CN108793422B - 光催化电极耦合微生物燃料电池促进焦化废水处理方法 - Google Patents
光催化电极耦合微生物燃料电池促进焦化废水处理方法 Download PDFInfo
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Abstract
本发明提供了一种光催化电极耦合微生物燃料电池促进焦化废水处理方法，属于焦化废水处理与节能资源化技术领域。用La‑ZnIn2S4/RGO/BiVO4和硅溶胶在不锈钢网上固定涂覆的方法形成导电催化复合膜电极，并在其焦化废水中加入HSO3 ‑,阳极微生物中插入碳棒，用导线连接，构成电路回路，施加卤钨灯作为光源，作用于催化电极上，构成光催化电极耦合微生物燃料电池处理焦化废水系统。分别实现了在不同RGO含量的La‑ZnIn2S4/RGO/BiVO4催化剂条件下催降解焦化废水的效果影响，相同浓度的NaHSO3和Na2SO4溶液对焦化废水的降解效果的影响。
Description
技术领域
本发明属于焦化废水处理与节能资源化技术领域，涉及La-ZnIn2S4/RGO/BiVO4复合催化剂及光催化电极耦合微生物燃料电池组件的制备，及其协同作用，并在反应过程中加入HSO3 -降解处理焦化废水，HSO3 -有助于提高焦化废水降解率，为处理焦化废水起到促进作用。
背景技术
焦化废水主要是由煤工业和石油工业产生的，它是炼焦、煤气在960-1000摄氏度高温干馏、净化过程中，产生的一种较难处理的工业有机废水，其组成成分非常复杂，有硫化物、氰化物、高浓度的氨氮及大量难以生物降解的杂环多环芳香烃化合物等有毒有害物质。不同的处理方法(物理化学法，生化处理法，光催化氧化技术，Fenton试剂法，催化湿式氧化技术等)，在能够发挥降解作用的同时都存在着各自的局限性。目前，将La-ZnIn2S4/RGO/BiVO4三元复合催化剂运用到光催化型微生物燃料电池中降解焦化废水的报道还未出现。
为了提高焦化废水降解效果，实验前期将光催化技术和微生物燃料电池相结合，将催化剂La-ZnIn2S4/RGO/BiVO4引入光催化型微生物燃料电池反应器中，以达到降解的目的。目前，以La-ZnIn2S4/RGO/BiVO4作为催化剂，将光催化技术与微生物燃料电池二者技术相结合，很大程度上降解了焦化废水中的有机污染物含量，在焦化废水处理工艺中有重要意义。
目前，用于穿梭光产生电荷的固态电子介体中已被证明有前景的主要有两种材料，贵金属和还原的氧化石墨烯(RGO)。片状RGO材料在特定的层状结构，化学稳定性，提供了优于贵金属的形态多样性和较低的制备成本。
另外，钒酸铋(BiVO4)因其带隙窄，波长响应范围宽，已被证明是一种具有很好应用前景的光催化剂。BiVO4主要有单斜白钨矿，四方锆石和四方钨白矿3种晶型，其中单斜白钨矿相由于具有较窄的带隙能(2.4eV)，对紫外光和可见光都能产生响应，表现出较好的光催化活性。在以前的研究中，为了提高电荷分离效率和调节BiVO4和底物相互作用，各种金属盐(例如，AgNO3，Cu(NO3)2，Ni(NO3)2，RuCl3，PdCl2等)作为助催化剂负载在BiVO4表面可以改善它的光催化效率。而RGO电子介体可以很容易地扩展到基于半导体的复合光催化系统中,用RGO处理的BiVO4不论在光催氧化分解水还是在有机污染物的降解方面都表现出独特的活性。
而属于ABXCY型半导体三元硫化物ZnIn2S4，因带隙较窄、光催化性能强、比表面积大、吸附性能好等优点，在降解染料废水、光催化分解水制氢等方面受到了广泛好评。通过耦合不同催化剂形成的异质结构可有效提高电荷分离，将不同吸收波长范围的光催化进行耦合可以增大其波长吸收范围，从而提高光催化效率。
