高鹽有機(jī)廢水離子膜電解脫鹽處理機(jī)制研究
發(fā)布時(shí)間：2018-07-26 18:30
【摘要】：高鹽有機(jī)廢水作為現(xiàn)代工業(yè)化的產(chǎn)物,不僅量大而且成分復(fù)雜,處理不當(dāng)很容易造成水資源浪費(fèi)和環(huán)境污染。目前,高鹽有機(jī)廢水的傳統(tǒng)物理化學(xué)處理方法存在著諸如處理成本高,需投加額外藥劑,容易造成二次污染等缺點(diǎn),并且廢水中的高鹽環(huán)境會(huì)抑制微生物的活性,從而限制微生物方法的應(yīng)用和發(fā)展。但高鹽廢水具有較好的導(dǎo)電性,可以為電化學(xué)的應(yīng)用提供契機(jī)。膜電解技術(shù)作為電化學(xué)工藝中的重要組成部分,結(jié)合了傳統(tǒng)電滲析分離提純的作用和電解技術(shù)的特性,并具有能耗低、環(huán)境危害小等特點(diǎn),該技術(shù)對高鹽有機(jī)廢水的處理而言,無疑是一種有著巨大應(yīng)用潛力和研究價(jià)值的處理方法。本課題采用膜電解的方式對高鹽度染料模擬廢水進(jìn)行了脫鹽以及有機(jī)物降解處理,旨在研究高鹽有機(jī)廢水體系中鹽離子的去除機(jī)制以及有機(jī)物降解過程對脫鹽效果的影響和相互作用關(guān)系。研究采用自制的可拆卸多級膜電解槽裝置,以Ti/RO2-Ir O2-Sn O2為陰、陽極板材料,以Na~+、Cl-為目標(biāo)去除離子,分別在與甲基橙、酸性大紅3R、直接深棕、活性艷蘭X-BR等染料物質(zhì)的混合體系下進(jìn)行了直流電場作用下的膜電解脫鹽實(shí)驗(yàn)。探討了單膜電解過程中電流密度、極板間距、電解液濃度和進(jìn)樣流速等控制條件對離子膜電解脫鹽效果的影響,以及雙膜電解過程中的脫鹽效果和有機(jī)物降解情況,并對實(shí)驗(yàn)中使用的均相陰、陽離子交換膜的污染清洗問題進(jìn)行了淺析。通過對不同時(shí)間點(diǎn)所取水樣的p H、電導(dǎo)率、鹽離子(Na~+、Cl-)濃度、溶液中TOC濃度和色度的定量分析,以及對離子膜表面形貌的掃描電鏡觀察和有機(jī)物電解產(chǎn)物的紅外光譜分析,得出以下結(jié)論:膜電解脫鹽過程中電流密度對脫鹽效果的影響最為顯著,是引起膜表面發(fā)生極化現(xiàn)象的關(guān)鍵因素。在本實(shí)驗(yàn)的參數(shù)設(shè)置條件下,電流密度55.6m A/cm2、極板間距2cm、電解液濃度2g/L、進(jìn)樣流速50m L/min為最優(yōu)條件。此條件下,單膜電解過程中Cl-和Na~+去除率分別為70%和90%左右;而在雙膜電解處理模擬染料廢水過程中兩種鹽離子的去除率均可達(dá)到90%左右,并且在一定程度上實(shí)現(xiàn)了幾種染料物質(zhì)的降解處理,其中甲基橙的降解效果最好,其TOC去除率可達(dá)到75%左右。同時(shí),因?yàn)榫嚓帯㈥栯x子膜的特殊結(jié)構(gòu),有效阻擋了有機(jī)物分子的遷移,從而實(shí)現(xiàn)了有機(jī)物與鹽離子的分離。膜電解過程中,Na~+和Cl-在電場作用下發(fā)生定向遷移,同時(shí),均相陽、陰離子交換膜表面和孔道內(nèi)的靜電作用會(huì)對相應(yīng)的離子進(jìn)行吸附,并發(fā)生遷移,從而實(shí)現(xiàn)Na~+和Cl-的去除。實(shí)驗(yàn)表明,該過程中,極板表面會(huì)發(fā)生一系列的電化學(xué)反應(yīng),陽極發(fā)生的析氯和析氧反應(yīng)會(huì)使該側(cè)溶液的p H維持在強(qiáng)酸性狀態(tài)(p H 2-3),陰極發(fā)生的析氫反應(yīng)則使該側(cè)溶液的p H維持在13左右。當(dāng)鹽溶液中存在有機(jī)物時(shí),電化學(xué)反應(yīng)產(chǎn)生的活性氯物質(zhì)(Cl2、HCl O、Cl-)和氫氧自由基(?OH)會(huì)對溶液中的有機(jī)物進(jìn)行氧化降解。通過模擬染料廢水的膜電解實(shí)驗(yàn)結(jié)果表明,該條件下的電解過程可有效去除染料廢水的色度,并結(jié)合電解產(chǎn)物的紅外光譜分析證明,幾種染料物質(zhì)的分子結(jié)構(gòu)均遭到破壞,特別是-N=N-、=C=C=、=C=O等基團(tuán),并且分子結(jié)構(gòu)越簡單電解效果越好,色度取去除率也越高。最后,均相陰、陽離子交換膜的掃描電鏡圖像表明,均相陽離子交換膜使用后表面會(huì)吸附大量的物質(zhì),均相陰離子交換膜表面出現(xiàn)許多裂痕。通過酸堿清洗和超聲清洗后,陽膜表面會(huì)變得平整光滑,而陰膜表面的裂痕并沒有發(fā)生太大變化。經(jīng)對清洗前后離子膜的脫鹽效果的對比,結(jié)果表明清洗可使離子膜的離子去除率恢復(fù)到使用過一次時(shí)的狀態(tài),證明實(shí)驗(yàn)中所用的組合膜清洗方法可有效去除膜表面的有機(jī)物和無機(jī)鹽沉淀造成的污染,進(jìn)而在一定程度上恢復(fù)離子膜的脫鹽性能。
[Abstract]:As a product of modern industrialization, high salt organic wastewater is not only large and complex, but it is easy to cause waste of water resources and environmental pollution. At present, the traditional physical and chemical treatment methods of high salt organic wastewater have the disadvantages such as high treatment cost, adding extra medicine agent, easily causing two pollution and so on, and waste water The high salt environment inhibits the activity of microbes and