CN107020100B - 一种硅基光催化型磁性分子印迹材料及其制备方法 - Google Patents
一种硅基光催化型磁性分子印迹材料及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种硅基光催化型磁性分子印迹材料及其制备方法,该分子印迹材料是将一定重量和次序的氟钛酸铵、硼酸、氟硅酸铵、氧四环素、FeCl2 1~5%,FeCl3酒石酸钾钠和氢氧化钠通过化学反应合成,之后再经过洗涤、离心、干燥、低温煅烧等步骤制得硅基光催化型磁性分子印迹材料纳米粉体。本发明可准确捕捉水环境中存在的痕量氧四环素,并对之进行催化降解、同时回收率高、不易分解且环境友好的特点。对水环境中存在的痕量抗生素物质有很好的去除作用。
Description
技术领域
本发明属于废水处理技术领域,具体涉及一种硅基光催化型磁性分子印迹材料及其制备方法。
背景技术
当今环境污染日趋严重,水环境污染更是关系到国计民生。国家对水污染的防治措施也越来越重视。城市污水处理厂出水中则检出多种难降解有机污染物,如:抗生素类污染物质等。这是因为现在所应用的污水处理工艺主要是针对COD,氮和磷类污染物的去除。传统的城市污水处理工艺尽管对难降解有机物有一定去除,但是其去除率不高,尤其是微量难降解有机物的去除存在一定问题,而且难降解有机物多是通过物理、化学吸附等途径进行污染转移到活性污泥等吸附载体,并未实现真正去除,因此仍存在一定的二次污染危险。现行的深度处理工艺去除有毒染物,也在不同程度上存在着局限性:活性炭对有毒污染物的吸附效能受到水中天然有机物、pH以及温度的影响,导致竞争吸附;普通膜处理技术对有毒污染物的去除有一定的效果,而这主要取决于有毒污染物的物理和化学性质、膜的特性以及膜的操作条件等;微生物处理方法虽然成本低廉,但是对高毒性污染物降解存在着周期长、自身不具备抗毒性、易受环境因素限制等弱点;一些高级氧化技术理论上可以彻底去除高毒性污染物,但是由于这些方法反应过程比较复杂、没有选择性,去除效果也不明显。因此,如何控制和消除水环境中的高毒性污染物已成为水工业领域亟待解决的难点问题。而既能高效、灵敏、针对性强的对废水中痕量污染物进行捕捉,又能将之去除、且回收率高、可重复性强的水处理材料,则未见报道。
发明内容
针对现有制备技术的缺陷和不足,本发明提供了一种硅基光催化型磁性分子印迹材料及其制备方法,既能高效、灵敏、针对性强的对废水中痕量污染物进行捕捉,又能将之去除,且回收率高、可重复性强。
为了解决上述技术问题,本发明采用如下技术方案予以实现:
一种硅基光催化型磁性分子印迹材料,由以下原料组成:氟钛酸铵、硼酸、氟硅酸铵、氧四环素、醋酸锌、FeCl2、FeCl3、酒石酸钾钠和氢氧化钠。
进一步的,以质量百分计,由以下原料组成:氟钛酸铵为10%~15%、硼酸为10%~15%、氟硅酸铵为1%~5%、氧四环素为10%~15%、醋酸锌为1%~5%、FeCl2为1%~5%、FeCl3为10%~15%、酒石酸钾钠为5%~10%、氢氧化钠为30%~40%,原料的重量百分数之和为100%。
硅基光催化型磁性分子印迹材料的制备方法,包括以下步骤:
步骤一:按原料比将氟钛酸铵和硼酸加入去离子水中,在30~35℃下以280~300r/min的速度搅拌30min;再按原料比加入氟硅酸铵,以280~300r/min的速度搅拌30min;再按原料比加入氧四环素,以280~300r/min的速度搅拌30min;再按原料比一次性加入醋酸锌、FeCl2、FeCl3、酒石酸钾钠和氢氧化钠,以450~500r/min的速度搅拌60min,放置4~6h,得到混合液;
