本文選題：原子轉(zhuǎn)移自由基聚合　切入點(diǎn)：酚類污染物　出處：《哈爾濱工業(yè)大學(xué)》2017年博士論文　論文類型：學(xué)位論文

【摘要】：近年來(lái)酚類污染物對(duì)水體的污染日趨嚴(yán)重,吸附技術(shù)尤其是使用活性炭的吸附技術(shù)已經(jīng)成為去除水中有機(jī)污染物最為有效和廣泛的方法,然而吸附性能較好的粉末活性炭(PAC)、石墨烯等材料往往粒度較小,應(yīng)用于水處理后難以分離回收,因此提升此類材料的分離回收能力具有重要的實(shí)踐意義。本文選用多孔材料粉末活性炭和片狀材料氧化石墨烯(GO)和氮化硼(BN),對(duì)其進(jìn)行接枝聚(N-異丙基丙烯酰胺)(PNIPAM)改性,研究改性吸附材料具有的獨(dú)特溫度敏感絮凝性能和對(duì)特征酚類污染物雙酚A、苯酚和對(duì)苯二酚的吸附性能和脫附能力,為自絮凝材料應(yīng)用于吸附酚類污染物領(lǐng)域的研究提供理論基礎(chǔ)。分別采用酸化改性和氧化改性的方法對(duì)活性炭表面進(jìn)行前處理,在此基礎(chǔ)上對(duì)活性炭表面改姓,采用原子轉(zhuǎn)移自由基聚合的(ATRP)方法在改性活性炭表面接枝PNIPAM,通過(guò)傅里葉紅外光譜(FT-IR)、掃描電子顯微鏡(SEM)、熱重分析(TGA)、X-射線光電子能譜(XPS)對(duì)不同改性方法、不同接枝量的接枝產(chǎn)物的熱穩(wěn)定性、表面結(jié)構(gòu)和成分進(jìn)行了表征和檢測(cè)。采用相似的合成工藝,分別在氧化石墨烯和片狀氮化硼表面接枝了PNIPAM,并對(duì)接枝產(chǎn)物的結(jié)構(gòu)和成分進(jìn)行了表征。分別對(duì)常溫下接枝PNIPAM的活性炭、氧化石墨烯和氮化硼材料在水中的粒度和分散性能進(jìn)行考察,表明接枝改性后,吸附材料的分散性能明顯優(yōu)化。在低濃度下(0.1 mg/L),考察接枝PNIPAM的吸附材料在最低臨界相容溫度(LCST)的粒度收縮效應(yīng),以此研究接枝的PNIPAM的微觀鏈段變化。在較高濃度范圍內(nèi)(0.01 g/L-10 g/L),通過(guò)渾濁度分析及定量計(jì)算,考察因?yàn)镻NIPAM的鏈段收縮和親疏水相轉(zhuǎn)變,而產(chǎn)生的接枝吸附材料的自絮凝效應(yīng)。結(jié)果表明,在0.01 g/L-10g/L的濃度范圍內(nèi),接枝改姓的材料隨溫度升高產(chǎn)生明顯的自絮凝沉降現(xiàn)象,高濃度下去除率大于95%。在此基礎(chǔ)上,分別研究了前處理方法、接枝PNIPAM的密度、不同材料基體對(duì)自絮凝性能的影響。選用內(nèi)分泌干擾物雙酚A(BPA)作為特征污染物,通過(guò)考察目標(biāo)物吸附能力與改性活性炭比表面積和表面性質(zhì)關(guān)系這一關(guān)鍵問(wèn)題,詳細(xì)地研究了BPA在各類改性活性炭表面的吸附行為,討論了不同的前處理方法,以及接枝PNIPAM量對(duì)BPA吸附性能的影響。表明可以選用酸化或酸化氧化改性活性炭的工藝,并控制PNIPAM的接枝量,制備出對(duì)BPA吸附能力較強(qiáng)的PAC-PNIPAM,吸附容量可以達(dá)到247.5 mg/g。機(jī)理分析表明,BPA在接枝改性活性炭上的吸附主要來(lái)源于π-π色散作用和氫鍵作用,其中傳統(tǒng)的π-π色散作用依然處于主導(dǎo)地位。選出一種接枝PNIPAM的活性炭,探討了影響B(tài)PA吸附的環(huán)境因素。同時(shí)考察了在臨界相容溫度時(shí),PNIPAM鏈段變化對(duì)吸附飽和的接枝活性炭脫附性能的影響,進(jìn)而研究接枝改性活性炭的再生性能。確定可以在溫水中(溫度高于最低臨界相容溫度),使用超聲再生的方式實(shí)現(xiàn)接枝改性的粉末炭再生,3次再生后仍然保留75%以上的吸附性能。制備表面接枝PNIPAM的氧化石墨烯和氮化硼材料,對(duì)接枝前后的兩種片狀材料的比表面積進(jìn)行分析,表明接枝后可明顯促進(jìn)片狀材料的分散和比表面積的提升。之后重點(diǎn)考察兩種接枝改性的片狀材料分別對(duì)雙酚A、苯酚和對(duì)苯二酚的吸附性能,表明接枝PNIPAM的材料對(duì)酚類污染物有選擇性吸附能力。以接枝PNIPAM的氧化石墨烯為例,對(duì)其選擇性吸附的機(jī)理進(jìn)行了研究。同時(shí)研究了在臨界相容溫度時(shí),對(duì)苯二酚在接枝改性氧化石墨烯材料上吸附性能的變化,并與吸附機(jī)理進(jìn)行印證,表明接枝PNIPAM的材料對(duì)于小尺寸親水酚類污染物的選擇性吸附能力。最后對(duì)溫水中接枝改姓石墨烯的脫附回用能力進(jìn)行了研究。
[Abstract]:In recent years, the pollution of phenolic pollutants in water is becoming more and more serious, especially the adsorption technology using activated carbon adsorption technology has become the most effective for the removal of organic pollutants in water and a wide range of methods, however, the adsorption of powdered activated carbon (PAC), the better performance of graphene materials to smaller particle size, used in water treatment is difficult to separate recovery, so to enhance the ability of separation and recovery of these materials has important practical significance. This paper selects the porous materials of powder activated carbon and graphite oxide graphene sheet material (GO) and boron nitride (BN), the grafted poly (N- isopropylacrylamide) (PNIPAM) modification, modification of temperature sensitive flocculation performance is unique adsorption materials and characteristics of phenolic pollutants bisphenol A, adsorption of phenol and hydroquinone and desorption ability, provide a theoretical study of self flocculating material applied to the adsorption of phenolic pollutants in the field On the basis of. The surface of the activated carbon was pretreated by acidification method modification and oxidation modification, on the basis of the surface modification of activated carbon by atom transfer radical polymerization (ATRP) method on modified activated carbon surface grafted PNIPAM by Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), thermogravimetric analysis (TGA), X- ray photoelectron spectroscopy (XPS) of different modification methods, the thermal stability of the grafted product of different grafting amount, surface structure and composition were characterized and detected by synthesis of similar, respectively in graphene oxide and boron nitride sheet