limits the application and development of microbiological methods. However, the high salinity wastewater has good conductivity and can provide an opportunity for the application of electrochemistry. As an important part of the electrochemical technology, membrane electrolysis technology combines the effect of traditional electrodialysis separation and purification and the characteristics of electrolysis technology. With the characteristics of low energy consumption and small environmental harm, this technology is undoubtedly a treatment method with great potential and research value for the treatment of high salt organic wastewater. This subject uses membrane electrolysis to desalination and organic degradation treatment of high salinity dyestuff wastewater, aiming at the study of high salt organic wastewater. The removal mechanism of salt ions and the influence of the organic matter degradation process on the desalting effect and the interaction relationship. The study uses a self-made detachable multistage membrane electrolyzer, taking Ti/RO2-Ir O2-Sn O2 as the shade, anode plate material, Na~+, Cl- as the target to remove ions, respectively, with the methyl orange, acid red 3R, direct dark brown, active bright brown. The membrane electrolysis desalination experiment under direct current electric field was carried out under the mixed system of blue X-BR and other dyes. The influence of current density, plate spacing, electrolyte concentration and injection velocity on the effect of electrolysis desalination in ion membrane electrolysis, as well as the effect of desalination and organic degradation in the process of double membrane electrolysis were discussed. The pollution cleaning problem of the cation exchange membrane used in the experiment was analyzed. The quantitative analysis of the P H, electrical conductivity, salt ion (Na~+, Cl-) concentration, TOC concentration and chromaticity in the solution at different time points, and the scanning electron microscope observation of the surface surface morphology of the ionic membrane and the infrared of the organic matter electrolysis products were analyzed. The following conclusion is drawn by spectral analysis: the effect of current density on desalination is the most significant in the process of membrane electrolysis desalination, which is the key factor causing polarization on the membrane surface. Under the conditions of setting the parameters of this experiment, the current density is 55.6m A/cm2, the spacing of the plate is 2cm, the electrolyte concentration is 2g/L, and the inlet velocity 50m L/min is the best condition. In the process of single film electrolysis, the removal rates of Cl- and Na~+ were 70% and 90%, respectively, while the removal rate of two