本文關(guān)鍵詞：非均相催化臭氧氧化處理造紙廢水生化尾水的研究　出處：《浙江大學(xué)》2017年碩士論文　論文類型：學(xué)位論文

  更多相關(guān)文章： 造紙廢水 生化尾水 炭基催化劑 催化臭氧氧化 深度處理

【摘要】：造紙行業(yè)是與我國國民經(jīng)濟(jì)關(guān)系密切的重要基礎(chǔ)原材料產(chǎn)業(yè),其生產(chǎn)過程利用廢紙等再生纖維部分替代不可再生資源,具有可持續(xù)發(fā)展特點(diǎn)。然而,造紙過程產(chǎn)生的廢水組成復(fù)雜、污染物濃度高,多數(shù)造紙企業(yè)出水仍存在有機(jī)物含量高、色度重等問題,因此研究高效穩(wěn)定的造紙廢水深度處理技術(shù)需求迫切。論文以杭州市某造紙廠生化處理單元出水為研究對(duì)象,應(yīng)用催化臭氧氧化技術(shù)開展造紙廢水生化尾水深度處理研究,取得如下主要研究成果:1、通過構(gòu)建催化臭氧氧化反應(yīng)裝置,研究其處理造紙廢水生化尾水性能,發(fā)現(xiàn)隨著反應(yīng)時(shí)間與臭氧濃度的增加,處理尾水性能得到改善;在反應(yīng)60min、臭氧濃度6mg/L條件下臭氧氧化性能最佳。在反應(yīng)體系中,催化劑投加量及體系pH影響催化臭氧化性能,隨著催化劑用量的增加及初始pH的升高尾水色度、COD去除性能提高,在臭氧濃度6mg/L、初始pH 7.8-8.2、催化劑投加量5g/L、反應(yīng)時(shí)間60min、溫度25℃條件下,Fe-ZMY、TiO2兩種催化劑催化臭氧氧化性能較好,廢水色度、COD去除率分別為86.8%、83.8%和43.3%、47.6%。應(yīng)用GC-MS等技術(shù)分析發(fā)現(xiàn),造紙廢水中大部分多環(huán)類物質(zhì)經(jīng)催化臭氧氧化后仍未得到去除,導(dǎo)致出水COD偏高并存在一定的生態(tài)風(fēng)險(xiǎn)。2、為進(jìn)一步提高造紙廢水催化臭氧氧化性能,以具有多孔高吸附特性的顆粒狀椰殼活性炭作為載體,采用過量浸漬法制備Fe型/TiO2型炭基催化劑。應(yīng)用XRD、SEM技術(shù)對(duì)炭基催化劑進(jìn)行結(jié)構(gòu)表征發(fā)現(xiàn),105℃、550℃焙燒溫度下制備的炭基催化劑表面均勻負(fù)載金屬Fe、Ti,相比而言高溫條件下制備的炭基復(fù)合催化劑表面更為粗糙、孔穴明顯增多。FTIR分析表明,催化劑負(fù)載前后炭紅外吸收變化較大,炭表面負(fù)載催化劑后在3420-3411cm-1出現(xiàn)新的伸縮振動(dòng)峰,其中Fe型炭基催化劑的相應(yīng)峰值高于TiO2型炭基催化劑,該峰主要由-OH剪切振動(dòng)產(chǎn)生,分析認(rèn)為炭基負(fù)載催化劑較高的表面羥基基團(tuán)可增強(qiáng)羥基自由基生成與催化臭氧氧化性能。3、應(yīng)用制備的炭基催化劑處理造紙廢水生化尾水發(fā)現(xiàn),在臭氧濃度6mg/L、初始pH 7.8-8.2、催化劑投加量5g/L、反應(yīng)時(shí)間60min、溫度25℃時(shí),焙燒溫度550℃、載體粒徑0.6-0.9mm條件下制備的Fe/GC復(fù)合催化劑性能明顯提升,其色度、COD去除率分別達(dá)92.0%、71.3%,優(yōu)于制備前商業(yè)催化劑的86.8%、43.3%,出水COD濃度穩(wěn)定在33±3mg/L。炭基催化劑重復(fù)利用五次后,造紙廢水生化尾水COD去除率穩(wěn)定在55%以上,出水COD濃度低于50mg/L。進(jìn)一步對(duì)催化臭氧氧化前后造紙廢水生化尾水組成分析發(fā)現(xiàn),造紙廢水中鄰苯二甲酸二異丁酯、2,6-二叔丁基酚、酰胺等難降解有機(jī)物均得到有效去除。綜合分析認(rèn)為,載體活性炭高溫處理后孔穴增多、比表面積增大、-OH鍵增加,導(dǎo)致更多的臭氧分子被吸收并生成OH·,強(qiáng)化鄰苯二甲酸二異丁酯等難降解有機(jī)物的吸附與氧化,實(shí)現(xiàn)造紙廢水生化尾水高效穩(wěn)定深度處理。
[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.
【學(xué)位授予單位】：浙江大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：X793

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