生物炭强化Fenton技术处理难降解有机废水的应用研究

doi:10.19965/j.cnki.iwt.2025-0243

摘要/Abstract

摘要：

为解决工业废水深度处理中难降解有机物去除的难题，将自制生物炭（BAC）作为助催化剂应用于传统Fenton体系中，考察体系对四川某制药工业园区二级生化出水的处理效能。结果表明，自制BAC的投加使COD去除率从传统Fenton法的34.0%显著提升至78.5%，出水COD由初始的130~150 mg/L降至30 mg/L以下，达到《地表水环境质量标准》（GB 3838—2002）Ⅳ类水标准。BAC的引入不仅促进了·OH的生成，还改善了体系的混凝沉降性能。相关性分析表明，BAC对Fenton反应的强化作用主要源于其C $̿$ O、碳缺陷及良好的导电性。此外，优化后的BAC/Fe²⁺/H₂O₂体系在较宽的pH范围（3~7）内均能有效降低水中的COD，且BAC在不经再生的情况下可重复使用4次。因此，BAC作为Fenton反应的理想环保型助催化剂材料，在工业废水深度处理领域具有广阔的工程应用前景。

关键词: 生物炭, Fenton反应, 助催化剂, 难降解有机物

Abstract:

In order to solve the problem of removing refractory organic matter in the deep treatment of industrial wastewater, self-made biochar(BAC) applied as a co-catalyst into the traditional Fenton system, and the treatment efficiency of secondary biochemical effluent in a pharmaceutical industrial park in Sichuan was investigated. The results showed that the addition of self-made BAC significantly increased the COD removal rate from 34.0% in the traditional Fenton method to 78.5%, and COD in the effluent was reduced from 130-150 mg/L initially to less than 30 mg/L, meeting the standard of Class Ⅳ water in Environmental Quality Standard for Surface Water (GB 3838—2002). The introduction of BAC not only promoted the generation of ·OH, but also improved the agulation sedimentation performance of the system. Correlation analysis showed that the reinforcement of Fenton reaction by BAC was mainly due to its C $̿$ O, carbon defects and conductivity. In addition, the optimized BAC/Fe²⁺/H₂O₂ system could effectively reduce the COD in water over a wide pH range (3-7). BAC could be reused for 4 times without regeneration. Therefore, BAC was an ideal environmental friendly co-catalyst material for Fenton reaction, which had engineering application prospects in the field of deep treatment of industrial wastewater.

Key words: biochar, Fenton reaction, co-catalyst, refractory organic matter

中图分类号:

X703.1

王倩, 黄昆明, 冯润芸, 张怀民, 李江荣, 刘思强. 生物炭强化Fenton技术处理难降解有机废水的应用研究[J]. 工业水处理, 2026, 46(2): 142-149.

Qian WANG, Kunming HUANG, Runyun FENG, Huaimin ZHANG, Jiangrong LI, Siqiang LIU. Application study of biocarbon-enhanced Fenton technology for treating refractory organic wastewater[J]. Industrial Water Treatment, 2026, 46(2): 142-149.

https://www.iwt.cn/CN/Y2026/V46/I2/142

图/表 12

表1 自制BAC的理化参数

Table 1 Physical and chemical parameters of self-made BAC

样品	比表面积/（m²·g^-1）	粒径/nm	C $̿$ O/%	O—C—O/%	缺陷密度/cm^-2	电导率/（S·m^-1）
BAC	857	2.55	16.29	11.96	2.65×10¹¹	2.53

表1 自制BAC的理化参数

Table 1 Physical and chemical parameters of self-made BAC

样品	比表面积/（m²·g^-1）	粒径/nm	C $̿$ O/%	O—C—O/%	缺陷密度/cm^-2	电导率/（S·m^-1）
BAC	857	2.55	16.29	11.96	2.65×10¹¹	2.53

图1 不同体系中COD的去除效果

Fig.1 The removal effect of COD in different systems

图2 自由基猝灭剂对BAC/Fe²⁺/H₂O₂降解效能的影响

Fig.2 The effect of free radical scavenger on the degradation efficiency of BAC/Fe²⁺/H₂O₂

图3 BAC/H₂O₂体系与BAC/Fe²⁺/H₂O₂体系的ESR谱

Fig.3 ESR spectra of BAC/H₂O₂ system and BAC/Fe²⁺/H₂O₂ system

图4 Fe²⁺/H₂O₂和BAC/Fe²⁺/H₂O₂体系反应后的沉降性能（a）及出水对比（b）

Fig.4 Sedimentation performance（a）and effluent comparison（b）of Fe²⁺/H₂O₂ and BAC/Fe²⁺/H₂O₂ systems

图5 BAC指标与强化Fenton体系降解性能的相关性分析注：C

̿

O和O—C—O含量以BAC表面该基团原子数占据BAC表面总原子数的百分数计。

Fig.5 Analysis of the correlation between BAC index and degradation performance of enhanced Fenton system

