【摘要】：環(huán)境內分泌干擾物是由人類、動物的生活及工業(yè)生產所產生的干擾激素分泌的一類有害物質。內分泌干擾物由于很難被生物降解且具有抗氧化性等長期存在于環(huán)境中,對于人類健康和環(huán)境產生很大的危害,因此如何經濟高效地治理水體中的內分泌干擾物已經成為水處理領域研究的熱點。吸附法的最大優(yōu)勢在于對生物法難以處理的金屬離子和難降解的有機物有較好的處理效果,在飲用水源中的內分泌干擾物類污染物的去除方面應用很多。本論文在實驗室中合成不同氧化程度的氧化石墨烯、GO-Ti O2和GO-CTAB三種吸附劑,并對三種吸附劑進行物理化學性質的表征。然后利用這三種吸附劑對水中四環(huán)素和雙酚A(BPA)進行吸附去除實驗,研究溫度、初始濃度、吸附時間、溶液p H和陽離子濃度等因素對吸附過程的影響。結合吸附劑的表征結果和吸附實驗數據,得到如下結論:GO-1、GO-2、GO-3對四環(huán)素的吸附:(1)石墨經過氧化后得到的GO-1、GO-2和GO-3表面都含有不同程度的羧基和羥基等官能團,晶型和結構也發(fā)生了相應的變化,隨著氧化程度的增加,其表面的氧含量也隨之升高。(2)GO-1、GO-2和GO-3對四環(huán)素具有很好的吸附性能,實驗條件下,25℃時GO-1、GO-2和GO-3對四環(huán)素的最大吸附量分別為為74.63mg/g、55.25mg/g和47.26mg/g,且吸附過程在150min內達到吸附平衡。吸附等溫線均能用Frendlich方程很好的擬合,吸附為非均質吸附過程,吸附動力學均可以用擬二級動力學方程進行擬合。(3)隨著溶液p H值的增加,GO-1、GO-2、GO-3對四環(huán)素的吸附量逐漸降低,酸性環(huán)境下更有利于吸附的進行。溶液中陽離子的存在會降低吸附劑對四環(huán)素的吸附量,影響的大小順序為Ca2+K+≈Na+。(4)堿性溶液可以對吸附平衡后的GO-1進行脫附,脫附效果良好,脫附后仍具有較高的吸附量,吸附劑具有較好的循環(huán)再生性能。GO-Ti O2對四環(huán)素的吸附:(1)Ti O2通過水熱反應聚合在GO表面,使GO的晶型和結構有所改變,復合材料中含有Ti元素,表明GO-Ti O2吸附劑的成功合成。(2)GO-Ti O2對四環(huán)素具有優(yōu)越的吸附能力,實驗條件下,25℃時GO-Ti O2對四環(huán)素的最大吸附量為117.98mg/g,吸附等溫線能用Freundlich方程很好的擬合,吸附為吸熱反應,以物理吸附為主。吸附動力學均可以用擬二級動力學方程進行擬合,吸附過程屬于非均質吸附,受邊界層擴散的影響。(3)p H顯著影響GO-Ti O2對四環(huán)素的吸附,隨著p H值的增加,吸附量逐漸降低。二價陽離子Ca2+明顯抑制了吸附的進行。(4)吸附后的吸附劑可在紫外光照射下進行光降解再生,光降解再生率為81.20%,再生4次后對四環(huán)素的吸附量為87.96mg/g,再生性能良好。GO-CTAB對BPA的吸附:(1)通過FTIR、XRD、EDS等手段對GO-CTAB進行表征分析可知,CTAB已成功包覆在GO表面,GO的晶型發(fā)生了改變。(2)GO-CTAB相比G和MWCNT對BPA具有更好的吸附能力,25℃條件下GO-CTAB、G和MWCNT對BPA的最大吸附量分別為236.18mg/g、12.42 mg/g和81.76 mg/g,吸附等溫線均能用Langmuir方程很好的擬合,吸附為放熱的熵減少的過程。吸附動力學均可以用擬二級動力學方程進行擬合,吸附過程屬于單層吸附,邊界層擴散會影響吸附劑BPA的吸附。吸附過程在150min內達到吸附平衡。(3)在酸性和中性范圍內,GO-CTAB、G和MWCNT對BPA的吸附量變化很小,在堿性條件下吸附量明顯降低。陽離子的存在會增強BPA在GO-CTAB上的吸附效果,其中Ca2+對其吸附量增加的效果最明顯。(4)吸附平衡后的GO-CTAB可在0.1mol/L的Na OH堿性溶液中進行脫附,脫附效果良好,脫附4次后仍具有較高的吸附量,吸附劑具有較好的循環(huán)再生性能。
[Abstract]:Environmental endocrine disruptors are a kind of harmful substance secreted by human, animal and industrial production. Endocrine disruptors, which are difficult to be biodegraded and have oxidation resistance, are very harmful to human health and the environment, so how to economically and efficiently manage the endocrine disruptors in the water body has become a hot spot in the field of water treatment. The biggest advantage of the adsorption method is that the metal ions and the hard-degradable organic matters which are difficult to be treated by the biological method have better treatment effect, and the adsorption method has a plurality of application in the removal of the endocrine disruptors in the drinking water source. In this paper, three kinds of adsorbents such as graphene oxide, GO-TiO2 and GO-CTAB were synthesized in the laboratory, and the physical and chemical properties of the three kinds of adsorbents were characterized. The effects of temperature, initial concentration, adsorption time, solution p H and cation concentration on the adsorption process were studied. The adsorption of GO-1, GO-2 and GO-3 on the tetracycline was obtained by combining the characterization results of the adsorbent and the experimental data. (1) The GO-1, GO-2 and GO-3 surfaces obtained after the oxidation of the graphite contain functional groups of different degrees, The crystal form and the structure have also changed correspondingly, and with the increase of the oxidation degree, the oxygen content of the surface of the crystal form also increases. (2) GO-1, GO-2 and GO-3 have good adsorption property to tetracycline. Under the experimental conditions, the maximum adsorption amount of GO-1, GO-2 and GO-3 on tetracycline at 25 鈩，

本文編號：2501037