CN108654557A - 一种水体六价铬深度吸附稳定化材料及其制备方法和应用 - Google Patents

一种水体六价铬深度吸附稳定化材料及其制备方法和应用 Download PDF

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CN108654557A
CN108654557A CN201810542183.8A CN201810542183A CN108654557A CN 108654557 A CN108654557 A CN 108654557A CN 201810542183 A CN201810542183 A CN 201810542183A CN 108654557 A CN108654557 A CN 108654557A
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郭进进
章文贵
龚梅玲
宁小飞
奉向东
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ENVIRONMENTAL PROTECTION TECHNOLOGY Co Ltd
Wuhu Feng Feng Environmental Protection Science And Technology Research Institute Co Ltd
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Wuhu Feng Feng Environmental Protection Science And Technology Research Institute Co Ltd
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Abstract

本发明公开了一种水体六价铬深度吸附稳定化材料及其制备方法和应用。所述水体六价铬深度吸附稳定化材料包括以下重量份的原料，5份海泡石、15‑20份凹凸棒土、25‑55份的膨润土、8‑25份的金属氧化物、25‑35份铁盐、5‑10份的辅助吸附剂。其制备方法为：将海泡石、凹凸棒土、膨润土粉碎至粒径为200～300目后与配方量的金属氧化物、铁盐、辅助吸附剂混合。制备工艺简单，实施方便快捷、去除六价铬效率高，在六价铬浓度低于50ppm的水样中，六价铬去除率均可达99％以上，处理后水体六价铬浓度远低于0.050mg/L，达到国家《地表水环境质量标准》GB3838‑2002 II类水体标准要求，且无二次释放风险，适用于各类工业含Cr(VI)废水、六价铬污染天然水体等深度治理。

