铁锰复合氧化膜对水中双酚A的去除及影响因素

doi:10.16085/j.issn.1000-6613.2020-0828

摘要/Abstract

摘要：

前期研究已发现表面负载铁锰氧化膜的石英砂滤料，对水中常见污染物（氨氮、铁、锰等）具有较高的催化氧化能力。本文利用中试过滤系统研究成熟滤料对水中双酚A（BPA）的去除能力，同时考察进水中Mn²⁺的负荷变化对去除水中BPA的影响。结果表明：该系统在仅有BPA负荷时，可去除ΔC_BPA为0.48mg/L，去除率高达95.6%，消耗溶解氧（DO）为5.44mg/L；进水中同时投加BPA和Mn²⁺，当Mn²⁺浓度达到2.0mg/L时，在滤柱前65cm处即可去除ΔC_BPA为0.56mg/L，BPA在后半段无法有效去除。由扫描电子显微镜（SEM）可知，BPA氧化后生成了某种物质，阻塞在氧化膜的孔隙结构中，造成滤料板结，同时发现少许氧化膜裂开脱落；能谱仪（EDS）能谱图显示投加BPA后，C、O元素的含量分别由之前的12.14%、18.50%增加到21.10%、22.58%，而Mn元素由之前的63.18%减少至42.49%，导致氧化膜表面锰氧化物减少；X射线光电子能谱（XPS）能谱图显示，在不同阶段氧化膜的主要化学形态为Mn₃O₄和MnFe₂O₄，而投加BPA后，有机物[—CH₂—H(OH)]_n覆盖在氧化膜表面及空隙中，降低了氧化膜表面的有效活性位，导致了BPA去除效果下降。

关键词: 铁锰氧化膜, 双酚A, 催化氧化, 锰

Abstract:

Previous studies have found that the iron-manganese co-oxide film on the surface of the quartz sand has a high catalytic oxidation capacity for the removal of ammonium and manganese in water. In this study, two pilot-scale filter columns were used to study the removal of bisphenol A (BPA) by the ripening filters, and how the loading change of Mn²⁺ affected the removal of BPA was also investigated. The results showed that 0.48mg/L of BPA was removed with 95.6% of the removal efficiency of BPA and 5.44mg/L of consumed dissolved oxygen (DO). When the Mn²⁺ in influent was about 2.0mg/L, 0.56mg/L of BPA was removed in the 65cm depth of the filter column, and the concentration of BPA did not change obviously in the rest layers of the filter. From scanning electron microscope (SEM), some substance was generated after the oxidation of BPA, which was blocked in the pore structure of the oxide film, causing the compaction of the filter material. At the same time, a small amount of oxide film was found to crack and fall off. Energy dispersive spectrometer (EDS) spectrum indicated that the content increased from 12.14% to 21.10% for C and from 18.50% to 22.58% for O, respectively, but the Mn on the film surface decreases from 63.18% to 42.49%. The reduced manganese substance on the film surface may lead to the decrease in removal of BPA. X-ray Photoelectron Spectroscopy (XPS) energy spectrum showed that the main chemical forms of the oxide film were Mn₃O₄ and MnFe₂O₄, and the presence of [—CH₂—H(OH)]_n covered and blocked the dense porous pores of the film after dosing BPA, which was the main reason for the decrease in the removal efficiency of BPA.

Key words: iron-manganese co-oxide film, bisphenol A, catalytic oxidation, manganese

中图分类号:

X523

黄建雄, 郭英明, 杨靖, 许伟, 王旭, 张瑞峰. 铁锰复合氧化膜对水中双酚A的去除及影响因素[J]. 化工进展, 2021, 40(3): 1551-1557.

HUANG Jianxiong, GUO Yingming, YANG Jing, XU Wei, WANG Xu, ZHANG Ruifeng. Removal of bisphenol A in water by iron-manganese co-oxide film and its influencing factors[J]. Chemical Industry and Engineering Progress, 2021, 40(3): 1551-1557.

图/表 7

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水质指标	单位	数值	地下水质量标准（GB/T 14848—2017）	水质指标	单位	数值	地下水质量标准（GB/T 14848—2017）
氨氮	mg·L^-1	0.018~0.022	≤0.50	溶解氧	mg·L^-1	7.07~8.22	—
硝态氮	mg·L^-1	3.862~4.103	≤20.0	COD_Mn	mg·L^-1	1.98~2.10	—
亚硝态氮	mg·L^-1	0~0.001	≤1.00	总硬度CaCO₃计	mg·L^-1	166~180	≤450
铁	mg·L^-1	0.051~0.062	≤0.30	温度	℃	15.2~18.1	—
锰	mg·L^-1	0~0.05	≤0.10	pH	—	7.2~7.6	6.5~8.5

水质指标	单位	数值	地下水质量标准（GB/T 14848—2017）	水质指标	单位	数值	地下水质量标准（GB/T 14848—2017）
氨氮	mg·L^-1	0.018~0.022	≤0.50	溶解氧	mg·L^-1	7.07~8.22	—
硝态氮	mg·L^-1	3.862~4.103	≤20.0	COD_Mn	mg·L^-1	1.98~2.10	—
亚硝态氮	mg·L^-1	0~0.001	≤1.00	总硬度CaCO₃计	mg·L^-1	166~180	≤450
铁	mg·L^-1	0.051~0.062	≤0.30	温度	℃	15.2~18.1	—
锰	mg·L^-1	0~0.05	≤0.10	pH	—	7.2~7.6	6.5~8.5

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