CN107500382A - 新型三维电极光电催化降解工业废水反应器的构建及其催化材料的制备方法 - Google Patents
新型三维电极光电催化降解工业废水反应器的构建及其催化材料的制备方法 Download PDFInfo
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Abstract
本发明公开了一种新型三维电极光电催化降解工业废水反应器的构建及其催化材料的制备方法，其特征在于：反应器为长方体有机玻璃体，反应器外置铝箔壳用以防止紫外光外泄，充分利用光能，反应器的下部设出水管，上部设进水管，管中间连接循环水泵，不锈钢电极为阴极，钛板电极为阳极，分别用导线与直流电源负极和正极相连，紫外灯置于反应器中间，负载Fe2O3的石墨和涂覆TiO2的玻璃珠依次加入反应装置内部，作为催化床层，中间用带孔的隔膜隔开，反应装置底部设曝气装置。本发明结构简单，所用催化材料价格低廉，对废水的处理效率高，解决了粉末状催化剂不利于回收的缺点，极大的增加了反应面积，高效利用了光能。
Description
技术领域
本发明涉及难降解工业废水处理技术领域，具体涉及一种新型三维电极光电催化降解工业废水反应器的构建及其催化材料的制备方法。
背景技术
近年来，随着生活水平的不断提高和工业的不断发展，环境污染引起了广泛的关注。水体中的污染物，尤其是工业生产过程中所排放的高浓度有机污染物种类多，危害大。特别是随着制药行业的不断发展，药物废水的处理给人类带来了巨大挑战。MartaCarballa等在加利西亚，西北西班牙的一个市政污水处理厂的不同单元发现了2种化妆品成分(佳乐麝香，吐纳)，8种药物(卡马西平，双氯芬酸，布洛芬，萘普生***、罗红霉素、磺胺甲恶唑、碘普罗胺)，3种激素(雌酮，***和17a炔雌醇)。相关数据表明药物残留和其代谢产物通常在痕量水平也可以检测到，甚至超低水平也会产生毒性。实际上，传统废水处理工艺如沉降、过滤、混凝絮凝，不足以去除这些。因此，急需有前景的制药废水的处理技术。
近来，光电催化引起了广泛的关注。然而催化剂的回收是阻碍其应用的重大问题，因此迫切需要合适的解决方案。但目前这类研究大多基于二维电极体系，重点在平板电极的制备与性能研究，但薄膜电极面积极其有限，薄膜容易脱落，传质效率、时空产率低，电能消耗较高。与二维电极相比，三维电极光电催化效率能得到显著提高。除了具备一般的电催化效应外，还具备如下特点：粒子电极的介入极大提高了传质与反应面积，立体构型可使催化床内有许多空隙，光透过床层促进液体在三维空间内与催化剂发生作用，负载了催化剂的粒子电极表面上的OH-离子和H2O分子被光生空穴氧化为羟基自由基，该自由基和空穴可共同氧化溶液中的物质及其中间产物；通过粒子电极表面的接触和溶液的介电作用，将阳极的偏压作用传递给整个催化剂体系等。与二维电极方法相比，三维电极光电催化的方法可以获得更高的效率。本发明构建了高效、稳定的三维光电催化反应器，有望提高难降解工业废水处理的效率。
发明内容
本发明的意义在于提供一种高效稳定的新型光电催化反应器，这种催化反应器具有良好的催化降解有机物的活性，同时其催化材料制备过程简便、成本低廉。
本发明的技术方案是这样的：新型三维电极光电催化降解工业废水反应器的构建及其催化材料的制备方法，其特征在于：包括反应器为长方体，反应器的下部设出水管，上部设进水管，管中间连接循环水泵，不锈钢电极为阴极，钛板电极为阳极，通过导线将两电极与直流电源连接，紫外灯置于反应器中间，负载Fe2O3的石墨和涂覆TiO2的玻璃珠依次加入反应装置内部，中间用带孔的隔膜隔开，反应装置底部设曝气装置，反应过程中不断曝气。
