CN109289814B - 一种用于吸附废水中抗生素的磁性碳气凝胶及其制备方法 - Google Patents
一种用于吸附废水中抗生素的磁性碳气凝胶及其制备方法 Download PDFInfo
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Abstract
本发明涉及一种用于吸附废水中抗生素的磁性碳气凝胶及其制备方法,属于环境材料技术领域。一种用于吸附废水中抗生素的磁性碳气凝胶,所述磁性碳气凝胶由碳气凝胶和均匀分布于碳气凝胶孔道中的磁性Fe3O4粒子构成。发明通过在碳气凝胶的反应前驱液中加入适量的磁性纳米粒子分散液,合成出具有磁性响应的磁性碳气凝胶。通过分散剂的作用,使磁性Fe3O4粒子均匀分布于碳气凝胶结构网络中,大大解决了磁性粒子在前驱液中分散不均匀的情况,且磁性粒子的引入并没有影响碳气凝胶的高吸附能力。
Description
技术领域
本发明涉及一种用于吸附废水中抗生素的磁性碳气凝胶及其制备方法,属于环境材料技术领域。
背景技术
自20世纪70年代以来,抗生素广泛使用以及滥用所导致的细菌耐药性已成为威胁人类健康的焦点问题。许多研究表明,污水处理厂并不能完全去除抗生素类药物。目前已有多种抗生素在我国河水、沉积物和污水处理厂中被检测到。此外,由于受到二级处理工艺自身的限制,水污染物浓度在现有水平上已不能再大幅下降。为改善水质和保障人群健康,需要对污水进行深度处理来进一步减少这些化合物,最大限度减少它们与环境和人类的接触,吸附处理是一种有效的途径。
专利CN104525160B公开了一种用于吸附水中抗生素的复合吸附材料的制备方法,通过制备改性多孔炭微球和改性氧化石墨烯,采用包覆和单体聚合的方法制备复合吸附材料,但这种吸附剂制备过程较繁琐,且原料相对昂贵,对抗生素的去除率也不够高。专利CN105642236报道了一种用于去除水溶液中四环素的石墨烯碳纳米管复合气凝胶材料,同样存在原料相对昂贵的问题。
发明内容
基于上述问题,本发明的目的是提供一种用于吸附废水中抗生素的磁性碳气凝胶,所述磁性碳气凝胶同时具有高比表面积、高孔容积和强磁性特点,适用于吸附废水中不同种类的抗生素,吸附速度快且吸附效率高。
一种用于吸附废水中抗生素的磁性碳气凝胶,所述磁性碳气凝胶由碳气凝胶和均匀分布于碳气凝胶孔道中的磁性Fe3O4粒子构成。
本发明所述磁性碳气凝胶180min后对模拟废水中土霉素的吸附去除率为96%,对水中左氧氟沙星的去除率最高可达99.8%。
上述技术方案中,所述碳气凝胶的平均孔直径为10nm,比表面积为500~700m2/g,孔容积为1.2~1.5cm3/g。
上述技术方案中,所述磁性Fe3O4粒子的平均粒径为5~40nm。
本发明的另一目的是提供上述用于吸附废水中抗生素的磁性碳气凝胶的制备方法,所述制备方法能够使磁性粒子在碳气凝胶网络结构中分布均匀,并且所制备的磁性碳气凝胶吸附抗生素后可方便从水中分离,能够实现多次循环利用,具有高的回收利用吸附效率。
一种用于吸附废水中抗生素的磁性碳气凝胶的制备方法,所述方法包括如下工艺步骤:
①以间苯二酚和甲醛为原料,无水碳酸钠作催化剂,磁性Fe3O4粒子分散液为溶剂,将反应物共混均匀后,进行酚醛聚合反应,得到有机湿凝胶,其中所述磁性Fe3O4粒子分散液中Fe3O4浓度为0.01~1.0mol/L;
②将步骤①所得有机湿凝胶进行陈化、溶剂替换、冷冻干燥,得有机气凝胶;
③将步骤②所得有机气凝胶在氮气下进行碳化处理,得到磁性碳气凝胶。
