纳滤膜技术在抗生素制药废水深度处理中的应用研究

CORC > 生态环境研究中心 > 中国科学院生态环境研究中心 > 水污染控制实验室

题名	纳滤膜技术在抗生素制药废水深度处理中的应用研究
作者	王健行
学位类别	博士
答辩日期	2014-05
授予单位	中国科学院研究生院
授予地点	北京
导师	魏源送
关键词	抗生素制药废水纳滤有机污染物膜污染 Antibiotic production wastewater Nanofiltration(NF) Organic pollutants Membrane fouling
其他题名	Application of Nanofiltration Membrane in the Advanced Treatment of Antibiotic Production Wastewater
学位专业	环境工程
中文摘要	我国是制药大国，制药工业被列为重点治理的12 个行业之一。随着制药工业水污染物排放标准的日益严格，现有废水处理技术难以达到排放标准。纳滤膜技术作为废水处理领域的一种新兴技术，受到了广泛关注，但其在工业废水处理中的应用还缺乏系统研究。因此，本文采用纳滤膜技术对实际抗生素制药废水二级生化出水进行深度处理研究，在纳滤膜预处理、纳滤膜组件筛选及其操作参数优化、膜污染形成机制及其控制等方面开展系统研究，并通过实验室小试—现场中试—示范工程研究，研发适于抗生素制药废水深度处理的纳滤膜技术，以期为纳滤膜技术在抗生素制药废水处理中的推广应用提供科技支撑。针对常规工艺处理抗生素制药废水二级生化出水中有机物含量较高的水质特征和纳滤膜处理要求，本研究以去除有机物为目的，采用活性炭过滤作为纳滤膜预处理方法。通过静态试验筛选出KC16杏壳颗粒活性炭为最优炭种，其吸附过程可用Langmuir方程描述，符合准二级吸附动力学模型。动态试验结果表明在滤速为1.0m/h，柱高为1200mm，进水COD约为400mg/L时，出水COD可小于120mg/L，预处理每吨抗生素制药废水生化出水的活性炭用量为2.45kg。纳滤膜组件筛选及其参数优化的小试试验结果表明，不同膜组件的性能存在较大差异，从GE、Sepro、Synder 三个厂家的纳滤膜组件中筛选出GE公司的DK膜作为小试纳滤膜组件，并优化了纳滤膜操作参数分别为TMP 10bar，pH 6.0，进水流量为8L/min。统计分析结果表明TMP对纳滤膜通量和单价阴离子的去除具有显著影响(P<0.05)，纳滤膜种类对废水中除Na+、K+以外的各种物质去除影响显著，pH对污染物去除和纳滤膜通量均无显著性影响。现场中试结果表明，MBR可直接作为纳滤膜深度处理抗生素制药废水的预处理工艺。因NF90膜对盐度（主要为单价离子）的截留效率远高于DK膜，故筛选NF90膜作为中试纳滤膜组件。据此构建了基于纳滤膜浓水回流的MBR-NF组合工艺，系统运行稳定，纳滤膜产水的TOC、NH4+-N和TP 浓度稳定在5.52mg/L、0.68mg/L和0.34mg/L，浊度稳定在0.15NTU，抗生素去除率高达95%以上。通过纳滤膜浓水回流，该系统的水回收率达到92%。经济分析结果表明，厌氧-MBR-NF组合工艺处理抗生素制药废水的吨水处理费用为11.521元，并且吨水可产生3.82元的经济效益。中试结果表明，抗生素制药废水二级生化出水的有机物种类主要为蛋白质、多糖和腐殖酸类物质，这些物质可被纳滤膜有效截留，并通过纳滤膜浓水回流到MBR被进一步生物降解；浓水回流对MBR系统的处理效果有一定影响，但不会破坏MBR系统活性污泥的微生物群落结构。基于上述研究结果，构建了处理规模为300m3/d纳滤膜深度处理抗生素制药废水示范工程，示范工程运行稳定，产水COD为19mg/L，电导率去除率达到83.8%，这为纳滤膜深度处理抗生素制药废水的推广应用具有重要意义。膜污染机理及其控制的研究结果表明，纳滤膜深度处理抗生素制药废水的膜污染类型主要为有机物污染，DK膜的污染程度大于NF90膜，对UV254响应高的有机物质易对NF90膜造成污染。可溶性微生物代谢物（SMP）和芳香类蛋白质Ⅱ类物质是产生有机物污染的主要物质，疏水性的腐殖酸类物质不易对纳滤膜造成污染。采用酸(HCl，pH2.5)、碱(0.1wt%NaOH+0.03wt%SDS，pH10.5)共同清洗可达到较好的纳滤膜清洗效果。处理活性炭出水时，宜采用先酸洗后碱洗的清洗策略；处理MBR出水时，宜采用先碱洗后酸洗的清洗策略。
英文摘要	China is one of the biggest countries producing pharmaceuticals in the world,and the pharmaceutical industry in China is listed as one of the top 12 industries for wastewater pollution control and treatment. However it is difficult for pharmaceutical wastewater to meet with discharge standards using current wastewater treatment technologies due to more and more restrict regulations. As an emerging membrane technology in wastewater treatment, nanofiltration (NF) has been paid more and more attention recently, but there is still gap between research and application of NF in wastewater treatment and reclamation. In this study, NF was used to treat secondary effluent of antibiotic production wastewater biological treatment. The purpose of this study was to research and develop NF membrane technology suitable for advanced treatment of antibiotic produnctiom wastewater in practice from lab scale to demonstration engineering through selecting pretreatment for NF membrane, optimizing NF membrane module and its operational parameters, investigating NF membrane fouling and developing membrane fouling control strategy. Activated carbon filtration was chosen for the pretreatment of NF membrane in order to remove organics in secondary effluent of antibiotic production wastewater which had high concentration of organics. KC16 granular activated carbon (GAC) prepared by apricot shells was the optimal activated carbon, by which the adsorption of pollutants met with the Langmuir isotherm and the adsorption process fitted a pseudo second - order kinetics model. The results of the dynamic adsorption experiments of KC16 GAC showed that the COD concentration in the effluent was less than 120 mg/L when the influent was at about 400mg/L, and the amount of GAC used for advanced treatment of antibiotic production wastewater was at 2.45kg KC16/m3 effluent at the filtration rate of 