本发明提供的光电催化材料是TiO2涂覆玻璃珠和负载Fe2O3的石墨。
本发明提供的TiO2涂覆玻璃珠的制备方法如下：
(1)在室温下，将酞酸丁酯逐滴加入40mL无水乙醇中，搅拌1-2h并静置；
(2)将去离子水和无水乙醇以1∶1的比例混合，并滴加1-5mL的硝酸，充分搅拌1-2h；
(3)将(1)制得溶液逐滴(速率在2滴/秒左右，不能太快)加入(2)的溶液中，同时剧烈搅拌1-5h即得淡黄色透明的溶胶；
(4)将直径为3-4cm的玻璃珠用氢氟酸刻蚀5-10min，用蒸馏水洗净并干燥备用；
(5)将上述玻璃珠浸入所制备的TiO2溶胶中，在室温下沉化5-10d形成凝胶；
(6)将所得凝胶玻璃珠在烘箱中干燥5-10h，干燥后焙烧2-4h；
(7)重复以上步骤，直到得到2-5层稳定的TiO2涂层，即得TiO2涂覆玻璃珠。
本发明提供的负载Fe2O3的石墨催化剂制备方法如下：
(1)将石墨用10％的盐酸浸泡24-48h，反复用蒸馏水冲洗，洗去其灰分，直至为中性，80-120℃烘干5-8h，备用；
(2)配置0.5-1mol/L的Fe(NO)3溶液，将上述石墨浸渍于该溶液中24-48h，80℃烘干5-10h，直到没有水分，将上述石墨于马弗炉中焙烧2-4h，即得负载Fe2O3的石墨催化剂。
在进行光、电及光电催化降解前反应器催化床层经有机废水多次浸泡，直至催化剂吸附饱和，以消除吸附作用的影响。
所述催化床层，解决了催化剂回收问题，极大提高了传质与反应面积，有效利用了光能。
本发明以不锈钢板为阴极，钛板为阳极，并与直流电源相连。当紫外光照射时，催化床层中的TiO2和Fe2O3会产生大量光生电子和空穴，由于TiO2导带负于Fe2O3，所以TiO2上的电子会转移Fe2O3上，而施加的阳极偏压，又促使电子从阳极经过导线转移到阴极，光生电子转移到阴极后一方面与H+和O2生成H2O2，并将Fe3+还原成Fe2+，从而促进芬顿反应的进行(Fe2++H2O2→Fe3++·OH+OH-)，在Fe2O3表面不断发生Fe3+/Fe2+的循环反应，使·OH不断产生，另一方面光生电子与O2反应产生O2 -，而光生空穴则在催化剂表面与H2O反应产生·OH，从而加速污染物的降解，大大降低光生电子和空穴的复合，提高其量子效率，这些活性物质的不断产生，也促使只需较低的外加电压、光电协同效应就十分明显，从而使光电协同催化降解有机废水的效率大大提高。
本发明的有益效果：结构简单，催化床层材料价格低廉，制备方法简便，对废水的处理效率高，解决了粉末状催化剂不利于回收的缺点，极大的增加了反应面积，高效利用了光能，处理过程中产生了大量的活性氧物质(h+，·OH等)，这些物质加速了有机污染物的降解，使得本发明处理废水时间短，效率高。
附图说明
图1是本发明的三维电极光电催化反应器一种具体实施方式的结构示意图。
图2是采用本发明(光电催化)与其它方法光催化、电催化对盐酸黄连素和其COD的去除效果的比较。
图3是本发明对不同pH的盐酸黄连素和其COD的去除效果。
图4是本发明对不同含盐量的盐酸黄连素和其COD的去除效果。
参照附图，图1中1.直流电源；2.不锈钢电极；3.有机玻璃器壁；4.铝箔外壳；5.涂覆TiO2的玻璃珠；6.带孔隔膜；7.负载Fe2O3的石墨；8.曝气装置；9.出水口；10.紫外灯；11.石英管；12.钛板电极；13.进水口；14.循环水泵。
具体实施方案
下面结合附图与应用实例对本发明做进一步说明。