本申请以La-ZnIn2S4/RGO/BiVO4作为实验催化剂，希望以此催化剂能够有效降解焦化废水，以达到吸附和降解焦化废水中有机污染物的效果。
发明内容
本发明设计了La-ZnIn2S4/RGO/BiVO4光催化型微生物燃料电池组件，成功构建了光催化电极耦合微生物燃料电池系统。该系统不仅可以用作电极，还兼具光催化效果以及导电作用,整体处理焦化废水的效率大大提高，能耗较低，焦化废水中有机污染物浓度大大降低。该系统理论上可降解焦化废水，扩展了负载型光催化剂的应用，以及在处理其他废水时提供了一些思路。
本发明的技术方案：
光催化电极耦合微生物燃料电池降解焦化废水的方法，步骤如下：
(1)制备La-ZnIn2S4/RGO/BiVO4系列复合物：将Bi(NO3)3·5H2O溶于14wt％HNO3中，搅拌，然后向其中加入CTAB溶液，控制CTAB与Bi(NO3)3·5H2O的质量比为1:15；再添加GO，搅拌，得到混合液A液；
将NH4VO3溶于2mo/l NaOH溶液中，逐滴加入到A液，控制NH4VO3与A液中Bi(NO3)3·5H2O的摩尔比为1:1；用2mol/l NaOH溶液调节pH＝6，搅拌；于200℃温度条件下反应2h，冷却，得到混合物；洗涤，离心，烘干，研磨，获得x RGO/BiVO4，碾磨成粉，即为xRGO/BiVO4；其中，x为RGO/BiVO4中RGO与BiVO4的质量比不大于1.5％；
将Zn(NO3)3·6H2O、In(NO3)3·5H2O以及过量的TAA溶于去离子水中，再加入La(NO3)3和RGO/BiVO4，加入去离子水，搅拌；于80℃温度条件下反应6h，冷却，得到混合物；经离心，烘干，研磨，获得y La-ZnIn2S4/RGO/BiVO4，碾磨成粉，即为yLa-ZnIn2S4/xRGO/BiVO4；其中，La-ZnIn2S4与RGO/BiVO4的质量比为1：5，y为La与ZnIn2S4的质量比0.01；
(2)光催化电极耦合微生物燃料电池膜组件制备：向步骤(1)制备得到的yLa-ZnIn2S4/xRGO/BiVO4系列复合物中添加硅溶胶，yLa-ZnIn2S4/xRGO/BiVO4系列复合物与硅溶胶的比例为1g:1ul，利用超声均匀，将其涂抹于不锈钢网片上，干燥；
(3)光催化电极耦合微生物燃料电池催化处理系统构建：系统通过质子交换膜分为两室，一室中放有微生物，碳棒插入其中，作为阴极；另一室中为加有NaHSO3的焦化废水，步骤(2)制备得到的光催化电极耦合微生物燃料电池膜组件作为阳极，并放置卤钨灯，通过导线连接，形成电路，卤钨灯垂直照射光催化电极耦合微生物燃料电池膜组件。
所述的污染物为焦化废水中的有机污染物。
本发明的有益效果：该系统集成了光催化膜电极和微生物燃料电池产电性能以及耦合协同作用，吸附和降解焦化废水中的有机污染物；对焦化废水中难降解的有机污染物能够有效吸附和降解，该系统中的光催化剂和微生物能够很好地保证其不失去活性，并且能够持续产电。
附图说明
图1是光催化电极与微生物燃料电池耦合系统作用下，加入相同浓度的NaHSO3，不同RGO含量的La-ZnIn2S4/RGO/BiVO4催化剂条件下，降解焦化废水的效果对比题，图中，横坐标为时间(h)，纵坐标为焦化废水的TOC降解效率(％)。
图2是光催化电极与微生物燃料电池耦合系统作用下，阳极焦化废水中分别加入相同浓度的NaHSO3和Na2SO4处理条件下，降解焦化废水效果对比图。图中，横坐标为时间(h)，纵坐标为焦化废水TOC降解效率的(％)。
具体实施方式
以下结合技术方案和附图详细叙述本发明的具体实施方式。
实施例一：不同RGO含量的催化剂降解焦化废水
