Degradation of refractory organics in the pharmaceutical wastewater by bioelectrochemical system

doi:10.16085/j.issn.1000-6613.2021-2421

Abstract

Abstract:

The "electro-Fenton + bioelectrochemistry" was used to treat pharmaceutical wastewater, and degradation effect of dissolved organic matter (DOM) and refractory organic matters was analyzed to explore the effective degradation of refractory organics in pharmaceutical wastewater by three-dimensional fluorescence spectroscopy(EEMs) and gas chromatography-mass spectrometry(GC-MS). When Electro-Fenton was used to pretreat pharmaceutical wastewater,the average removal rate of COD_Cr in wastewater was 28.75%±1.29%, and the average removal rate of tetrahydrofuran was 41.18%±2.95%, which initially reduced the biological toxicity of wastewater and achieved good pre-treatment of pharmaceutical wastewater. The electrochemical bioreactor had a significant degradation effect on the chemical oxygen demand (COD_Cr) of pharmaceutical wastewater and was significantly better than the single biofilm reactor. After the electrochemical bioreactor operated for 39 days, COD_Cr was decreased from (3438.30—4775.70)mg/L to (20.18—331.09)mg/L, and the average removal rate was 95.89%±1.63%; after the single biofilm reactor operated for 10 days, COD_Cr was decreased from (3943.90—4631.20)mg/L to (345.08—1264.3)mg/L, and the average removal rate was 79.86%±6.21%. The soluble organic components in the pharmaceutical wastewater were mainly tyrosine-like proteins, tryptophan-like proteins and soluble microbial by-products (SMPs). The electrochemistry bioreactor had a significant degradation effect on the fluorescent components in the 3 areas with the removal rates of 58.88%, 37.16% and 36.26% respectively. Tetrahydrofuran, the main refractory organic matter in pharmaceutical wastewater, could be effectively degraded by the electrochemistry bioreactor, and the removal rate of tetrahydrofuran was as high as 97.65%. This study investigated the treatment effect of bioelectrochemical system on pharmaceutical wastewater from the three aspects of COD_Cr removal rate, EEMs degradation effect and refractory organics degradation effect, and provided a scientific basis for the application of electrochemistry bioreactor in the field of pharmaceutical wastewater treatment.

Key words: waste water, pharmaceuticals, electrochemistry bioreactors, organic compounds

摘要：

为探究制药废水中难生化有机物的有效降解方法，本文采用“电Fenton+生物电化学”联合处理制药废水，通过三维荧光光谱（EEMs）及气相色谱-质谱联用法（GC-MS）分析进、出水中溶解性有机物（DOM）和难生化有机物的降解效果，结果如下。①采用电Fenton预处理制药废水，对废水COD_Cr的平均去除率为28.75%±1.29%，对四氢呋喃的平均去除率为41.18%±2.95%，初步降低废水生物毒性，实现了制药废水的良好预处理效果。②电化学生物反应器对制药废水的化学需氧量（COD_Cr）有显著的降解效果且明显优于单一生物膜反应器。其中电化学生物反应器运行39天，COD_Cr从(3438.30~4775.70)mg/L降至(20.18~331.09)mg/L，平均去除率达95.89%±1.63%；单一生物膜反应器运行10天，COD_Cr从(3943.90~4631.20)mg/L降至(345.08~1264.3)mg/L，平均去除率为79.86%±6.21%。③制药废水中溶解性有机物成分以酪氨酸类蛋白、色氨酸类蛋白、溶解性微生物副产物（SMPs）为主，电化学生物反应器对3个区域的荧光组分降解效果明显，去除率分别为58.88%、37.16%和36.26%。④针对制药废水中的主要难生化有机物四氢呋喃，电化学生物反应器可实现四氢呋喃的有效降解，四氢呋喃去除率高达97.65%。本研究从COD_Cr去除率、EEMs降解效果和难生化有机物降解效果三方面考察生物电化学系统对制药废水的处理效果，为电化学生物反应器在制药废水处理领域的应用提供科学依据。

关键词: 废水, 药物, 电化学生物反应器, 有机化合物

CLC Number:

X787

XU Yabing, WANG Baoshan, WANG Guangzong, ZHANG Yang. Degradation of refractory organics in the pharmaceutical wastewater by bioelectrochemical system[J]. Chemical Industry and Engineering Progress, 2022, 41(9): 5055-5064.

许亚兵, 王宝山, 汪光宗, 张洋. 生物电化学系统对制药废水中难生化有机物的降解[J]. 化工进展, 2022, 41(9): 5055-5064.

Figures/Tables 10

References 47

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荧光区域	λ_Ex/nm	λ_Em/nm	物质类型
Ⅰ	200~250	250~330	酪氨酸类蛋白质
Ⅱ	200~250	330~380	色氨酸类蛋白质
Ⅲ	200~250	380~550	富里酸类腐殖质
Ⅳ	250~400	280~380	含苯环蛋白质、溶解性微生物代谢产物
Ⅴ	250~400	380~550	腐植酸类腐殖质

荧光区域	λ_Ex/nm	λ_Em/nm	物质类型
Ⅰ	200~250	250~330	酪氨酸类蛋白质
Ⅱ	200~250	330~380	色氨酸类蛋白质
Ⅲ	200~250	380~550	富里酸类腐殖质
Ⅳ	250~400	280~380	含苯环蛋白质、溶解性微生物代谢产物
Ⅴ	250~400	380~550	腐植酸类腐殖质

样品	四氢呋喃浓度/µg·L^-1	乙酸乙酯浓度/µg·L^-1	二氯甲烷浓度/µg·L^-1	三氯甲烷浓度/µg·L^-1	COD_Cr浓度/mg·L^-1
进水	201847	205915	521.5	474.8	4547.9
出水	4744	18.5	4.9	13.8	84.4
去除率	97.65%	99.99%	99.06%	97.09%	98.14%

样品	四氢呋喃浓度/µg·L^-1	乙酸乙酯浓度/µg·L^-1	二氯甲烷浓度/µg·L^-1	三氯甲烷浓度/µg·L^-1	COD_Cr浓度/mg·L^-1
进水	201847	205915	521.5	474.8	4547.9
出水	4744	18.5	4.9	13.8	84.4
去除率	97.65%	99.99%	99.06%	97.09%	98.14%

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