三维粒子电极光电催化氧化难降解有机废水的装置为长方体有机玻璃(3)材质，反应器外置铝箔壳(4)用以防止紫外光外泄，充分利用光能，反应器的下部设出水管(9)，上部设进水管(13)，管中间连接循环水泵(14)，不锈钢电极(2)为阴极，钛板电极(12)为阳极，极板间距为6.5cm，通过导线将两电极与直流电源(1)连接，紫外灯(10)置于反应器中间靠近阳极的位置，功率为40W，主波长253.7nm，负载Fe2O3的石墨(7)和涂覆TiO2的玻璃珠(5)依次加入反应装置内部，中间用带孔的隔膜隔开(6)，反应装置底部设曝气装置(8)，反应过程中不断曝气，使得反应中氧气充沛，不断产生·OH和O2 -，提高反应速率。在进行光、电及光电催化降解前反应器催化床层经有机废水多次浸泡，直至粒子吸附饱和，以消除吸附的影响。
所述玻璃珠直径为3-4cm，反应前用氢氟酸刻蚀5-10min，使其表面粗糙，便于TiO2的涂覆。
所述TiO2为溶胶凝胶方法制备，其为锐钛矿和金红石的混晶，比例为80∶20。
所述二氧化钛涂覆玻璃珠和负载三氧化二铁的石墨催化床层质量比为3∶4。
使用例1：
用本发明新型三维电极光电催化反应器降解600mL，pH值为9，COD为308.2mg/L，含硫酸钠9.6g的200mg/L的黄连素药物废水，电流密度为9mA/cm2，光电催化120min时黄连素去除率为86.26％，COD去除率为70.02％，远高于光催化时的43.81％和33.08％及电催化时的74.83％和56.36％，表明在较低的外加电流和电压下取得了较好的光电协同作用。
使用例2：
用本发明新型三维电极光电催化反应器处理不同pH，600mL，COD为308.2mg/L，含硫酸钠9.6g的200mg/L的黄连素药物废水，其电流密度为9mA/cm2，光电催化60min时pH为3，6，9的黄连素废水黄连素去除率分别为93％，80.04％和77.77％，光电催化120min时COD去除率分别为98.64％，74.12％，59.09％，表明所述光电催化反应器在处理酸性废水时效果最好。
使用例3：
用本发明新型三维电极光电催化反应器处理不同含盐量，600mL，pH值为3，COD为308.2mg/L，200mg/L的黄连素药物废水，电流密度为9mA/cm2，光电催化60min时含盐量为16g/L和8g/L的黄连素废水COD去除率分别为89.23％和65.93％，光电催化120min时分别为98.64％和70.02％，表明所述光电催化反应器对于高盐废水处理效果也很好。
Claims (4)
1.新型三维电极光电催化降解工业废水反应器的构建及其催化材料的制备方法，其特征在于：包括反应器为长方体，反应器的下部设出水管，上部设进水管，管中间连接循环水泵，不锈钢电极为阴极，钛板电极为阳极，通过导线将两电极与直流电源连接，紫外灯置于反应器中间，负载Fe2O3的石墨和涂覆TiO2的玻璃珠依次加入反应装置内部，中间用带孔的隔膜隔开，反应装置底部设曝气装置，反应过程中不断曝气。
2.根据权利要求1所述的新型三维电极光电催化降解工业废水反应器的构建及其催化材料的制备方法，其特征在于：TiO2涂覆玻璃珠和Fe2O3负载石墨作为催化床层，二者最佳质量比为3∶4。
3.根据权利要求1所述的新型三维电极光电催化降解工业废水反应器的构建及其催化材料的制备方法，其特征在于：玻璃珠直径为3-4cm，反应前用氢氟酸等刻蚀5-10min，使其表面粗糙，便于TiO2的涂覆。
4.根据权利要求1或2所述的新型三维电极光电催化降解工业废水反应器的构建及其催化材料的制备方法，其特征在于：TiO2为溶胶凝胶方法制备，其为锐钛矿和金红石的混晶，比例为80∶20。
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