饮用水中内分泌干扰物的深度处理技术

发布时间：2018-03-27 06:00

本文选题：甲羟孕酮　切入点：孕酮　出处：《江南大学》2012年硕士论文

【摘要】：随着社会工农业的不断发展,水体污染日益加剧,饮用水受污染情况越来越严重。内分泌干扰物是饮用水中非常重要的一类风险物质,它是一种外源性物质,在体内干扰自然激素的合成、分泌、运输、结合、生效和排泄过程,严重干扰和破坏内分泌系统。常规水处理工艺对内分泌干扰物不能完全去除,本文采用臭氧-活性炭深度处理技术以孕酮和甲羟孕酮为目标物进行实验研究。首先从臭氧氧化出发,探究臭氧对孕酮和甲羟孕酮的氧化降解过程,主要包括臭氧氧化动力学以及臭氧降解机理;其次从活性炭吸附处理出发,探究臭氧-活性炭联用技术对水源水的处理效果,主要包括处理出水的毒性、活性炭吸附等温线拟合以及臭氧-活性炭联用工艺的出水水质达标情况。主要结论如下: (1)采用臭氧氧化工艺降解甲羟孕酮,对臭氧降解过程动力学进行研究,考察液相臭氧浓度、pH、羟基自由基(·OH)清除剂(HCO3-)对降解过程的影响。臭氧在本研究条件下能够有效降解水溶液中的甲羟孕酮,采用连续臭氧曝气方式降解时,降解过程遵守一级反应动力学模型obs(?)采用序批式臭氧投加方式进行降解时,降解过程符合二级反应动力学模型(?)。pH的升高和HCO3-的添加都会对降解效果产生负面影响,甲羟孕酮的去除率从pH=3.10时的89.8%下降到pH=9.02时的74.6%,同等反应条件下,添加羟基自由基HCO3-后,降解反应速率常数由0.1463 L·(mg·min)-1下降到0.0495 L·(mg·min)-1,去除率下降了22.2个百分点。 (2)臭氧能够有效地降解孕酮,在连续臭氧曝气方式下,降解过程遵循一级动力学模型(?)。臭氧氧化孕酮去除率可达90%,与甲羟孕酮相同,臭氧降解孕酮同样是在酸性条件下降解速率较高。溶液初始pH从3.23升高到11.04时,孕酮的去除率则从97%下降到了55%。自然水体中存在的HCO3-、Cl-和SO42-均对孕酮的降解过程有一定的抑制作用,只有NO3-对降解过程存在积极意义,NO3-的存在使得孕酮的降解速率提高了1.67倍。采用LC/MS分析臭氧氧化孕酮的降解途径,并且得到A(C20H30O4),、B(C21H30O4)两种氧化产物,分子量分别为334 g·mol-1和346 g·mol-1。 (3)采用煤质活性炭和椰壳活性炭对比吸附孕酮,去除率可达85%以上。且两种活性炭的吸附过程均符合Freundlich等温吸附方程,R20.98。通过以斑马鱼为试验生物,对孕酮的急性毒性进行测定,得出24 h孕酮的LC50=0.73 mg·L-1,EC0=0.5 mg·L-1,EC100=1.0 mg·L-1。整个臭氧-活性炭联合工艺对水源水中的饮用水常规指标均有很好的去除,活性炭吸附能够很好地去除由于臭氧氧化而生成的甲醛和溴酸盐这两种污染物,对甲醛的去除率可达85%以上,对溴酸盐的去除率达100%。
[Abstract]:With the development of social industry and agriculture, water pollution is becoming more and more serious, and drinking water is polluted more and more seriously. Endocrine disruptors are very important risk substances in drinking water, it is a kind of exogenous substances. Disrupting the synthesis, secretion, transport, binding, effective and excretion of natural hormones in vivo, seriously disrupting and disrupting the endocrine system. In this paper, the advanced treatment technology of ozone and activated carbon was used to study the degradation process of progesterone and medroxyprogesterone by ozone. It mainly includes the kinetics of ozone oxidation and the mechanism of ozone degradation. Secondly, from the adsorption treatment of activated carbon, the effect of ozonation combined with activated carbon on the treatment of source water is explored, including the toxicity of treated effluent. The adsorption isotherm fitting of activated carbon and the quality of the effluent from the ozonic-activated carbon combined process are up to standard. The main conclusions are as follows:. 1) degradation of medroxyprogesterone by ozone oxidation process was studied. The effects of pH value of liquid ozone concentration and hydroxyl radical scavenger (OHCO3) on the degradation process were investigated. In this study, the methyloxyprogesterone in aqueous solution could be effectively degraded by ozone, and the degradation was carried out by continuous ozone aeration. The degradation process obeys the first-order reaction kinetics model obsn? The degradation process is in accordance with the second-order reaction kinetic model. The removal rate of medroxyprogesterone decreased from 89.8% of pH=3.10 to 74.6% at pH = 9.02. Under the same reaction conditions, the hydroxyl radical HCO _ 3- was added. The degradation rate constant decreased from 0.1463 L / g min)-1 to 0.0495 L / L / mg / min ~ (-1), and the removal rate decreased by 22.2%. Ozone can effectively degrade progesterone. Under continuous ozone aeration, the degradation process follows a first-order kinetic model. The removal rate of progesterone by ozone oxidation can reach 90%, which is similar to that of medroxyprogesterone. The degradation rate of progesterone by ozone is also higher under acidic conditions. When the initial pH of the solution increases from 3.23 to 11.04, The removal rate of progesterone decreased from 97% to 55%. The degradation of progesterone was inhibited by the presence of HCO3-Cl- and SO42- in natural water. The degradation rate of progesterone was increased by 1.67 times with the presence of no _ 3-. The degradation pathway of progesterone was analyzed by LC/MS and two kinds of oxidation products were obtained, the molecular weight of which were 334g mol-1 and 346g mol -1, respectively. The removal rate of progesterone from coal activated carbon and coconut shell activated carbon was more than 85%. The adsorption process of the two kinds of activated carbon was in accordance with Freundlich isothermal adsorption equation R20.98. the acute toxicity of progesterone was determined by using zebrafish as experimental organism. The results showed that the LC50=0.73 mg L ~ (-1) EC _ (0.5) mg / L ~ (-1) EC _ (100) mg / L ~ (-1) of progesterone was 0.5 mg / L ~ (-1) for 24 h. The combined process of ozone and activated carbon had a good effect on the removal of conventional drinking water indexes in source water. The adsorption of activated carbon can remove formaldehyde and bromate which are produced by ozone oxidation. The removal rate of formaldehyde and bromate can reach more than 85% and 100% respectively.
【学位授予单位】：江南大学
【学位级别】：硕士
【学位授予年份】：2012
【分类号】：R123.1

【引证文献】