CN108993429A - 一种染料及印染废水处理用吸附剂及其制备方法 - Google Patents
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Abstract
本发明公开了一种染料及印染废水处理用吸附剂,其特征在于按如下步骤制备而得:将粉末状活性炭,交联阳离子淀粉,交联阳离子聚乙烯醇微球分别粉碎,过筛;将过筛的活性炭与过筛的交联阳离子淀粉混合,或将过筛的活性炭与过筛的交联阳离子聚乙烯醇混合,或将过筛的活性炭与过筛的交联阳离子淀粉和过筛的交联阳离子聚乙烯醇微球混合,即得一种印染废水处理用吸附剂。吸附脱色实验证明,本发明的一种染料及印染废水处理用吸附剂可用作固定床吸附剂,对染料及印染废水中的有机染料具有很高的吸附脱除能力,吸附性能明显优于常用吸附剂活性炭,并且可同时高效地去除印染废水中的染料、淀粉和PVA有机污染物。
Description
技术领域
本发明涉及废水处理用吸附剂领域,特别是涉及一种适合染料及印染废水处理用吸附剂及其制备方法。
背景技术
浆纱工艺在纺织生产过程中发挥着极其重要的作用,在浆纱生产过程中,通常采用淀粉或变性淀粉,PVA,以及聚丙烯酸类浆料对经纱进行上浆,以增加纱线的强度,降低纱线毛羽,提高纱线的耐摩擦牢度,进而确保纺织品生产质量与生产效率。为了确保纺织品的印染与整理加工效果,在纺织品印染加工过程中,退浆与染色便成了必不可少的两道加工工艺。因此印染厂在生产加工过程中通常会产生大量含有淀粉、PVA和有色染料废水。对于印染废水处理,目前国内外普遍采用先絮凝脱色,再采用活性污泥生化法技术进行处理,而对于染料废水,除采用先絮凝脱色,膜过滤后,再采用活性污泥生化法技术进行处理方法外,还采用多效蒸发法处理。然而,印染废水中所含的PVA由于难以絮凝与生物降解,通过常规废水处理工艺很难从废水中去除,因而给环境,特别是水资源环境造成了严重污染。为此,发达国家,特别是欧洲已禁止使用PVA作为纺织经纱上浆剂。
为了能够有效处理染料及印染废水,近年来,(电)芬顿氧化法,催化光氧化降解法等系列新技术正在不断地被研发,但由于氧化降解反应速率与效率相对较低,成本较高,到目前为止,这些新技术还难以得到实际推广应用。因此,在印染废水处理过程中,目前国内外还普遍采用投资与占地面积较大的絮凝/活性污泥生化法处理技术。
投资与占地面积较小,操作简便,利用固定床技术,通过吸附剂吸附处理染料与印染废水的技术一直是人们的关注热点。其中活性炭为常用吸附剂。活性炭对高分子有机污染物淀粉和PVA具有较高的吸附容量,但对染料等小分子的污染物的吸附容量却相对较低,因此当采用单一的活性炭作为吸附剂处理印染废水时,很难高效率地将废水中的淀粉、PVA和有机染料污染物同时去除,从而导致印染废水处理成本相对较高。
已有研究报道阳离子淀粉和阳离子PVA可用作染料及印染废水高效脱色絮凝剂。然而具有一定取代度的阳离子淀粉和阳离子PVA会遇水溶解,因此不能直接用作固定床吸附剂处理染料及印染废水。即使通过交联反应,使其失去水溶性,但依然会存在遇水溶胀问题,单独作为吸附剂使用也常常会导致液体通过固定床时流体阻力较大的问题。因此,可利用遇水稳定且具有助滤剂作用的活性炭,与交联阳离子淀粉或交联阳离子PVA,或其混合物组成混合吸附剂。这样即充分发挥活性炭对高分子有机污染物淀粉和PVA具有较高的吸附容量,又可以发挥交联阳离子淀粉和交联阳离子PVA对阴离子染料的高效吸附脱色性能。
本发明就是利用交联阳离子淀粉,或交联阳离子PVA具有遇水不溶解,且具有对有机染料良好的吸附脱色性能,同时利用活性炭对高分子污染物淀粉和PVA具有较高的吸附容量,遇水稳定,可作为助滤剂使用的特点,研制开发了一种由活性炭和交联阳离子淀粉组成的两组分混合吸附剂,或由活性炭与交联阳离子聚乙烯醇组成的两组分混合吸附剂,或由活性炭和交联阳离子淀粉及交联阳离子聚乙烯醇组成的三组分混合吸附剂。本发明的一种染料及印染废水处理用吸附剂对染料废水中的染料具有很高的吸附脱除能力,并能够同时高效地去除印染废水中的染料、淀粉和PVA有机污染物。
发明内容
本发明的目的在于针对现有固定床用吸附剂处理染料染料及印染废水时吸附有机污染物能力不强,不能同时高效地去除印染废水中的染料、淀粉和PVA有机污染物的缺陷,提供一种对染料废水中的染料具有很高的吸附脱除能力,并能同时高效地去除印染废水中的染料、淀粉和PVA有机污染物的一种染料及印染废水处理固定床用吸附剂。
