Preparation of copper modified biochar and its effect on catalyzing persulfate to remove the tetracycline from water

doi:10.19965/j.cnki.iwt.2023-0961

Abstract

Abstract:

Copper modified corn stalk biochar(CBC) was prepared by hydrothermal method and used as a catalyst to activate potassium persulfate(PS) to remove tetracycline (TC) from water. The results showed that CBC+PS system had high efficiency and stability for TC removal. Under the conditions of solution pH=7, PS dosage of 3 mmol/L, and CBC dosage of 0.5 g/L, the removal rate of TC with mass concentration of 20 mg/L by the CBC+PS system reached 84.46% within 10 min, and 96.75% after 2 h. Mechanism study indicated that Cu, hydroxyl and carboxyl groups supported on CBC surface could promote electron transfer, and then accelerate the production of reactive oxygen species such as SO₄ ^·-and·OH. After 5 cycles experiments, the removal rate of TC could still be maintained at 85.62%, which showed that CBC had good stability and reusability. This study provided an efficient and stable TC removal system, and also provided a new way for the recovery and reuse of corn stalk.

Key words: copper modified, hydrothermal method, corn stalk biochar, persulfate, tetracycline

摘要：

通过水热法制备铜改性玉米秸秆生物炭（CBC），并将其作为催化剂活化过硫酸钾（PS）去除水体中四环素（TC）。研究结果表明，CBC+PS体系对于TC具有高效且稳定的去除效果。在溶液pH=7，PS投加量3 mmol/L，CBC投加量0.5 g/L条件下，CBC+PS体系在反应10 min内对20 mg/L TC的去除率达到84.46%，2 h后去除率达到96.75%。机理研究表明，CBC表面负载的Cu以及表面羟基、羧基等基团能够促进电子的转移，进而加速SO₄ ^·-和·OH等活性氧物种的生成。在经过5次循环实验后，体系对TC的去除率仍能保持在85.62%，说明CBC具有良好的稳定性并能够重复利用。该研究提供了一种高效且稳定的去除TC的体系，同时也为玉米秸秆的回收再利用提供了一条新的途径。

关键词: 铜改性, 水热法, 玉米秸秆生物炭, 过硫酸盐, 四环素

CLC Number:

X703.1
TQ424

Xiulei FAN, Shenpeng WANG, Shu ZHANG, Wei JI, Yue CUI, Xizhe KONG, Bowen LÜ. Preparation of copper modified biochar and its effect on catalyzing persulfate to remove the tetracycline from water[J]. Industrial Water Treatment, 2024, 44(10): 133-142.

范秀磊, 王申鹏, 张舒, 纪伟, 崔月, 孔熙哲, 吕博文. 铜改性生物炭的制备及催化过硫酸盐去除水体中四环素的研究[J]. 工业水处理, 2024, 44(10): 133-142.

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URL: https://www.iwt.cn/EN/10.19965/j.cnki.iwt.2023-0961

https://www.iwt.cn/EN/Y2024/V44/I10/133

Figures/Tables 12

Fig.1 The microstructure of BC and CBC，and element distribution of CBC

Table 1 BET specific surface area and pore size parameters of BC and CBC

样品名称	BET比表面积/（m²·g^-1）	BJH吸附平均孔径/nm	t-Plot微孔面积/（m²·g^-1）
BC	115.59	4.75	97.75
CBC	23.11	5.21	9.13

Fig.2 XRD of CBC

Fig.3 Removal of TC by different systems

Table 2 Effects of different types of biochar on TC removal

催化剂名称	催化剂投加量/ （g∙L^-1）	TC/（mg∙L^-1）	PS/（mmol·L^-1）	10 min时TC去除率/%	TC最终去除率/%
N-Cu/biochar^〔22〕	0.2	20.00	2.00	约60	99.0
SC^〔24〕	0.5	10.00	2.44	约40	97.2
GBC^〔25〕	0.2	22.75	8.00	约25	78.7
CBC（本研究）	0.5	20.00	3.00	84.46	96.75

Fig.4 Effects of operating parameters on TC removal

Fig.5 Effects of anions and HA on TC removal

Fig.6 Recycling performance of CBC+PS system

Fig.7 Effects of quenchers on TC removal

Fig.8 Raman spectroscopy （a） and FT-IR spectroscopy （b） of materials

Fig.9 XPS spectra of the CBC before and after the reaction

Fig.10 Possible removal pathways of TC in the CBC+PS system

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