COD removal from practical pharmaceutical wastewater drived by nZVI/g-C3N4

doi:10.19965/j.cnki.iwt.2022-1006

Abstract

Abstract:

The pharmaceutical wastewater has the characteristics of high COD concentration， high salinity and poor biodegradability， so it is difficult to treat with by simple physical， chemical or biological methods. While the advanced oxidation process is expected to be used for the advanced treatment of pharmaceutical wastewater because of its strong oxidation capacity.Nano zero-valent iron（nZVI） was prepared by liquid phase reduction of ferric chloride with sodium borohydride. Taking graphite phase C₃N₄（g-C₃N₄） as the carrier，a series of Fe/g-C₃N₄ composite materials with different mass ratio of nZVI and g-C₃N₄ were prepared by liquid phase reduction surface deposition for catalyzing the advanced oxidation of COD in pharmaceutical wastewater. g-C₃N₄ can disperse the nZVI load on its surface well and inhibits its agglomeration. In the experiment of removing pharmaceutical wastewater，g-nZVI with mass ratio of nZVI∶g-C₃N₄=2∶1 showed the highest COD removal efficiency. The highest COD removal efficiency determined by treated pharmaceutical wastewater by g-nZVI reached 75% at pH=3 and the dosage of g-nZVI=1.5 g/L. It has sufficed the standard of continuing degradation in the biochemical reaction tank. Mechanism study showed that the main active substances for COD removal were superoxide radicals and hydroxyl radicals generated by molecular oxygen activated processes driven by nZVI.

Key words: nZVI, g-C₃N₄ compound material, activated molecular oxygen, pharmaceutical wastewater

摘要：

制药废水因具有COD高、盐度高、生化毒性大等特点，难以通过简单的物理、化学或生物法净化，高级氧化法因具有极强的氧化能力而有望用于制药废水的深度处理。采用硼氢化钠液相还原三氯化铁的方法制备了纳米零价铁（nZVI），并将石墨相C₃N₄（g-C₃N₄）作为载体，采用液相还原表面沉积法制备了不同nZVI和g-C₃N₄质量比的系列石墨相C₃N₄负载纳米铁材料（Fe/g-C₃N₄），用于催化制药废水中COD的高级氧化。结果表明，g-C₃N₄能很好地分散负载其表面的nZVI，抑制其团聚。在去除实际制药废水的实验中，nZVI和g-C₃N₄质量比为2∶1的复合材料（g-nZVI）具备最好的COD去除能力，当废水的pH=3、g-nZVI投加量为1.5 g/L时，2 h内实际磺胺类制药废水中的COD去除率可高达75%，已经达到进入生化反应池继续降解的标准。经过机理研究表明，去除COD的主要活性物质来自于受石墨相C₃N₄改性后nZVI活化的分子氧所产生的超氧自由基和羟基自由基。

关键词: 纳米零价铁, g-C₃N₄, 分子氧活化, 制药废水

CLC Number:

X703.1

Xiaonan LE, Yunjie ZOU, Ruimin HUANG. COD removal from practical pharmaceutical wastewater drived by nZVI/g-C₃N₄[J]. Industrial Water Treatment, 2023, 43(9): 153-160.

乐孝楠, 邹云杰, 黄瑞敏. 石墨相C₃N₄负载纳米铁材料处理制药废水[J]. 工业水处理, 2023, 43(9): 153-160.

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URL: https://www.iwt.cn/EN/10.19965/j.cnki.iwt.2022-1006

https://www.iwt.cn/EN/Y2023/V43/I9/153

Figures/Tables 12

Table 1 Actual and theoretical values of iron content

铁占材料质量分数理论值/%	铁占材料质量分数实际值/%
33.33	31.74
50.00	50.17
60.00	58.16
66.70	67.99
75.00	75.83

Fig. 1 Schematic diagram of the synthesis of g-nZVI

Fig.2 SEM characterization of the samples

Fig. 3 XRD characterization of the samples

Fig.4 XPS characterization of the samples

Fig. 5 Removal efficiency of COD by 5 groups of different materials

Fig. 6 Effect of pH on COD removal from wastewater

Fig. 7 Effect of Fe mass fraction on COD removal in wastewater

Fig. 8 Effect of g-C₃N₄dosage on COD removal from wastewater

Fig. 9 Effect of anaerobic and oxygen enriched conditions on COD removal

Fig. 10 Continuous effect of g-nZVI under multiple recycling

Fig. 11 Effect of TBA and BQ on COD removal

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COD removal from practical pharmaceutical wastewater drived by nZVI/g-C₃N₄

石墨相C₃N₄负载纳米铁材料处理制药废水

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