一种染料及印染废水处理用吸附剂,其特征在于该吸附剂是由活性炭和交联阳离子淀粉两组分混合物组成,或由活性炭与交联阳离子聚乙烯醇两组分混合物组成,或由活性炭和交联阳离子淀粉及交联阳离子聚乙烯醇三组分混合物组成;其中活性炭的质量占混合吸附剂总质量的质量百分比含量为10%-80%;上述所述的交联阳离子淀粉,其阳离子基团为3-三甲氨基-2-羟基丙基,其取代度≥0.1,粒径≤80目;上述所述交联阳离子聚乙烯醇,其阳离子基团为3-三甲氨基-2-羟基丙基,其阳离子取代度≥0.1,粒径≤80目;上述所述的活性炭,是经过粉碎的粉末状活性炭,或是经过粉碎的棒状活性炭,或是经过粉碎的块状活性炭,或是经过粉碎的再生活性炭,或是经过粉碎的生物质活性炭,其比表面积大于200m2/g,粒径≤80目。
一种染料及印染废水处理用吸附剂的制备方法,其特征按以下步骤进行制备:分别将活性炭,交联阳离子淀粉,交联阳离子聚乙烯醇进行粉碎,过筛;将过筛的活性炭与过筛的交联阳离子淀粉混合,或将过筛的活性炭与过筛的交联阳离子聚乙烯醇混合,或将过筛的活性炭与过筛的交联阳离子淀粉和过筛的交联阳离子聚乙烯醇混合,即得染料及印染废水处理用吸附剂。
本发明的一种染料及印染废水处理用吸附剂用作固定床吸附剂处理染料及印染废水,对染料废水中的染料具有很高的吸附脱除能力,吸附性能明显优于常用吸附剂活性炭,并且可同时高效地去除印染废水中的染料、淀粉和PVA有机污染物。
此外,本发明的一种染料及印染废水处理用吸附剂用于吸附处理染料及印染废水后,失活的吸附剂可通过活性炭制备工艺中的化学活化工艺进行再生,其中,吸附有机污染物的交联阳离子淀粉及交联阳离子聚乙烯醇组分会转变成生物质活性炭。再生活性炭,即使循环再生五次,也可重新用来与粉末状交联阳离子淀粉或粉末状交联阳离子聚乙烯醇制备染料及印染废水处理用吸附剂,且对染料及印染废水处理的处理效率不降反生,因此本发明的一种染料及印染废水处理用吸附剂具有避免固废产生,吸附剂可持续性循环使用的特点。
具体实施方式
下面通过实施例对本发明作进一步阐述。其中实施例中所用原料活性炭是由块状活性炭经粉碎,并过80目筛得到的粉末状活性炭,其比表面积为386m2/g;交联阳离子淀粉是阳离子取代基团为3-三甲氨基-2-羟基丙基,阳离子取代度分别为0.43的交联阳离子淀粉;交联阳离子聚乙烯醇时阳离子取代基团为3-三甲氨基-2-羟基丙基,阳离子取代度为0.26的交联阳离子聚乙烯醇;实施例中所用模拟染料废水由活性黑5染料与去离子水配置,其中活性黑5染料浓度为500 mg/L;实施例中所用模拟印染废水由活性黑5染料,玉米淀粉,聚乙烯醇(PVA-1799)和去离子水配置,其中活性黑5染料浓度为500 mg/L,玉米淀粉浓度为100 mg/L,聚乙烯醇浓度为100 mg/L。
实施例1
称取经粉碎、过80目筛的粉末状活性炭50克,再称取经粉碎、过80目筛的交联阳离子淀粉50克,将两者进行充分混合后,即得一种染料及印染废水处理用吸附剂A。
实施例2
称取经粉碎、过120目筛的粉末状活性炭50克,再称取经粉碎、过120目筛的交联阳离子聚乙烯醇50克,将两者进行充分混合后,即得一种印染废水处理用吸附剂B。
实施例3
称取经粉碎、过80目筛的粉末状活性炭40克,再分别称取经粉碎、过80目筛的交联阳离子淀粉30克和称取经粉碎、过80目筛的交联阳离子聚乙烯醇30克,将三者进行充分混合后,即得一种印染废水处理用吸附剂C。
实施例4
在直径为20mm的固定床柱中,加入10克吸附剂,采用干法装柱,制备固定床吸附柱。在室温下,采用所制备的固定床吸附柱对模拟染料废水和模拟印染废水进行吸附实验。采用紫外可见吸收光谱仪检测流出液中无染料流出时的液体体积;利用淀粉与聚乙烯醇遇碘液会发生络合反应变色的特点,采用碘液作显色剂,采用紫外可见吸收光谱仪检测流出液中无淀粉和聚乙烯醇流出时的液体体积。
经测试,活性炭,吸附剂A,吸附剂B,吸附剂C对染料废水及印染废水的吸附能力见表1所示。
表1 不同吸附剂固定床柱吸附实验结果。
实施例5
