非均相催化臭氧氧化处理造纸废水生化尾水的研究

发布时间：2017-12-28 06:40

本文关键词：非均相催化臭氧氧化处理造纸废水生化尾水的研究　出处：《浙江大学》2017年硕士论文　论文类型：学位论文

【摘要】：造纸行业是与我国国民经济关系密切的重要基础原材料产业,其生产过程利用废纸等再生纤维部分替代不可再生资源,具有可持续发展特点。然而,造纸过程产生的废水组成复杂、污染物浓度高,多数造纸企业出水仍存在有机物含量高、色度重等问题,因此研究高效稳定的造纸废水深度处理技术需求迫切。论文以杭州市某造纸厂生化处理单元出水为研究对象,应用催化臭氧氧化技术开展造纸废水生化尾水深度处理研究,取得如下主要研究成果:1、通过构建催化臭氧氧化反应装置,研究其处理造纸废水生化尾水性能,发现随着反应时间与臭氧浓度的增加,处理尾水性能得到改善;在反应60min、臭氧浓度6mg/L条件下臭氧氧化性能最佳。在反应体系中,催化剂投加量及体系pH影响催化臭氧化性能,随着催化剂用量的增加及初始pH的升高尾水色度、COD去除性能提高,在臭氧浓度6mg/L、初始pH 7.8-8.2、催化剂投加量5g/L、反应时间60min、温度25℃条件下,Fe-ZMY、TiO2两种催化剂催化臭氧氧化性能较好,废水色度、COD去除率分别为86.8%、83.8%和43.3%、47.6%。应用GC-MS等技术分析发现,造纸废水中大部分多环类物质经催化臭氧氧化后仍未得到去除,导致出水COD偏高并存在一定的生态风险。2、为进一步提高造纸废水催化臭氧氧化性能,以具有多孔高吸附特性的颗粒状椰壳活性炭作为载体,采用过量浸渍法制备Fe型/TiO2型炭基催化剂。应用XRD、SEM技术对炭基催化剂进行结构表征发现,105℃、550℃焙烧温度下制备的炭基催化剂表面均匀负载金属Fe、Ti,相比而言高温条件下制备的炭基复合催化剂表面更为粗糙、孔穴明显增多。FTIR分析表明,催化剂负载前后炭红外吸收变化较大,炭表面负载催化剂后在3420-3411cm-1出现新的伸缩振动峰,其中Fe型炭基催化剂的相应峰值高于TiO2型炭基催化剂,该峰主要由-OH剪切振动产生,分析认为炭基负载催化剂较高的表面羟基基团可增强羟基自由基生成与催化臭氧氧化性能。3、应用制备的炭基催化剂处理造纸废水生化尾水发现,在臭氧浓度6mg/L、初始pH 7.8-8.2、催化剂投加量5g/L、反应时间60min、温度25℃时,焙烧温度550℃、载体粒径0.6-0.9mm条件下制备的Fe/GC复合催化剂性能明显提升,其色度、COD去除率分别达92.0%、71.3%,优于制备前商业催化剂的86.8%、43.3%,出水COD浓度稳定在33±3mg/L。炭基催化剂重复利用五次后,造纸废水生化尾水COD去除率稳定在55%以上,出水COD浓度低于50mg/L。进一步对催化臭氧氧化前后造纸废水生化尾水组成分析发现,造纸废水中邻苯二甲酸二异丁酯、2,6-二叔丁基酚、酰胺等难降解有机物均得到有效去除。综合分析认为,载体活性炭高温处理后孔穴增多、比表面积增大、-OH键增加,导致更多的臭氧分子被吸收并生成OH·,强化邻苯二甲酸二异丁酯等难降解有机物的吸附与氧化,实现造纸废水生化尾水高效稳定深度处理。
[Abstract]:Paper industry is an important raw material industry closely related to China's national economy. Its production process uses some recycled fibers instead of non renewable resources, which has the characteristics of sustainable development. However, the wastewater produced by papermaking process is complex and high concentration of pollutants. Most papermaking enterprises still have problems such as high organic matter content and heavy chromaticity. Therefore, it is urgent to study efficient and stable technology for advanced treatment of papermaking wastewater. The water unit of a paper mill in Hangzhou biochemical treatment as the research object, the application of ozone oxidation catalytic technology to carry out research on biochemical tail water depth treatment of papermaking wastewater, the main results were as follows: 1, through the construction of catalytic ozone oxidation reaction device, research paper wastewater biochemical tail water treatment performance, it is found that with the increase of reaction time and ozone the concentration of treatment of tail water performance is improved; in the reaction of 60min, ozone concentration under the condition of 6mg/L ozone oxidation performance. In the reaction system, the catalyst quantity and the influence of pH system in catalytic ozonation process, with the increase of the dosage of catalyst and initial pH tail water chroma and COD removal performance increase in ozone concentration 6mg/L, initial pH 7.8-8.2, catalyst dosage 5g/L, reaction time 60min, temperature 25 DEG C, and Fe-ZMY TiO2 two catalytic ozone oxidation catalyst performance, the removal rates of chroma and COD were 86.8%, 83.8%, 47.6% and 43.3%. Application of GC-MS and other technical analysis found that most of the polycyclic substances in papermaking wastewater had not been removed after catalytic ozonation, resulting in high COD and some ecological risks. 2, in order to further improve the catalytic ozonation performance of papermaking wastewater and prepare granular coconut shell activated carbon with high porous adsorption capacity as carrier, Fe type /TiO2 carbon based catalyst was prepared by over impregnation method. The application of XRD and SEM technology were used to characterize the structures of carbon based catalyst, 105 C and 550 C temperature carbon based catalyst surface by uniform load of metal Fe and Ti, compared with the high temperature carbon based composite catalyst surface preparation is more rough and holes increased significantly. FTIR analysis showed that the catalyst before and after carbon absorption varies greatly and the carbon surface supported catalyst after stretching vibration peak in the new 3420-3411cm-1, the corresponding peak of Fe type carbon based catalyst is higher than that of TiO2 type carbon based catalyst, the peak was mainly caused by -OH shear vibration and analysis of surface hydroxyl groups of carbon based catalyst can be higher enhanced oxidation of hydroxyl radical production and catalytic ozonation. 3, the application for preparing a carbon based catalyst for treatment of papermaking wastewater biochemical tail water found in the ozone concentration 6mg/L, initial pH 7.8-8.2, catalyst dosage 5g/L, reaction time 60min, temperature 25 degrees, significantly enhance the catalytic performance of Fe/GC composite agent prepared by the calcination temperature of 550 DEG C, carrier size under the condition of 0.6-0.9mm, the the color and COD removal rate was 92% and 71.3% respectively, better than the commercial catalyst preparation before 86.8%, 43.3%, the effluent COD concentration is stable at 33 + 3mg/L. After repeated use of carbon based catalyst for five times, the removal rate of COD in the biochemical tail water of papermaking wastewater is more than 55%, and the concentration of COD in effluent is lower than that of 50mg/L. Further the catalytic ozonation of papermaking wastewater biochemical tail water composition analysis showed that two formic acid isobutyl phthalate two, 2,6- di Ding Jifen, amide in papermaking wastewater refractory organic compounds were effectively removed. Comprehensive analysis shows that the carrier activated carbon after heat treatment cavity increased, the specific surface area increased, the -OH bond increases, lead to more ozone molecules are absorbed and generate OH, strengthen the adjacent benzene two formic acid two isobutyl to the adsorption and oxidation of organic pollutants, papermaking wastewater to achieve efficient and stable biochemical tail water depth treatment.
【学位授予单位】：浙江大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：X793

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