發(fā)布時間：2019-06-11 03:50

【摘要】：近年來,隨著化工、醫(yī)藥、農(nóng)藥等生產(chǎn)工業(yè)的迅速發(fā)展,越來越多的人工合成的有機物在生產(chǎn)和使用過程中進入到飲用水源水環(huán)境中。其中許多化合物對人.和動物具有細胞和遺傳毒性,長期攝取可能會危害人體健康甚至導(dǎo)致死亡。常規(guī)的水處理工藝難以有效去除此類有機污染物,需要結(jié)合相應(yīng)的深度處理工藝才能達到較好的去除效果�；钚蕴课绞侨コ杏袡C污染物的最有效技術(shù)之一,然而由于傳統(tǒng)活性炭原料來源有限,成本較高,加之粉末活性炭的分離回收問題,限制了活性炭在水處理領(lǐng)域的應(yīng)用。近年來,許多研究以碳含量高、來源廣泛、價格低廉的工農(nóng)業(yè)廢棄物為原料制備活性炭,其中多種活性炭都具有較高的比表面積和顯著的吸附性能,表現(xiàn)出良好的應(yīng)用前景。離子交換樹脂是一種常見的離子交換劑,應(yīng)用廣泛,需求量大。樹脂使用飽和后可以通過酸、堿或鹽溶液進行再生,由于部分雜質(zhì)不易洗脫,多次使用會使其逐漸積累,導(dǎo)致樹脂交換效能降低,出水水質(zhì)難以達到處理要求。這種情況下,往往會更換新的樹脂,這就導(dǎo)致原來的樹脂被廢棄。全球每年有大量的廢舊樹脂產(chǎn)生。廢舊的樹脂一般采用焚燒的方式進行處理,費用較高。離子交換樹脂的基本組成元素為碳和氫,碳含量高;廢舊樹脂的價格低廉,且來源廣泛。如果可以以此為原料制備活性炭,不僅可以解決廢舊離子交換樹脂的處理處置問題,而且還可以為活性炭制備提供一種新的原料。近年來,有研究人員開展了部分相關(guān)研究,以多種離子交換樹脂為原料,采用水蒸氣或二氧化碳活化法制備活性炭。然而,所得活性炭往往比表面積和孔容較低,吸附性能有限�；谏鲜霰尘�,本研究以廢舊的苯乙烯系離子交換樹脂為原料,開展了高比表面積磁性活性炭的制備及應(yīng)用研究。主要內(nèi)容和結(jié)果如下:(1)以廢舊的陽離子樹脂為原料,通過陽離子交換負載鐵,然后通過氫氧化鈉高溫活化法制備活性炭。分析載鐵樹脂的高溫熱解過程,研究制備條件對活性炭物理化學(xué)性質(zhì)的影響。結(jié)果顯示,載鐵樹脂的熱解伴隨著脫水、磺酸基脫落及樹脂骨架的斷裂等過程,氣體產(chǎn)物主要有二氧化硫、二氧化碳和水。鐵的添加限制了部分微孔的形成或?qū)⒉糠治⒖锥氯?導(dǎo)致平均孔徑增大�；罨瘻囟葘钚蕴康目讖椒植�、晶體結(jié)構(gòu)以及磁性性能都具有顯著的影響�；钚蕴康拇判孕阅芘c它的晶體結(jié)構(gòu)有關(guān)。(2)以廢舊陰離子樹脂為原料,通過絡(luò)合物陰離子交換負載鐵,然后通過氫氧化鈉高溫活化法制備活性炭。分析載鐵樹脂的高溫熱解過程,研究制備條件對活性炭物理化學(xué)性質(zhì)的影響。結(jié)果顯示,樹脂基團可以顯著影響活性炭的制備過程及其物理化學(xué)性質(zhì)。載鐵陰離子樹脂高溫熱解過程中的氣體產(chǎn)物主要有甲胺、二甲胺、二氧化碳和水等。載鐵樹脂炭化后,其內(nèi)部即生成了磁性鐵氧化物,經(jīng)過氫氧化鈉高溫活化,部分鐵氧化物被還原,生成單質(zhì)鐵。鐵的添加導(dǎo)致了活性炭比表面積的顯著降低,但沒有改變其孔徑分布。改變活化劑用量和活化溫度會影響活性炭的比表面積和孔徑分布。(3)優(yōu)化條件下制備的兩種樹脂基磁性活性炭的比表面積高達1700 m2/g以上,以此為吸附劑,用于水源水中的兩種典型的有機物鄰苯二甲酸二乙酯和雙酚A的去除。結(jié)果顯示,樹脂基磁性活性炭對鄰苯二甲酸二乙酯和雙酚A的吸附表現(xiàn)出了良好的動力學(xué)性能,其過程符合準二級動力學(xué)方程,中孔的增加有利于活性炭初期吸附速率的提高。與商業(yè)活性炭相比,樹脂基磁性活性炭具有更高的吸附性能�；钚蕴繉︵彵蕉姿岫阴ズ碗p酚A的吸附是自發(fā)放熱的過程。pH值對雙酚A吸附的影響是通過改變其分子形態(tài)而實現(xiàn)的,在實驗條件下pH值對鄰苯二甲酸二乙酯的吸附影響不大。溶液中存在的天然有機物尺寸越小,越易進入孔道占據(jù)位點,降低活性炭的吸附性能。吸附鄰苯二甲酸二乙酯和雙酚A飽和后的活性炭,可以采用氫氧化鈉溶液進行再生。(4)以樹脂基磁性活性炭為吸附劑,研究其對實際水源水的凈化效果及毒性削減。結(jié)果顯示,活性炭可有效去除水源水的DOC和UV254,凈化前后水源水中有機物的分子量分布沒有顯著變化,自制活性炭ACS-1對類腐殖酸區(qū)的熒光物質(zhì)去除效果顯著。經(jīng)活性炭凈化后,水源水中的多種半揮發(fā)性有機物都有不同程度的去除,其中嗪草酮、敵敵畏和1-乙基-4-硝基苯三種物質(zhì)去除效果顯著。選取HepG2作為受試對象,進行細胞毒性及氧化損傷研究,結(jié)果顯示,經(jīng)活性炭凈化處理后,水樣的細胞毒性以及對細胞的氧化損傷等都有不同程度的減弱。
[Abstract]:In recent years, with the rapid development of the production industry, such as chemical industry, medicine and pesticide, more and more synthetic organic substances enter the drinking water source water environment in the process of production and use. In which many of the compounds are human. And the long-term ingestion can be harmful to human health and even cause death. The conventional water treatment process is difficult to effectively remove such organic pollutants, and a corresponding advanced treatment process needs to be combined to achieve better removal effect. Active carbon adsorption is one of the most effective techniques for removing organic pollutants in water. However, due to the limited source of the traditional activated carbon raw materials, the cost is high, and the separation and recovery of the powdered activated carbon have limited the application of the activated carbon in the water treatment field. In recent years, many studies have made active carbon from industrial and agricultural wastes with high carbon content, wide source and