图5 BAC指标与强化Fenton体系降解性能的相关性分析注：C

̿

O和O—C—O含量以BAC表面该基团原子数占据BAC表面总原子数的百分数计。

Fig.5 Analysis of the correlation between BAC index and degradation performance of enhanced Fenton system

图6 Fe²⁺/H₂O₂体系（a）和BAC/Fe²⁺/H₂O₂体系（b）中 Fe²⁺和Fe³⁺的浓度变化

Fig.6 The concentration changes of Fe²⁺ and Fe³⁺ in Fe²⁺/H₂O₂ system （a） and BAC/Fe²⁺/H₂O₂ system （b）

图7 H₂O₂投加量对BAC/Fe²⁺/H₂O₂体系降解效能的影响

Fig.7 The influence of H₂O₂ dosage on the degradation efficiency of BAC/Fe²⁺/H₂O₂ system

图8 FeSO₄·7H₂O投加量对BAC/Fe²⁺/H₂O₂体系降解效能的影响

Fig.8 The influence of FeSO₄·7H₂O dosage on the degradation efficiency of BAC/Fe²⁺/H₂O₂ system

图9 BAC投加量对BAC/Fe²⁺/H₂O₂体系降解效能的影响

Fig.9 The influence of BAC dosage on the degradation efficiency of BAC/Fe²⁺/H₂O₂ system

