CN110479270A - 一种壳聚糖石墨烯-Cu-CuFe2O4复合光催化剂及其制备方法与应用 - Google Patents
一种壳聚糖石墨烯-Cu-CuFe2O4复合光催化剂及其制备方法与应用 Download PDFInfo
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Abstract
本发明公开了一种壳聚糖石墨烯‑Cu‑CuFe2O4复合光催化剂及其制备方法与应用，涉及复合光催化剂应用印染污水领域，所述复合光催化剂，其原料包括由壳聚糖制得的壳聚糖石墨烯‑Cu‑CuFe2O4复合光催化剂。所述制备方法安全环保、成本低，在利用壳聚糖石墨烯/Cu/CuFe2O4光催化印染废液制氢的同时，还可降解印染废水中的有机物，生产工艺过程环保，容易操作。
Description
技术领域
本发明涉及复合光催化剂应用印染污水领域，尤其是一种壳聚糖石墨烯-Cu-CuFe2O4复合光催化剂及其制备方法与应用。
背景技术
近年来，随着工业化进程的加快，产生了大量不达标的工业废水，使工业废水的治理成为亟待解决的环境问题。染料废水是工业废水的主要组成部分，它主要来自印刷、食品、印染、纺织及染料生产等行业。2010年，我国染料的产量达到了75.6万吨，占到了当年世界染料总产量60％。染料的生产过程伴随着大量水资源的使用；有数据表明，我国每生产1t的染料就会产生大约744m3的废水。而且在生产和使用染料的过程中流失的染料占到了全部染料产量的15％。染料废水危害极大，主要有以下危害：
1)色度高，大部分合成有机染料都存在芳香环，如苯、蒽、萘、醌等结构，并带有显色团和助色团，使其溶于水后色度很高且化学性质稳定不易分解、难以处理；
2)化学需氧量(COD)高，水溶性极强；通常，酚类、蒽醌类、萘类、芳香类有机物是染料成产所需的原料，在生产过程中原料和染料的流失使得废水中COD含量极高；
3)水质条件波动大，由于染料生产和使用条件的不同，导致染料废水的温度、pH值、色度等具有很大差异，例如硫化染料产生的废水的pH值就可达到10左右；
4)成分复杂，毒性强，染料及染料的中间体都具有可对人类及其他生物产生“三致”(致癌、致畸、致突变)作用的化学结构，具有很强的生物毒性；
5)可生化性差，由于染料及其中间体的化学性质稳定，且废水成分十分复杂多样，使得染料废水的可生化性很差。
2015年4月，我国发布《水污染防治行动计划》，将印染行业列入专项治理的十大重点行业之一，制定了专项治理方案，突显了染料废水治理的重要性。为了处理染料废水，基于物理、化学、生物基础产生的吸附、离子交换、混凝-絮凝、高级氧化、电化学、生物、膜分离等技术被广泛研究。
发明内容
本发明旨在提供一种壳聚糖石墨烯-Cu-CuFe2O4复合光催化剂及其制备方法与应用，该方法安全环保、成本低，在利用壳聚糖石墨烯/Cu/CuFe2O4光催化印染废液制氢的同时，还可降解印染废水中的有机物，生产工艺过程环保，容易操作。
为了实现上述目的，本发明提供的技术方案是：一种壳聚糖石墨烯-Cu-CuFe2O4复合光催化剂，其特征在于，其原料包括由壳聚糖制得的壳聚糖石墨烯-Cu-CuFe2O4复合光催化剂。
一种如上所述壳聚糖石墨烯-Cu-CuFe2O4复合光催化剂的制备方法，包括以下步骤：
1)取壳聚糖干粉在氮气氛围下进行加热升温至550-900℃，得到壳聚糖碳产物，将壳聚糖碳产物与醋酸钾混合进行升温加热反应，即得到壳聚糖石墨烯；
2)将Cu(NO3)2与Fe(NO3)3分别溶解后，按1:1-4的比例逐滴加入100-200mL 2M的柠檬酸溶液中，然后加入1-5g壳聚糖石墨烯，加热至70-90℃恒温搅拌一个小时形成前驱体溶液；然后将其放置在120-150℃的烘箱中将水蒸干，得到CuFe2O4胶体，随后将CuFe2O4胶体放置在400-600℃的马弗炉中高温煅烧，并持续通入空气，确保得到的产物中Cu：Fe的化学计量比为1:1-4的CuFe2O4，即得壳聚糖石墨烯-CuFe2O4复合光催化剂；
3)在含10-20ml乳酸的60-100ml印染污水溶液中，加入1-5g聚乙二醇作为分散剂，加入1-20ml 2mmol/L醋酸铜溶液、铜铁氧体0.05-5g和壳聚糖石墨烯1-5g，搅拌、降温、密封、抽真空，光照，即得原位合成的壳聚糖石墨烯-Cu-CuFe2O4复合光催化剂。
所述步骤1)中壳聚糖碳产物与醋酸钾混合为1:1～10。
