CN106179500A - 一种高效脱氯复合材料及其制备方法 - Google Patents
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- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 abstract description 26
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 abstract description 16
- 229960002415 trichloroethylene Drugs 0.000 abstract description 15
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Abstract
本发明涉及一种可用于处理地下水含氯烃有机污染物的淀粉负载纳米铁镍高效脱氯复合材料及其制备方法。该脱氯复合材料是以硼氢化钠作为还原剂还原硫酸亚铁，以氯化镍置换出一部分纳米铁作为纳米铁镍双金属，以淀粉为载体，通过液相还原法，获得一种高效脱氯复合材料。本发明制备出的淀粉负载纳米铁镍双金属复合材料不仅可以利用淀粉的还原性实现对纳米铁镍双金属脱氯性能的保护，而且还可以避免纳米铁镍双金属的团聚，增大纳米铁镍双金属的比面积，增强对目标污染物的吸附，从而促进了纳米铁镍双金属对三氯乙烯、氯仿的高效还原脱氯效果。
Description
技术领域
本发明涉及一种原位修复含氯代烃类污染物的地下水的复合试剂的开发，具体来说是一种淀粉负载纳米铁镍双金属脱氯复合材料及其制备方法，属于水处理技术领域。
背景技术
根据污染物的可溶性，可将地下水中污染物分为可溶性污染物和非可溶性污染物。可溶性污染物多为无机物和对水溶解度高的有机物，大多数研究集中在这类污染物；非溶解性污染物为微溶于水的有机碳氢化合物，这类物质与水呈不可混合的状态，与水接触后会形成明显的分层状态，根据其密度的大小，可将其分为低密度非水相流体(Light non-aqueous phase liquid，LNAPL)和高密度非水相流体(dense non-aqueous phase liquid，DNAPL)，LNAPL集中在地下水的表层，而DNAPL由于密度比水大，容易向地下迁移，从而增加了地下水与土壤受污染的深度和广度，进而增加了地下水治理和修复的难度。受DNAPL污染的土壤与地下水的修复已成为国外的研究热点，而国内对此的研究报道甚少。最近，有关国内土壤与地下水的污染情况调查数据引起了广泛的关注，可以预期在未来的一段时间内，特别是“十三”五时间里，治理和修复受污染的地下水和土壤将是我国环境保护领域一项极其重要的工程。
受污染的地下水中最常见的DNAPL污染物有氯仿、三氯乙烯(TCE)、四氯乙烯(PCE)、多氯联苯(PCBs)等氯代有机物(COCs)，它们被广泛地应用于飞机发动机、汽车部件、电子元件以及衣服的脱脂等领域。TCE和氯仿在环境中具有持久性的特点，具有很强的生物毒性和致畸性，已被列入美国环保局优先控制污染物，中国环境优先监测和控制污染物以及欧盟公布的污染物“黑名单”。因此，开展以TCE和氯仿作为DNAPL的代表污染物的修复研究具有极其重要的研究价值和环境意义。
发明内容
本发明的目的在于提供一种高效脱氯复合材料及其制备方法，本发明的高效脱氯复合材料稳定性好，脱氯效果优异，而且制备方法简单、经济，投加到地下水中能高效地将三氯乙烯、氯仿还原，降低地下水中三氯乙烯、氯仿的浓度甚至完全消除，以达到使其转变成无毒或低毒的降解产物的目的，提高地下水的安全性，去除三氯乙烯和氯仿致癌、致畸、致突变的危害。
为达到上述目的，本发明采取的技术方案是：一种高效脱氯复合材料，所述脱氯复合材料是由淀粉和纳米铁镍颗粒所组成，纳米铁镍颗粒均匀地负载在淀粉上。
在复合材料的催化作用下，10小时内对三氯乙烯的降解效率可达到97.2％，对氯仿的降解效率可达到95.6％。