Description

一种水体六价铬深度吸附稳定化材料及其制备方法和应用
技术领域
本发明属于水处理技术领域，具体涉及一种水体六价铬深度吸附稳定化材料及其制备方法和应用。
背景技术
铬及其化合物广泛参与工业生产的各个领域，如冶金、电镀、制革、油漆、颜料、印染、制药等行业都有含铬污染物的产生，在追求快发展、高效益的同时，不完善的生产工艺、不合理的排污手段都使得这些行业排出大量含铬的有害物质污染环境。铬在水中主要以Cr(Ⅲ)和Cr(Ⅵ)两种价态存在形式，其中，六价铬是主要的环境污染毒素，毒性比三价铬高100倍，具有强氧化性，能引发皮肤、肠道溃疡，甚至诱发癌变，其在环境中不易被代谢、易被生物富集，严重威胁着人类健康及环境的可持续发展。
目前，对于废水中六价铬离子的去除方法较多，最常见的为化学沉淀法和物理吸附法，其中化学沉淀法主要是还原沉淀法，该方法一般需分段处理，前期需加酸调节废水pH值在2.0～3.0，并投加大量的还原剂将六价铬还原为三价铬，再加入氢氧化钠，调节废水的pH值为8.0～9.0之间，使三价铬完全形成氢氧化铬的沉淀，最后还需要加入絮凝剂加速沉淀沉降，使固、液相分离后，废水排放。该技术方案去除工艺繁琐，且大量处理时成本较高，天然水体无法实施。
物理吸附法利用具有高表面积或表面具有多孔隙结构的物质作为复合吸附材料，其吸附性能稳定，但仅靠单一种类材料的吸附作用，很难完全去除铬污染，并达到国家污水排放标准。
发明内容
为解决上述技术问题，本发明提供了一种水体六价铬深度吸附稳定化材料及其制备方法和应用。将天然多孔粘土矿物如凹凸棒土、海泡石、膨润土等作为吸附材料主体成分的同时，添加了廉价铁盐、金属氧化物及辅助吸附剂等组分，协同高效去除废水中六价铬，所述水体六价铬深度吸附稳定化材料的吸附效率高、去除工艺简单，且原料易得、成本低廉又满足含铬废水深度处理的要求，处理后废水能达到国家排放要求。
本发明采取的技术方案为：
一种水体六价铬深度吸附稳定化材料，包括以下重量份的原料，5份海泡石、15-20份凹凸棒土、25-55份的膨润土、8-25份的金属氧化物、25-35份铁盐、5-10份的辅助吸附剂。
所述海泡石、凹凸棒土、膨润土的粒径均为200～300目。粒径大小直接影响它们的吸附性能，粒径过大吸附性能差，对六价铬去除效果下降，粒径过小，工业生产成本增加，经济效益下降。
所述金属氧化物为铁氧化物、铝氧化物的一种或多种。所述金属氧化物占所述凹凸棒土、膨润土和海泡石质量之和的10-30％。金属氧化物具有绿色高效且易得的优点，可用于水体含氧阴离子官能团的辅助吸附去除。
所述铁盐可以为七水合硫酸亚铁、无水硫酸铁、六水合氯化铁的一种或多种。所述铁盐占所述凹凸棒土、膨润土和海泡石质量之和的30-65％。以上这些铁盐均是廉价易得产品，相较其他的铁盐去除效率无明显改变且大大降低水体六价铬深度吸附稳定化材料的生产成本。
所述辅助吸附剂为聚合硫酸铁、聚丙烯酰胺、聚合氯化铝的一种或多种。所述辅助吸附剂占所述凹凸棒土、膨润土和海泡石质量之和的2-15％。辅助吸附剂的加入能够加速水体微粒的絮凝、下沉、分离，快速清洁水体环境。
本发明还提供了所述水体六价铬深度吸附稳定化材料的制备方法，包括以下步骤：
(1)将凹凸棒土、膨润土、海泡石分别破碎过筛至200～300目，并于回转窑中110～150℃下干燥1～3h；
(2)将配方量的各原料真空吸料于混料机器中，混合搅拌10-30min，出料密封包装，即可得到所述水体六价铬深度吸附稳定化材料。
本发明还提供了所述水体六价铬深度吸附稳定化材料在含铬废水处理中的应用。
在应用于含铬废水处理时，针对pH值3～10、六价铬浓度低于50ppm污染水体，将占水体质量0.05％～0.1％的水体六价铬深度吸附稳定化材料均匀投加于水中并震荡吸附4h，静置后六价铬去除率可达99.9％以上，即可达到国家《地表水环境质量标准》GB3838-2002II类水体标准要求，且材料吸附稳定后无二次释放风险，适用于各类工业含Cr(VI)废水、六价铬污染天然水体等深度治理。
本发明提供的水体六价铬深度吸附稳定化材料的配方中，将海泡石、凹凸棒土、膨润土作为主体吸附材料，并添加了廉价铁盐、金属氧化物及辅助吸附剂对六价铬进一步吸附，并加速微粒的絮凝和下沉。
与现有技术相比，本发明具备以下优点：
(1)本发明中的水体六价铬深度吸附稳定化材料的原料易得、成本低廉、制备工艺简单；
(2)针对六价铬的去除效果优异；在六价铬浓度为10mg/L和50mg/L的水样中铬去除率均可达99％以上，处理后的六价铬浓度可以降低到0.050mg/L以下，达到国家《地表水环境质量标准》GB3838-2002II类水体标准要求；
(3)应用于含铬废水的处理时，水体六价铬深度吸附稳定化材料的投加量小，投加水体质量的0.05％～0.1％的水体六价铬深度吸附稳定化材料，10mg/L的含六价铬水样铬浓度即可降低至0.050mg/L以下；
(4)在进行含铬废水处理时，无需任何大型设备，直接投撒即可；
(5)水体六价铬深度吸附稳定化材料适用于pH 3～10范围的含铬水体处理，且使用后能有效调节水体酸碱度，使水体pH值稳定在6.0～7.5，有利于水体生态环境的恢复。
具体实施方式
下面结合实施例对本发明进行详细说明。
实施例1
一种水体六价铬深度吸附稳定化材料，包括以下重量份的原料：5份海泡石、20份凹凸棒土、25份的膨润土、5份的铁氧化物、5份铝氧化物、25份七水合硫酸亚铁、5份的聚丙烯酰胺。
其制备方法包括以下步骤：
(1)凹凸棒土、膨润土、海泡石分别破碎过筛至200～300目，并于回转窑中110℃下干燥2h后，于料仓中存储备用；
(2)将处理后的5份海泡石、20份凹凸棒土、25份的膨润土和配方量的铁铝氧化物、七水合硫酸亚铁、聚丙烯酰胺称量、真空吸料于混料机器中混合搅拌30min，即可得到所述水体六价铬深度吸附稳定化材料。