优选地,所述磁性Fe3O4粒子分散液按下述方法制得:首先,配制总Fe离子浓度为0.5~5.0mol/L的氯化亚铁与氯化铁的混合水溶液,然后在N2气氛下,将氯化亚铁与氯化铁的混合水溶液10~30mL与浓度为1.0~7.0mol/L的氨水10~50mL滴加到含有分散剂的NH4NO3溶液50~300mL中,其中分散剂用量为0.5~5.0g,NH4NO3溶液浓度为0.1~1.5mol/L,制备出Fe3O4前驱体沉淀物;经过水和乙醇的离心洗涤后,再次加入分散剂0.5~5.0g和去离子水,经搅拌均匀后制得Fe3O4磁性粒子分散液,其中,
所述分散剂为聚乙烯醇、十六烷基三甲基溴化胺、聚乙二醇、有机硅烷偶联剂;所述氯化亚铁与氯化铁的摩尔比为0.45~0.80,优选为0.50~0.75;含有全部原料的总反应液中总Fe离子浓度为0.10~0.50mol/L,优选0.2~0.35mol/L。
上述技术方案中,所述“总Fe离子浓度”指溶液中Fe离子浓度的总和,包括亚铁离子和三价铁离子。
上述技术方案中,所述间苯二酚与甲醛的摩尔比为1:0.5~1:5,优选为1:1~1:4,最优选为1:2~1:3;所述间苯二酚与无水碳酸钠的摩尔比为1:100~1:1000,优选为1:200~1:800,最优选为1:400~1:600;间苯二酚与甲醛混合液与Fe3O4粒子分散液中水的质量比为1:0.5~1:20。
上述技术方案中,所述步骤②中,所述陈化温度为60℃~90℃,优选陈化温度65℃~85℃,最优选陈化温度为75℃~85℃;陈化时间为24h~120h,优选陈化时间48h~90h,最优选陈化时间为60h~80h。
上述技术方案中,所述步骤②中,所述用于替换的有机溶剂为叔丁醇或丙酮,最优选为叔丁醇;冷冻干燥时间为2~48h,优选6~36h,最优为12~30h。
上述技术方案中,所述步骤③中,所述碳化温度为600℃~1100℃,碳化时间为1h~4h,升温速率5~10℃/min;优选碳化温度700℃~1000℃,碳化时间1.5h~3.5h;最优选碳化温度800℃~900℃,碳化时间2h~3h。
本发明的又一目的提供由上述制备方法制得的用于吸附废水中抗生素的磁性碳气凝胶,所述磁性碳气凝胶由碳气凝胶和均匀分布于碳气凝胶孔道结构网络中的磁性Fe3O4粒子构成。
上述磁性碳气凝胶180min后对模拟废水中土霉素的吸附去除率为96%,对水中左氧氟沙星的去除率最高可达99.8%。
上述技术方案中,所述碳气凝胶的平均孔直径为10nm,比表面积为500~700m2/g,孔容积为1.2~1.5cm3/g。
上述技术方案中,所述磁性Fe3O4粒子的平均粒径为5~40nm。
本发明的有益效果:本发明通过在碳气凝胶的反应前驱液中加入适量的磁性纳米粒子分散液,合成出具有磁性响应的磁性碳气凝胶。通过分散剂的作用,使磁性Fe3O4粒子均匀分布于碳气凝胶结构网络中,大大解决了磁性粒子在前驱液中分散不均匀的情况,且磁性粒子的引入并没有影响碳气凝胶的高吸附能力。所述磁性碳气凝胶具有气凝胶结构的典型特征,构成磁性碳气凝胶的纳米粒子均呈现3D网络结构,孔隙分布均匀,具有高的比表面积和孔容积,对模拟废水中的抗生素表现出非常优异的吸附效果(最高吸附去除率可达99.8%);并且磁性粒子的加入使得回收再利用成为可能,再回收利用率高,循环回收利用4次对抗生素的吸附去除率仍然能够达到90%以上。因此,在吸附消除抗生素和水净化方面具有非常广阔的应用前景。此外,本发明所述磁性碳气凝胶的制备方法工艺简单,成本低,对环境无污染,适合于规模化生产。
附图说明
图1为不同实施例所得产物的XRD衍射谱图;a、b、c、d分别为实施例1、实施例2、实施例3和实施例5的XRD衍射谱图,由图可见,所制备的磁性碳气凝胶均含有Fe3O4晶相,说明磁性Fe3O4粒子均匀分散于气凝胶结构中;
