CN114029067B - 一种高效降解有机废水的材料 - Google Patents
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Abstract
本发明涉及一种高效降解有机废水的材料，其特征在于，采用如下方法制备：将硝酸铁、硫酸钠和乙醇胺加入一定体积比的乙二醇和去离子水的混合溶液中，搅拌混合均匀，转入高压水热釜中，在180℃‑200摄氏度条件下下水热反应10‑25h，将产物采用去离子水和乙醇交替洗涤，得到球状α‑Fe2O3；将α‑Fe2O3溶于去离子水中，依次加入KMnO4和柠檬酸、硝酸铋，180‑200摄氏度条件下水热反应，得球状α‑Fe2O3表面负载纳米线Bi‑MnO2复合光催化材料。
Description
技术领域
本发明属于废水处理领域，具体涉及一种含抗生素废水的处理材料。
背景技术
抗生素是抵抗微生物活性的化合物，其主要用于人和动物传染病疾病的预防和治疗。近年来，随着制药业和畜禽养殖养殖业不断发展，滥用抗生素现象越来越多，人体或者动物摄入的抗生素以代谢产物的形式和未变化形态的抗生素进入土壤和水环境，造成水环境、土壤污染，严重威胁生态系统。光催化氧化工艺是抗生素类难降解污染物的一种极具潜力的处理工艺。其中，高效可见光催化剂开发及抗生素光催化降解机制研究至关重要。
CN113426454A公开了一种三维多孔石墨烯负载纳米零价铁/锰氧化物复合材料及其在抗生素水污染方面的应用，其中的制备方法是向氧化石墨烯胶体溶液中加入二价锰盐和高锰酸钾进行水热反应，然后在无氧条件下向水热反应得到的溶液体系中加入二价铁盐和还原剂，搅拌混合以进行还原反应，从而即可得到三维多孔石墨烯负载纳米零价铁/锰氧化物复合材料。
CN113398914A公开了一种一锅水热合成新型p-n异质结Bi2O3/TiO2高效可见光催化剂的制备方法。步骤为：选用钛酸四丁酯和五水硝酸铋，经一锅水热制得钛和铋复合的多孔纳米粒子，最后经程序升温煅烧制备出新型p-n异质结Bi2O3/TiO2可见光催化剂。
发明内容
本发明的目的在于提供一种高效降解有机废水的材料及其制备方法，通过简单水热制备方法制备得到复合材料能够有效促进催化剂对废水中抗生素的催化分解，解决了抗生素废水的处理难题。
一种高效降解有机废水的材料，其特征在于，采用如下方法制备：
将硝酸铁、硫酸钠和乙醇胺加入一定体积比的乙二醇和去离子水的混合溶液中，搅拌混合均匀，转入高压水热釜中，在180℃-200摄氏度条件下反应10-25h，将产物采用去离子水和乙醇交替洗涤，得到球状α-Fe2O3；
将α-Fe2O3溶于去离子水中，依次加入KMnO4和柠檬酸、硝酸铋，180-200摄氏度条件下水热反应，得球状α-Fe2O3表面负载纳米线Bi-MnO2复合光催化材料。
优选的，硝酸铁、硫酸钠和乙醇胺的摩尔比为1：(0.1-1)：(0.2-0.8)；
优选的，乙二醇和去离子水的体积比为1：(1-2)；
优选的，KMnO4和柠檬酸、硝酸铋的摩尔比为1：(0.3-0.8)：(0.01-0.10)。
技术效果：本发明以乙二醇和去离子水作为溶剂，引入乙醇胺，制备得到球状的粒径尺寸在400-700nm的α-Fe2O3，随后将其作为负载体负载线状Bi-MnO2，通过对复合材料形貌的精确调控，避免了活性颗粒团聚的同时，保证Bi-MnO2负载的均一性，通过对MnO2进行Bi掺杂，Bi不仅对调控MnO2形貌有着至关重要的作用，同时，增强MnO2光生载流子的分离效率，能够高效光催化降解废水中的有机抗生素。该光催化材料制备简单，价格低廉，结构稳定，污染物光催化降解效率高，是一种高效的抗生素废水处理光催化材料，为废水尾水中抗生素的治理提供新思路和新材料。
附图说明
图1为本申请制备得到实施例1复合材料的SEM图。
具体实施方式
实施例1
将0.1mol的硝酸铁、0.05mol的硫酸钠和0.05mol乙醇胺加入体积比为1：1的乙二醇和去离子水的混合溶液中，搅拌混合均匀，转入高压水热釜中，在180℃摄氏度条件下反应10h，将产物采用去离子水和乙醇交替洗涤，得到球状α-Fe2O3；
将α-Fe2O3溶于100ml去离子水中，依次加入0.05mol KMnO4和0.025mol柠檬酸、0.002mol硝酸铋，200摄氏度条件下水热反应12h，得球状α-Fe2O3表面负载纳米线Bi-MnO2复合光催化材料。将该光催化剂加入至50ml、浓度30mg/l四环素溶液中，以800W氙灯照射15min，经检测四环素降解率为89％。
对比例1
将0.1mol的硝酸铁、0.05mol的硫酸钠和0.05mol乙醇胺加入体积比为1：1的乙二醇和去离子水的混合溶液中，搅拌混合均匀，转入高压水热釜中，在180℃摄氏度条件下反应10h，将产物采用去离子水和乙醇交替洗涤，得到球状α-Fe2O3。将该光催化剂加入至50ml、浓度30mg/l四环素溶液中，采用800W氙灯照射15min，经检测四环素降解率为76％。
对比例2
在100ml去离子水中，依次加入0.05mol KMnO4和0.025mol柠檬酸、0.002硝酸铋，200摄氏度条件下水热反应12h，得Bi-MnO2。将该光催化剂加入至50ml、浓度30mg/l四环素溶液中，采用800W氙灯照射15min，经检测四环素降解率为80％。
尽管已经示出和描述了本发明的实施例，对于本领域的普通技术人员而言，可以理解在不脱离本发明的原理和精神的情况下可以对这些实施例进行多种变化、修改、替换和变型，本发明的范围由所附权利要求等同物限定。
Claims (2)
1.一种高效降解有机废水的光催化剂，其特征在于，采用如下方法制备：
将硝酸铁、硫酸钠和乙醇胺加入一定体积比的乙二醇和去离子水的混合溶液中，搅拌混合均匀，转入高压水热釜中，在180℃-200摄氏度条件下反应10-25h，将产物采用去离子水和乙醇交替洗涤，得到球状α-Fe2O3；
将α-Fe2O3溶于去离子水中，依次加入KMnO4和柠檬酸、硝酸铋，180-200摄氏度条件下水热反应，得到球状α-Fe2O3表面负载纳米线Bi-MnO2复合光催化材料，该复合材料的粒径为400-700nm；硝酸铁、硫酸钠和乙醇胺的摩尔比为1：(0.1-1)：(0.2-0.8)；KMnO4和柠檬酸、硝酸铋的摩尔比为1：(0.3-0.8)：(0.01-0.10)。
2.根据权利要求1所述的一种高效降解有机废水的光催化剂，乙二醇和去离子水的体积比为1：(1-2)。
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