所述步骤1)中升温加热反应的反应温度为550-900℃，反应时间为1-5h。
所述步骤3)中铜铁氧体为CuFe2O4和/或壳聚糖石墨烯/Cu/CuFe2O4。
所述步骤3)中光照条件为300W的氙灯，光照时间为3h。
一种如权上所述壳聚糖石墨烯-Cu-CuFe2O4复合光催化剂用于将印染废液制氢及降解废水中的有机物。
本发明与现有技术相比，具有以下优点：
本发明采用壳聚糖石墨烯/Cu/CuFe2O4光催化剂对环境友好，可以将印染污水制备氢气的同时，降解水中有机物；本发明生产工艺简单，成本低廉，安全环保，可以实现连续工业化生产，具有广阔的市场应用前景。
本发明是利用非铁元素与铁元素之间的共沉淀作用生成铁氧体，去除废水中重金属和部分有机污染物、泥沙、微生物及其他可溶性无机盐的一种方法。研究表明，新生态的氧化物往往具有更大的比表面积和更好的吸附性能。故采用铁氧体法处理染料废水，在新生态铁氧体材料生成的同时，很可能实现对染料和重金属的同步有效去除，同时铁氧体自身的磁性会使固液分离更加简捷。
用铜铁氧体/壳聚糖石墨烯/Cu复合光催化剂降解染料废水中的罗丹明B、亚甲基蓝等染料废水的同时，还产生了清洁能源氢。铜铁氧体法具有投资小、设备简单、易操作、处理量大、去除率高、净化效果好和能回收磁性材料等优点，从效果与成本来看，铁氧体法是种较为理想实用的方法，因此在印染工业废水处理中有着广泛应用。
附图说明
图1为实施例1所得壳聚糖石墨烯的拉曼图谱；
图2为壳聚糖石墨烯/Cu/CuFe2O4光催化印染污水制氢。
具体实施方式
为更好地理解本发明，下面结合实施例对本发明做进一步的说明，但本发明的实施方式不限于此。
实施例1
一种利用壳聚糖为原料制备石墨烯材料/Cu/CuFe2O4制备光催化剂的方法取10ml2mmol/L醋酸铜溶液放入到70ml水溶液中，含60ml超纯水，10ml乳酸，1g PEG和5mg壳聚糖石墨烯/Cu/CuFe2O4光催化剂，磁力搅拌，冷却循环水(5℃)降温，将反应温度控制在5℃，在反应器与石英盖间放入橡胶圈，然后打开真空泵，将反应容器内部慢慢抽至真空状态。然后打开光源(300W，PLS-SXE300CUV,Perfect light.Co.Ltd.,Beijing，氙灯)，反应3小时后再次抽真空，光照，即得原位合成的壳聚糖石墨烯-Cu-CuFe2O4复合光催化剂。
在此之后为检测催化剂性能，采用气相色谱每1小时检测一次。检测条件为：选用氮气作为载气，设置柱温箱温度为40℃，设置进样口温度为130℃，设置检测器温度为150℃，设置检测桥电流为50mA。壳聚糖石墨烯/Cu/CuFe2O4光催化印染废水产氢效果1.23mmol/g-1h-1。
经显微拉曼光谱仪测试，壳聚糖拉曼图谱如图1所示，图2为壳聚糖石墨烯/Cu/CuFe2O4光催化印染废水产氢图。
实施例2
一种利用壳聚糖为原料制备石墨烯材料/Cu/CuFe2O4制备光催化剂的方法，取1ml2mmol/L醋酸铜溶液放入到70ml水溶液中，含60ml超纯水，10ml乳酸，1g PEG和10mg壳聚糖石墨烯/Cu/CuFe2O4光催化剂，磁力搅拌，冷却循环水(5℃)降温，将反应温度控制在5℃，在反应器与石英盖间放入橡胶圈，然后打开真空泵，将反应容器内部慢慢抽至真空状态。然后打开光源(300W，PLS-SXE300CUV,Perfect light.Co.Ltd.,Beijing，氙灯)，反应3小时后再次抽真空，在此之后使用气相色谱每1小时检测一次。检测条件为：选用氮气作为载气，设置柱温箱温度为40℃，设置进样口温度为130℃，设置检测器温度为150℃，设置检测桥电流为50mA。壳聚糖石墨烯/Cu/CuFe2O4光催化印染废水产氢效果2.26mmol/g-1h-1。
实施例3
一种利用壳聚糖为原料制备石墨烯材料/Cu/CuFe2O4制备光催化剂的方法，取5ml2mmol/L醋酸铜溶液放入到70ml水溶液中，含60ml超纯水，15ml乳酸，1g PEG和15mg壳聚糖石墨烯/Cu/CuFe2O4光催化剂，磁力搅拌，冷却循环水(5℃)降温，将反应温度控制在5℃，在反应器与石英盖间放入橡胶圈，然后打开真空泵，将反应容器内部慢慢抽至真空状态。然后打开光源(300W，PLS-SXE300CUV,Perfect light.Co.Ltd.,Beijing，氙灯)，反应3小时后再次抽真空，在此之后使用气相色谱每1小时检测一次。检测条件为：选用氮气作为载气，设置柱温箱温度为40℃，设置进样口温度为130℃，设置检测器温度为150℃，设置检测桥电流为50mA。壳聚糖石墨烯/Cu/CuFe2O4光催化印染废水产氢效果1.63mmol/g-1h-1。