kinds of salt ions could reach about 90% in the process of electrolytic treatment of dyestuff wastewater with double membrane electrolysis, and the degradation of several dyes was achieved to a certain extent. The degradation of methyl orange was the best, and the removal rate of TOC could be reached. At the same time, the special structure of the cationic membrane has effectively blocked the migration of organic molecules, thus realizing the separation of organic compounds from salt ions. In the process of membrane electrolysis, Na~+ and Cl- have directed migration under the action of the electric field. At the same time, the electrostatic action of the surface of the anion exchange membrane and the channel in the channel will be corresponding to the electrostatic action of the surface of the exchange membrane and the channel. The ions are adsorbed and migrate to remove the Na~+ and Cl-. The experiment shows that a series of electrochemical reactions occur on the surface of the plate in this process. The chlorine evolution and oxygen evolution of the anode will keep the P H of the side solution in the strong acid state (P H 2-3), and the hydrogen evolution reaction of the cathode causes the P H of the side solution to be maintained at 13. When organic matter exists in the salt solution, the active chlorine substance (Cl2, HCl O, Cl-) and hydrogen oxygen free radical (? OH) produced by the electrochemical reaction will oxidize and degrade the organic matter in the solution. The electrosolution process of the simulated dye wastewater shows that the chromaticity of the dye wastewater can be effectively removed and combined with electrolysis under this condition. The infrared spectrum analysis of the products showed that the molecular structures of several dyes were destroyed, especially the groups such as -N=N-, =C=C=, =C=O and other groups, and the more simple the molecular structure was, the better the electrolysis effect and the higher the chromaticity removal rate. There are many cracks on the surface of the homogeneous anion exchange membrane. After cleaning and ultrasonic cleaning, the surface of the film will become smooth and smooth, and the cracks on the surface of the film have not changed too much. The results show that the removal rate of ion membrane can be removed by the comparison of the effect of the desalination of the ion membrane before and after the cleaning. It was restored to the state when used once, and it was proved that the cleaning method used in the experiment can effectively remove the pollution caused by the organic matter and the inorganic salt precipitation on the surface of the membrane, and then to some extent, it can restore the desalination performance of the ion membrane to some extent.