在本发明中，优选的，纳米铁镍颗粒均匀地分散淀粉上，铁镍颗粒的直径为20-50nm；淀粉与铁镍双金属质量比为16～4:1，双金属中铁镍摩尔比为4:1。
进一步的，本发明还提供了上述高效脱氯复合材料的制备方法,将淀粉作为载体加入到蒸馏水于三颈瓶中，同时加入一定量的六水合硫酸亚铁晶体并持续地通入氮气鼓泡，直至制得无氧溶液，并持续通N2，同时进行搅拌，再将采用无氧水配制的硼氢化钠溶液缓慢滴加至上述水溶液中，滴加完毕后再机械搅拌15min使其反应完全；最后向黑色悬浮液中滴加氯化镍溶液机械搅拌15min，并持续通氮气，随后经过一系列处理即得淀粉负载纳米铁镍颗粒脱氯复合材料。
在本发明中，优选的，采用0.8mol/L，100mL的硼氢化钠溶液缓慢滴加到0.05mol/L，100mL的硫酸亚铁溶液中。
在本发明中，优选的，采用一定量的六水氯化镍置换20％的纳米铁，理论上应得铁镍摩尔比为4：1的纳米铁镍双金属。
在本发明中，优选的，反应完全后先采用真空抽滤机对产物进行过滤分离，用无氧水洗涤，紧接着将经过抽滤的饼状双金属块放入真空干燥箱干燥；设置温度50℃，干燥12h，即得到半干的纳米铁镍双金属脱氯复合材料。
上述高效脱氯复合材料的制备方法具体包括以下步骤：
(1)称取1.39g FeSO4·7H2O和2.256g淀粉共同溶解于100mL的无氧水中，放入三口烧瓶，通N2搅拌15min；
(2)用分液漏斗将100mL 0.8mol/L的NaBH4溶液缓慢滴加到Fe2+溶液中，滴加反应过程中产生大量的气体，持续通N2，搅拌15min，将产生的H2及时赶走；理论得到的零价纳米Fe质量为0.28g；
(3)观察反应至不产生气泡，持续通入N2，然后加入0.237g的NiCl2·6H2O到三口烧瓶，置换20％的Fe，反应15min即停止反应，理论得到含有0.224g的Fe、0.058g的Ni的纳米Fe/Ni双金属，双金属的理论质量为0.282g。理论得到的摩尔比Fe：Ni＝4：1的纳米双金属负载在2.256g淀粉表面，淀粉与双金属质量比为8：1；反应完成后，采用真空抽滤机对产物进行过滤分离，用无氧水洗涤，紧接着将经过抽滤的饼状双金属块放入真空干燥箱干燥；设置温度50℃，干燥12h，得到半干的纳米铁镍双金属脱氯复合材料样品。
本发明的淀粉负载纳米铁镍双金属脱氯复合材料的制备方法中，加入的淀粉不但作为载体，分散纳米铁镍双金属，提高纳米铁镍双金属的比表面积，从而提高材料的催化效果；而且淀粉具有的还原性能在制备过程中保护纳米铁镍以免被氧化，发挥复合材料的最大脱氯效能。
本发明与现有技术相比具有以下优点：
(1)本发明制备出的纳米铁镍双金属脱氯剂具有高的比表面积，纳米颗粒比表面积约为2.59㎡/g，比微米级铁颗粒高几十甚至几百倍。
(2)本发明制备出的淀粉负载纳米铁镍双金属脱氯剂具有高的反应活性。例如纳米颗粒对氯代烯烃降解时标准化后的降解速率比文献中报道的微米级铁颗粒高一至两个数量级；在本发明脱氯复合材料的催化作用下，10小时内对三氯乙烯的降解效率可达到97.2％，对氯仿的降解效率可达到95.6％。
(3)本发明成本低廉，对于双金属体系，催化剂为金属钯时，脱氯效果最好，但是由于钯为贵重金属，考虑工程应用的经济性，本发明采用相对更廉价的金属镍替代钯，效果相同的前提下，成本大大降低。
(4)本发明采用淀粉负载铁镍双金属，不仅可以利用淀粉的还原性实现对纳米铁镍双金属脱氯性能的保护，而且还可以避免纳米铁镍双金属的团聚，增大纳米铁镍双金属的比面积，增强对目标污染物的吸附，从而促进了纳米铁镍双金属对三氯乙烯、氯仿的高效还原脱氯效果。
附图说明
图1为淀粉负载纳米铁镍双金属复合材料的SEM图；
图2为三氯乙烯的降解效率随淀粉负载纳米铁镍双金属投加量的关系图；
图3为氯仿的降解效率随淀粉负载纳米铁镍双金属投加量的关系图。
具体实施方式
下面将结合具体实施例进一步阐明本发明的内容，但这些实施例并不限制本发明的保护范围。
实施例1：淀粉负载铁镍双金属纳米颗粒脱氯复合材料的制备
具体步骤如下：
(1)称取1.39g FeSO4·7H2O和2.256g淀粉共同溶解于100mL的无氧水中，放入三口烧瓶，通N2搅拌15min；