low price. Ion exchange resin is a kind of common ion exchanger, and has wide application and large demand. After the resin is saturated, the resin can be regenerated by an acid, a base or a salt solution, and because some impurities are not easy to be eluted, the resin is gradually accumulated in a plurality of times, so that the resin exchange efficiency is reduced, and the water quality of the effluent is difficult to reach the processing requirement. In this case, a new resin is often replaced, which causes the original resin to be discarded. The world has a large number of waste resins every year. The waste resin is generally treated by incineration, and the cost is higher. The basic components of the ion exchange resin are carbon and hydrogen, the carbon content is high, the price of the waste resin is low, and the source is wide. If that active carbon can be prepare as a raw material, not only the treatment and treatment problem of the waste ion exchange resin can be solved, but also a new raw material can be provided for the preparation of the active carbon. In recent years, some relevant research has been carried out by researchers, and the active carbon is prepared by using a variety of ion-exchange resins as raw materials and by using water vapor or carbon dioxide activation method. However, the activated carbon is often lower in surface area and pore volume and limited in adsorption performance. Based on the above background, the preparation and application of high specific surface area magnetic activated carbon were carried out by using the waste styrene-based ion-exchange resin as the raw material. The main contents and results are as follows: (1) The waste-used cationic resin is used as the raw material, and the loaded iron is exchanged through the cation, and then activated carbon is prepared by the high-temperature activation method of sodium hydroxide. The effects of preparation conditions on the physical and chemical properties of activated carbon were studied. The results show that the pyrolysis of the iron-carrying resin is accompanied by the process of dehydration, the shedding of the sulfonic acid group and the fracture of the resin skeleton, and the gas product mainly contains sulfur dioxide, carbon dioxide and water. The addition of iron limits the formation of some of the pores or the plugging of a portion of the pores, resulting in an increase in the average pore size. The activation temperature has a significant effect on the pore size distribution, crystal structure and magnetic properties of the activated carbon. The magnetic properties of activated carbon are related to its crystal structure. (2) the waste anion resin is used as a raw material, the loaded iron is exchanged through a complex anion, and then activated carbon is prepared by a sodium hydroxide high-temperature activation method. The effects of preparation conditions on the physical and chemical properties of activated carbon were studied. The results show that the resin group can significantly influence the preparation process and the physical and chemical properties of the activated carbon. The gas products in the high-temperature pyrolysis of the iron-carrying anion resin are mainly