【作者】 张建磊；

【导师】 沈照理； 任立人；

【作者基本信息】 中国地质大学（北京） ， 环境工程， 2009， 博士

【摘要】 半合成抗生素废水污染物浓度高、成份复杂、化学性质稳定,目前处理方法主要有物化法、生物法及其组合工艺,但抗生素废水中污染物难生物降解,残留抗生素对生物菌种有很强的抑制作用,难以发挥生物处理的优势,使处理效果不理想,达标排放费用高。针对这些问题,作者提出采用高级氧化技术对半合成抗生素废水进行预处理,进行了Fenton预处理、电催化氧化预处理和生物处理试验。研究了Fenton试剂和电催化氧化预处理半合成抗生素废水的可行性、影响因素、COD去除率及对废水可生性的改善,并对两种预处理的反应机理进行了探讨。Fenton试验表明,所选因素中对COD去除率影响大小依次为:[FeSO4]>[H2O2]>pH>[絮凝剂]。在pH=3、[FeSO4]=240 mg/L、[H2O2]=1 mL/L、[絮凝剂]=1 mg/L、搅拌时间30 min条件下,COD去除效果最好,去除率可达29.4%。说明高级氧化技术可用于半合成抗生素废水的处理,但单独采用Fenton试剂法处理,废水的COD去除率偏低。电催化氧化试验表明,其最佳工艺参数为:槽间距60 cm,槽电压50 V,空气流量为50 L/h,反应时间为30 min。超声波可提高废水COD去除率。在处理过程中装置内有絮凝物产生,采用两级电催化氧化可减小絮凝物对处理效果的影响。头孢曲松综合废水、氨苄/阿莫废水经两级电催化氧化处理后,COD去除率分别可达到62.1%和74.6%,优于单级装置的去除效果。生物处理试验表明,未经预处理的废水,系统运行一段时间后COD去除率显著下降,降低进水浓度后,系统仍难以恢复。电催化氧化预处理后的废水经水解酸化、厌氧消化和好氧生物处理后,COD去除率分别可达20～40%、60%、76～80%,表明电催化氧化预处理后废水的可生化性得到了明显改善。在水解酸化-厌氧-好氧连续生化处理装置中,进水COD浓度约6000 mg/L,装置的最终出水COD可降至约250 mg/L。实际工程运行表明,电催化氧化工艺处理半合成抗生素废水,COD去除率可稳定在50%左右,平均为54.1%,系统运行一个月没出现去除率明显下降的现象。按电压40 V,平均电流300 A,处理能力5 t/h计算,电耗为24 kW,即4.8度电/吨水。室内试验和实际工程均表明,电催化氧化技术预处理半合成抗生素废水,COD的去除率大于50%,并且可显著提高废水的可生化性,有利于后续的生物处理,提高污染的去除率,降低处理成本。更多还原

【Abstract】 The characteristics of Semi-synthetic antibiotics waste water are high pollutants concentration, complex composition, and chemical stability. Semi-synthetic antibiotics wastewater treatment technology mainly consist physical treatment, chemical treatment, biological treatments and its combination. However, the residual antibiotics in the wastewater have a strong inhibitory effect on biological species, so it is difficult to play the advantages of biological treatment. The main issues include low COD removal efficient, high operating costs and the difficulty to reach the emissions standards. In view of the fact that Semi-synthetic antibiotics waste water is difficult to be biodegraded,the author, on the basis of systematic study, puts forward a pretreatment using advanced oxidation processes, and the Fenton, electro-catalytic oxidation and bio-oxidation test pilot was conducted. The feasibility of the pretreatment using Advanced Oxidation Processes for semi-synthetic waste water was discussed, and then the impact effect and mechanism of the treatment of semi-synthetic antibiotics using Fenton reagent and electricity Oxidation were studied.Fenton experiment showed: influencing factors of COD removal effect were: [FeSO4]> [H2O2]> pH> [flocculent]. At pH=3, [FeSO4]=240 mg/L, [H2O2]=1 mL/L, [flocculants]=1 mg/L, stirring time=30 min, COD removal efficiency was best and the removal of COD was 29.4%.Electro-catalytic oxidation experiment showed: The best process parameters was: slot spacing 60 cm, voltage 50 V, air flow 50 L/h. Ultrasonic could improve COD removal efficiency. On the initial response phase, the wastewater COD removal rate increased soon, but after 20min the COD removal rate growth slowed down. When the reaction time was 30min, COD removal rate of ampicillin waste water, amoxicillin waste water, amoxicillin waste water removing condensation mother liquor and ceftriaxone waste water reached 55%, 25%, 39% and 35%. There were flocculation-generated in the process of dealing with different waste water, two-stage treatment may slowed the effect of coagulation. COD removal efficiency of ceftriaxone integrated waste water and ampicillin/amoxicillin waste water treated by two-stage electro-catalyzed oxygen could reach 62.1% and 74.6%, better than the single-stage effect.Biological treatment tests showed that: without a pretreatment of wastewater, when the system operated for some time, the COD removal rate dropped significantly. Even the influent COD concentration was decreased; it was still difficult to restore the system. When the waste water pretreated by electro-catalytic oxidation was treated by acid hydrolysis, anaerobic digestion and aerobic biological treatment, COD removal rates reached respectively 20 to 40%, 60%, 76 to 80%, indicating that the Biodegradability of wastewater had been improved remarkably. In the acid hydrolysis-anaerobic-aerobic biological treatment plant, a similar result can be obtained. When the influent COD concentration was about 6000 mg/L, the final effluent COD concentration could be stabilized at 250 mg/L, the total COD removal rate reached 95.7 %.On-site engineering operation showed that semi-synthetic antibiotics waste water was processed by electro-catalytic oxidation, COD removal rate could be stabilized at around 54.1%, and the COD removal efficient did not decreased after the system run a month. With voltage 40 V, average current 300 A, 5 t/h influent water, the power consumption was 24 kW, that is, 4.8 degrees percent tons of waste water.More than the pilot test and engineering show that advanced oxidation processes can be used for the pretreatment of semi-synthetic antibiotics wastewater. The waste water dealing with Electro-catalytic oxidation technology, COD removal rate can reach 60%, and also can significantly improve the biodegradability of waste water, creating the conditions for the follow-up biological processing .so it is a viable technology.更多还原