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  本文關(guān)鍵詞： 金屬-有機框架 MIL-101 土霉素 吸附 廢水處理　出處：《昆明理工大學》2017年碩士論文　論文類型：學位論文

【摘要】：藥物抗生素的大量生產(chǎn)和使用對環(huán)境造成嚴重的危害,如何高效去除廢水中抗生素污染物成為目前人們研究的一個熱點問題。金屬-有機框架材料(Metal-Organic Frameworks,MOFs)作為一類先進多功能材料,具有高比表面積、可調(diào)節(jié)的孔尺寸和表面易于修飾等優(yōu)良特性受到國內(nèi)外研究者們廣泛關(guān)注。本研究采用高度多孔性的MIL-101對土霉素進行吸附,發(fā)現(xiàn)雖然吸附速率很快,吸附量卻沒有達到預(yù)期效果。為進一步開發(fā)MIL-101對土霉素吸附潛力,我們采用乙二胺對其進行合成后修飾改性,改性后的MIL-101吸附土霉素效果較原始MIL-101材料具有十分顯著的提高。本文首先以九水硝酸鉻、對苯二甲酸為反應(yīng)物,HF為礦化劑和水作為溶劑在高壓反應(yīng)釜中合成MIL-101材料。隨后又以甲苯為溶劑通過回流反應(yīng)對合成后的MIL-101進行乙二胺(ED)修飾,得到改性后的MIL-101材料(ED-MIL-101)。通過XRD、SEM、FT-IR、TGA和BET等手段對改性前、后的MIL-101材料進行表征,MIL-101的表征結(jié)果與文獻報道一致,表明本研究中MIL-101產(chǎn)物成功合成。改性前后對比發(fā)現(xiàn):嫁接后,材料ED-MIL-101比表面積和孔容變小,晶體結(jié)晶性能稍微變差,但框架結(jié)構(gòu)依然保持完整。為測試兩種材料對土霉素吸附效果,我們對其展開動力學研究,動力學結(jié)果表明:ED-MIL-101在同等條件下對土霉素吸附量是MIL-101的5倍,兩種材料的吸附行為滿足擬二級動力學模型;為探索土霉素吸附機理,我們對材料吸附行為進行等溫線和熱力學研究,結(jié)果表明:MIL-101和ED-MIL-101吸附土霉素能較好滿足Langmuir模型,并且吸附反應(yīng)為自發(fā)放熱反應(yīng)。pH實驗研究表明:隨pH增加,ED-MIL-101表面電荷由正變?yōu)樨?溶液pH為4-10時對土霉素吸附效果較好,ED-MIL-101吸附土霉素存在電子效應(yīng)。最后我們采用“HCl溶液+乙醇”的方法在超聲條件下對吸附劑進行再生,發(fā)現(xiàn)ED-MIL-101在經(jīng)歷3輪吸附-脫附實驗后仍然具有很高的吸附量。
[Abstract]:The mass production and use of drug antibiotics cause serious harm to the environment. How to efficiently remove antibiotic pollutants from wastewater has become a hot issue. Metal-Organic Frameworks is a metal-organic framework material. As a kind of advanced multifunctional materials, MOFs has high specific surface area. The excellent properties of adjustable pore size and easy surface modification have attracted wide attention of researchers at home and abroad. In this study, oxytetracycline was adsorbed by highly porous MIL-101. In order to further develop the potential of MIL-101 to adsorb oxytetracycline, ethylenediamine was used to modify the surface of oxytetracycline. The adsorption of oxytetracycline by modified MIL-101 was much better than that of MIL-101. Firstly, chromium nitrate nine hydrate and terephthalic acid were used as reactants. HF was used as mineralizer and water as solvent to synthesize MIL-101 material in autoclave, then MIL-101 was modified by ethylenediamine (EDN) with toluene as solvent through reflux reaction. The modified MIL-101 material ED-MIL-101 was obtained by means of XRDX SEMT-IRGA-TGA and BET. The results showed that the MIL-101 products were successfully synthesized in this study. The results of comparison before and after modification showed that: after grafting. The specific surface area and pore volume of the material ED-MIL-101 become smaller, the crystalline properties of the crystal become a little worse, but the structure of the frame remains intact, to test the adsorption effect of the two materials to oxytetracycline. The kinetic results show that the adsorption capacity of Otochlomycin at the same conditions is 5 times of that of MIL-101. The adsorption behavior of the two materials meets the pseudo-second-order kinetic model. In order to explore the adsorption mechanism of oxytetracycline, the adsorption behavior of materials was studied by isotherms and thermodynamics. The results showed that the adsorption of oxytetracycline by ED-MIL-101 and WMIL-101 could satisfy the Langmuir model. The adsorption reaction was spontaneous exothermic reaction. The experimental results showed that the surface charge of ED-MIL-101 changed from positive to negative with the increase of pH, and the adsorption effect of oxytetracycline was better when pH was 4-10. ED-MIL-101 adsorbed oxytetracycline has an electronic effect. Finally, we use the method of "HCl solution ethanol" to regenerate the adsorbent under ultrasonic condition. It is found that ED-MIL-101 still has a high adsorption capacity after three rounds of adsorption-desorption experiments.
【學位授予單位】：昆明理工大學
【學位級別】：碩士
【學位授予年份】：2017
【分類號】：X703;O647.3

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本文編號：1484079