将经过实施例4吸附过模拟染料及印染废水的吸附剂C,分别按文献方法(肖刚, 吴荣兵, 周慧龙,等. KOH活化木质素制备高比表面积活性炭特性研究[J]. 燃烧科学与技术,2014(1):14-20.)进行活化再生,再生后,过80目筛,则得粉末状再生活性炭CD和粉末状再生活性炭CP。分别称取40克粉末状再生活性炭CD,30克经粉碎、过80目筛的交联阳离子淀粉和30克经粉碎、过80目筛的交联阳离子聚乙烯醇,将三者进行充分混合后;即得吸附剂D。再分别称取40克粉末状再生活性炭CP,30克经粉碎、过80目筛的交联阳离子淀粉和30克经粉碎、过80目筛的交联阳离子聚乙烯醇,将三者进行充分混合后;即得吸附剂F。将吸附剂D和吸附剂F再按照实施例4操作,对模拟染料及印染废水进行吸附实验,结果见表2所示。
表2 吸附剂D和吸附剂F固定床柱吸附实验结果。
表1和表2数据表明,本发明制备的印染废水处理用吸附剂对有机染料的吸附脱色能力均明显高于活性炭的吸附脱色能力。失活的印染废水处理用吸附剂通过化学活化工艺再生后吸附脱色能力不降反升,表明本发明的一种染料及印染废水处理用吸附剂具有避免固废产生,吸附剂经再生后可持续性循环使用的特点。
当然,上述说明并非是对本发明的限制,本发明也并不限于上述举例,本技术领域的普通技术人员,在本发明的实质范围内,做出的变化、添加或替换,都应属于本发明的保护范围。
Claims (2)
1.一种染料及印染废水处理用吸附剂,其特征在于该吸附剂是由活性炭和交联阳离子淀粉两组分混合物组成,或由活性炭与交联阳离子聚乙烯醇两组分混合物组成,或由活性炭和交联阳离子淀粉及交联阳离子聚乙烯醇三组分混合物组成;其中活性炭的质量占混合吸附剂总质量的质量百分比含量为10%-80%;上述所述的交联阳离子淀粉,其阳离子基团为3-三甲氨基-2-羟基丙基,其取代度≥0.1,粒径≤80目;上述所述交联阳离子聚乙烯醇,其阳离子基团为3-三甲氨基-2-羟基丙基,其阳离子取代度≥0.1,粒径≤80目;上述所述的活性炭,是经过粉碎的粉末状活性炭,或是经过粉碎的棒状活性炭,或是经过粉碎的块状活性炭,或是经过粉碎的再生活性炭,或是经过粉碎的生物质活性炭,其比表面积大于200m2/g,粒径≤80目。
2.一种染料及印染废水处理用吸附剂的制备方法,其特征按以下步骤进行制备:分别将活性炭,交联阳离子淀粉,交联阳离子聚乙烯醇进行粉碎,过筛;将过筛的活性炭与过筛的交联阳离子淀粉混合,或将过筛的活性炭与过筛的交联阳离子聚乙烯醇混合,或将过筛的活性炭与过筛的交联阳离子淀粉和过筛的交联阳离子聚乙烯醇混合,即得染料及印染废水处理用吸附剂。
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CN110624503A (zh) * | 2019-09-17 | 2019-12-31 | 中山大学 | 一种淀粉改性的生物炭及其制备方法与应用 |
CN111514866A (zh) * | 2020-05-15 | 2020-08-11 | 湖南宇洁活性炭环保科技有限公司 | 一种溶剂回收高效木质活性炭及其制备方法 |
CN115245814A (zh) * | 2021-12-06 | 2022-10-28 | 青岛大学 | 一种由固废制备的固定床用吸附剂及其制备方法 |
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
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CN110624503A (zh) * | 2019-09-17 | 2019-12-31 | 中山大学 | 一种淀粉改性的生物炭及其制备方法与应用 |
CN111514866A (zh) * | 2020-05-15 | 2020-08-11 | 湖南宇洁活性炭环保科技有限公司 | 一种溶剂回收高效木质活性炭及其制备方法 |
CN115245814A (zh) * | 2021-12-06 | 2022-10-28 | 青岛大学 | 一种由固废制备的固定床用吸附剂及其制备方法 |
CN115245814B (zh) * | 2021-12-06 | 2023-08-11 | 青岛大学 | 一种由固废制备的固定床用吸附剂及其制备方法 |
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