CN106944630B - 一种海藻渣稳定纳米零价铁及其制备方法与应用 - Google Patents
一种海藻渣稳定纳米零价铁及其制备方法与应用 Download PDFInfo
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Abstract
本发明涉及一种海藻渣稳定纳米零价铁及其制备方法与应用,该海藻渣稳定纳米零价铁,为海藻渣与铁组成的复合材料,其中,海藻渣包覆在纳米零价铁的表面,海藻渣与纳米零价铁的质量比为:(0.5‑4):(0.5‑4)。该制备方法以废弃的海藻渣为稳定材料,海藻渣与亚铁离子形成稳定的络合物,利用液相还原法将亚铁还原成零价铁,得到海藻渣包覆纳米零价铁的稳定材料,实现纳米零价铁的制备和包覆同时完成,得到的海藻渣稳定纳米零价铁具有颗粒均匀,分散性好,制备工艺简单以及成本低等特点,对消毒副产物处理效果尤为明显,对消毒副产物亚硝基二甲胺的去除率高达到99.1%,放置25天后无变化,仍保持91%的去除率。
Description
技术领域
本发明涉及一种海藻渣稳定纳米零价铁及其制备方法与应用,属于纳米合成工艺技术领域。
背景技术
纳米零价铁具有优良的表面吸附和化学反应活性,可通过还原、沉淀、吸附和絮凝等作用处理污水中的重金属和难降解有机污染物,在环境工程领域有着巨大的应用潜力。但是,由于纳米零价铁的活性较高,其表面易氧化,使反应性降低,并且纳米零价铁颗粒会快速团聚为微粒尺度甚至更大的颗粒,导致反应活性和流动性降低。因此,通过不同的修饰方法制备高效、廉价、性能稳定的纳米零价铁,解决纳米零价铁易失活易团聚的问题是开发基于纳米零价铁高效破络预处理技术的关键。
中国专利文献CN106006778A公开了一种包覆型纳米铁薄膜的制备方法及应用,包括如下步骤:(1)制备纳米铁颗粒:在水与乙醇的溶液中加入七水硫酸亚铁和聚乙二醇,搅拌后加入硼氢化钠,然后继续搅拌,反应结束后,用磁铁吸引使固液分离,固体用水和乙醇洗涤,真空干燥。整个过程都在氮气的保护下。(2)制备聚醚砜溶液:将聚醚砜、聚乙二醇、聚乙烯吡咯烷酮按比例溶解在二甲基乙酰胺溶液中,搅拌成均一溶液。(3)采用相转换法制备含纳米铁的聚醚砜薄膜。将纳米铁和聚醚砜溶液涂抹在玻璃上,将其浸入水中,数分钟后将薄膜真空干燥。(4)本发明制得的包覆型纳米铁薄膜既解决了纳米铁的团聚,还延长了纳米铁的暴露时间,并对处理水系中的铬有良好效果。但是,该方法包覆过程复杂;包覆材料为多种聚合有机物,进入水体之后不易分解,并且纳米铁的制备需要氮气的保护,程序繁琐,能耗高。
中国专利文献CN106000335A公开了一种包覆型纳米零价铁及其制备方法和应用,该包覆型纳米零价铁包括纳米零价铁和海藻酸钠,海藻酸钠包覆于纳米零价铁表面,海藻酸钠与纳米零价铁的质量比为0.1~0.4∶1。该制备方法是将纳米零价铁与海藻酸钠溶液混合经超声处理得到包覆型纳米零价铁,纳米零价铁的制备和包覆需分步进行,且超声会引起热效应,可能会使海藻酸钠的结构发生变化,导致包覆效果差。
海藻渣是以海藻为原料生产海藻酸、甘露醇、碘等产品的工艺过程中产生的残渣,在对海藻渣成分进行系统分析后发现,海藻渣中含有大量的粗蛋白、粗纤维、丰富的微量元素和少量的多糖、粗脂肪。但它与水形成一种胶性粘稠物,容易悬浮在水中构成工业废水。目前大部分海藻加工厂未经处理,直接将含海藻渣的废水排放入海,造成近海海域污染,少部分企业通过环保措施将海藻渣提取出来用做饲料添加剂、土壤改良剂、有机肥等产品,但由于这些产品附加值低、废水处理费用高,增加了企业的生产成本。随着海藻加工产业的迅速发展和海藻的大量使用,以及企业生产环保要求越来越高,如何处理及利用加工过程中产生的废渣就成为一个急需解决的问题。