步骤二:将混合液加热,获得上下分层的液体和粉体;
步骤三:将上下分层的液体和粉体分离,将下层的粉体清洗多次后离心,获得粉末材料;
步骤四:将获得的粉末材料干燥后在300℃下煅烧2h,得到硅基光催化型磁性分子印迹材料纳米粉体。
进一步的,所述的步骤三中,分别用蒸馏水和无水乙醇将下层的粉体清洗3次,以每分钟3500r/min的速度离心5min。
进一步的,所述的步骤二中,将混合液在45~50℃下加热20h。
进一步的,所述的步骤四中,将粉末材料在60~70℃下干燥3h。
进一步的,所述的步骤一的反应过程均在无氧状态下进行。
与现有技术相比,本发明的有益效果是:
(1)本发明的材料能够准确、灵敏的捕捉水环境中存在的痕量氧四环素,并对其进行光催化降解,使用精度达到0.001mg/L。
(2)本发明可以利用光催化将捕捉到的污染物质氧四环素矿化,降解为无机物质。
(3)本发明含有磁性材料,可以使粉末投入到水中完成捕捉及降解后,利用磁性快速全面的回收,便于下一次的重复利用。
(4)本发明不易分解,因此可以重复利用,且处理能力不易降低,对环境友好,价格相对便宜,适用广泛。
以下结合实施例对本发明的具体内容作进一步详细解释说明。
具体实施方式
本发明的硅基光催化型磁性分子印迹材料,以质量百分计,由以下原料组成:氟钛酸铵为10%~15%、硼酸为10%~15%、氟硅酸铵为1%~5%、氧四环素为10%~15%、醋酸锌为1%~5%、FeCl2为1%~5%、FeCl3为10%~15%、酒石酸钾钠为5%~10%、氢氧化钠为30%~40%,原料的重量百分数之和为100%。
本发明的上述原料均为市售分析纯制品。
本发明的硅基光催化型磁性分子印迹材料的制备方法,包括以下步骤:
步骤一:按原料比将氟钛酸铵和硼酸加入盛有100mL去离子水的烧杯中,在30~35℃下以280~300r/min的速度搅拌30min;再按原料比加入氟硅酸铵,以280~300r/min的速度搅拌30min;再按原料比加入氧四环素,以280~300r/min的速度搅拌30min;再按原料比一次性加入醋酸锌、FeCl2、FeCl3、酒石酸钾钠和氢氧化钠,以450~500r/min的速度搅拌60min,放置4~6h,得到混合液;
上述反应过程均在无氧状态(氮气吹扫)下进行;
步骤二:将混合液放入水浴中,在45~50℃下加热20h,获得上下分层的液体和粉体;
步骤三:将上下分层的液体和粉体分离,分别用蒸馏水和无水乙醇将下层的粉体清洗3次,以每分钟3500r/min的速度离心5min,倒掉上层清液,获得粉末材料;
步骤四:将获得的粉末材料在60~70℃下干燥3h后,在300℃下煅烧2h,得到硅基光催化型磁性分子印迹材料纳米粉体。
本发明利用以污染物分子为模板制备而得的分子印迹聚合物可以高效灵敏的捕捉该类污染物质,结合光催化剂可以利用光催化降解污染物质的性能,同时磁性材料的加入更加有利于纳米材料的再回首。因此,本硅基光催化型磁性分子印迹材料可准确捕捉水环境中存在的痕量氧四环素,并对之进行光催化降解、同时回收率高、不易分解且环境友好的特点。对水环境中存在的痕量抗生素物质有很好的去除作用。
以下给出本发明的具体实施例,需要说明的是本发明并不局限于以下具体实施例,凡在本申请技术方案基础上做的等同变换均落入本发明的保护范围。
实施例1