将本实施例得到的水体六价铬深度吸附稳定化材料进行六价铬静态吸附实验，具体为：称取干燥后的重铬酸钾配制六价铬浓度为9.89mg/L的水样，pH值为5.0。室温下，称取0.2g水体六价铬深度吸附稳定化材料加入到200mL含铬水样中，室温下在摇床上震荡吸附4h，静置后取样，过滤，使用水质快速检测仪检测水样中六价铬浓度，并计算六价铬去除率。
经检测，材料处理后9.89mg/L含六价铬水样中的铬浓度降为0.005mg/L，六价铬去除率为99.9％，处理后水体pH值为7.05。
实施例2
一种水体六价铬深度吸附稳定化材料，包括以下重量份的原料：5份海泡石、20份凹凸棒土、35份的膨润土、15份的铁氧化物、15份七水合硫酸亚铁、10份硫酸铁、9份的聚合氯化铝。
其制备方法包括以下步骤：
(1)凹凸棒土、膨润土、海泡石分别破碎过筛至200～300目，并于回转窑中120℃下干燥2h后，于料仓中存储备用；
(2)将处理后的5份海泡石、20份凹凸棒土、35份的膨润土和配方量的铁氧化物、七水合硫酸亚铁、硫酸铁、聚合氯化铝称量、真空吸料于混料机器中混合搅拌30min，即可得到所述水体六价铬深度吸附稳定化材料。
将本实施例得到的水体六价铬深度吸附稳定化材料进行六价铬静态吸附实验，具体为：称取干燥后的重铬酸钾配制六价铬浓度为9.44mg/L的水样，pH值为5.0。室温下，称取0.1g水体六价铬深度吸附稳定化材料加入到200mL含铬水样中，室温下在摇床上震荡吸附4h，静置后取样，过滤，使用水质快速检测仪检测水样中六价铬浓度，并计算六价铬去除率。
经检测，材料处理后9.44mg/L含六价铬水样中的铬浓度降为0.003mg/L，六价铬去除率为99.9％，处理后水体pH值为7.10。
实施例3
一种水体六价铬深度吸附稳定化材料，包括以下重量份的原料：5份海泡石、15份凹凸棒土、35份的膨润土、10份的铁氧化物、5份的铝氧化物、25份七水合硫酸亚铁、10份的氯化铁、5份的聚合硫酸铁。
其制备方法包括以下步骤：
(1)凹凸棒土、膨润土、海泡石分别破碎过筛至200～300目，并于回转窑中140℃下干燥2h后，于料仓中存储备用；
(2)将处理后的5份海泡石、15份凹凸棒土、35份的膨润土和配方量的铁铝氧化物、七水合硫酸亚铁、氯化铁、聚合硫酸铁称量、真空吸料于混料机器中混合搅拌30min，即可得到所述水体六价铬深度吸附稳定化材料。
将本实施例得到的水体六价铬深度吸附稳定化材料进行六价铬静态吸附实验，具体为：称取适量干燥后的重铬酸钾配制六价铬浓度为48.2mg/L的水样，pH值为4.8。室温下，称取0.2g制备的水体六价铬深度吸附稳定化材料加入到200mL含铬水样中，室温下在摇床上震荡吸附4h，分别静置1h和三个月后取样，过滤，使用水质快速检测仪检测水样中六价铬浓度，并计算六价铬去除率。
经检测，48.2mg/L含六价铬水样投加材料处理后，静置1h，水样中六价铬浓度降为0.03mg/L，六价铬去除率为99.9％，处理后水体pH值为6.45。放置三个月后，六价铬水样中的铬浓度为0.028mg/L，六价铬去除率仍为99.9％，处理后水体pH值为6.51，说明制备的水体六价铬深度吸附稳定化材料能够稳定去除六价铬且无二次释放风险。
对比例1
一种水体六价铬深度吸附稳定化材料，包括以下重量份的原料：5份海泡石、10份凹凸棒土、25份的膨润土、15份七水合硫酸亚铁、5份的聚合硫酸铁。
其制备方法包括以下步骤：将配方量的5份海泡石、10份凹凸棒土、25份的膨润土、15份七水合硫酸亚铁、5份的聚合硫酸铁在混料机中混合30min，即可得到所述水体六价铬深度吸附稳定化材料。
将本对比例得到的水体六价铬深度吸附稳定化材料进行六价铬静态吸附实验，具体为：称取干燥后的重铬酸钾配制六价铬浓度为48.0mg/L的水样，pH值为4.8。室温下，称取0.5g制备的水体六价铬深度吸附稳定化材料加入到200mL含铬水样中，室温下在摇床上震荡吸附4h，静置后取样，过滤，使用水质快速检测仪检测水样中六价铬浓度，并计算六价铬去除率。
经检测，材料处理后的48.0mg/L含六价铬水样中的铬浓度降为1.09mg/L，未达到国家《地表水环境质量标准》GB3838-2002II类水体标准要求，六价铬去除率为97.73％，处理后水体pH值为6.9。
对比例2
一种水体六价铬深度吸附稳定化材料，包括以下重量份的原料：5份海泡石、10份凹凸棒土、25份的膨润土、5份的铁氧化物、10份无水硫酸铁、5份的聚合硫酸铁。
其制备方法包括以下步骤：将5份海泡石、10份凹凸棒土、25份的膨润土、5份的铁氧化物、10份无水硫酸铁、5份的聚合硫酸铁直接真空吸料于混料机中混合30min，即可得到所述水体六价铬深度吸附稳定化材料。
将本比较例得到的水体六价铬深度吸附稳定化材料在含六价铬水样中进行铬的静态吸附实验，具体为：称取干燥后的重铬酸钾配制六价铬浓度为52.15mg/L的水样，pH值为4.8。室温下，称取0.5g制备的水体六价铬深度吸附稳定化材料加入到200mL含铬水样中，室温下在摇床上震荡吸附4h，静置后取样，过滤，使用水质快速检测仪检测水样中六价铬浓度，并计算六价铬去除率。
经检测，水体六价铬深度吸附稳定化材料处理后的52.15mg/L含六价铬水样中的磷浓度降为1.85mg/L，未达到国家《地表水环境质量标准》GB3838-2002II类水体标准要求，六价铬去除率为96.45％，处理后水体pH值为6.8。
上述参照实施例对一种水体六价铬深度吸附稳定化材料及其制备方法和应用进行的详细描述，是说明性的而不是限定性的，可按照所限定范围列举出若干个实施例，因此在不脱离本发明总体构思下的变化和修改，应属本发明的保护范围之内。