(2)用分液漏斗将100mL 0.8mol/L的NaBH4溶液缓慢滴加到Fe2+溶液中，滴加反应过程中产生大量的气体，持续通N2，搅拌15min，将产生的H2及时赶走；理论得到的零价纳米Fe质量为0.28g；
(3)观察反应至不产生气泡，持续通入N2，然后加入0.237g的NiCl2·6H2O到三口烧瓶，置换20％的Fe，反应15min即停止反应，理论得到含有0.224g的Fe、0.058g的Ni的纳米Fe/Ni双金属，双金属的理论质量为0.282g。理论得到的摩尔比Fe：Ni＝4：1的纳米双金属负载在2.256g淀粉表面，淀粉与双金属质量比为8：1。反应完成后，采用真空抽滤机对产物进行过滤分离，用无氧水洗涤，紧接着将经过抽滤的饼状双金属块放入真空干燥箱干燥；设置温度50℃，干燥12h，得到半干的纳米铁镍双金属脱氯复合材料样品。
淀粉负载纳米铁镍双金属复合材料的SEM图见图1。由图1可知：本发明制备出的纳米铁镍双金属脱氯剂粒径范围20-50nm，具有高的比表面积，纳米颗粒比表面积约为2.59㎡/g，比微米级铁颗粒高几十甚至几百倍。
实施例2：淀粉负载铁镍双金属纳米颗粒脱氯复合材料降解三氯乙烯的实验
具体实验步骤如下：
分别称取实施例1制备的淀粉负载铁镍双金属纳米颗粒0.3g、0.5g、0.7g、0.9g、1.1g、1.3g分别放入6瓶装有40mL的三氯乙烯溶液(浓度为73ppm)血清瓶中，编号1-6，以未加入脱氯复合材料装有40mL的三氯乙烯溶液(浓度为73ppm)作为空白对照。置于室温搅拌(650rpm)反应10h后测试脱氯降解效果，如图2所示，除了1号外，所有样品中的三氯乙烯降解效率都在80％以上，最佳投加量是0.7g，10小时内其对三氯乙烯的降解效率可达到97.2％。
实施例3：淀粉负载铁镍双金属纳米颗粒脱氯复合材料降解氯仿的实验
具体实验步骤如下：
分别称取实施例1制备的淀粉负载铁镍双金属纳米颗粒0.3g、0.5g、0.7g、0.9g、1.1g、1.3g分别放入6瓶装有40mL的氯仿溶液(浓度为75ppm)血清瓶中，编号1-6，以未加入脱氯复合材料装有40mL的氯仿溶液(浓度为75ppm)作为空白对照。置于室温搅拌(650rpm)反应10h后测试脱氯降解效果，如图3所示，除了1号外，所有样品中的氯仿降解效率都在80％以上，最佳投加量是0.7g，10小时内其对氯仿的降解效率可达到95.6％。
Claims (6)
1.一种高效脱氯复合材料，其特征在于：所述脱氯复合材料是由淀粉和纳米铁镍颗粒所组成，纳米铁镍颗粒均匀地负载在淀粉上。
2.如权利要求1所述的一种高效脱氯复合材料，其特征在于：纳米铁镍颗粒均匀地分散淀粉上，铁镍颗粒的直径为20-50nm；淀粉与铁镍双金属质量比为16～4:1，双金属中铁镍摩尔比为4:1。
3.一种如权利要求1所述的一种高效脱氯复合材料的制备方法，其特征在于：将淀粉作为载体加入到蒸馏水于三颈瓶中，同时加入一定量的六水合硫酸亚铁晶体并持续地通入氮气鼓泡，直至制得无氧溶液，并持续通N2，同时进行搅拌，再将采用无氧水配制的硼氢化钠溶液缓慢滴加至上述水溶液中，滴加完毕后再机械搅拌15min使其反应完全；最后向黑色悬浮液中滴加氯化镍溶液机械搅拌15min，并持续通氮气，随后经过一系列处理即得淀粉负载纳米铁镍颗粒脱氯复合材料。
4.如权利要求3所述的一种高效脱氯复合材料的制备方法，其特征在于：采用0.8mol/L，100mL的硼氢化钠溶液缓慢滴加到0.05mol/L，100mL的硫酸亚铁溶液中。
5.如权利要求3所述的一种高效脱氯复合材料的制备方法，其特征在于：采用一定量的六水氯化镍置换20％的纳米铁，理论上应得铁镍摩尔比为4：1的纳米铁镍双金属。
6.如权利要求3所述的一种高效脱氯复合材料的制备方法，其特征在于：反应完全后先采用真空抽滤机对产物进行过滤分离，用无氧水洗涤，紧接着将经过抽滤的饼状双金属块放入真空干燥箱干燥；设置温度50℃，干燥12h，即得到半干的纳米铁镍双金属脱氯复合材料。
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