将1.98g的氟钛酸铵和1.55g的硼酸放入盛有100mL去离子水的烧杯中,在温度为30~35℃下以300r/min的速度搅拌30min;再加入0.356g氟硅酸铵,以300r/min的速度搅拌30min;再加入1.96g氧四环素继续以300r/min的速度搅拌30min,再一次性加入0.45g醋酸锌、0.6g的FeCl2、1.8g的FeCl3、1g酒石酸钾钠和5g氢氧化钠,以500r/min的速度搅拌60min,放置4h。以上反应在氮气吹扫下进行;
将烧杯放置水浴中,在45~50℃下加热20h;
加热完成后,将上层液体丢弃,轻轻将在烧杯底部散粉刮出,并分别蒸馏水和无水乙醇冲清洗洗3次,然后以3500r/min速度离心5min,倒掉上层清液,得到粉末材料;
将得到的粉末材料放入真空干燥箱中,在70℃下干燥3h,然后将干粉末放入马弗炉中,在300℃下煅烧2小时,最终得到硅基光催化型磁性分子印迹材料纳米粉体。
实施例2
某城市污水厂出水中检测到氧四环素为0.01mg/L,以50mg/L将实施例1获得材料投加至污水中,经过紫外灯(300W)光催化反应30min后,出水中检测不到氧四环素,说明氧四环素得以降解。
利用磁铁将粉末收集后,在真空干燥箱中,在70℃下干燥3h,可重复使用10次,氧四环素均得以降解。
实施例3
自配含氧四环素浓度为20mg/L的废水,经实施例1获得的材料处理后(投加量为500mg/L废水),经过紫外灯(300W)光催化反应30min后,出水中氧四环素去除率可以达到95%。利用磁铁将粉末收集后,在真空干燥箱中在70℃下干燥3h后,可重复使用5次,均得到90%以上去除率的良好效果。
Claims (5)
1.一种硅基光催化型磁性分子印迹材料的制备方法,其特征在于:包括以下步骤:
步骤一:按原料比将氟钛酸铵和硼酸加入去离子水中,在30~35℃下以280~300r/min的速度搅拌30min;再按原料比加入氟硅酸铵,以280~300r/min的速度搅拌30min;再按原料比加入氧四环素,以280~300r/min的速度搅拌30min;再按原料比一次性加入醋酸锌、FeCl2、FeCl3、酒石酸钾钠和氢氧化钠,以450~500r/min的速度搅拌60min,放置4~6h,得到混合液;
其中,制备原料组成为:氟钛酸铵为10%~15%、硼酸为10%~15%、氟硅酸铵为1%~5%、氧四环素为10%~15%、醋酸锌为1%~5%、FeCl2为1%~5%、FeCl3为10%~15%、酒石酸钾钠为5%~10%、氢氧化钠为30%~40%,原料的重量百分数之和为100%;
步骤二:将混合液加热,获得上下分层的液体和粉体;
步骤三:将上下分层的液体和粉体分离,将下层的粉体清洗多次后离心,获得粉末材料;
步骤四:将获得的粉末材料干燥后在300℃下煅烧2h,得到硅基光催化型磁性分子印迹材料纳米粉体。
2.权利要求1所述的硅基光催化型磁性分子印迹材料的制备方法,其特征在于:所述的步骤三中,分别用蒸馏水和无水乙醇将下层的粉体清洗3次,以每分钟3500r/min的速度离心5min。
3.权利要求1所述的硅基光催化型磁性分子印迹材料的制备方法,其特征在于:所述的步骤二中,将混合液在45~50℃下加热20h。
4.权利要求1所述的硅基光催化型磁性分子印迹材料的制备方法,其特征在于:所述的步骤四中,将粉末材料在60~70℃下干燥3h。
5.权利要求1所述的硅基光催化型磁性分子印迹材料的制备方法,其特征在于:所述的步骤一的反应过程均在无氧状态下进行。
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