图2为实施例2所得产物的SEM照片,由图可看出结构中粒子间堆积形成的分布均匀的孔隙与气凝胶3D网络结构;
图3为实施例2所得产物的磁性响应照片,由图可见,所制备的气凝胶具有良好的磁性,有利于在外加磁场的作用下进行回收再处理,达到重复利用以降低成本的效果。
具体实施方式
下述非限制性实施例可以使本领域的普通技术人员更全面地理解本发明,但不以任何方式限制本发明。
下述实施例中所述试验方法,如无特殊说明,均为常规方法;所述试剂和材料,如无特殊说明,均可从商业途径获得。
下述实施例中,对制备的磁性碳气凝胶的微观结构和吸附性能测试中:
(1)利用以N2为载气的SSA-4200型BET孔径及比表面积分析仪测定磁性碳气凝胶的比表面积、孔径分布、孔体积及平均孔径。
(2)利用X射线衍射仪(D/max-3B,XRD)分析所合成的晶相组成,采用CuKα射线,管电压40.0kV,电流20mA。
(3)配制300毫升50mg/L土霉素溶液和300毫升3×10-5mg/L左氧氟沙星溶液,分别加入0.1g磁性碳气凝胶。室温条件下进行吸附实验,每隔一定时间取上清液离心,测定上清液的吸光度。通过吸光度计算出浓度,并计算出吸附去除率。
实施例1
(1)磁性分散液的制备:在N2气氛保护下,分别将2.9g氯化亚铁和5.2g氯化铁加入到20mL水中配制成氯化亚铁/氯化铁混合液,然后将所得氯化亚铁/氯化铁混合液和3.0mol/L氨水溶液5mL滴加到含有分散剂十六烷基三甲基溴化铵0.36g的100mL0.25mol/L硝酸铵溶液中,制备出Fe3O4前驱体沉淀物;经过水和乙醇的离心洗涤后,再次加入同种等量分散剂十六烷基三甲基溴化铵和100mL去离子水,经搅拌均匀后制得Fe3O4磁性粒子分散液。
(2)磁性碳气凝胶的制备:取1ml磁性Fe3O4分散液和19ml水超声混合均匀作溶剂,加入间苯二酚5.5g,甲醛10ml,催化剂无水碳酸钠0.0106g;将反应物共混均匀后,在80℃进行聚合反应,生成有机湿凝胶,将有机湿凝胶在60℃陈化72h后用叔丁醇进行溶剂置换,冷冻后进行冷冻干燥24h,得有机气凝胶;然后将所得有机气凝胶在N2气氛下于800℃进行碳化处理2h,升温速率为10℃/min,即可制得磁性碳气凝胶。
实施例2
(1)磁性分散液的制备:在N2气氛保护下,分别将2.9g氯化亚铁和5.2g氯化铁加入到20mL水中配制成氯化亚铁/氯化铁混合液,然后将氯化亚铁/氯化铁混合液和3.5mol/L氨水溶液5mL滴加到含有分散剂聚乙二醇2000 1.0g的100mL 0.25mol/L硝酸铵溶液中,制备出Fe3O4前驱体沉淀物;经过水和乙醇的离心洗涤后,再次加入同种等量分散剂聚乙二醇2000和100mL去离子水,经搅拌均匀后制得Fe3O4磁性粒子分散液。
(2)磁性碳气凝胶的制备:取2ml磁性Fe3O4分散液和18ml水超声混合均匀作溶剂,加入间苯二酚5.5g,甲醛10ml,催化剂无水碳酸钠0.0106g;将反应物共混均匀后,在80℃进行聚合反应,生成有机湿凝胶,将有机湿凝胶在60℃下陈化72h后用叔丁醇进行溶剂置换,冷冻后进行冷冻干燥24h,得有机气凝胶;然后将所得有机气凝胶在N2气氛下于800℃经碳化处理2h,升温速率为10℃/min,制得磁性碳气凝胶。
实施例3
(1)磁性分散液的制备:在N2气氛保护下,分别将2.9g氯化亚铁和5.2g氯化铁加入到20mL水中配制成氯化亚铁/氯化铁混合液,然后将氯化亚铁/氯化铁混合液和4.0mol/L氨水溶液5mL滴加到含有分散剂聚乙二醇2000 2.0g的100mL 0.35mol/L硝酸铵溶液中,制备出Fe3O4前驱体沉淀物;经过水和乙醇的离心洗涤后,再次加入同种等量分散剂聚乙二醇2000和100mL去离子水,经过磁力搅拌和超声分散,获得磁性Fe3O4粒子分散液。
