Tributyl phosphate modified biochar activated PMS for degradation of bisphenol A

doi:10.19965/j.cnki.iwt.2023-1242

Abstract

Abstract:

Using bisphenol A(BPA) as the target pollutant, phosphorus-doped biochar(P-bio) was prepared by impregnation pyrolysis with corn stover and tributyl phosphate as the raw materials. The structure of P-bio was characterized and analyzed, and the effects of persulfate(PMS) concentration, P-bio dosage, and initial pH on BPA degradation by P-bio activated PMS system were further explored. The results indicated that the surface of P-bio was a sheet-like structure composed of obvious folds, which was porous and loose. The specific surface area of P-bio was 173.985 m²/g, which was 93.4 times higher than that of pure biochar(1.863 m²/g). Under the conditions of BPA concentration of 10 mg/L, P-bio dosage of 2 g/L, pH of 3.21, and PMS dosage of 2 mmol/L, the removal rate of BPA by P-bio activated PMS system was 99.47% after 30 minutes, and the reaction rate constant was 0.164 3 min^-1. It was further confirmed by EPR quenching that active radicals SO₄ ^·-and ·OH were generated in the P-bio activated PMS system, which contributed to the degradation of BPA by 12.07% and 87.93%, respectively. For the reuse of P-bio, BPA removal rate was 74.1% at the 2nd use and 68% at the 3rd use, and BPA removal rate recovered to 80.7% after calcination of P-bio after three consecutive uses, which indicated that the P-bio catalyst had strong reusability and regeneration performance.

Key words: persulfate, endocrine disruptor, modified biochar, bisphenol A, phosphorus doping

摘要：

以双酚A（BPA）为目标污染物，以玉米秸秆和磷酸三丁酯为原料，通过浸渍热解法制备出磷掺杂生物炭（P-bio），对P-bio的结构进行了表征分析，进一步探讨了过硫酸盐（PMS）浓度、P-bio投加量和初始pH等因素对P-bio活化PMS降解BPA效能的影响。结果表明，P-bio表面为由明显褶皱组成的片状结构，呈现多孔且疏松的状态；P-bio的比表面积为173.985 m²/g，相比原始生物炭（1.863 m²/g）提高了93.4倍。在BPA质量浓度为10 mg/L、P-bio投加量为2 g/L、pH为3.21、PMS投加量为2 mmol/L条件下，反应30 min后P-bio活化PMS体系对BPA的去除率为99.47%，反应速率常数为0.164 3 min^-1。进一步通过EPR猝灭实验证实，在P-bio活化PMS体系中产生了SO₄ ^·-和·OH，两种活性自由基对BPA降解的贡献率分别为12.07%和87.93%。对P-bio重复利用，第2次使用时BPA去除率为74.1%，第3次使用时BPA去除率为68%，连续使用3次后对P-bio进行煅烧，BPA去除率恢复至80.7%，说明P-bio催化剂具有较强的可重复利用性和再生性能。

关键词: 过硫酸盐, 内分泌干扰物, 改性生物炭, 双酚A, 磷掺杂

CLC Number:

X703

Xiangyu FU, Yafeng LI, Yihan LIU, Keqing CUI, Lingping WANG. Tributyl phosphate modified biochar activated PMS for degradation of bisphenol A[J]. Industrial Water Treatment, 2025, 45(1): 87-93.

傅翔宇, 李亚峰, 刘奕含, 崔可清, 王玲萍. 磷酸三丁酯改性生物炭活化PMS降解双酚A的效能[J]. 工业水处理, 2025, 45(1): 87-93.

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URL: https://www.iwt.cn/EN/10.19965/j.cnki.iwt.2023-1242

https://www.iwt.cn/EN/Y2025/V45/I1/87

Figures/Tables 12

Fig.1 SEM of P-bio

Fig.2 N₂ adsorption/desorption isothermal curve of P-bio

Table 1 Surface properties of P-bio and pure biochar

样品	比表面积/（m²·g^-1）	孔容积/（cm³·g^-1）	孔径/nm
原始生物炭	1.863	0.016	1.874
P-bio	173.985	0.213	4.907

Fig.3 FT-IR（a） and XPS full spectrum（b） of P-bio

Fig.4 Effect of P-bio dosage on BPA degradation by P-bio activated PMS

Fig.5 Effect of PMS dosage on BPA degradation by P-bio activated PMS

Fig.6 Effect of initial pH on BPA degradation by P-bio activated PMS

Fig.7 Efficacy of P-bio activated PMS for degradation of typical pollutants

Fig.8 Reproducibility of P-bio

Fig.9 EPR identification of free radicals in P-bio activated PMS system

Fig.10 Quenching experiment of free radicals in BPA degradation by P-bio activated PMS

Fig.11 Mechanism of free radical generation and organic degradation in PMS system activated by P-bio

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