高铁酸钾强化铁锰氧化膜过滤去除水中有机物

doi:10.16085/j.issn.1000-6613.2022-0155

摘要/Abstract

摘要：

前期研究发现铁锰氧化膜（MeO _x ）对水中氨氮、铁、锰等污染物具有较高的去除率，但对水中有机物（以COD_Mn计）的去除效果较差。为了提高MeO _x 对COD_Mn的去除率，本研究采用高铁酸钾强化MeO _x 的催化氧化过程，探究其对水中COD_Mn的有效去除及相关影响因素。实验结果表明：仅投加0.1mg/L的高铁酸钾强化MeO _x 过滤，对于进水中20mg/L的COD_Mn，去除率可达到约92.5%；滤速对其具有一定的影响，去除率随着滤速的提高呈下降的趋势，在6~10m/h出水滤速中的COD_Mn均能达到3.0mg/L以下，当滤速达到11m/h时去除率下降到81.65%；较低的pH（约6.51）具有一定的不利影响，COD_Mn的去除率随着pH的降低而逐渐下降；进水中NH₄⁺也会影响COD_Mn的去除，NH₄⁺浓度越高其去除率越低。扫描电子显微镜（SEM）结果显示，高铁酸碱强化过滤约60天后，可在MeO _x 的表面生成某种物质；由电子能谱（EDS）分析MeO _x 表面可知，约60天后C元素和O元素的比例明显增加，Mn元素和Fe元素的比例明显降低，但MeO _x 表面减少的部分铁锰物质并未影响COD_Mn的去除；由X射线光电子能谱（XPS）分析可知，Mn元素强化过滤前后对应的化合物主要为MnO、Mn₂O₃以及Mn₃O₄，对C、O元素分析后发现附着在MeO _x 表面的物质为(CH₂)₄O_n。

关键词: 高铁酸钾, 高锰酸盐指数, 强化过滤, 铁锰氧化膜

Abstract:

Previous studies have found that the iron-manganese oxide film (MeO _x ) has a high removal efficiency for ammonium, iron and manganese in water, but the removal efficiency of organic matter (in COD_Mn) is poor. To improve the removal efficiency of MeO _x for COD_Mn, the potassium ferrate was used to strengthen the catalytic oxidation process of MeO _x, and its effective removal of COD_Mn and some influencing factors were explored in this study. The experimental results were showed that when only 0.1mg/L of potassium ferrate was added into the influent, the removal efficiency could be about 92.5% for 20mg/L COD_Mn in the influent. The filtration rate (v) had a certain influence on the removal of COD_Mn. The removal efficiency of COD_Mn would gradually decrease with increasing filtration rate, and the concentration of COD_Mn in the effluent could be 3.0mg/L (v=6—10m/h). When the filtration rate reached 11m/h, the removal efficiency of COD_Mn would reduce to 81.65%. The lower pH (about 6.51) had certain adverse effect, and the removal efficiency of COD_Mn would gradually decrease with the decrease of pH. The NH₄⁺ in the influent would also affect the removal of COD_Mn, and the higher the concentration of NH₄⁺, the lower the removal efficiency for COD_Mn. Scanning electron microscope (SEM) results indicated that some brown substances was formed on the surface of MeO _x after ferric acid-base enhanced filtration for about 60 days. The surface of MeO _x was analyzed by electron energy dispersive spectrometer (EDS). It was found that the proportion of C and O elements were increased and that of Mn and Fe elements were decreased significantly, but the reduced Fe and Mn species did not affect the removal of COD_Mn. X-ray photoelectron spectroscopy (XPS) analysis showed that the compounds corresponding to Mn elements were MnO, Mn₂O₃ and Mn₃O₄ before and after enhanced filtration, and the substances on the surface of MeO _x for C and O elements was (CH₂)₄O_n .

Key words: potassium ferrate, COD_Mn, enhanced filtration, iron-manganese oxide film

中图分类号:

TU991.2

郭英明, 张宇宏, 麻奔, 袁晟晨, 邱文瑄, 杨靖. 高铁酸钾强化铁锰氧化膜过滤去除水中有机物[J]. 化工进展, 2022, 41(11): 6130-6138.

GUO Yingming, ZHANG Yuhong, MA Ben, YUAN Shengchen, QIU Wenxuan, YANG Jing. Removal of COD_Mn in water by potassium ferrate enhanced iron-manganese oxide film filtration and its influencing factors[J]. Chemical Industry and Engineering Progress, 2022, 41(11): 6130-6138.

图/表 11

图1 中试过滤装置示意图

表1 原水水质指标

水质指标	数值	地表水质量标准Ⅲ类（GB 3838—2002）
氨氮/mg·L^-1	0~0.2	≤1.0
硝氮/mg·L^-1	3.8~4.3	≤10.0
锰/mg·L^-1	0~0.05	≤0.10
铁/mg·L^-1	0.051~0.062	≤0.300
COD_Mn/mg·L^-1	0.87~2.10	≤6.00
水温/℃	14.9~26.5	—
pH	7.0~8.0	6.0~9.0
溶解氧/mg·L^-1	8.0~9.5	≥5.0

图2 高铁酸钾对MeO x 的强化作用

图3 不同浓度高铁酸钾对CODMn浓度沿程的影响

图4 不同滤速对CODMn浓度沿程的影响

图5 不同pH对CODMn浓度沿程的影响

图6 NH4+对高铁酸钾强化过滤去除CODMn的影响

图7 60天持续运行进水、出水中CODMn的浓度变化

图8 强化过滤60天后的SEM微观表征

图9 高铁酸钾强化60天后氧化膜表面元素含量的变化

图10 强化过滤60天后XPS能谱图对比

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