Claims (10)

1.一种水体六价铬深度吸附稳定化材料，其特征在于，包括以下重量份的原料，5份海泡石、15-20份凹凸棒土、25-55份的膨润土、8-25份的金属氧化物、25-35份铁盐、5-10份的辅助吸附剂。
2.根据权利要求1所述的水体六价铬深度吸附稳定化材料，其特征在于，所述海泡石、凹凸棒土、膨润土的粒径均为200～300目。
3.根据权利要求1所述的水体六价铬深度吸附稳定化材料，其特征在于，所述金属氧化物为铁氧化物、铝氧化物的一种或多种。
4.根据权利要求1或3所述的水体六价铬深度吸附稳定化材料，其特征在于，所述金属氧化物占所述凹凸棒土、膨润土和海泡石质量之和的10-30％。
5.根据权利要求1所述的水体六价铬深度吸附稳定化材料，其特征在于，所述铁盐可以为七水合硫酸亚铁、无水硫酸铁、六水合氯化铁的一种或多种。
6.根据权利要求1或5所述的水体六价铬深度吸附稳定化材料，其特征在于，所述铁盐占所述凹凸棒土、膨润土和海泡石质量之和的30-65％。
7.根据权利要求1所述的水体六价铬深度吸附稳定化材料，其特征在于，所述辅助吸附剂为聚合硫酸铁、聚丙烯酰胺、聚合氯化铝的一种或多种。
8.根据权利要求1或7所述的水体六价铬深度吸附稳定化材料，其特征在于，所述辅助吸附剂占所述凹凸棒土、膨润土和海泡石质量之和的2-15％。
9.根据权利要求1所述的水体六价铬深度吸附稳定化材料的制备方法，其特征在于，包括以下步骤：
(1)将凹凸棒土、膨润土、海泡石分别破碎过筛至200～300目，并于回转窑中110～150℃下干燥1～3h；
(2)将配方量的各原料真空吸料于混料机器中，混合搅拌10-30min，出料密封包装，即可得到所述水体六价铬深度吸附稳定化材料。
10.根据权利要求1所述的水体六价铬深度吸附稳定化材料在含铬废水处理中的应用，其特征在于，对于pH值3～10、六价铬浓度低于50ppm污染水体，将占水体质量0.05％～0.1％的水体六价铬深度吸附稳定化材料均匀投加于水中并震荡吸附4h，静置后六价铬去除率可达99.9％以上，即可达到国家《地表水环境质量标准》GB3838-2002II类水体标准要求，且吸附稳定后无二次释放风险。
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