surface grafting of PNIPAM. And the structure and composition of the grafted products were characterized respectively. Activated carbon on room temperature grafting PNIPAM, graphene oxide and boron nitride materials were investigated in the water particle size and dispersion properties, show that the modified dispersion, adsorption materials The performance was optimized. At low concentration (0.1 mg/L), on grafting of PNIPAM adsorbent at lower critical solution temperature (LCST) size contraction effect, in order to study the grafted PNIPAM micro segment changes. At higher concentration range (0.01 g/L-10 g/L), using the turbidity analysis and quantitative calculation, because of the PNIPAM chain segment contraction and hydrophobic phase transition, self flocculating effect of graft materials resulting from the adsorption. The results showed that in the concentration range of 0.01 g/L-10g/L, the graft material with the increase of temperature has changed significantly since the flocculation phenomenon, high concentration on removal rate of more than 95%. on the basis of this, the pretreatment method study of PNIPAM grafting density, effect of different material matrix on the self flocculating performance. Using bisphenol A (BPA) as the characteristic pollutants, through the investigation of the target and the adsorption capacity of modified activated carbon surface The key problem of the area and surface properties, a detailed study of the adsorption behavior of BPA on all kinds of surface modification of activated carbon, discusses different pretreatment methods, effects on Adsorption Properties of BPA and PNIPAM grafted amount. Indicate that the process can be selected or acidification acidification oxidation modification of activated carbon, the grafting amount and control PNIPAM the preparation of BPA PAC-PNIPAM adsorption ability, the adsorption capacity can reach 247.5 mg/g. analysis showed that the adsorption of BPA on modified activated carbon mainly originates from the Pi Pi dispersion interaction and hydrogen bonding interaction, in which the traditional Pi Pi dispersion effect is still in a dominant position. Select a graft of activated carbon PNIPAM, to explore the factors influencing the adsorption of BPA environment. At the same time on the critical solution temperature, effect of PNIPAM segment change desorption performance of the grafted activated carbon adsorption saturation, and then study the grafting modification The regeneration performance of activated carbon can be determined. In warm water (temperature above the lower critical solution temperature), carbon powder with ultrasonic regeneration method of graft modified regeneration after 3 times regeneration still retain the adsorption performance of more than 75%. The preparation of PNIPAM grafted onto the surface of graphene oxide and boron nitride materials, two kinds of sheet the material of the grafted surface area analysis showed that grafting can obviously promote the dispersion of sheet material and surface area increase. After focusing on two kinds of sheet material grafted respectively on bisphenol A, adsorption of phenol and hydroquinone, PNIPAM showed that the graft material has selective adsorption ability of phenolic pollutants in graphene oxide grafted PNIPAM as an example, the mechanism of selective adsorption was studied. At the same time in the study of the critical solution temperature, hydroquinone in graft modification of graphene oxide material Adsorption properties of the material, and were verified with the adsorption mechanism, PNIPAM showed that the graft material for selective adsorption ability of hydrophilic phenolic pollutants in small size. At the end of the warm water in the grafted graphene surname desorption and reuse ability were studied.

【學(xué)位授予單位】：哈爾濱工業(yè)大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2017
【分類號(hào)】：X52
，

本文編號(hào)：1579307