
实施例1使用过的油水分离用织物用水冲洗10s,就可除去表面残留的油污,获得干净的织物,可重复多次使用。
将实施例1所得PVA改性布样用于油水分离实验,重复10次,油水分离效率仍然在98%以上,对于模拟海水的油水混合物溶液,循环10次的分离效率维持在94%~96%之间,具体数值如图1所示。
本发明中所用原料、设备,若无特别说明,均为本领域的常用原料、设备;本发明中所用方法,若无特别说明,均为本领域的常规方法。
以上所述,仅是本发明的较佳实施例,并非对本发明作任何限制,凡是根据本发明技术实质对以上实施例所作的任何简单修改、变更以及等效变换,均仍属于本发明技术方案的保护范围。
Claims (8)
1.一种用于油水分离的亲水性高分子交联膜改性纺织品的制备方法,其特征在于包括如下步骤:
(1)聚乙烯醇溶液和交联剂溶液的配制:所述聚乙烯醇溶液的浓度为5wt%-20wt%,且聚乙烯醇的分子量为30000-100000;所述交联剂溶液由以下成分组成:戊二醛1wt%-20wt%,甲醇浓度1wt%-40wt%,醋酸浓度0.1wt%-10wt%,硫酸浓度0.1wt-10wt%,水余量;
(2)纺织品浸轧和烘干:按1:10-50的浴比将平均孔径为200-500微米的纺织品浸入聚乙烯醇溶液中搅动10-60min,接着将纺织品取出放在轧车上均匀浸轧,辊轮压力为0.1-0.5MPa;然后取出,按1:10-50的浴比将纺织品放入交联剂溶液中反应2-30min,用轧车轧掉多余交联剂溶液,辊轮压力为0.1-0.5 MPa;最后放入烘箱,温度为40-90℃,保温时间为1-5h;
(3)保温完毕后,取出纺织品,经过冷水洗和烘干,制得成品。
2.如权利要求1所述的一种用于油水分离的亲水性高分子交联膜改性纺织品的制备方法,其特征在于,所述聚乙烯醇溶液的浓度为10wt%,所述交联剂溶液由以下成分组成:戊二醛3wt%,甲醇浓度12wt%,醋酸浓度1wt%,硫酸浓度0.5wt%,水余量。
3.如权利要求1所述的一种用于油水分离的亲水性高分子交联膜改性纺织品的制备方法,其特征在于,所述聚乙烯醇的分子量为60000。
4.如权利要求1所述的一种用于油水分离的亲水性高分子交联膜改性纺织品的制备方法,其特征在于,所述纺织品为涤纶、尼龙、丙纶中的一种,且纺织品结构为针织或网孔。
5.如权利要求4所述的一种用于油水分离的亲水性高分子交联膜改性纺织品的制备方法,其特征在于,所述纺织品为涤纶针织布。
6.如权利要求1所述的一种用于油水分离的亲水性高分子交联膜改性纺织品的制备方法,其特征在于,所述纺织品的平均孔径为300-400微米。
7.如权利要求1所述的一种用于油水分离的亲水性高分子交联膜改性纺织品的制备方法,其特征在于,步骤(2)中,辊轮压力均为0.2-0.3MPa;烘箱温度为50-60℃。
8.如权利要求1-7之一所述的一种用于油水分离的亲水性高分子交联膜改性纺织品的制备方法,其特征在于,步骤(2)中,所述纺织品与聚乙烯醇的浴比为1:20,纺织品在聚乙烯醇溶液中搅动时间为30min;纺织品与交联剂溶液的浴比为1:20,交联反应时间为5min。
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