(2)磁性碳气凝胶的制备:取3ml磁性Fe3O4分散液和17ml水超声混合均匀作溶剂,加入间苯二酚5.5g,甲醛10ml,催化剂无水碳酸钠0.0106g;将反应物共混均匀后,80℃进行聚合反应,生成有机湿凝胶,将有机湿凝胶在60℃下陈化72h后用叔丁醇进行溶剂置换,冷冻后进行冷冻干燥24h,得有机气凝胶;然后将所得有机气凝胶在N2气氛下于800℃经碳化处理2h,升温速率为10℃/min,制得磁性碳气凝胶。
实施例4
(1)磁性分散液的制备:在N2气氛保护下,分别将2.9g氯化亚铁和5.2g氯化铁加入到20mL水中配制成氯化亚铁/氯化铁混合液,然后将氯化亚铁/氯化铁混合液和6.0mol/L氨水溶液5mL滴加到含有分散剂十六烷基三甲基溴化铵0.36g的100mL 0.35mol/L硝酸铵溶液中,制备出Fe3O4前驱体沉淀物;经过水和乙醇的离心洗涤后,再次加入同种等量分散剂十六烷基三甲基溴化铵和100mL去离子水,经过磁力搅拌和超声分散,获得磁性Fe3O4粒子分散液。
(2)磁性碳气凝胶的制备:取4ml磁性Fe3O4分散液和16ml水超声混合均匀作溶剂,加入间苯二酚5.5g,甲醛10ml,催化剂无水碳酸钠0.0106g;将反应物共混均匀后,80℃进行聚合反应,生成有机湿凝胶,将有机湿凝胶在60℃下陈化72h后用叔丁醇进行溶剂置换,冷冻后进行冷冻干燥24h,得有机气凝胶;然后将所得有机气凝胶在N2气氛下于800℃经碳化处理2h,升温速率为10℃/min,制得磁性碳气凝胶。
实施例5
磁性分散液的制备:在N2气氛保护下,分别将2.9g氯化亚铁和5.2g氯化铁加入到20mL水中配制成氯化亚铁/氯化铁混合液,然后将氯化亚铁/氯化铁混合液和4.0mol/L氨水溶液5mL滴加到含有分散剂十六烷基三甲基溴化铵0.36g的100mL 0.45mol/L硝酸铵溶液中,制备出Fe3O4前驱体沉淀物;经过水和乙醇的离心洗涤后,再次加入同种等量分散剂十六烷基三甲基溴化铵和100mL去离子水,经过磁力搅拌和超声分散,获得磁性Fe3O4粒子分散液。
磁性碳气凝胶的制备:取5ml磁性Fe3O4分散液和15ml水超声混合均匀作溶剂,加入间苯二酚5.5g,甲醛10ml,催化剂无水碳酸钠0.0106g;将反应物共混均匀后,80℃进行聚合反应,生成有机湿凝胶,将有机湿凝胶在60℃下陈化72h后用叔丁醇进行溶剂置换,冷冻后进行冷冻干燥24h,得有机气凝胶;然后将所得有机气凝胶在N2气氛下于800℃经碳化处理2h,升温速率为10℃/min,制得磁性碳气凝胶。
对比例1
(1)磁性分散液的制备:在N2气氛保护下,分别将2.9g氯化亚铁和5.2g氯化铁加入到20mL水中配制成氯化亚铁/氯化铁混合液,然后将氯化亚铁/氯化铁混合液和4.0mol/L氨水溶液5mL滴加到含有分散剂5040 0.5mL的100mL水溶液中,经过磁力搅拌和超声分散,获得磁性Fe3O4粒子分散液,经过静置观察,发现有明显的沉淀分层现象,因此该工艺制备的Fe3O4粒子分散液未能用于制备磁性碳气凝胶。
对比例2
(1)磁性分散液的制备:在N2气氛保护下,分别将2.9g氯化亚铁和5.2g氯化铁加入到20mL水中配制成氯化亚铁/氯化铁混合液,然后将氯化亚铁/氯化铁混合液和4.0mol/L氨水溶液5mL滴加到100mL去离子水中,经过磁力搅拌和超声分散,静置后有明显的沉淀生成和分层现象,因此该工艺制备的Fe3O4粒子分散液未能用于制备磁性碳气凝胶。表1为实施例1~实施例5所对应样品的比表面积、孔容积和平均孔直径测试结果。表2为实施例1~实施例5所对应样品磁性碳气凝胶对抗生素的吸附去除率结果。
