【摘要】：填充床電化學(xué)水處理工藝是一種被環(huán)保工作者寄予厚望的水處理技術(shù),而床層中填料的制備是該技術(shù)的主要研究方向之一,尤其是對(duì)于炭載金屬氧化物粒子電極的全面評(píng)價(jià)及其催化氧化有機(jī)物機(jī)理的探究,將為炭載金屬氧化物種類的比選提供依據(jù)�；诖�,本研究以活性炭為載體,進(jìn)行了Mn、Sn及Sb等單組份金屬氧化物或復(fù)合型金屬氧化物負(fù)載型粒子電極的制備,通過物化表征、苯酚氧化實(shí)驗(yàn),充分研究了不同粒子電極的電催化氧化性能,也對(duì)其電催化氧化苯酚機(jī)理進(jìn)行了探討。主要結(jié)論如下:在填料的制備中,利用浸漬法制備了Mn O2/AC(后文簡(jiǎn)稱錳型)、利用溶膠凝膠法制備了Sn O2-Sb Ox/AC(錫銻型)和Mn O2-Sn O2-Sb Ox/AC(錳錫銻型)。在物理表征中,SEM分析表明,三種填料負(fù)載物負(fù)載均勻,分散性好,無大塊負(fù)載物團(tuán)聚。XRD分析表明,錳型填料中二氧化錳的物相為α與β相相混合型;錫銻型中二氧化錫為四方晶系;錳錫銻型中,二氧化錳為β相,二氧化錫為四方晶系。BET分析表明,負(fù)載過后,比表面積及孔容孔徑均有大范圍下降,負(fù)載物侵占孔道能力較強(qiáng),負(fù)載充分,其中以錳錫銻型最為顯著。在電化學(xué)表征中,0~1.8V的循環(huán)伏安(CV)表明,錳錫銻型出現(xiàn)了氧化還原峰,推測(cè)為金屬氧化物與過氧化物的氧化還原過程引起,填料的活性點(diǎn)位數(shù)較未負(fù)載的均有了明顯的提高,三者差異不大。-0.1~0.6V的CV表明,填料負(fù)載過后,通過雙電層電場(chǎng)氧化苯酚的能力均有了提高。極化曲線分析表明,在析氧電位方面,錳錫銻型優(yōu)于錫銻型優(yōu)于未負(fù)載型優(yōu)于錳型;交換電流密方面,負(fù)載型普遍優(yōu)于未負(fù)載型,錳錫銻型最為顯著。交流阻抗的測(cè)試表明,在電荷轉(zhuǎn)移電阻方面,錫銻型填料的電阻最小,其次為錳錫銻型,錳型,這三者均小于未負(fù)載型;在擴(kuò)散控制方面,則是錳錫銻型擴(kuò)散最具優(yōu)勢(shì),其次為錫銻型,錳型。以填料做粒子電極,在填充床反應(yīng)器內(nèi)進(jìn)行了苯酚廢水水處理實(shí)驗(yàn)。水處理結(jié)果顯示錳錫銻型填料的COD及苯酚濃度去除效果最優(yōu),其次為錫銻型、錳型及未負(fù)載型。UV分析來看,負(fù)載過后填料對(duì)苯酚的中間產(chǎn)物苯醌等閉環(huán)有機(jī)物的降解均有了提高,其中以錳型填料最優(yōu),其次為錳錫銻型、錫銻型。結(jié)合相關(guān)水處理指標(biāo)及電化學(xué)表征等分析,在電化學(xué)水處理中,推測(cè)二氧化錳生成了Mn Ox+1,其促進(jìn)了填料對(duì)苯酚及苯醌等閉環(huán)有機(jī)物的選擇性氧化;推測(cè)二氧化錫型生成了Sn O2(?OH),其促進(jìn)了填料對(duì)苯環(huán)等有機(jī)物的電化學(xué)燃燒。能耗及電流效率分析表明,錳錫銻型填料優(yōu)勢(shì)明顯,其次錫銻型、錳型。
[Abstract]:The electrochemical water treatment process in packed bed is a kind of water treatment technology which is highly expected by environmental protection workers, and the preparation of the filler in the bed is one of the main research directions of the technology. In particular, the comprehensive evaluation of carbon-loaded metal oxide particle electrodes and the study of the mechanism of catalytic oxidation of organic compounds will provide the basis for the comparison and selection of carbon-loaded metal oxides. Based on this, the single component metal oxide or composite metal oxide supported particle electrodes, such as Mn,Sn and Sb, were prepared with activated carbon as the carrier, and were characterized by physicochemical characterization and phenol oxidation experiments. The electrocatalytic oxidation performance of different particle electrodes was studied and the mechanism of phenol oxidation was also discussed. The main conclusions are as follows: in the preparation of filler, Mn O2/AC (manganese type) was prepared by impregnation method, Sn O2-Sb Ox/AC (tin antimony type) and Mn O2-Sn O2-Sb Ox/AC (manganese tin antimony type) were prepared by sol-gel method. In physical characterization, SEM analysis showed that the three fillers had uniform loading, good dispersion and no agglomeration of bulk loads. XRD analysis showed that the phase of manganese dioxide in manganese type fillers was a mixture of 偽 and 尾 phase. Tin dioxide is tetragonal in antimony type. In the manganese-tin antimony type, manganese dioxide is 尾 phase and tin dioxide is tetragonal system. BET analysis shows that after loading, the specific surface area and pore volume pore size decrease in a wide range, and the load has a strong ability to encroach on the pore channel and has sufficient load. Among them, manganese, tin and antimony type is the most significant. In the electrochemical characterization, the cyclic voltammetry (CV) of 0 ~ 1.8V indicates that the oxidation and reduction peaks of manganese, tin and antimony type appear, which may be caused by the redox process of metal oxides and peroxides. The number of active sites of fillers was significantly higher than that of unloaded fillers, and the difference among the three was not significant. The CV of -0.1 ~ 0.6V showed that the ability of phenol oxidation by double-layer electric field was improved after the filler was loaded. The analysis of polarization curves shows that the manganese tin antimony type is superior to the unloaded type in oxygen evolution potential, and the load type is generally superior to the unloaded type in the exchange current density, and the manganese tin antimony type is the most significant. The measurement of AC impedance shows that the resistance of tin antimony type filler is the smallest, followed by manganese tin antimony type and manganese type in charge transfer resistance, which are all smaller than that of unloaded type. In the aspect of diffusion control, manganese, tin and antimony type have the most advantages, followed by tin antimony type and manganese type. Phenol wastewater treatment experiment was carried out in packed bed reactor with filler as particle electrode. The results of water treatment showed that the removal efficiency of COD and phenol was the best, followed by tin antimony type, manganese type and unloaded type. UV analysis showed that, After loading, the degradation of phenol intermediate products, such as benzoquinone, was improved, among which manganese filler was the best, followed by manganese tin antimony type and tin antimony type. Based on the analysis of related water treatment indexes and electrochemical characterization, it was suggested that manganese dioxide formed Mn Ox _ 1 in electrochemical water treatment, which promoted the selective oxidation of phenol and benzoquinone by fillers. It is inferred that tin dioxide type produces Sn O 2 (? OH),) which promotes the electrochemical combustion of benzene ring and other organic compounds. The analysis of energy consumption and current efficiency showed that Mn-Sn-Sb-type filler had obvious advantage, followed by Sn-Sb-type and Mn-type.
【學(xué)位授予單位】：中國(guó)礦業(yè)大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2015
【分類號(hào)】：X703

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本文編號(hào)：2423727