从污染源排出的污(废)水,因含污染物总量或浓度较高,达不到排放标准要求或不符合环境容量要求,从而降低水环境质量和功能目标时,必需经过污水处理厂处理。污水通过机械处理、生物处理之后成为二级出水,消毒后排放。采用次氯酸钠消毒后虽然可以灭活水中的致病微生物,同时也会产生消毒副产物,如亚硝基二甲胺(NDMA)。亚硝基二甲胺产生的慢性毒性作用可引起肝癌、肺癌及神经系统的损伤。基于NDMA对健康的危害性,研究饮用水处理过程中NDMA的去除对保护公众健康和发展安全的饮用水工业具有重要的现实意义。
发明内容
针对现有技术的不足,本发明提供一种海藻渣稳定纳米零价铁及其制备方法。
本发明还提供一种海藻渣稳定纳米零价铁的应用。
发明概述
本发明提供的海藻渣稳定纳米零价铁,以废弃的海藻渣为稳定材料,海藻渣与亚铁离子形成稳定的络合物,利用液相还原法将亚铁还原成零价铁,得到海藻渣包覆纳米零价铁的稳定材料,实现纳米零价铁的制备和包覆同时完成,得到的海藻渣稳定纳米零价铁具有颗粒均匀,分散性好,制备工艺简单以及成本低等特点,对消毒副产物处理效果尤为明显,对消毒副产物亚硝基二甲胺的去除率高达到99.1%,放置25天后无变化,仍保持91%的去除率。
本发明的技术方案如下:
一种海藻渣稳定纳米零价铁,为海藻渣与铁组成的复合材料,其中,海藻渣包覆在纳米零价铁的表面,海藻渣与纳米零价铁的质量比为:(0.5-4):(0.5-4)。
根据本发明,优选的,海藻渣与纳米零价铁的质量比为:1:1,所述海藻渣稳定纳米零价铁的平均粒径为50~100nm。
根据本发明,一种海藻渣稳定纳米零价铁的制备方法,包括步骤如下:
(1)收集海藻渣干燥、粉碎,加入水中搅拌,制得质量浓度为1~3wt%的海藻渣悬浊液;
(2)称取可溶性铁盐溶于乙醇与水的混合溶液中,制得溶液A,溶液A中硫酸亚铁的浓度为0.3~0.6mol/L;
(3)取硼氢化钠溶于水中,制得浓度为0.3~1.2mol/L的硼氢化钠溶液;
(4)搅拌下,将步骤(2)的溶液A与步骤(1)的海藻渣悬浊液按体积比为1:(1~5)的比例混合,搅拌均匀,再逐滴加入硼氢化钠溶液,使得Fe2+:BH4-的摩尔比为1:(1~6),继续搅拌至反应停止;
(5)筛选出纳米零价铁粒子,用超纯水和无水乙醇分别清洗,然后于真空干燥箱中干燥,得海藻渣稳定纳米零价铁。
本发明优选的,步骤(1)中,所述的干燥、粉碎是将海藻渣于温度50~70℃下干燥5-8小时,然后粉碎过100目筛,海藻渣悬浊液的质量浓度为1%。
本发明优选的,步骤(2)中,所述的可溶性铁盐为七水合硫酸亚铁。
本发明优选的,步骤(2)中,溶液A中硫酸亚铁的浓度为0.3~0.4mol/L,最为优选的,溶液A中硫酸亚铁的浓度为0.36mol/L。
本发明优选的,步骤(2)中,乙醇与水的体积比为:(1~3):(5~10),优选的,乙醇与水的体积比为:3:7。
本发明优选的,步骤(3)中,硼氢化钠溶液的浓度为1.0~1.2mol/L,最为优选的,硼氢化钠溶液的浓度为1.0mol/L。
本发明优选的,步骤(4)中,溶液A与海藻渣悬浊液的体积比为1:(1~3)。
本发明优选的,步骤(4)中,Fe2+:BH4-的摩尔比为1:(3~6),优选的,Fe2+:BH4-的摩尔比为1:3。
本发明优选的,步骤(5),采用磁选法选出纳米零价铁粒子,真空干燥温度为50~70℃,干燥时间5-8小时。
本发明以废弃的海藻渣为稳定材料,海藻渣中含有的粗蛋白、粗纤维、丰富的微量元素和少量多糖、粗脂肪等成分在水溶液中存在着羧基、羟基、胺基等基团,反应活性大,与亚铁离子形成稳定的络合物,利用液相还原法将亚铁还原成零价铁,实现纳米零价铁的制备和包覆一步同时完成,制备工艺简单以及成本低,对消毒副产物处理效果尤为明显,对消毒副产物亚硝基二甲胺的去除率高达到99.1%,放置25天后无变化,仍保持91%的去除率,同时也解决了海藻加工企业海藻渣处理的问题,以废治废、变废为宝。