表1磁性碳气凝胶的比表面积、孔容积和平均孔直径
表2磁性碳气凝胶对抗生素的吸附去除率
Claims (8)
1.一种用于吸附废水中抗生素的磁性碳气凝胶,其特征在于:所述磁性碳气凝胶由碳气凝胶和均匀分布于碳气凝胶孔道中的磁性Fe3O4粒子构成,
所述用于吸附废水中抗生素的磁性碳气凝胶按下述方法制得:
以间苯二酚和甲醛为原料,无水碳酸钠作催化剂,磁性Fe3O4粒子分散液为溶剂,将反应物共混均匀后,进行酚醛聚合反应,得到有机湿凝胶,其中所述磁性Fe3O4粒子分散液中Fe3O4浓度为0.01~1.0 mol/L;
其中,所述磁性Fe3O4粒子分散液按下述方法制得:首先,配制总Fe离子浓度为0.5~5.0mol/L的氯化亚铁与氯化铁的混合水溶液,然后在N2气氛下,将氯化亚铁与氯化铁的混合水溶液10~30 mL与浓度为1.0~7.0mol/L的氨水10~50 mL滴加到含有分散剂的NH4NO3溶液50~300mL中,其中分散剂用量为0.5~5.0g,NH4NO3溶液浓度为0.1~1.5 mol/L,制备出Fe3O4前驱体沉淀物;经过水和乙醇的离心洗涤后,再次加入分散剂0.5~5.0g和去离子水,经搅拌均匀后制得Fe3O4磁性粒子分散液,其中,
所述分散剂为聚乙烯醇、十六烷基三甲基溴化胺、聚乙二醇、有机硅烷偶联剂;所述氯化亚铁与氯化铁的摩尔比为0.45~0.80;含有全部原料的总反应液中总Fe离子浓度为0.10~0.50mol/L。
2.根据权利要求1所述的磁性碳气凝胶,其特征在于:所述碳气凝胶的平均孔直径为10nm,比表面积为500~700m2/g,孔容积为1.2~1.5cm3/g。
3.根据权利要求1所述的磁性碳气凝胶,其特征在于:所述磁性Fe3O4粒子的平均粒径为5~40nm。
4.权利要求1所述用于吸附废水中抗生素的磁性碳气凝胶的制备方法,其特征在于:所述方法包括如下工艺步骤:
以间苯二酚和甲醛为原料,无水碳酸钠作催化剂,磁性Fe3O4粒子分散液为溶剂,将反应物共混均匀后,进行酚醛聚合反应,得到有机湿凝胶,其中所述磁性Fe3O4粒子分散液中Fe3O4浓度为0.01~1.0 mol/L;
其中,所述磁性Fe3O4粒子分散液按下述方法制得:首先,配制总Fe离子浓度为0.5~5.0mol/L的氯化亚铁与氯化铁的混合水溶液,然后在N2气氛下,将氯化亚铁与氯化铁的混合水溶液10~30 mL与浓度为1.0~7.0mol/L的氨水10~50 mL滴加到含有分散剂的NH4NO3溶液50~300mL中,其中分散剂用量为0.5~5.0g,NH4NO3溶液浓度为0.1~1.5 mol/L,制备出Fe3O4前驱体沉淀物;经过水和乙醇的离心洗涤后,再次加入分散剂0.5~5.0g和去离子水,经搅拌均匀后制得Fe3O4磁性粒子分散液,其中,
所述分散剂为聚乙烯醇、十六烷基三甲基溴化胺、聚乙二醇、有机硅烷偶联剂;所述氯化亚铁与氯化铁的摩尔比为0.45~0.80;含有全部原料的总反应液中总Fe离子浓度为0.10~0.50mol/L。
5.根据权利要求4所述的方法,其特征在于:所述间苯二酚与甲醛的摩尔比为1:0.5~1:5;所述间苯二酚与无水碳酸钠的摩尔比为1:100~1:1000;间苯二酚与甲醛混合液与Fe3O4粒子分散液中水的质量比为1:0.5~1:20。
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