实施例4
一种利用壳聚糖为原料制备石墨烯材料/Cu/CuFe2O4制备光催化剂的方法，取15ml2mmol/L醋酸铜溶液放入到75ml水溶液中，含60ml超纯水，15ml乳酸，1g PEG和10mg壳聚糖石墨烯/Cu/CuFe2O4光催化剂，磁力搅拌，冷却循环水(5℃)降温，将反应温度控制在5℃，在反应器与石英盖间放入橡胶圈，然后打开真空泵，将反应容器内部慢慢抽至真空状态。然后打开光源(300W，PLS-SXE300CUV,Perfect light.Co.Ltd.,Beijing，氙灯)，反应3小时后再次抽真空，在此之后使用气相色谱每1小时检测一次。检测条件为：选用氮气作为载气，设置柱温箱温度为40℃，设置进样口温度为130℃，设置检测器温度为150℃，设置检测桥电流为50mA。壳聚糖石墨烯/Cu/CuFe2O4光催化印染废水产氢效果1.29mmol/g-1h-1。
实施例5：
一种利用壳聚糖为原料制备石墨烯材料/Cu/CuFe2O4制备光催化剂的方法，取10ml2mmol/L醋酸铜溶液放入到70ml水溶液中，含60ml超纯水，20ml乳酸，1g PEG和10mg壳聚糖石墨烯/Cu/CuFe2O4光催化剂，磁力搅拌，冷却循环水(5℃)降温，将反应温度控制在5℃，在反应器与石英盖间放入橡胶圈，然后打开真空泵，将反应容器内部慢慢抽至真空状态。然后打开光源(300W，PLS-SXE300CUV,Perfect light.Co.Ltd.,Beijing，氙灯)，反应3小时后再次抽真空，在此之后使用气相色谱每1小时检测一次。检测条件为：选用氮气作为载气，设置柱温箱温度为40℃，设置进样口温度为130℃，设置检测器温度为150℃，设置检测桥电流为50mA。壳聚糖石墨烯/Cu/CuFe2O4光催化印染废水产氢效果0.94mmol/g-1h-1。
Claims (7)
1.一种壳聚糖石墨烯-Cu-CuFe2O4复合光催化剂，其特征在于，其原料包括由壳聚糖制得的壳聚糖石墨烯-Cu-CuFe2O4复合光催化剂。
2.一种如权利要求1所述壳聚糖石墨烯-Cu-CuFe2O4复合光催化剂的制备方法，其特征在于，包括以下步骤：
1)取壳聚糖干粉在氮气氛围下进行加热升温至550-900℃，得到壳聚糖碳产物，将壳聚糖碳产物与醋酸钾混合进行升温加热反应，即得到壳聚糖石墨烯；
2)将Cu(NO3)2与Fe(NO3)3分别溶解后，按1:1-4的比例逐滴加入100-200mL 2M的柠檬酸溶液中，然后加入1-5g壳聚糖石墨烯，加热至70-90℃恒温搅拌一个小时形成前驱体溶液；然后将其放置在120-150℃的烘箱中将水蒸干，得到CuFe2O4胶体，随后将CuFe2O4胶体放置在400-600℃的马弗炉中高温煅烧，并持续通入空气，确保得到的产物中Cu：Fe的化学计量比为1:1-4的CuFe2O4，即得壳聚糖石墨烯-CuFe2O4复合光催化剂；
3)在含10-20ml乳酸的60-100ml印染污水溶液中，加入1-5g聚乙二醇作为分散剂，加入1-20ml 2mmol/L醋酸铜溶液、铜铁氧体0.05-5g和壳聚糖石墨烯1-5g，搅拌、降温、密封、抽真空，光照，即得原位合成的壳聚糖石墨烯-Cu-CuFe2O4复合光催化剂。
3.根据权利要求2所述壳聚糖石墨烯-Cu-CuFe2O4复合光催化剂的制备方法，其特征在于，所述步骤1)中壳聚糖碳产物与醋酸钾混合为1:1～10。
4.根据权利要求2所述壳聚糖石墨烯-Cu-CuFe2O4复合光催化剂的制备方法，其特征在于，所述步骤1)中升温加热反应的反应温度为550-900℃，反应时间为1-5h。
5.根据权利要求2所述壳聚糖石墨烯-Cu-CuFe2O4复合光催化剂的制备方法，其特征在于，所述步骤3)中铜铁氧体为CuFe2O4和/或壳聚糖石墨烯/Cu/CuFe2O4。
6.根据权利要求2所述壳聚糖石墨烯-Cu-CuFe2O4复合光催化剂的制备方法，其特征在于，所述步骤3)中光照条件为300W的氙灯，光照时间为3h。
7.一种如权利要求1所述壳聚糖石墨烯-Cu-CuFe2O4复合光催化剂用于将印染废液制氢及降解废水中的有机物。
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