多羟基结构态亚铁化合物预处理含亚硒酸盐工业废水的影响机制

doi:10.7503/cjcu20160435

摘要/Abstract

摘要：

采用沉淀法制备了多羟基结构态亚铁化合物(FHC), 对其用于含亚硒酸盐的工业废水处理进行了研究. 实验结果表明, 当pH=8时, FHC对Se(Ⅳ)的去除率为40%; 当Cu(Ⅱ)的浓度为0.5 mmol/L, pH=6.5, 8.0和9.5时, FHC对Se(Ⅳ)去除率为80%, 90%和53%. 在其它条件都相同时, 银(Ⅰ)浓度为0.3 mmol/L时, Se(Ⅳ)的去除率为93%, 99%, 98%. 而当pH=8, 亚硝酸根(N $O 2 -$ )离子浓度分别为0.2, 2.0和20.0 mmol/L时, FHC对Se(Ⅳ)去除率依次为30%, 24%和21%, 亚硝酸盐的存在明显抑制Se(Ⅳ)的去除. 采用光电子能谱(XPS)和X射线衍射(XRD)对产物进行了表征, 发现Ag(Ⅰ)被还原为银单质, Cu(Ⅱ)被还原为氧化亚铜, 亚硒酸盐被固定在FHC表面. 采用连续浸提技术对反应后Se形态的分析结果表明, 元素硒、硒化物结合态为主要的形态, 还原是阻滞硒迁移的主要路径. FHC对含硒废水以及其它污染物具有较强的混凝吸附作用, 并且有较大的还原作用, 为处理工业废水提供了新的工艺技术.

关键词: 多羟基结构态亚铁化合物, 亚硒酸盐, 金属离子, 亚硝酸盐, 连续浸提

Abstract:

Se(Ⅳ) and Se(Ⅵ) were found in treatment of industrial wastewater, especially toxicity and highly radioactivity of Se(Ⅳ) are seriously hazardous to the natural environment. The ferrous hydroxyl complex(FHC), structural Fe(Ⅱ), was synthesized by precipitation method, and for the treatment of industrial wastewater containing selenite were investigated by FHC. The results showed that Se(Ⅳ) removal rate was 40% by FHC when pH value was 8. Se(Ⅳ) removal rate were 80%, 90%, 53% by FHC when pH values were 6.5, 8, 9.5, respectiverly, and Cu(Ⅱ) concentration was 0.5 mmol/L. In other conditions being the same, Se(Ⅳ) removal rate was 93%, 99%, 98% when Ag(Ⅰ) concentration was 0.3 mmol/L. However, in the pH value of 8, Se(Ⅳ) removal rate was 30%, 24% and 21% when nitrite concentration was 0.2, 2 and 20 mmol/L. This result showed that the nitrite has an obviously inhibition in Se(Ⅳ) removal. The samples were characterized via X-ray photoelectron spectroscopy(XPS) and X-ray diffraction(XRD), which indicated silver ions converted into elemental silver, copper ions were reduced into cuprous oxide, selenite were fixed onto the structure state ferrous surface and reduced for oxidation state of selenium. By sequential extraction procedure, analysis on selenium in sediments has been found that selenide and element Se was the main reduction product, which indicated the reduction immobilization was mainly selenite removal envelope. Owing to FHC strong coagulation and reduction ability, it should be of practically potential for treatment of industrial waste water.

Key words: Structure state ferrous hydroxyl complex, Selenite, Metal ion, Nitrite, Sequential extraction

中图分类号:

TrendMD:

付茂, 吴德礼, 张亚雷, 张勇. 多羟基结构态亚铁化合物预处理含亚硒酸盐工业废水的影响机制. 高等学校化学学报, 2016, 37(12): 2221.

FU Mao, WU Deli, ZHANG Yalei, ZHANG Yong. Removal Research of Selenite in Wastewater with the Ferrous Hydroxyl Complex(FHC)^†. Chem. J. Chinese Universities, 2016, 37(12): 2221.

图/表 8

Fig.1 Effect of nitrite on FHC reacted with Se(Ⅳ)Initial [Se(Ⅳ)]=20 mg/L; FHC dosage=35 mg/L; pH=8; ion concentrations of nitrite was 0.2, 2.0 and 20.0 mmol/L; t=1 h.

Fig.2 Effects of pH values and different concentrations of Ag(Ⅰ) on FHC reacted with Se(Ⅳ)Initial [Se(Ⅳ)]=20 mg/L; FHC dosage=35 mg/L; pH=6.5, 8, 9.5; ion concentrations of Ag(Ⅰ) was 0.03, 0.1 and 0.3 mmol/L; t=1 h.

Fig.3 Effects of pH values or different concentrations of Cu(Ⅱ) on FHC reacted with Se(Ⅳ) Initial [Se(Ⅳ)]=20 mg/L; FHC dosage=35 mg/L;pH=6.5, 8, 9.5; ion concentrations of Cu(Ⅱ) was 0.1, 0.5 and 1 mmol/L; t=1 h.

Fig.4 Ag3d3 XPS survey spectrum(A) and XPS spectrum(B) of FHC reacted with Se(Ⅳ) in the presence of Ag(Ⅰ)

Fig.5 XPS survery spectrum(A) and Cu3p XPS spectra(B, C) of FHC reacted with Se(Ⅳ) in the presence of Cu(Ⅱ)

Fig.6 XRD patterns of FHC reacted with Se(Ⅳ) in the presence of Ag(Ⅰ)(A) and Cu(Ⅱ)(B)

Fig.7 XPS spectra of FHC reacted with Se(Ⅳ)(A) Blank; (B) FHC(1∶1); (C) FHC+Se+NO2-; (D) FHC+Se+Cu2+; (E) FHC+Se+Ag+.

Fig.8 Result of sequential extraction of selenium

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