本发明海藻渣稳定纳米零价铁的应用,用于处理降解消毒后溶液中的三卤甲烷和亚硝基二甲胺,适用pH为3-6,投加量为0.5-1.5g/L。
进一步优选的,适用pH为4-5,投加量为1.0-1.5g/L,最为优选的,适用pH为5.0,投加量为1.0g/L。
本发明与现有技术相比具有以下优良效果:
1、本发明的海藻渣稳定纳米零价铁具有颗粒均匀,分散性好,制备工艺简单以及成本低等特点,对消毒副产物处理效果尤为明显,对消毒副产物亚硝基二甲胺的去除率高达到99.1%,放置25天后无变化,仍保持91%的去除率。
2、本发明的海藻渣稳定纳米零价铁的制备过程不需要氮气保护,采用液相还原的方法,纳米零价铁的制备和包覆一步同时完成,制备快捷,操作简便,制作成本低廉。
3、本发明制备的稳定型纳米零价铁可用于二级出水消毒后NDMA的去除,降低NDMA的浓度,减少NDMA对人体的危害。本发明的应用方法操作简便,稳定效果好,且清洁无污染,对环境无毒害作用,在NDMA去除技术领域具有广泛的应用前景。
附图说明
图1为本发明实施例1制得的海藻渣稳定纳米零价铁的SEM照片。
图2为本发明实施例1制得的海藻渣稳定纳米零价铁的XRD谱图。
图3为本发明实施例1制得的海藻渣稳定纳米零价铁暴露于空气中的时间对消毒后二级出水中NDMA去除影响曲线图。
具体实施方式
下面通过具体实施例对本发明做进一步说明,但不限于此。
实施例中的海藻渣取自日照洁晶海洋生物技术开发有限公司。
实施例1
一种海藻渣稳定纳米零价铁的制备方法,步骤如下:
(1)收集海藻渣置于烘箱中60℃烘干,过100目筛,粉碎后的海藻渣加入水中搅拌,配制质量浓度为1wt%的海藻渣悬浊液100mL;
(2)称取FeSO4·7H2O溶于乙醇与水的混合溶液(乙醇:水的体积比=3:7)中,配制溶液A 50mL,溶液A中硫酸亚铁的浓度为0.36mol/L;
(3)取硼氢化钠溶于水中,制得浓度为1.08mol/L的硼氢化钠溶液;
(4)搅拌下,将溶液A倒入海藻渣悬浊液中,搅拌混合均匀,再逐滴加入硼氢化钠溶液,使得Fe2+:BH4-的摩尔比为1:1,继续搅拌至反应停止;
(5)用磁选法选出纳米零价铁粒子,先用超纯水洗涤3次,然后用无水乙醇充分洗涤3次,于真空干燥箱中60℃干燥,得海藻渣稳定纳米零价铁粉体。
所得的海藻渣稳定纳米零价铁粉体的电镜照片如图1所示,从图1中可以看出,材料呈球状分散,分散性好,平均粒径100nm左右。
所得的海藻渣稳定纳米零价铁粉体的XRD图如图2所示,XRD测试结果表明:在扫描衍射角度(2θ)为10°~80°时,出现衍射峰时对应的2θ分别为44.67°,刚好对应的110晶面衍射(44.6732°),表明颗粒为单质铁,而没有出现氧化铁物质。
实验例处理水中的消毒副产物效果
1、分别取污水处理厂的二级出水1L,加1mL10%的次氯酸钠于暗处25℃消毒7天,加1mL浓度1mol/L硫代硫酸钠溶液终止消毒,得消毒后水,设置三个处理做平行实验,向每个处理消毒后水分别投加1g海藻渣、纳米零价铁、实施例1制得的海藻渣稳定的纳米零价铁,25℃震荡24小时,取水样测NDMA浓度。重复3次,取平均值;
实验结果表明:海藻渣、纳米零价铁、海藻渣稳定的纳米零价铁对NDMA的去除率分别为21%、9%、91.8%,说明本发明制备的稳定纳米零价铁对NDMA的去除率很高,效果显著。
2、将纳米零价铁和实施例1制得的海藻渣稳定的纳米零价铁干燥后,放置于空气中,每天观察纳米零价铁的颜色变化,判断其氧化程度。
实验结果表明:一天后,部分未加海藻渣的纳米零价铁由黑色变成黄色,3天后完全变黄。而实施例1制得的稳定纳米零价铁3天后无任何变化。加入海藻渣做稳定剂,有效地防止了零价铁团聚与氧化。