在光催化膜电极耦合微生物燃料电池的双室长方体反应器系统中，将膜组件和卤钨灯均放入系统中，用碳棒放入用质子交换膜隔开的微生物阳极中，光催化剂接触系统中的含有NaHSO3的焦化废水为光电阴极，阴极室底部有曝气头持续曝气，用鳄鱼夹连接膜上方，将卤钨灯放入反应装置中，反应前关闭卤钨灯电源，先进行0.5h的暗反应后，再打开卤钨灯电源，光反应4h，反应开始后，前2.5小时每隔0.5h用移液枪进行取样，后两小时每隔1.0h取样，反应共进行4.5h，用TOC/TN检测仪检测样品中TOC含量，并计算焦化废水中有机污染物的降解效果。
图1中，0.5％RGO降解效果最佳，为82.02％。
实施例二：含有相同浓度的NaHSO3和Na2SO4的体系降解焦化废水
在光催化膜电极耦合微生物燃料电池的双室长方体反应器系统中，将膜组件和卤钨灯均放入系统中，用碳棒放入用质子交换膜隔开的微生物阳极中，一个是光催化剂接触系统中的含有NaHSO3的焦化废水为光电阴极(另一个是光催化剂接触系统中的含有Na2SO4的焦化废水为光电阴极，其他条件相同)阴极室底部有曝气头持续曝气，用鳄鱼夹连接膜上方，将卤钨灯放入反应装置中，反应前关闭卤钨灯电源，先进行0.5h的暗反应后，再打开卤钨灯电源，光反应4h，反应开始后，前2.5小时每隔0.5h用移液枪进行取样，后两小时每隔1.0h取样，反应共进行4.5h，用TOC/TN检测仪检测样品中TOC含量，并计算焦化废水中有机污染物的降解效果。
图2中，含有NaHSO3的焦化废水和含有Na2SO4的焦化废水进行对比，发现含有NaHSO3的焦化废水光催化膜电极耦合微生物燃料电池的系统中降解焦化废水的效率(82％)远远优于含有Na2SO4的焦化废水的降解效率(15％)。
Claims (2)
1.一种光催化电极耦合微生物燃料电池降解焦化废水的方法，其特征在于，步骤如下：
(1)制备La-ZnIn2S4/RGO/BiVO4系列复合物：将Bi(NO3)3·5H2O溶于14wt％HNO3中，搅拌，然后向其中加入CTAB溶液，控制CTAB与Bi(NO3)3·5H2O的质量比为1:15；再添加GO，搅拌，得到混合液A液；
将NH4VO3溶于2mo/l NaOH溶液中，逐滴加入到A液，控制NH4VO3与A液中Bi(NO3)3·5H2O的摩尔比为1:1；用2mol/l NaOH溶液调节pH＝6，搅拌；于200℃温度条件下反应2h，冷却，得到混合物；洗涤，离心，烘干，研磨，获得x RGO/BiVO4，碾磨成粉，即为xRGO/BiVO4；其中，x为RGO/BiVO4中RGO与BiVO4的质量比不大于1.5％；
将Zn(NO3)3·6H2O、In(NO3)3·5H2O以及过量的TAA溶于去离子水中，再加入La(NO3)3和RGO/BiVO4，加入去离子水，搅拌；于80℃温度条件下反应6h，冷却，得到混合物；经离心，烘干，研磨，获得y La-ZnIn2S4/RGO/BiVO4，碾磨成粉，即为yLa-ZnIn2S4/xRGO/BiVO4；其中，La-ZnIn2S4与RGO/BiVO4的质量比为1：5，y为La与ZnIn2S4的质量比0.01；
(2)光催化电极耦合微生物燃料电池膜组件制备：向步骤(1)制备得到的yLa-ZnIn2S4/xRGO/BiVO4系列复合物中添加硅溶胶，yLa-ZnIn2S4/xRGO/BiVO4系列复合物与硅溶胶的比例为1g:1ul，利用超声均匀，将其涂抹于不锈钢网片上，干燥；
(3)光催化电极耦合微生物燃料电池催化处理系统构建：系统通过质子交换膜分为两室，一室中放有微生物，碳棒插入其中，作为阴极；另一室中为加有NaHSO3的焦化废水，步骤(2)制备得到的光催化电极耦合微生物燃料电池膜组件作为阳极，并放置卤钨灯，通过导线连接，形成电路，卤钨灯垂直照射光催化电极耦合微生物燃料电池膜组件。
2.根据权利要求1所述的光催化电极耦合微生物燃料电池降解焦化废水的方法，其特征在于，所述的污染物为焦化废水中的有机污染物。
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