图10 pH对BAC/Fe²⁺/H₂O₂体系降解效能的影响

Fig.10 The influence of pH on the degradation efficiency of BAC/Fe²⁺/H₂O₂ system

图11 BAC的重复使用性能

Fig.11 The reuse performance of BAC

参考文献 25

[1]	BAYRAKDAR M， ATALAY S， ERSÖZ G. Efficient treatment for textile wastewater through sequential photo Fenton-like oxidation and adsorption processes for reuse in irrigation［J］. Ceramics International，2021，47（7）：9679-9690. doi:10.1016/j.ceramint.2020.12.107
[2]	王杰鹏，童文华，张永奎，等. 芬顿氧化-活性炭吸附联用法处理偏二甲肼废水及其生物毒性研究［J］. 应用化工，2023，52（3）：789-794.
	WANG Jiepeng， TONG Wenhua， ZHANG Yongkui，et al. Fenton oxidation-activated carbon adsorption combination treatment of UDMH and its biotoxicity［J］. Applied Chemical Industry，2023，52（3）：789-794.
[3]	DONG Guihua， CHEN Bing， LIU Bo，et al. Advanced oxidation processes in microreactors for water and wastewater treatment：Development，challenges，and opportunities［J］. Water Research，2022，211：118047. doi:10.1016/j.watres.2022.118047
[4]	陈洪雪，张智慧，白成英，等. 高级氧化技术降解四环素类抗生素的研究进展［J］. 精细化工，2025，42（3）：479-491.
	CHEN Hongxue， ZHANG Zhihui， BAI Chengying，et al. Research progress on degradation of tetracycline antibiotics by advanced oxidation processes［J］. Fine Chemicals，2025，42（3）：479-491.
[5]	LUO Zirui， YAO Bin， YANG Xiao，et al. Novel insights into the adsorption of organic contaminants by biochar：A review［J］. Chemosphere，2022，287：132113. doi:10.1016/j.chemosphere.2021.132113
[6]	LI Ling， LAI Cui， HUANG Fanglong，et al. Degradation of naphthalene with magnetic bio-char activate hydrogen peroxide：Synergism of bio-char and Fe-Mn binary oxides［J］. Water Research，2019，160：238-248. doi:10.1016/j.watres.2019.05.081
[7]	OUYANG Da， CHEN Yun， YAN Jingchun，et al. Activation mechanism of peroxymonosulfate by biochar for catalytic degradation of 1，4-dioxane：Important role of biochar defect structures［J］. Chemical Engineering Journal，2019，370：614-624. doi:10.1016/j.cej.2019.03.235
[8]	HUANG Cheng， ZHANG Chen， HUANG Danlian，et al. Influence of surface functionalities of pyrogenic carbonaceous materials on the generation of reactive species towards organic contaminants：A review［J］. Chemical Engineering Journal，2021，404：127066. doi:10.1016/j.cej.2020.127066
[9]	RIBEIRO R S， SILVA A M T， FIGUEIREDO J L，et al. The influence of structure and surface chemistry of carbon materials on the decomposition of hydrogen peroxide［J］. Carbon，2013，62：97-108. doi:10.1016/j.carbon.2013.06.001
[10]	HOU Liwei， WANG Liguo， ROYER S，et al. Ultrasound-assisted heterogeneous Fenton-like degradation of tetracycline over a magnetite catalyst［J］. Journal of Hazardous Materials，2016，302：458-467. doi:10.1016/j.jhazmat.2015.09.033
[11]	ZHOU Chenying， ZHOU Peng， SUN Minglu，et al. Nitrogen-doped carbon nanotubes enhanced Fenton chemistry：Role of near-free iron（Ⅲ） for sustainable iron（Ⅲ）/iron（Ⅱ） cycles［J］. Water Research，2022，210：117984. doi:10.1016/j.watres.2021.117984
[12]	CHEN Meiling， DING Lin， ZHU Shijun，et al. De complexation of Ni-EDTA enhanced by Fe（Ⅲ） reduction in the Fenton reaction：Insight into the role of carbonyl groups［J］. Journal of Environmental Chemical Engineering，2023，11（5）：111097. doi:10.1016/j.jece.2023.111097
[13]	GUO Yang， ZHANG Yixin， YU Gang，et al. Revisiting the role of reactive oxygen species for pollutant abatement during catalytic ozonation：The probe approach versus the scavenger approach［J］. Applied Catalysis B：Environmental，2021，280：119418. doi:10.1016/j.apcatb.2020.119418
[14]	NDAGIJIMANA P， RONG Hongwei， DUAN Luchun，et al. Synthesis and evaluation of a novel cross-linked biochar/ferric chloride hybrid material for integrated coagulation and adsorption of turbidity and humic acid from synthetic wastewater：Implications for sludge valorisation［J］. Environmental Research，2024，255：119134. doi:10.1016/j.envres.2024.119134
[15]	ZHANG Ting， WEN Yichan， PAN Zhelun，et al. Overcoming acidic H₂O₂/Fe（Ⅱ/Ⅲ） redox-induced low H₂O₂ utilization efficiency by carbon quantum dots Fenton-like catalysis［J］. Environmental Science & Technology，2022，56（4）：2617-2625. doi:10.1021/acs.est.1c06276
[16]	ZHONG Shuang， HU Kunsheng， WANG Yantao，et al. Hierarchically ordered porous carbon crystals for nanoconfined and sustainable Fenton oxidation of water pollutants［J］. Applied Catalysis B：Environment and Energy，2025，361：124665. doi:10.1016/j.apcatb.2024.124665
[17]	ZHANG Zixuan， ZHOU Chenying， SUN Yiming，et al. Exceptionally accelerated Fe（Ⅲ）/Fe（Ⅱ） redox couple by niobium carbide MXene：A green and long-lasting enhanced Fenton oxidation［J］. Applied Catalysis B：Environmental，2024，342：123385. doi:10.1016/j.apcatb.2023.123385
[18]	DINDA S， BRAUN T， PAMMER F D，et al. Quantifying defects in carbon nanotubes undergoing prolonged electrochemical cycling with Raman phase map［J］. Carbon，2024，218：118753. doi:10.1016/j.carbon.2023.118753
[19]	WANG Yuxian， CAO Hongbin， CHEN Lulu，et al. Tailored synthesis of active reduced graphene oxides from waste graphite：Structural defects and pollutant-dependent reactive radicals in aqueous organics decontamination［J］. Applied Catalysis B：Environmental，2018，229：71-80. doi:10.1016/j.apcatb.2018.02.010
[20]	YU Shuiping， PENG Yanhua， SHAO Penghui，et al. Electron-transfer-based peroxymonosulfate activation on defect-rich carbon nanotubes：Understanding the substituent effect on the selective oxidation of phenols［J］. Journal of Hazardous Materials，2023，442：130108. doi:10.1016/j.jhazmat.2022.130108
[21]	ZHANG Kaikai， KHAN A， SUN Peng，et al. Simultaneous reduction of Cr（Ⅵ） and oxidization of organic pollutants by rice husk derived biochar and the interactive influences of coexisting Cr（VI）［J］. Science of the Total Environment，2020，706：135763. doi:10.1016/j.scitotenv.2019.135763
[22]	ZHOU Hongyu， ZHANG Heng， HE Yongli，et al. Critical review of reductant-enhanced peroxide activation processes：Trade-off between accelerated Fe³⁺/Fe²⁺ cycle and quenching reactions［J］. Applied Catalysis B：Environmental，2021，286：119900. doi:10.1016/j.apcatb.2021.119900
[23]	张依含，史静，杜琼，等. 磁性生物炭非均相类Fenton体系去除水中四环素［J］. 工业水处理，2020，40（2）：32-35.
	ZHANG Yihan， SHI Jing， DU Qiong，et al. Tetracycline removal in the magnetic biochar heterogeneous Fenton-like system［J］. Industrial Water Treatment，2020，40（2）：32-35.
[24]	BRILLAS E. A review on the application of single and combined Fenton，photo-Fenton，and electrochemical advanced oxidation processes to remove diclofenac from aqueous media［J］. Journal of Environmental Chemical Engineering，2025，13（2）：115443.
[25]	朱紫燕，王孝文，王允东，等. Fenton反应中加速Fe^Ⅲ还原为Fe^Ⅱ的研究进展及展望［J］. 工业水处理，2022，42（2）：1-10.
	ZHU Ziyan， WANG Xiaowen， WANG Yundong，et al. Research progress and prospect of accelerating reduction of Fe^Ⅲ to Fe^Ⅱ in Fenton reaction［J］. Industrial Water Treatment，2022，42（2）：1-10.

选择文件类型/文献管理软件名称

选择包含的内容