1.0m/h in the GAC column with the height of 1.2m. NF membrane selection and operation optimization were carried out in the lab. It was found that there was great difference among different NF membranes. DK membrane produced by Osmonics Corp was selected through three membranes produced by Osmonics, Sepro and Synder Corp. And the optimal operational conditions of DK membrane were at TMP of 10 bar, pH of 6.0 and cross-flow of 8 L/min. Statistics results showed that the transmembrane pressure (TMP) was the major factor of NF permeate flux and monovalent anion removal (p<0.05), and NF membrane type was the major factor of removing most pollutants except Na+ and K+ in test conditions. The pH did not have any significant effect on neither permeate flux nor pollutants rejection rates. Membrane bioreactor (MBR) was used as the pretreatment process of NF directly in the pilot scale experiment. The salt rejection rate of NF90 was much higher than that of DK, especially for monovalent ions. Thus, NF90 membrane was selected as the optimal membrane in the pilot test. The pilot scale MBR-NF with recycling NF concentrate was built to treat antibiotic production wastewater, and operated steadily over the entire experiment period and had excellent performance of treatment in which the concentrations of TOC, NH4 +-N, TP, turbidity and conductivity in the NF permeate were stable at 5.52 mg/L, 0.68 mg/L, 0.34mg/L, 0.15NTU and 2.5 mS/cm, respectively. The antibiotic removal rates in wastewater by the pilot MBR-NF were over 95%. The water yield of MBR-NF system reached over 92% through recycling NF concentrate. The operational cost of anaerobic digestion-MBR-NF process treating antibiotic production wastewater was 11.521RMB per ton of wastewater treated, meanwhile there could be benefits of 3.82 RMB per ton through reusing treated wastewater. Organics analysis results showed that the main organics in secondary effluent of antibiotic production wastewater biological treatment were proteins,polysaccharides and humic-like substances. These organics was perfectly rejected by the NF membrane and further biodegraded in the MBR through recycling NF concentrate. Though the MBR effluent was affected to some degree due to recycling NF concentrate, the microbial community of the MBR was not changed too much. A demonstration project of the NF for advanced treatment antibiotic production wastewater at 300m3/d was built according to the above results. The COD concentration in the NF permeate was as low as 19 mg/L, and removal rates of conductivity was about 83.8%. These results provided significant support for spreading application of NF in the treatment of antibiotic production wastewater. The main foulants of NF membrane in treating antibiotic production wastewater were organics, in which SMP and aromatic protein Ⅱ were the major components. The humic acid-like substances which were hydrophobic had little contribution to NF membrane fouling. The membrane fouling of DK membrane was more serious than that of NF90. The organics which have high response to UV254 were easy to foul NF90 membrane. The foulants of NF membrane could be removed by chemical cleaning, including an acid cleaning at pH 2.0-2.5 which was diluted by concentrated hydrochloric acid (HCl, 37%) and a basic cleaning at pH 10.0-10.5 with 0.3 wt% sodiu dodecyl sulfate (NaDS) (C12H25SO4Na), but the chemical cleaning sequence could be different. For treating MBR effluent, it was appropriate to clean fouled membrane with alkali cleaning firstly then acid cleaning. For GAC effluent, the order of chemical cleaning was opposite.
公开日期	2015-07-08
内容类型	学位论文
源URL	[http://ir.rcees.ac.cn/handle/311016/15711]
专题	生态环境研究中心_水污染控制实验室
推荐引用方式 GB/T 7714	王健行. 纳滤膜技术在抗生素制药废水深度处理中的应用研究[D]. 北京. 中国科学院研究生院. 2014.