3、分别取污水处理厂的二级出水1L,加1mL10%的次氯酸钠于暗处25℃消毒7天,加1mL浓度1mol/L硫代硫酸钠溶液终止消毒,得消毒后水,设置五个处理做平行实验,向每个处理消毒后水分别投加在空气中放置5天、10天、15天、20天、25天的实施例1制得的海藻渣稳定纳米零价铁1g,25℃震荡24小时,取水样测NDMA浓度。重复3次,取平均值;
海藻渣稳定纳米零价铁暴露于空气中的时间对消毒后二级出水中NDMA去除的影响如图3所示,实验结果表明:海藻渣稳定纳米零价铁在空气中暴露25天时,依然保持很高的活性,对NDMA的去除率高达91.5%。
实施例2
一种海藻渣稳定纳米零价铁的制备方法,如实施例1所述,所不同的是:
步骤(4)搅拌下,将步骤(2)的溶液A与步骤(1)的海藻渣悬浊液按体积比为1:1的比例混合,搅拌均匀,再逐滴加入硼氢化钠溶液,使得Fe2+:BH4-的摩尔比为1:2,继续搅拌至反应停止。
实施例3
一种海藻渣稳定纳米零价铁的制备方法,如实施例1所述,所不同的是:
步骤(4)搅拌下,将步骤(2)的溶液A与步骤(1)的海藻渣悬浊液按体积比为1:3的比例混合,搅拌均匀,再逐滴加入硼氢化钠溶液,使得Fe2+:BH4-的摩尔比为1:4,继续搅拌至反应停止。
对比例1:中国专利文献CN106000335A公开的一种包覆型纳米零价铁。
对比实验
模拟消毒后水:250mg/L的苯扎氯铵溶液调pH为7.0,取1mL质量浓度10%次氯酸钠溶液加入1L苯扎氯铵溶液中,在25℃的振荡箱中于暗处消毒7天,硫代硫酸钠终止氯反应,反应终止后得消毒后水,消毒后水中消毒副产物亚硝基二甲胺含量183.56ug/L。
分别量取1L消毒后水于1L锥形瓶中,调节pH至7.0,将实施例1-3的海藻渣稳定纳米零价铁与对比例1的包覆型纳米零价铁处理消毒后水,投加量均为1.0g,在25℃条件下震荡24小时,取样测亚硝基二甲胺浓度,计算亚硝基二甲胺的去除率,结果见下表1所示:
表1亚硝基二甲胺的去除率对比
项目 | 亚硝基二甲胺去除率 |
实施例1 | 91.8% |
实施例2 | 90.5% |
实施例3 | 94.5% |
对比例1 | 15.2% |
从上表1中可以看出,本发明的海藻渣稳定纳米零价铁对消毒副产物亚硝基二甲胺有明显处理降解效果,而对比例1的包覆型纳米零价铁处理效果很弱,远远小于本发明的。
Claims (1)
1.一种海藻渣稳定纳米零价铁的制备方法,所述的海藻渣稳定纳米零价铁为海藻渣与铁组成的复合材料,其中,海藻渣包覆在纳米零价铁的表面,海藻渣与纳米零价铁的质量比为:1:1,所述海藻渣稳定纳米零价铁的平均粒径为50~100 nm;
海藻渣稳定纳米零价铁的制备方法,包括步骤如下:
(1)收集海藻渣于温度50~70℃下干燥5-8小时,然后粉碎过100目筛,加入水中搅拌,制得质量浓度为1wt%的海藻渣悬浊液;
(2)称取可溶性铁盐溶于乙醇与水的混合溶液中,制得溶液A,溶液A中硫酸亚铁的浓度为0.3~0.4mol/L;所述的可溶性铁盐为七水合硫酸亚铁;乙醇与水的体积比为:(1~3):(5~10);
(3)取硼氢化钠溶于水中,制得浓度为1.0~1.2mol/L的硼氢化钠溶液;
(4)搅拌下,将步骤(2)的溶液A与步骤(1)的海藻渣悬浊液按体积比为1:(1~3)的比例混合,搅拌均匀,再逐滴加入硼氢化钠溶液,使得Fe2+:BH4 -的摩尔比为1: (3~6),继续搅拌至反应停止;
(5)采用磁选法选出纳米零价铁粒子,用超纯水和无水乙醇分别清洗,然后于真空干燥箱中干燥,真空干燥温度为50~70℃,干燥时间5-8小时,得海藻渣稳定纳米零价铁。
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