methylamine, dimethylamine, carbon dioxide and water. After the iron-carrying resin is carbonized, a magnetic iron oxide is generated inside the iron-carrying resin, the iron oxide is activated at high temperature through the sodium hydroxide, and a part of the iron oxide is reduced to generate the elementary iron. The addition of iron results in a significant reduction in the specific surface area of the activated carbon, but does not change its pore size distribution. Changing the amount of the activator and the activation temperature will affect the specific surface area and pore size distribution of the activated carbon. And (3) the specific surface area of the two kinds of resin-based magnetic activated carbon prepared under the optimized condition is as high as 1700 m2/ g or more, thus the adsorbent is used for the removal of two typical organic matter phthalate and bisphenol A in the water source water. The results show that the adsorption of diethyl phthalate and bisphenol A by the resin-based magnetic activated carbon shows good dynamic performance, and the process is in accordance with the quasi-second-order kinetic equation, and the increase of the mesopore is favorable to the increase of the initial adsorption rate of the activated carbon. Compared with commercial activated carbon, the resin-based magnetic activated carbon has higher adsorption performance. The adsorption of diethyl phthalate and bisphenol A by activated carbon is a spontaneous exothermic process. The effect of pH on the adsorption of bisphenol A was achieved by changing its molecular morphology, and the pH value in the experimental conditions had little effect on the adsorption of diethyl phthalate. The smaller the size of the natural organic matter present in the solution, the more easily enter the pore-occupied site and lower the adsorption property of the activated carbon. The adsorption of diethyl phthalate and the activated carbon after the bisphenol A is saturated can be carried out by adopting a sodium hydroxide solution. And (4) using the resin-based magnetic activated carbon as an adsorbent to study the purification effect and the toxicity reduction of the water in the actual water source. The results show that the active carbon can effectively remove the DOC and the UV254 of the water, and the molecular weight distribution of the organic matter in the water source water before and after purification is not changed significantly, and the self-made active carbon ACS-1 has a significant effect on the removal of the fluorescent substance in the humic acid region. After the purification of activated carbon, the various semi-volatile organic compounds in the water source water have different degree of removal, among which, the removal effect of the three substances of the trione, the dichlorvos and the 1-ethyl-4-nitrophenol is significant. HepG2 was selected as the subject to study the cytotoxicity and oxidative damage. The results showed that the cytotoxicity of the water sample and the oxidative damage to the cells were reduced after the treatment with activated carbon.
【學(xué)位授予單位】：南京大學(xué)
【學(xué)位級別】：博士
【學(xué)位授予年份】：2014
【分類號】：TU991.2;TQ424.1

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