【學(xué)位授予單位】：陜西科技大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：X703
本文編號(hào)：2146918
[Abstract]:As a product of modern industrialization, high salt organic wastewater is not only large and complex, but it is easy to cause waste of water resources and environmental pollution. At present, the traditional physical and chemical treatment methods of high salt organic wastewater have the disadvantages such as high treatment cost, adding extra medicine agent, easily causing two pollution and so on, and waste water The high salt environment inhibits the activity of microbes and limits the application and development of microbiological methods. However, the high salinity wastewater has good conductivity and can provide an opportunity for the application of electrochemistry. As an important part of the electrochemical technology, membrane electrolysis technology combines the effect of traditional electrodialysis separation and purification and the characteristics of electrolysis technology. With the characteristics of low energy consumption and small environmental harm, this technology is undoubtedly a treatment method with great potential and research value for the treatment of high salt organic wastewater. This subject uses membrane electrolysis to desalination and organic degradation treatment of high salinity dyestuff wastewater, aiming at the study of high salt organic wastewater. The removal mechanism of salt ions and the influence of the organic matter degradation process on the desalting effect and the interaction relationship. The study uses a self-made detachable multistage membrane electrolyzer, taking Ti/RO2-Ir O2-Sn O2 as the shade, anode plate material, Na~+, Cl- as the target to remove ions, respectively, with the methyl orange, acid red 3R, direct dark brown, active bright brown. The membrane electrolysis desalination experiment under direct current electric field was carried out under the mixed system of blue X-BR and other dyes. The influence of current density, plate spacing, electrolyte concentration and injection velocity on the effect of electrolysis desalination in ion membrane electrolysis, as well as the effect of desalination and organic degradation in the process of double membrane electrolysis were discussed. The pollution cleaning problem of the cation exchange membrane used in the experiment was analyzed. The quantitative analysis of the P H, electrical conductivity, salt ion (Na~+, Cl-) concentration, TOC concentration and chromaticity in the solution at different time points, and the scanning electron microscope observation of the surface surface morphology of the ionic membrane and the infrared of the organic matter electrolysis products were analyzed. The following conclusion is drawn by spectral analysis: the effect of current density on desalination is the most significant in the process of membrane electrolysis desalination, which is the key factor causing polarization on the membrane surface. Under the conditions of setting the parameters of this experiment, the current density is 55.6m A/cm2, the spacing of the plate is 2cm, the electrolyte concentration is 2g/L, and the inlet velocity 50m L/min is the best condition. In the process of single film electrolysis, the removal rates of Cl- and Na~+ were 70% and 90%, respectively, while the removal rate of two kinds of salt ions could reach about 90% in the process of electrolytic treatment of dyestuff wastewater with double membrane electrolysis, and the degradation of several dyes was achieved to a certain extent. The degradation of methyl orange was the best, and the removal rate of TOC could be reached. At the same time, the special structure of the cationic membrane has effectively blocked the migration of organic molecules, thus realizing the separation of organic compounds from salt ions. In the process of membrane electrolysis, Na~+ and Cl- have directed migration under the action of the electric field. At the same time, the electrostatic action of the surface of the anion exchange membrane and the channel in the channel will be corresponding to the electrostatic action of the surface of the exchange membrane and the channel. The ions are adsorbed and migrate to remove the Na~+ and Cl-. The experiment shows that a series of electrochemical reactions occur on the surface of the plate in this process. The chlorine evolution and oxygen evolution of the anode will keep the P H of the side solution in the strong acid state (P H 2-3), and the hydrogen evolution reaction of the cathode causes the P H of the side solution to be maintained at 13. When organic matter exists in the salt solution, the active chlorine substance (Cl2, HCl O, Cl-) and hydrogen oxygen free radical (? OH) produced by the electrochemical reaction will oxidize and degrade the organic matter in the solution. The electrosolution process of the simulated dye wastewater shows that the chromaticity of the dye wastewater can be effectively removed and combined with electrolysis under this condition. The infrared spectrum analysis of the products showed that the molecular structures of several dyes were destroyed, especially the groups such as -N=N-, =C=C=, =C=O and other groups, and the more simple the molecular structure was, the better the electrolysis effect and the higher the chromaticity removal rate. There are many cracks on the surface of the homogeneous anion exchange membrane. After cleaning and ultrasonic cleaning, the surface of the film will become smooth and smooth, and the cracks on the surface of the film have not changed too much. The results show that the removal rate of ion membrane can be removed by the comparison of the effect of the desalination of the ion membrane before and after the cleaning. It was restored to the state when used once, and it was proved that the cleaning method used in the experiment can effectively remove the pollution caused by the organic matter and the inorganic salt precipitation on the surface of the membrane, and then to some extent, it can restore the desalination performance of the ion membrane to some extent.
【學(xué)位授予單位】：陜西科技大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：X703
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